CN111244310A - Organic electroluminescent device and organic electroluminescent display device - Google Patents
Organic electroluminescent device and organic electroluminescent display device Download PDFInfo
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- 238000004770 highest occupied molecular orbital Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 49
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 125000001072 heteroaryl group Chemical group 0.000 claims description 19
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
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- 238000006467 substitution reaction Methods 0.000 description 6
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- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 5
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- 101100115215 Caenorhabditis elegans cul-2 gene Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- LONBOJIXBFUBKQ-UHFFFAOYSA-N 2,7-dibromo-9,9-dimethylfluorene Chemical group C1=C(Br)C=C2C(C)(C)C3=CC(Br)=CC=C3C2=C1 LONBOJIXBFUBKQ-UHFFFAOYSA-N 0.000 description 1
- MDXCDMSVFQIDGN-UHFFFAOYSA-N 2,7-dibromo-9-phenylcarbazole Chemical group C=1C(Br)=CC=C(C2=CC=C(Br)C=C22)C=1N2C1=CC=CC=C1 MDXCDMSVFQIDGN-UHFFFAOYSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 1
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- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
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- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
-
- 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
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides an organic electroluminescent device and an organic electroluminescent display device, wherein the organic electroluminescent device comprises a hole injection layer, a hole transport layer and one or more luminescent layers, the hole injection layer comprises a material with the HOMO energy level of-4.9 eV-5.2 eV, the mobility of the material is 3/4-1/50 of the material of the hole transport layer used in cooperation, the voltage of the device can be reduced, and the service life of the device can be prolonged. Meanwhile, the display device uses the device structure provided by the invention, and the hole injection layer is prepared in a mode of not distinguishing the light-emitting points, so that the crosstalk problem of the display device can be effectively reduced, and the stability of the product is improved.
Description
Technical Field
The invention belongs to the technical field of organic light-emitting materials, and relates to an organic electroluminescent device and an organic electroluminescent display device.
Background
The basic structure and technology of Organic Light-Emitting Diodes (OLEDs) was first discovered by professor dungeon (china w.tang) in 1979 in kodak corporation. The OLED technology has the advantages of self-luminescence, wide viewing angle, high contrast, low power consumption, fast response speed, etc., and is widely applied to high-end products in the fields of flat panel display, lamp illumination, micro-display, etc. Since the OLED has a unique multi-layer organic film structure, the construction of thin film materials with different functional layers is always the research focus of the OLED industry, which restricts the production process and application range of OLED products and affects the industrialization process of OLED products in the fields of display, illumination and the like.
In a plurality of functional layers, the hole injection layer is used between the anode and the hole transport layer, plays a role in connecting the anode and the hole transport layer, can effectively control the hole injection rate and enhance the hole injection performance, and can modify the defects of the anode and improve the stability of hole injection. In the OLED structure with the multiple light-emitting layers, the hole injection layer can control the photoelectric property of the device by controlling the material property and the film thickness, and plays an important role in the stability of the device. Therefore, the method has very important significance for the practical application of the OLED.
The common hole injection method mainly utilizes the tunneling effect, and generally uses a material with a HOMO level higher than 6eV and a LUMO level less than 3eV, which can be used as a monolayer or doped into a hole transport material. However, when such materials are used, whether they are used as a single layer or doped into a hole transport material, crosstalk between light emitting points in a display device is easily caused, and the photoelectric properties of the product are affected, so that the doping ratio needs to be strictly controlled, usually below 3%, which is very difficult for production control, and the device performance is high and the doping ratio is poor.
Therefore, in the field, it is of great significance to select a proper hole injection material, develop a device with better photoelectric performance, avoid the crosstalk problem of a display device and improve the performance and stability of a product.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention provides an organic electroluminescent device and an organic electroluminescent display device. The structure of the organic electroluminescent device is matched with the energy level of the material, so that the voltage of the device is reduced, the stability of the material is improved, the service life of the device is prolonged, and meanwhile, the organic electroluminescent display device is provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides an organic electroluminescent device comprising a hole injection layer, a hole transport layer and one or more emissive layers, wherein the hole injection layer comprises a material having a HOMO level between-4.9 eV and-5.2 eV and has a mobility of 3/4-1/50 of the material of the hole transport layer in contact therewith.
In the present invention, one or more layers may also be expressed as at least one layer.
In the invention, a material with the HOMO energy level between-4.9 eV and-5.2 eV (such as-4.9 eV, -4.95eV, -5.0eV, -5.1eV, -5.12eV, -5.14eV, -5.16eV, -5.18eV or-5.2 eV) is used as a hole injection layer material, so that the energy level of the material is matched with that of the device, the voltage of the device is reduced, the stability of the material is increased, and the service life of the device is prolonged; materials with mobility of 3/4-1/50 (3/4, 1/1, 1/2, 1/3, 1/4, 1/5, 1/6, 1/7, 1/8, 1/9, 1/10, 1/12, 1/15, 1/18, 1/20, 1/25, 1/28, 1/30, 1/33, 1/35, 1/38, 1/40, 1/42, 1/45, 1/48 or 1/50) of the connected hole transport layer materials are used as hole injection materials, so that under the condition that the device performance is further stable, the problem of crosstalk of a display device based on the structure is reduced, the process difficulty is reduced, and the product stability is improved.
The hole injection layer further comprises a P-type doped material, and the doping proportion of the P-type doped material is 3% -10%, such as 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Preferably, the material of the hole injection layer is a material with a HOMO energy level between-4.95 eV and-5.15 eV.
Preferably, the material of the hole injection layer is a compound having a structure shown in formula I below:
wherein Ar is1Is selected fromAny one of the following groups:
dotted line represents Ar1The attachment position of the group;
Ar2、Ar3、Ar4and Ar5Each independently selected from substituted or unsubstituted aryl of C5-C30, substituted or unsubstituted heteroaryl of C5-C30, substituted or unsubstituted fused ring aryl of C5-C30, and substituted or unsubstituted fused ring heteroaryl of C5-C30;
Ra、Rb、Rc、Rd、Re、Rf、Rgand RhIndependently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 fused ring aryl, substituted or unsubstituted C3-C30 fused ring heteroaryl;
na、nb、ncand nfEach independently is an integer of 1 to 5 (e.g., 1, 2, 3, 4, or 5), ndIs an integer of 1 to 3 (for example, 1, 2, 3), ne、ngAnd nhEach independently is an integer from 1 to 4 (e.g., may be 1, 2, 3, or 4).
X is selected from O, S, Se, NR2、CR3R4、SiR5R6Wherein R is2、R3、R4、R5、R6Each independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 fused ring aryl, and substituted or unsubstituted C3-C30 fused ring heteroaryl.
In the invention, the material is selected as the material of the hole injection layer, the substituent on the group where X is located keeps the para-position relationship, which is beneficial to the synergistic effect between two electron-donating groups and has stronger electron-rich characteristic, and the material of the relative connection mode of other substituent can cause the charge transport property to be reduced, thereby causing the luminous efficiency of the organic electroluminescent device to be poor. In addition, in the invention, extra aryl is introduced at the ortho position of the arylamine aryl in the material structure to generate steric effect, adjust the intermolecular self-assembly and adjust the transmission performance.
In the structure of formula I of the present invention, each R1Each independently represents any number from 0 to the maximum possible number; plural R1Identical or different, two R in adjacent position1May be linked to form a ring; plural R1Identical or different, two R in adjacent position1May be joined to form a ring.
R3And R4Are independent of one another or are linked to one another to form a ring, R5And R6Are independent of each other or are linked to each other to form a ring;
preferably, R3And R4Are connected with each other to form a ring. R5And R6Are connected with each other to form a ring.
In the present invention, the term "substituted or unsubstituted" means that the substituent is substituted with one or more substituents selected from the group consisting of halogen, alkyl, alkoxy, aryl, heteroaryl, cyano and hydroxyl, and the bond between the substituents "-" represents a ring structure, and means that the bond site is located at any position on the ring structure where a bond can be formed.
X is selected from CR3R4Wherein R is3And R4Each independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 fused ring aryl, and substituted or unsubstituted C3-C30 fused ring heteroaryl.
Ar2Is substituted or unsubstituted C7-C30 condensed ring aryl, substitutedOr unsubstituted fused ring heteroaryl of C7-C30.
Preferably, the material of the hole injection layer is a compound having a structure represented by the following formula II-1 or formula II-2:
ar in formula II1、Ar2、Ar3、R1X and n have the same limits as in formula I above.
Further preferably, the material of the hole injection layer is a compound having a structure represented by the following formula III:
in the formula III, Ar 2-Ar 5 and X, R1And n has the same limits as above.
In the material structure of the invention Ar2The substitution positions are all positioned at the ortho positions of the N atoms, and the inventor of the invention finds that the substitution positions are important, so that the photoelectric efficiency can be further improved, and the service life of the organic electroluminescent device can be greatly improved. The reason for this is not clear, and it is possible to guess the following: the aromatic substituent at the ortho position ensures that the steric hindrance of the whole aromatic ammonia part is larger, so that the three-dimensional space orientation of the structure is fixed, the whole molecule can be in a unique energy level structure, the charge transmission performance is further enhanced, in addition, the molecule with large steric hindrance can also have a unique intermolecular self-assembly form during film formation, the film formation is more facilitated, the stable film formation can bring more beneficial life characteristics, further, under the condition of larger steric hindrance, the sublimation temperature is generally reduced, so that the high temperature is not needed during film formation by evaporation, and the reduction of the life caused by the thermal decomposition or thermal denaturation of the molecule during film formation can be reduced.
For the same reasons, Ar in the preferred structure4The substitution position of (b) is also preferably located ortho to the N atom. And Ar3、Ar5The substitution position(s) is preferably located para to the N atom so as not to render the steric hindrance too large, resulting in an excessively inaccessible molecule, and the compound of the substitution position(s) can also provide better charge transport properties.
In a preferred embodiment of the present invention, the material of the hole injection layer is any one of compounds having structures represented by InvP-1 to InvP-41:
preferably, the organic electroluminescent device has a structure comprising an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode in sequence from bottom to top;
or the organic electroluminescent device sequentially comprises an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode from bottom to top;
or the organic electroluminescent device sequentially comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode from bottom to top;
or the organic electroluminescent device sequentially comprises an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode from bottom to top.
Preferably, the hole injection layer has a thickness of 0.5nm to 200nm, for example 0.5nm, 1nm, 3nm, 5nm, 8nm, 10nm, 13nm, 15nm, 18nm, 20nm, 30nm, 50nm, 80nm, 90nm, 100nm, 130nm, 150nm, 180nm or 200nm, preferably 1nm to 20nm, more preferably 5nm to 15 nm.
In the present invention, the hole injection layer is preferably prepared by vacuum evaporation or spin coating or ink jet printing.
In the invention, the hole injection layer is positioned between the anode and the hole transport layer, is used as a medium for leading holes from the electrode to enter, and has the functions of electrode modification, energy level modification and hole transport, thereby influencing the stability, the electrical property and the service life of the device. The organic electroluminescent device with the structure has better stability, more excellent electrical property and longer service life.
In another aspect, the present invention also provides an organic electroluminescent display device using the organic electroluminescent device as described above.
In the present invention, the hole injection layer of the organic electroluminescent display device is prepared in a manner that does not distinguish between light emitting points.
In the present invention, the organic electroluminescent display device includes 2 or more light emitting points, and a single light emitting point includes a structure having one or more organic electroluminescent devices as described above.
In the organic electroluminescent display device, the hole injection layer positioned between the anode and the hole transport layer is uniformly prepared in a manner of not distinguishing the luminous points, so that the lower mobility reduces the occurrence of crosstalk problems, the device effectively avoids the occurrence of crosstalk problems under the condition of greatly reducing the difficulty of the preparation process, the product cost is lower, and the stability is better.
In the present invention, one or more represents at least one.
In general, organic electroluminescent devices and devices include first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) may be used2) And transparent conductive oxide materials such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer is a single compound material. The material is selected from, for example, compounds represented by InVP-1 to InVP-41 below. The HOMO energy level of the hole transport layer matched with the hole injection layer is between 5.10 and 5.45eV, the mobility of the hole injection material is 3/4 to 1/50 of the hole transport material, the hole injection layer further comprises a P-type dopant with the doping proportion of 3 to 10 percent, and the P-type dopant comprises organic materials with large steric hindrance deep energy levels, including but not limited to F4-TCNQ.
The hole transport layer material is selected from aromatic amine derivatives such as compounds shown in HT-1 to HT-34 below or any combination thereof:
the light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.
According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.
In one aspect of the invention, the light-emitting layer employs a fluorescent electroluminescence technique. The luminescent layer fluorescent host material may be selected from, but not limited to, one or more of BFH-1 to BFH-16 listed below.
In one aspect of the invention, the light-emitting layer employs a fluorescent electroluminescence technique. The luminescent layer fluorescent dopant may be selected from, but is not limited to, the combination of one or more of BFD1-BFD09 listed below.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The host material of the light emitting layer is selected from, but not limited to, one or more of GPH-1-GPH-80
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer can be selected from, but is not limited to, one or more combinations of GPD-1-GPD-57, RPD-1-RPD-29 and YPD-1-YPD-11 listed below.
The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
In one aspect of the invention, the electron transport layer material may be selected from, but is not limited to, the combination of one or more of ET-1 through ET-57 listed below.
The device and apparatus may further comprise an electron injection layer between the electron transport layer and the cathode, the electron injection layer being made of materials including, but not limited to, one or more of the following: LiF, NaCl, CsF, Li2O、Cs2CO3、BaO、Na、Li、Ca。
Each of the organic layers in the organic electroluminescent device and apparatus of the present invention can be prepared by a vacuum evaporation method, a molecular beam evaporation method, a spin coating method in a solvent, a bar coating method, an ink jet printing method, or the like. The metal electrode can be prepared by an evaporation method or a sputtering method.
Compared with the prior art, the invention has the following beneficial effects:
the material is used as a hole injection layer material, so that the energy level of the material is matched with that of a device, the voltage of the device is reduced, the stability of the material is improved, and the service life of the device is prolonged; the organic electroluminescent device based on the device effectively reduces the occurrence of crosstalk under simple preparation process conditions, reduces the cost and simultaneously improves the product stability.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the present invention, the preparation route of the compound is shown as G1 or G2 below.
Scheme G1:
scheme G2:
preparation example 1
Preparation of Compound InvP-4
To a solution of compound M1(29g,118.21mmol), bromobenzene (18.56g,118.21mmol) and sodium tert-butoxide (t-BuoNa) (26.13g,271.89mmol) in toluene (toluene) (350ml) was added pd (dppf) cl2(0.86g,1.18mmol) and SPhos (0.97g,2.36 mmol). The resulting reaction mixture was heated to 90C under nitrogen and stirred overnight. After the reaction solution was cooled to room temperature, it was diluted with toluene and washed with water. After separation, the organic phase is MgSO4And (5) drying. The solvent was evaporated to dryness and the residue was purified by column chromatography on silica gel with ethyl acetate/petroleum ether (1/10) as the mobile phase to give compound M2(25.6g) as an off-white solid.
To a solution of compound M2(26g,80.89mmol), M3(16g,33.74mmol) and sodium tert-butoxide (t-BuoNa) (9.72g,101.12mmol) in toluene (toluene, 240ml) was added Pd2(dba)3(1.23g, 1.35mmol) and tri-tert-butylphosphine (tert-Bu3P, 0.54g, 2.70 mmol). The resulting reaction mixture was heated to 110C under nitrogen and stirred overnight. Cooling the reaction solution to room temperature, diluting the reaction solution with toluene, and washing the reaction solution with water. After separation, the organic phase is MgSO4And (5) drying. After evaporation of the solvent to dryness, the residue was purified by column chromatography on silica gel using methylene chloride/petroleum ether (1/10) as a mobile phase to give compound InvP-4(16g) as a white solid. Calculated molecular weight: 955.22, found C/Z: 954.4.
Preparation example 2
Compound InvP-14
The preparation of (1):
different from the preparation of the compound InvP-4, the compound M1 is replaced by
The compound InvP-14 was prepared under otherwise identical conditions, e.g., molar ratios of starting materials and reaction temperatures and times, as in InvP-4. Calculated molecular weight: 933.21, found C/Z: 933.42.
Preparation example 3
Preparation of Compound InvP-37:
to a solution of compound M2(11g,35mmol), M4(13g,30mmol) and sodium tert-butoxide (t-BuoNa) (5.8g,60mmol) in toluene (toluene, 150ml) was added Pd2(dba)3(1.23g, 1.35mmol) and tri-tert-butylphosphine (tert-Bu3P, 0.54g, 2.70 mmol). The resulting reaction mixture was heated to 110C under nitrogen and stirred overnight. The reaction mixture was diluted with toluene, the solid was removed by filtration, and the filtrate was evaporated to dryness, and the residue was purified by column chromatography on silica gel using methylene chloride/petroleum ether (1/10) as a mobile phase to give compound InvP-37(12.2g) as a white solid. Calculated molecular weight: 678.88, found C/Z: 678.30.
Preparation example 4
In this example, the compounds InvP-1, InvP-2, InvP-3, InvP-5, InvP-7, InvP-30, and InvP-31 were prepared.
InvP-1
The procedure of preparation was similar to InvP-4, except that starting material M3 was replaced with 2, 7-dibromo-9, 9-dimethyl-9H-fluorene to give compound InvP-1: calculated molecular weight: 833.09, found C/Z: 832.38.
InvP-2
The preparation process of (A) is similar to that of InvP-4 except that the preparation raw material M3 is replaced by 2',7' -dibromospiro [ cyclopentyl-1, 9' -fluorene]To give compound InvP-2: calculated molecular weight: 859.12, found C/Z: 858.40.
InvP-3
The preparation process of (A) is similar to that of InvP-4 except that the preparation raw material M3 is replaced by 2',7' -dibromospiro [ cyclohexyl-1, 9' -fluorene ]]To obtain compound InvP-3: calculated molecular weight: 873.16, found C/Z: 873.25.
InvP-5
The preparation process is similar to InvP-4, except that the preparation raw material M3 is replaced by 3, 7-dibromodibenzo [ b, d ]]Furan to give compound InvP-5: calculated molecular weight: 807.01, found C/Z: 807.87.
InvP-7
Was prepared similarly to InvP-4, except that starting material M3 was replaced with 2, 7-dibromo-9-phenyl-9H-carbazole to give compound InvP-7: calculated molecular weight: 882.12, found C/Z: 881.54.
InvP-30
The preparation process is similar to InvP-37, and the synthetic route is as follows:
in the specific preparation process, the conditions in the specific preparation process are selected to obtain a compound InvP-30: calculated molecular weight: 1005.28, found C/Z: 1004.31.
HOMO and LUMO were determined for compounds InvP-1, InvP-14, InvP-2, InvP-3, InvP-5, InvP-7, InvP-30, InvP-31 and InvP-37, and HOMO and LUMO were determined for HAT (CN)6, NPB and F4-TCNQ simultaneously for comparison. The measurement method is as follows:
(1)HOMO&LUMO
and (3) carrying out cyclic voltammetry test on the sample by using an electrochemical workstation, wherein the workstation adopts a three-electrode system, a platinum electrode is a working electrode, a platinum wire electrode is a counter electrode, and an Ag wire electrode is a reference electrode. The sample is dissolved in 10mL of dry dichloromethane or ultra-dry tetrahydrofuran, tetra-n-butyl perchloric acid or tetra-n-butyl ammonium hexafluorophosphate is used as electrolyte salt, argon is introduced into the test sample for protection, the voltage range is-2V, the scanning speed is 50-200 mV/s, and the number of scanning turns is 2-50.
HAT (CN) for comparison6NPB (HT2) and F4-TCNQ (HI-1) have the following structures:
(2) mobility ratio
Thin film samples were tested using the TOF method. The sample adopts ITO glass with the substrate thickness of 150nm as an anode, a 2000nm test film is evaporated in a test area after cleaning and drying, Ag with the thickness of 150nm is evaporated as a cathode, and an electric field E is applied to the sample to be 1 multiplied by 105V/cm. Wherein the product of the invention is InvP-1, InvP-14, InvP-2, InvP-3, InvP-5, InvP-7, InvP-30, InvP-31, InvP-37, HAT (CN)6And HT2 evaporated single layer film, HT2: 2% HI1 was co-evaporated.
The results are shown in Table 1.
TABLE 1
| Compound (I) | HOMO(eV) | LUMO(eV) | Mobility (cm/V.s) |
| InvP-1 | -4.9 | -1.8 | 2.5×10-5 |
| InvP-2 | --5.1 | --2.1 | 6.5×10-5 |
| InvP-3 | -4.8 | -2.1 | 3.4×10-5 |
| InvP-4 | -5.1 | -2.0 | 8.5×10-5 |
| InvP-5 | -5.2 | -2.3 | 2.5×10-4 |
| InvP-7 | -5.2 | -2.1 | 3.1×10-4 |
| InvP-14 | -5.1 | -1.6 | 8×10-5 |
| InvP-30 | -5.0 | -2.7 | 2.6×10-5 |
| InvP-31 | -5.3 | -2.6 | 2.1×10-5 |
| InvP-37 | -5.0 | -1.8 | 1×10-4 |
| HAT(CN)6 | -7.5 | -4.4 | 2×10-4 |
| HT2：3％HI1 | / | / | 8×10-4 |
| Compound HT2 | -5.2 | -3.6 | 5.1×10-4 |
| Compound HI1 | -8.3 | -5.2 | / |
According to the invention, the HOMO energy level of the compound material is 4.95-5.15 eV, the mobility is lower than that of a contrast compound, the potential barrier of hole migration can be effectively reduced, the diffusion of holes is inhibited, the electron injection performance is enhanced, and the efficiency of an organic electroluminescent device manufactured by using the compound as a hole injection layer material is further improved.
Example 1
The preparation process of the organic electroluminescent device in the embodiment is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
device example IVD-1
The device structure sequentially comprises an anode, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode from bottom to top.
Placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to<1×10-5Pa, performing vacuum thermal evaporation on the anode layer film sequentially to obtain a 10nm InvP-1: 3% of HI-1(F4-TCNQ) is used as a hole injection layer, 60nm of a compound HT2 is used as a hole transport layer, 20nm of a compound BFH-4: 5% of BFD-7 (weight percentage) is used as a light emitting layer, 25nm of a compound ET-46: 50% of ET-57 (weight percentage) mixture is used as an electron transport layer, 1nm of LiF is used as an electron injection layer, and 150nm of metal aluminum is used as a cathode. What is needed isThe total evaporation rate of the organic layer and LiF is controlled at 0.1 nm/s, and the evaporation rate of the metal electrode is controlled at 1 nm/s.
Examples 2 to 10
The difference from example 1 is only that InvP-1 is replaced by InvP-2, InvP-3, InvP-5, InvP-7, InvP-14, InvP-30, InvP-31, InvP-37 and F4-TCNQ co-steaming, respectively, in the same proportions as in example 1.
Example 11
The only difference from example 1 is that the thickness of the hole injection layer was 0.5 nm.
Example 12
The only difference from example 1 is that the thickness of the hole injection layer was 1 nm.
Example 13
The only difference from example 1 is that the thickness of the hole injection layer was 5 nm.
Example 14
The only difference from example 1 is that the thickness of the hole injection layer was 20 nm.
Example 15
The only difference from example 1 is that the thickness of the hole injection layer was 50 nm.
Example 16
The only difference from example 1 is that the thickness of the hole injection layer was 100 nm.
Example 17
The only difference from example 1 is that the thickness of the hole injection layer was 200 nm.
Example 18: IVD-2
This example provides an organic electroluminescent display device comprising two independently controllable light-emitting points, one of which employs the same device structure as in example 1, and the other employs a device structure differing from example 1 only in that a 30nm compound GPH-77: 5% PRD-2 (weight percentage) is employed as a light-emitting layer.
Comparative example 1
A CCD-1 device was fabricated in the same manner as in device example IVD-1, except that InvP-1 in the hole injection layer was replaced with HAT (CN) 6.
Comparative example 2
Device CCD-2 provides an organic electroluminescent device comprising two independently controllable light-emitting points, one of which employs the same device structure as CCD-1, and the other employs a device structure differing from CCD-1 only in that 30nm of compound GPH-77: 5% PRD-2 (weight percentage) is employed as a light-emitting layer.
Comparative example 3
Device CCD-3 was fabricated in the same manner as device example IVD-1, except that the total thickness of the hole injection layer was changed to 120nm of a mixture of HT2: 2% HI1 (wt.%).
Comparative example 4
Device CCD-4 provides an organic electroluminescent display device comprising two independently controllable light emitting points, one of which employs the same device structure as in comparative example 3, and the other employs a device structure differing from CCD-3 only in that 30nm of compound GPH-77: 5% PRD-2 (weight percentage) is employed as a light emitting layer.
Comparative example 5
The only difference compared to example 1 is that the hole injection layer has a thickness of 0.3 nm.
Comparative example 6
The only difference compared to example 1 is that the hole injection layer has a thickness of 300 nm.
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the organic electroluminescent devices prepared in examples 1 to 3 and comparative examples 1 to 2 were measured at the same brightness using a digital source meter and a luminance meter. Specifically, the driving voltage and the current efficiency were 1000cd/m in luminance2And (5) recording. The luminance of the device is reduced from an initial luminance of 3000cd/m2 to 2850cd/m in order to maintain the constant current at the lifetime LT95 of the device2The elapsed time. The device lifetime LT95 reported in the table is a relative value, i.e. a value relative to the device CCD-1.
The properties of the organic electroluminescent devices of examples 1 to 10 and comparative examples 1 and 3 are shown in Table 2 below:
TABLE 2
The properties of the organic electroluminescent devices of examples 11 to 17 and comparative examples 5 to 6 are shown in Table 3 below:
TABLE 3
The properties of the organic electroluminescent display device of example 18 and comparative examples 2 and 4 are shown in table 4 below:
TABLE 4
As can be seen from the data in tables 1-3, the device and the material combination can effectively reduce the voltage of the device, improve the efficiency and the service life of the device, ensure that the voltage of the device is reduced to be below 2.8V, and the efficiency of the device can reach more than 0.33Cd/A, even more than 1.1 Cd/A; LT95 can be up to 40% or more, and even up to 110% or more.
As can be seen from the data in table 4, the device of the present invention has a significant effect on reducing crosstalk between devices in the device, and it can be seen that the single color devices in the device of the comparative example are lit simultaneously with a significant color shift compared to the single color devices, whereas the device of the present invention has a color coordinate deviation of less than 0.002 under the same conditions.
The applicant states that the present invention is illustrated by the above embodiments of the organic electroluminescent device of the present invention, but the present invention is not limited to the above embodiments, i.e. it does not mean that the present invention must rely on the above embodiments to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (14)
1. An organic electroluminescent device comprises a hole injection layer, a hole transport layer and one or more luminescent layers, and is characterized in that the hole injection layer comprises a material with an HOMO energy level of-4.9 eV-5.2 eV, and the mobility of the material is 3/4-1/50 of the material of the hole transport layer used in combination.
2. The organic electroluminescent device according to claim 1, wherein the hole injection layer further comprises a P-type dopant material, and the doping ratio of the P-type dopant material is 3% to 10%.
3. The organic electroluminescent device according to claim 1 or 2, wherein the material of the hole injection layer has a HOMO level of between-4.95 eV and-5.15 eV.
4. The organic electroluminescent device according to any one of claims 1 or 2, wherein the material of the hole injection layer is a compound having a structure represented by formula I below:
wherein Ar is1Any one selected from the following groups:
dotted line represents Ar1The attachment position of the group;
Ar2、Ar3、Ar4and Ar5Each independently selected from substituted or unsubstitutedSubstituted aryl of C5-C30, substituted or unsubstituted heteroaryl of C5-C30, substituted or unsubstituted condensed ring aryl of C5-C30, substituted or unsubstituted condensed ring heteroaryl of C5-C30;
Ra、Rb、Rc、Rd、Re、Rf、Rgand RhEach independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 fused ring aryl, and substituted or unsubstituted C3-C30 fused ring heteroaryl;
na、nb、ncand nfEach independently is an integer of 1 to 5, ndIs an integer of 1 to 3, ne、ngAnd nhEach independently is an integer from 1 to 4;
x is selected from O, S, Se, NR2、CR3R4、SiR5R6Wherein R is2、R3、R4、R5、R6Each independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 fused ring aryl, and substituted or unsubstituted C3-C30 fused ring heteroaryl; r3And R4Are independent of one another or are linked to one another to form a ring, R5And R6Are independent of one another or are linked to one another to form a ring.
5. The organic electroluminescent device of claim 4, wherein R is3And R4Are connected with each other to form a ring;
R5and R6Are connected with each other to form a ring;
x is selected from CR3R4Wherein R is3And R4Each independently selected from substituted or unsubstitutedThe aryl group of the compound is C1-C15, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 fused ring aryl, and substituted or unsubstituted C3-C30 fused ring heteroaryl;
Ar2is a substituted or unsubstituted condensed ring aryl of C7-C30, or a substituted or unsubstituted condensed ring heteroaryl of C7-C30.
6. The organic electroluminescent device according to claim 4, wherein the material of the hole injection layer is a compound having a structure represented by formula II-1 or formula II-2 below:
ar in formula II1、Ar2、Ar3、R1X and n have the same limits as in claim 4.
7. The organic electroluminescent device according to claim 4, wherein the material of the hole injection layer is a compound having a structure represented by the following formula III:
in the formula III, Ar 2-Ar 5 and X, R1And n has the same limitations as claim 4.
8. The organic electroluminescent device according to claim 4, wherein the material of the hole injection layer is any one of compounds having a structure represented by InvP-1 to InvP-41:
9. the organic electroluminescent device according to claim 1, wherein the organic electroluminescent device has a structure comprising, from bottom to top, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode;
or the organic electroluminescent device sequentially comprises an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode from bottom to top;
or the organic electroluminescent device sequentially comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode from bottom to top;
or the organic electroluminescent device sequentially comprises an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode from bottom to top.
10. The organic electroluminescent device according to claim 1, wherein the hole injection layer has a thickness of 0.5nm to 200nm, preferably 1nm to 20nm, and more preferably 5nm to 15 nm.
11. The organic electroluminescent device according to claim 1, wherein the hole injection layer is prepared by vacuum evaporation or spin coating.
12. An organic electroluminescent display device, characterized in that the organic electroluminescent display device uses the organic electroluminescent device according to any one of claims 1 to 11.
13. The organic electroluminescent display device according to claim 12, wherein the hole injection layer of the organic electroluminescent display device is prepared in such a manner that a light emitting point is not distinguished.
14. The organic electroluminescent display device according to claim 12, wherein the organic electroluminescent display device comprises 2 or more light-emitting points, and a single light-emitting point comprises a structure having one or more organic electroluminescent devices according to claim 1.
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| CN113437231A (en) * | 2021-06-22 | 2021-09-24 | 云谷（固安）科技有限公司 | Display panel and display device |
| WO2023125276A1 (en) * | 2021-12-28 | 2023-07-06 | 北京鼎材科技有限公司 | Organic compound and use thereof |
| WO2024113176A1 (en) * | 2022-11-29 | 2024-06-06 | 京东方科技集团股份有限公司 | Organic electroluminescent component and display device |
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