CN116283790B - Pyrimidine structure-containing compound and organic electroluminescent device prepared from same - Google Patents
Pyrimidine structure-containing compound and organic electroluminescent device prepared from same Download PDFInfo
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- CN116283790B CN116283790B CN202111487632.1A CN202111487632A CN116283790B CN 116283790 B CN116283790 B CN 116283790B CN 202111487632 A CN202111487632 A CN 202111487632A CN 116283790 B CN116283790 B CN 116283790B
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- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a pyrimidine-containing compound and an organic electroluminescent device prepared from the same, and belongs to the technical field of semiconductor materials. The structure of the compound is shown as a general formula (1), a bridging mode is introduced between two pyrimidine structural units, and the formed compound has the characteristics of higher glass transition temperature, high molecular thermal stability, good electron mobility, lower evaporation temperature, proper HOMO/LUMO energy level and the like.
Description
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to a pyrimidine structure-containing compound and an organic electroluminescent device prepared from the same.
Background
The organic electroluminescent device (OLED: organic LightEmission Diodes) technology can be used for manufacturing novel display products and novel illumination products, is hopeful to replace the existing liquid crystal display and fluorescent lamp illumination, and has wide application prospect. The OLED device has a sandwich-like structure and comprises electrode material film layers and organic functional materials clamped between different electrode material film layers, and various organic functional materials are mutually overlapped together according to purposes to jointly form the OLED light-emitting device. When voltage is applied to the electrodes at the two ends of the OLED light-emitting device serving as a current device and positive and negative charges in the organic layer functional material film layer are acted through an electric field, the positive and negative charges are further compounded in the light-emitting layer, and thus OLED electroluminescence is generated.
Currently, the OLED display technology has been applied in the fields of smart phones, tablet computers and the like, and further will expand to the large-size application fields of televisions and the like. However, compared with the actual product application requirements, the performance of the OLED device, such as luminous efficiency and service life, needs to be further improved. In order to realize the continuous improvement of the performance of the OLED device, the OLED photoelectric functional material is required to be continuously researched and innovated, and an OLED functional material with higher performance is created.
The OLED photoelectric functional materials applied to OLED devices can be divided into two main categories in terms of application, namely charge injection transport materials and luminescent materials. Further, the charge injection transport material may be classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and as the charge transport material, it is required to have good carrier mobility, high glass transition temperature, and the like, and for an OLED device, electrons are injected from a cathode, then transferred to a hole blocking layer through an electron transport layer, and then transferred to a host material, and the holes are recombined in the host material, thereby generating excitons. Therefore, the injection capability and the transmission capability of the hole blocking layer and the electron transmission layer are improved, the device driving voltage is reduced, and meanwhile, the high-efficiency electron-hole recombination efficiency is obtained. Therefore, the hole blocking layer and the electron transporting layer are very important, and they are required to have high electron injection ability, transport ability, and high durability.
The heat resistance and film stability of the material are also important for device lifetime. A material having low heat resistance is likely to be decomposed not only at the time of material vapor deposition but also by heat generated by the device at the time of device operation, and causes material deterioration. Under the condition of poor phase stability of the material film, the material also generates film crystallization in a short time, so that the organic film layer is directly separated, and the device is deteriorated. Therefore, the materials used are required to have high heat resistance and good film stability.
With the remarkable progress of OLED devices, the performance requirements for materials are increasing, not only are they required to have good material stability, but also to achieve good efficiency and lifetime at low driving voltages. However, the current hole blocking layer has insufficient heat resistance stability, and meanwhile, the electron tolerance of the material has defects, so that the material is separated or decomposed in a phase state when the device works.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a compound containing a pyrimidine structure and an organic electroluminescent device prepared from the compound. The compound has the advantages of quick electron injection and transmission capability, good heat-resistant stability and excellent electron durability, is applied to an organic electroluminescent device, and can achieve good efficiency and service life under low driving voltage.
The technical scheme of the invention is as follows:
a pyrimidine structure-containing compound, the structure of which is shown in a general formula (1):
in the general formula (1), L is represented by a structure shown in a general formula (C-1), a general formula (C-2), a general formula (C-3) or a general formula (C-4);
Ar1 and Ar2 are respectively and independently represented by a structure shown in a general formula (a) or a general formula (b);
ra, rb, rc are each independently a phenyl group, a naphthyl group, or a biphenyl group.
Preferably, the structure of the compound is shown as a general formula (1):
in the general formula (1), L is represented by a structure shown in a general formula (C-1), a general formula (C-2), a general formula (C-3) or a general formula (C-4);
Ar1 and Ar2 are respectively and independently represented by a structure shown in a general formula (a), a general formula (b-1) or a general formula (b-2);
ra, rb, rc are each independently a phenyl group, a naphthyl group, or a biphenyl group.
Preferably, the structure of the compound is shown as any one of the general formulas (1-1) to (1-36):
In the general formulae (1-1) to (1-36), R 1、R2 is independently represented as phenyl, naphthyl or biphenyl.
Preferably, the general formula (a) is represented by any one of the following structures:
The general formula (b) is represented by any one of the following structures:
the general formula (c) is represented by any one of the following structures:
preferably, the structure of the compound is shown as any one of the general formulas (2-1) to (2-16):
in the general formulae (2-1) to (2-16), ra, rb, rc are each independently a phenyl group, a naphthyl group or a biphenyl group.
The specific structure of the compound is preferably one of the following structures:
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An organic electroluminescent device comprises a first electrode and a second electrode, wherein a plurality of organic thin film layers are arranged between the first electrode and the second electrode of the organic electroluminescent device, and at least one organic thin film layer contains the compound containing the pyrimidine structure.
Preferably, the multi-layered organic thin film layer includes a hole blocking layer containing the pyrimidine structure-containing compound.
Preferably, the multi-layered organic thin film layer includes an electron transport layer containing the pyrimidine structure-containing compound.
More preferably, the electron transport layer further comprises lithium octahydroxyquinoline.
The beneficial technical effects of the invention are as follows:
The compound disclosed by the invention is based on a pyrimidine structure, and two pyrimidine groups are bridged by a triphenyl bridging mode, so that the compound has higher glass transition temperature, good electron tolerance, good molecular thermal stability, proper HOMO/LUMO energy level, lower evaporation temperature and good electron mobility, and can effectively improve the photoelectric property and the service life of an OLED device when being used as a hole blocking layer or an electron transport layer of the OLED.
The compound can further delocalize the LUMO electron cloud distribution of the material, so that the electron tolerance of the material can be improved, and the electron stability of the material can be effectively improved. In addition, the structure of the invention can increase weak interaction in molecules, effectively reduce vapor deposition temperature of molecules and improve thermal durability of the material. Furthermore, the structure of the invention can inhibit pi-pi accumulation among molecules, obviously improve the electron mobility of the molecules and reduce the driving voltage of the device. In addition, due to the existence of the electricity-absorbing conjugation function of the junction, the vitrification transfer temperature of the material is raised, and the film stability of the material is effectively improved. Therefore, the device driving voltage can be effectively reduced, the device efficiency is improved, and the service life is prolonged.
The compound adopted by the invention is based on a bilateral pyrimidine structure, and the compound with the structure has high glass transition point Tg (for example, more than 125 ℃), lower evaporation temperature (for example, less than 335 ℃), higher electron mobility, stable film stability and excellent heat resistance.
The compound disclosed by the invention is used as a hole blocking layer material, has excellent electron transmission capability and good hole blocking capability, and can effectively reduce the device driving voltage, improve the device efficiency and prolong the service life.
Drawings
Fig. 1 is a schematic structural view of an organic electroluminescent device according to the present invention;
In the figure, 1, a substrate; 2. a first electrode layer; 3. a hole injection layer; 4. a hole transport layer; 5. an electron blocking layer; 6. a light emitting layer; 7. a hole blocking layer; 8. an electron transport layer; 9. an electron injection layer; 10. a second electrode layer; 11. a light extraction layer;
fig. 2 is a schematic structural diagram of an organic electroluminescent device according to the present invention;
in the figure, 1, a substrate; 2. a first electrode layer; 3. a hole injection layer; 4. a hole transport layer; 5. an electron blocking layer; 6. a light emitting layer; 7. an electron transport layer; 8. an electron injection layer; 9. a second electrode layer; 10. a light extraction layer.
Detailed Description
The technical aspects of the present invention will be described in detail below with reference to embodiments.
In the present application, HOMO means the highest occupied orbital of a molecule, and LUMO means the lowest unoccupied orbital of a molecule unless otherwise specified. Furthermore, in the present application, HOMO and LUMO energy levels are expressed in absolute values, and the comparison between energy levels is also a comparison of the magnitudes of the absolute values thereof, and those skilled in the art know that the larger the absolute value of an energy level, the lower the energy of the energy level.
In the drawings, the size of layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate, or intervening layers may also be present. Further, it will also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers or one or more intervening layers may also be present. Like numbers refer to like elements throughout.
Organic electroluminescent device
In another embodiment of the present application, there is provided an organic electroluminescent device comprising a first electrode, a second electrode, and a plurality of organic thin film layers between the first electrode and the second electrode, wherein at least one of the organic thin film layers contains the pyrimidine structure-containing organic compound.
In a preferred embodiment of the present application, the organic thin film layer comprises an electron transport layer, wherein the electron transport layer comprises the pyrimidine structure-containing organic compound according to the present application.
Preferably, the electron transport layer contains, in addition to the organic compound of the present invention, lithium octahydroxyquinoline which is another electron transport material.
In a preferred embodiment of the present application, the organic thin film layer comprises a hole blocking layer, wherein the hole blocking layer comprises the pyrimidine structure-containing organic compound according to the present application.
In a preferred embodiment of the present invention, the organic electroluminescent device according to the present invention comprises a substrate, a first electrode layer, an organic thin film layer, a second electrode layer, wherein the organic thin film layer includes, but is not limited to, a light emitting layer and a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron blocking layer, and/or an electron injection layer.
The preferred device structure of the present invention takes the form of top emission (top emission). Preferably, the anode of the organic electroluminescent device of the present invention employs an electrode having high reflectivity, preferably ITO/Ag/ITO; the cathode adopts a transparent electrode, preferably adopts a mixed electrode of Mg and Ag=1:9, thereby forming a microcavity resonance effect, and the light emitted by the device is emitted from the side of the Mg and Ag electrode.
Hereinafter, the structure of the organic electroluminescent device according to one embodiment of the present application will be described in detail with reference to fig. 1 and 2.
As shown in fig. 1, according to one embodiment of the present application, the present application provides an organic electroluminescent device comprising 1, a substrate, in order from bottom to top; 2. a first electrode layer (anode); 3. a hole injection layer; 4. a hole transport layer; 5. an electron blocking layer; 6. a light emitting layer; 7. a hole blocking layer; 8. an electron transport layer; 9. an electron injection layer; 10. a second electrode layer (cathode); 11. a light extraction layer;
As shown in fig. 2, according to one embodiment of the present application, the present application provides an organic electroluminescent device comprising 1, a substrate, in order from bottom to top; 2. a first electrode layer (anode); 3. a hole injection layer; 4. a hole transport layer; 5. an electron blocking layer; 6. a light emitting layer; 7. an electron transport layer; 8. an electron injection layer; 9. a second electrode layer (cathode); 10. a light extraction layer;
As the substrate of the organic electroluminescent device of the present invention, any substrate commonly used for organic electroluminescent devices may be used. Examples are transparent substrates, such as glass or transparent plastic substrates; an opaque substrate such as a silicon substrate; a flexible PI film substrate. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, and water repellency. The use direction of the substrate is different according to the property of the substrate. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.
A first electrode (anode) is formed on the substrate, and the anode material is preferably a material having a high work function so that holes are easily injected into the organic functional material layer. Non-limiting examples of anode materials include, but are not limited to, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin oxide (SnO 2), zinc oxide (ZnO), magnesium (Mg), aluminum (Al), silver (Ag), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The first electrode may have a single-layer structure or a multi-layer structure including two or more layers. For example, the anode may have a three-layer structure of ITO/Ag/ITO, but is not limited thereto. In addition, the thickness of the anode depends on the material used, and is usually 50 to 500nm, preferably 70 to 300nm and more preferably 100 to 200nm.
The hole injection layer 3, the hole transport layer 4, and the electron blocking layer 5 may be disposed between the first electrode layer (anode) 2 and the light emitting layer 6.
The hole injection layer structure is such that a hole injection layer material, which may be, for example, a P dopant, is uniformly or non-uniformly dispersed in the hole transport layer. The P-dopant may be selected from at least one compound selected from the group consisting of: quinone derivatives such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinone dimethane (F4-TCNQ); metal oxides such as tungsten oxide or molybdenum oxide; or cyano-containing compounds, such as the compounds P1, NDP or F4-TCNQ shown below:
According to the invention, P1 is preferably used as P dopant. The ratio of the hole transport layer to the P dopant used in the present invention is 99:1 to 70:30, preferably 99:1 to 85:15 and more preferably 97:3 to 87:13 on a mass basis.
The thickness of the hole injection layer of the present invention may be 1 to 100nm, preferably 2 to 50nm and more preferably 5 to 20nm.
The material of the hole transport layer is preferably a material having high hole mobility, which enables holes to be transferred from the anode or the hole injection layer to the light emitting layer. The hole transporting material may be a styrene compound such as a phthalocyanine derivative, a triazole derivative, a triarylmethane derivative, a triarylamine derivative, an oxazole derivative, an oxadiazole derivative, a hydrazone derivative, a stilbene derivative, a pyridinine derivative, a polysilane derivative, an imidazole derivative, a phenylenediamine derivative, an amino-substituted quininone derivative, a styrylanthracene derivative, a styrylamine derivative, a fluorene derivative, a spirofluorene derivative, a silazane derivative, an aniline copolymer, a porphyrin compound, a carbazole derivative, a polyarylalkane derivative, a polyphenylene ethylene and a derivative thereof, a polythiophene and a derivative thereof, a poly-N-vinylcarbazole derivative, a conductive polymer oligomer such as a thiophene oligomer, an aromatic tertiary amine compound, a styrylamine compound, a triamine, a tetramine, a biphenylamine, a propyne derivative, a p-phenylenediamine derivative, a m-phenylenediamine derivative, 1 '-bis (4-diarylaminophenyl) cyclohexane, 4' -bis (diarylamino) biphenyls, bis [4- (diarylamino) phenyl ] methane, 4 '-bis (diarylamino) triphenylbiphenyl, 4' -bis (diarylamino) tris-biphenyl, 4 '-bis (diarylamino) diaryl) 4' -diaryl ] methane, 4 '-diaryl (diarylamino) 4' -diaryl ] methane, 4 '-diaryl ] diphenyl ether, bis (diarylamino-4' -diaryl) methane, or bis (diarylmethane, bis [4- (diarylamino) phenyl ] -bis (trifluoromethyl) methanes or 2, 2-diphenylvinyl compounds, etc.
The thickness of the hole transport layer of the present invention may be 5 to 200nm, preferably 10 to 180nm and more preferably 20 to 150nm.
The electron blocking layer requires that the triplet state (T1) energy level of the material is higher than the T1 energy level of the main body material in the light emitting layer, and can play a role in blocking the energy loss of the light emitting layer material; the HOMO energy level of the electron blocking layer material is between the HOMO energy level of the hole transport layer material and the HOMO energy level of the luminescent layer main body material, so that holes are injected into the luminescent layer from the positive electrode, and meanwhile, the electron blocking layer material is required to have high hole mobility, hole transport is facilitated, and the application power of the device is reduced; the LUMO energy level of the electron blocking layer material is higher than that of the host material of the light emitting layer, and plays a role in blocking electrons, that is, the electron blocking layer material is required to have a wide forbidden bandwidth (Eg). The electron blocking layer material satisfying the above conditions may be a triarylamine derivative, a fluorene derivative, a spirofluorene derivative, a dibenzofuran derivative, a carbazole derivative, or the like. Among them, triarylamine derivatives such as N4, N4-bis ([ 1,1 '-biphenyl ] -4-yl) -N4' -phenyl N4'- [1,1':4',1 "-terphenyl ] -4-yl- [1,1' -biphenyl ] -4,4' -diamine; spirofluorene derivatives such as N- ([ 1,1 '-diphenyl ] -4-yl) -N- (9, 9-dimethyl-9H-furan-2-yl) -9,9' -spirobifluorene-2-amine; dibenzofuran derivatives such as, but not limited to, N-di ([ 1,1' -biphenyl ] -4-yl) -3' - (dibenzo [ b, d ] furan-4-yl) - [1,1' -biphenyl ] -4-amine.
According to the invention, the thickness of the electron blocking layer may be 1 to 200nm, preferably 5 to 150nm and more preferably 10 to 100nm.
According to the invention, the light emitting layer is located between the first electrode and the second electrode. The material of the light emitting layer is a material capable of emitting visible light by receiving holes from the hole transporting region and electrons from the electron transporting region, respectively, and combining the received holes and electrons. The light emitting layer may include a host material and a dopant material. The host material and the guest material of the light-emitting layer of the organic electroluminescent device can be one or two of anthracene derivatives, quinoxaline derivatives, pyrimidine derivatives, xanthone derivatives, diphenyl ketone derivatives, carbazole derivatives, pyridine derivatives and pyrimidine derivatives. The guest material can be pyrene derivative, boron derivative, flexo derivative, spirofluorene derivative, iridium complex or platinum complex.
According to the present invention, the ratio of the organic compound of the present invention and the other light-emitting layer host material in the light-emitting layer host material is 1:9 to 9:1, preferably 2:8 to 8:2, more preferably 4:6 to 6:4, and most preferably 5:5.
According to the present invention, the ratio of host material to guest material used is 99:1 to 70:30, preferably 99:1 to 85:15 and more preferably 97:3 to 87:13, on a mass basis.
The thickness of the light-emitting layer of the present invention may be 5 to 60nm, preferably 10 to 50nm, more preferably 20 to 45nm.
The hole blocking layer may be disposed over the light emitting layer. The triplet state (T1) energy level of the hole blocking layer material is higher than the T1 energy level of the luminescent layer main body material, so that the effect of blocking the energy loss of the luminescent layer material can be achieved; the HOMO energy level of the material is lower than that of the main body material of the luminescent layer, so that the hole blocking effect is achieved, and meanwhile, the hole blocking layer material is required to have high electron mobility, so that electron transmission is facilitated, and the application power of the device is reduced.
The hole blocking layer of the present invention may have a thickness of 2 to 200nm, preferably 5 to 150nm, and more preferably 10 to 100nm, but the thickness is not limited to this range.
An electron transport layer may be disposed over the hole blocking layer. The electron transport layer material is a material that easily receives electrons of the cathode and transfers the received electrons to the light emitting layer. The electron transport layer comprises one or more organic compounds of the invention containing pyrimidine structures. Preferably, the electron transport layer is composed of the organic compound of the present invention and other electron transport layer materials. More preferably, the other electron transport layer material is an electron transport material commonly used in the art. Most preferably, the electron transport layer consists of the organic compound of the present invention and Liq.
The thickness of the electron transport layer of the present invention may be 10 to 80nm, preferably 20 to 60nm, more preferably 25 to 45nm.
In the electron transport layer of the organic electroluminescent device according to the invention, the ratio of the organic compound according to the invention and the other electron transport layer material is 1:9 to 9:1, preferably 2:8 to 8:2, more preferably 4:6 to 6:4, most preferably 5:5.
As the electron-transporting compound of the present invention, one or more of the pyrimidine structure-containing compounds of the present invention are preferably used.
The electron injection layer material is preferably a material metal Yb having a low work function so that electrons are easily injected into the organic functional material layer. The thickness of the electron injection layer of the present invention may be 0.1 to 5nm, preferably 0.5 to 3nm, more preferably 0.8 to 1.5nm.
The second electrode may be a cathode and the material used to form the cathode may be a material having a low work function, such as a metal, an alloy, a conductive compound, or a mixture thereof. Non-limiting examples of cathode materials may include lithium (Li), ytterbium (Yb), magnesium (Mg), aluminum (Al), calcium (Ca), and aluminum-lithium (Al-Li), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The thickness of the cathode is generally 5 to 100nm, preferably 7 to 50nm and more preferably 10 to 25nm, depending on the material used.
Optionally, in order to improve the light-emitting efficiency of the organic electroluminescent device, a light extraction layer (i.e. CPL layer) may be further added on top of the second electrode (i.e. cathode) of the device. According to the optical absorption and refraction principles, the higher the refractive index of the CPL layer material is, the better the CPL layer material is, and the smaller the light absorption coefficient is, the better the CPL layer material is. Any material known in the art may be used as the CPL layer material, such as Alq 3. The CPL layer typically has a thickness of 5-300nm, preferably 20-100nm and more preferably 40-80nm.
Optionally, the organic electroluminescent device may further comprise an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.
Method for preparing organic electroluminescent device
The present invention also relates to a method of manufacturing the above organic electroluminescent device, comprising sequentially laminating a first electrode, a plurality of organic thin film layers, and a second electrode on a substrate. Wherein the multi-layered organic thin film layer is formed by sequentially laminating a hole transport region, a light emitting layer, and an electron transport region, i.e., sequentially laminating a hole injection layer, a hole transport layer, and an electron blocking layer, on the first electrode from bottom to top, and sequentially laminating a hole blocking layer, an electron transport layer, and an electron injection layer, i.e., sequentially laminating a hole transport layer, an electron transport layer, and an electron injection layer, on the light emitting layer, from bottom to top. In addition, optionally, a CPL layer may also be laminated on the second electrode to increase the light extraction efficiency of the organic electroluminescent device.
As for lamination, methods such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, or LITI may be used, but are not limited thereto. Wherein vacuum evaporation means heating and plating a material onto a substrate in a vacuum environment.
In the present invention, the layers are preferably formed using a vacuum evaporation process, wherein the layers may be formed at a temperature of about 100-500 ℃ and a vacuum of about 10 -8-10-2 torr and a vacuum of aboutVacuum evaporation was performed at a rate of (2). The vacuum degree is preferably 10 -6-10-2 Torr, more preferably 10 -5-10-3 Torr. The rate is about/>More preferably about/>/>
The material for forming each layer according to the present invention may be used as a single layer by forming a film alone, or may be used as a single layer by forming a film after mixing with another material, or may be a laminated structure between layers formed by forming a film alone, a laminated structure between layers formed by mixing, or a laminated structure between layers formed by forming a film alone and layers formed by mixing.
Exemplary embodiments have been disclosed herein, and although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes of limitation. In some cases, as will be apparent to one of ordinary skill in the art as the present disclosure proceeds, features, characteristics, and/or elements described in connection with a particular embodiment may be used alone or in combination with features, characteristics, and/or elements described in connection with other embodiments unless specifically indicated. Accordingly, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the application.
The following examples are intended to better illustrate the invention, but the scope of the invention is not limited thereto.
Examples
I. preparation of Compounds example
The present invention will be described in detail below with reference to the drawings and examples.
The starting materials involved in the synthetic examples of the present invention are all commercially available or are prepared by methods conventional in the art;
the starting materials F1, F2, F3, F4 and F8 are all commercially available.
Preparation of raw material F5:
Under the protection of nitrogen, sequentially adding a raw material M1 (40 mmol), a raw material L1 (44 mmol), K 2CO3 (120 mmol) and tetrahydrofuran (200 mL) into a 500-mL round-bottom flask, introducing nitrogen for 30min to replace air, adding Pd (PPh 3)4 (0.7 mmol), heating and refluxing for 18H under the protection of nitrogen, taking a reaction liquid TCL, detecting that the raw material M1 is completely reacted, naturally cooling the reaction system to room temperature after the reaction is completed, pouring the reaction liquid into a separating funnel, vibrating, standing for layering, extracting a water phase after the separation by using dichloromethane (60 mL) and drying the organic phases, adding anhydrous magnesium sulfate, filtering, and removing the dichloromethane from the filtrate by rotary evaporation to obtain an intermediate N1.LC-MS: 343.15 ([ M+H ] +), and the accurate mass of 342.09.
In a 500mL round bottom flask under the protection of nitrogen, sequentially adding an intermediate N1 (30 mmol), a bisboronic acid pinacol ester (40 mmol, CAS: 73183-34-3), KOAC (90 mmol) and dioxane (200 mL), introducing nitrogen for 30min to replace air, adding Pd (PPh 3)4 (0.6 mmol), heating and refluxing for 14H under the protection of nitrogen, taking a reaction liquid TCL to detect that the intermediate N1 is completely reacted, naturally cooling the reaction system to room temperature after the reaction is completed, pouring the reaction liquid into a separating funnel, vibrating, standing for layering, extracting an aqueous phase with dichloromethane (50 mL of x 3) after the separation, adding anhydrous magnesium sulfate after the combination of the organic phases, filtering, and removing the dichloromethane by rotary evaporation to obtain a raw material F5 LC-MS: measured value: 435.35 ([ M+H ] +), and accurately obtaining 434.22.
Raw material F6 is prepared by a synthesis method similar to that of F5, and raw materials M and L are shown in table 1;
raw material F7 is prepared by a synthesis method similar to that of F5, and raw materials M and L are shown in table 1;
TABLE 1
Preparation of intermediate C1, intermediate D1, intermediate E1:
Under the protection of nitrogen, sequentially adding a raw material A1 (30 mmol), a raw material B1 (30 mmol), K 2CO3 (90 mmol) and tetrahydrofuran (180 mL) into a 500-mL round-bottom flask, replacing air by water (60 mL), introducing nitrogen for 30min, adding Pd (PPh 3)4 (0.6 mmol), heating and refluxing for 12H under the protection of nitrogen, taking a reaction liquid TCL, detecting that the raw material A1 is completely reacted, naturally cooling the reaction system to room temperature after the reaction is completed, removing a solvent by rotary evaporation, adding 150mL of dichloromethane into residues for dissolution, adding 100mL of water for washing, pouring into a separating funnel for shaking, standing for layering, extracting an aqueous phase with dichloromethane (50 mL of x 3) after separating, adding anhydrous magnesium sulfate for drying after mixing, filtering, removing a dichloromethane crude product by rotary evaporation, and purifying the crude product by a silica gel chromatographic column to obtain an intermediate C1.LC-MS: measured value 266.91 ([ M+H ] +), wherein the accurate mass is 265.95.
Raw material G1 (20 mmol) and diethyl ether (150 mL) were added in sequence to a 500mL round bottom flask under nitrogen protection, cooled to-78 ℃, purged with nitrogen for 30min to replace air, 1.6mol/L of n-butyllithium in hexane (15 mL,25 mmol) was slowly added, and after 3h reaction at-78℃trimethyl borate (2.8 mL,25 mmol) was added and after 1h reaction at-78℃the mixture was reacted to room temperature for 18h. Taking the reaction liquid TCL to detect that the reaction of the raw material G1 is complete, adding a dilute solution (30 ml) of hydrochloric acid into a reaction system after the reaction is completed, removing the organic solvent by rotary evaporation, and filtering residues to obtain an intermediate D1 of a white solid. LC-MS: measurement value: 277.24 ([ M+H ] +); accurate quality: 276.11.
Under the protection of nitrogen, adding an intermediate C1 (15 mmol), an intermediate D1 (15 mmol), K 2CO3 (45 mmol) and tetrahydrofuran (180 mL) into a 500-mL round-bottom flask in sequence, introducing nitrogen for 30min to replace air, adding Pd (PPh 3)4 (0.3 mmol), heating and refluxing for 12H under the protection of nitrogen, taking a reaction liquid TCL, detecting to find that the intermediate C1 is completely reacted, naturally cooling the reaction system to room temperature after the reaction is completed, removing a solvent by rotary evaporation, adding 150mL of dichloromethane into residues for dissolution, adding 100mL of water for washing, pouring into a separating funnel, shaking and standing for layering, extracting an aqueous phase with dichloromethane (50 mL of 3) after separating, merging organic phases, adding anhydrous magnesium sulfate for drying, filtering, removing dichloromethane from the filtrate by rotary evaporation to obtain a crude product, and purifying the crude product by a silica gel chromatographic column to obtain an intermediate E1.LC-MS: 419.24 ([ M+H ] +), wherein the accurate quality is 418.12.
Intermediate C was prepared by a synthetic method similar to intermediate C1 using starting materials A and B as shown in Table 2;
intermediate D was prepared by a synthetic method similar to intermediate D1 using starting material G shown in Table 2;
intermediate E was prepared by a synthetic method similar to intermediate E1 using intermediate C and intermediate D as shown in Table 2;
TABLE 2
Example 1: synthesis of Compound 268
In a 500mL round bottom flask under nitrogen protection, intermediate E3 (4.18 g,10 mmol), raw material F1 (5.44 g,12 mmol), K 2CO3 (4.14 g,30 mmol), tetrahydrofuran (160 mL), water (40 mL) were added sequentially, air was replaced by introducing nitrogen for 30min, palladium acetate (0.022 g,0.10 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (0.095 g,0.20 mmol) were added, and heated under reflux for 20h under nitrogen protection. Taking the TCL of the reaction liquid to detect that the intermediate E3 is completely reacted, naturally cooling the reaction system to room temperature after the reaction is completed, removing the solvent by rotary evaporation, adding 200ml of dichloromethane to the residue for dissolution, adding 150ml of water for washing, pouring into a separating funnel, vibrating, standing for delamination, extracting the water phase with dichloromethane (50 ml of x 3) after liquid separation, merging the organic phases, adding anhydrous magnesium sulfate for drying, filtering, removing the dichloromethane by rotary evaporation to obtain a crude product, and purifying the crude product by a silica gel chromatographic column to obtain the compound 268. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,87.11; h,5.03; n,7.82.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.77.
Example 2: synthesis of Compound 433
Compound 433 was prepared following the synthetic procedure for compound 268 in example 1, except intermediate E4 was selected instead of intermediate E3. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,87.07; h,5.15; n,8.00.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.35.
Example 3: synthesis of Compound 257
Compound 257 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that starting material F2 was replaced with starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,87.02; h,4.89; n,7.97.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.23.
Example 4: synthesis of Compound 385
Compound 385 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E5 was selected to replace intermediate E3 and starting material F2 was selected to replace starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,86.68; h,4.70; n,8.04.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.62.
Example 5: synthesis of Compound 49
Compound 49 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E1 was selected to replace intermediate E3 and starting material F3 was selected to replace starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,86.63; h,4.71; n,7.82.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.72.
Example 6: synthesis of Compound 38
Compound 38 was prepared according to the procedure for the synthesis of compound 268, example 1, starting material F3 replacing starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,87.11; h,4.71; n,8.07.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.44.
Example 7: synthesis of Compound 177
Compound 177 was prepared according to the procedure for the synthesis of compound 268 in example 1, except intermediate E4 was selected to replace intermediate E3 and starting material F3 was selected to replace starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,86.99; h,5.03; n,8.16.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.48.
Example 8: synthesis of Compound 140
Compound 140 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E5 was selected to replace intermediate E3 and starting material F3 was selected to replace starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,87.18; h,5.19; n,8.08.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.67.
Example 9: synthesis of Compound 12
Compound 12 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that starting material E1 was selected instead of starting material E3 and starting material F4 was selected instead of starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,86.88; h,4.77; n,7.89.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.21.
Example 10: synthesis of Compound 1
Compound 1 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that starting material F4 was replaced with starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,87.16; h,5.16; n,8.28.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.35.
Example 11: synthesis of Compound 166
Compound 166 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E4 was selected to replace intermediate E3 and starting material F4 was selected to replace starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,86.94; h,5.12; n,8.23.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.45.
Example 12: synthesis of Compound 129
Compound 129 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E5 was selected to replace intermediate E3 and starting material F4 was selected to replace starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,87.13; h,4.91; n,7.87.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.69.
Example 13: synthesis of Compound 497
Compound 497 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E6 was substituted for intermediate E3. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,86.75; h,5.23; n,8.39.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.60.
Example 14: synthesis of Compound 241
Compound 241 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E6 was substituted for intermediate E3 and starting material F3 was substituted for starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,86.86; h,4.77; n,8.35.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.46.
Example 15: synthesis of Compound 193
Compound 193 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E7 was replaced with intermediate E3 and starting material F4 was replaced with starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,86.91; h,4.95; n,8.33.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.65.
Example 16: synthesis of Compound 662
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Compound 662 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E4 was substituted for intermediate E3 and starting material F5 was substituted for starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,86.77; h,5.25; n,8.30.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.31.
Example 17: synthesis of Compound 113
Compound 113 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E2 was selected to replace intermediate E3 and starting material F3 was selected to replace starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,87.19; h,4.74; n,8.06.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.47.
Example 18: synthesis of Compound 62
Compound 62 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E1 was selected to replace intermediate E3 and starting material F6 was selected to replace starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,87.13; h,5.15; n,8.27.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.71.
Example 19: synthesis of Compound 182
Compound 182 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E4 was selected to replace intermediate E3 and starting material F7 was selected to replace starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,86.87; h,4.80; n,7.91.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.59.
Example 20: synthesis of Compound 167
Compound 167 was prepared according to the procedure for the synthesis of compound 268 in example 1, except that intermediate E4 was selected to replace intermediate E3 and starting material F8 was selected to replace starting material F1. Elemental analysis (C 50H34N4) theory: c,86.93; h,4.96; n,8.11; test value: c,87.03; h,4.75; n,8.23.LC-MS: theoretical value: 690.28; measurement value ([ M+H ] +) 691.55.
The organic compound of the present invention can be used as an electron transport material in a light emitting device. The HOMO/LUMO energy level, the glass transition temperature Tg, the T1 energy level, the evaporation temperature and the electron mobility were measured for the inventive compound and the comparative compound, respectively, and the measurement results are shown in table 3. Wherein the comparative compounds M1 to M11 have the following structures:
TABLE 3 Table 3
Note 1: triplet energy level T1 was measured by a fluorescent-3 series fluorescence spectrometer from Horiba, and the material was measured under conditions of 2X 10 -5 mol/L toluene solution. The glass transition temperature Tg is determined by differential scanning calorimetry (DSC, german fast Co., DSC204F1 differential scanning calorimeter) at a heating rate of 10 ℃/min. The highest occupied molecular orbital HOMO energy level was tested by the ionization energy measurement system (IPS 3), tested as an atmospheric environment. When the vapor deposition temperature is 10 < -4 > Pa, the vapor deposition rate of the material is 1 angstrom/S. The electron mobility was measured using the time of flight (TOF) method, and the measuring equipment was CMM-250 for Japan spectroscopy. Eg, lumo=homo-Eg was tested by a double beam uv-vis spectrophotometer (beijing general purpose company, model: TU-1901).
As can be seen from Table 3, the organic compound of the invention has more suitable HOMO and LUMO energy levels and triplet energy levels (T1.gtoreq.2.4 eV), can be used as an electron transport material and a hole blocking material of an organic electroluminescent device, has good carrier mobility, and can effectively reduce the driving voltage of the device. The glass transition temperature of the material is higher than 125 ℃, which shows that the material has good film stability and inhibits crystallization of the material. In addition, the material has higher glass transition temperature and decomposition temperature, so that the evaporation heat stability of the material is improved, and the working stability of devices prepared from the material is improved. Finally, the material has lower evaporation temperature, and the difference between the evaporation temperature and the decomposition temperature is further increased, so that the evaporation stability of the material can be effectively improved, and the industrial window of material evaporation is improved.
Device preparation examples
The effect of the compounds synthesized according to the present invention applied as hole blocking materials in devices, the device structure of which is shown in fig. 1, will be described in detail below with reference to device examples 1 to 20 and device comparative examples 1 to 11. Device examples 2-20 and device comparative examples 1-11 were fabricated using exactly the same substrate material and electrode material, and the film thickness of the electrode material was also consistent, except that the hole blocking layer was changed in the device, as compared to device example 1. The device stack structure is shown in table 4, and the performance test results of each device are shown in table 5.
The molecular structural formula of the related material is shown as follows:
the structures of the comparative compounds M1 to M11 are described above. The above materials are all commercially available.
Device example 1
The preparation process comprises the following steps:
As shown in fig. 1, the transparent substrate layer 1 is a transparent PI film, the anode is ITO (15 nm)/Ag (150 nm)/ITO (15 nm), and the first electrode layer (anode) 2 is washed, i.e., alkali washing, pure water washing, drying are sequentially performed, and then ultraviolet-ozone washing is performed to remove organic residues on the surface of the anode layer. On the first electrode layer (anode) 2 after the above washing, HT-1 and P-1 having film thicknesses of 10nm were vapor deposited as hole injection layers 3 by a vacuum vapor deposition apparatus, and the mass ratio of HT-1 and P-1 was 97:3. Subsequently, HT-1 having a thickness of 135nm was evaporated as a hole transport layer 4. Subsequently EB-1 was evaporated to a thickness of 40nm as an electron blocking layer 5. After the evaporation of the electron blocking material is completed, a light emitting layer 6 of the OLED light emitting device is fabricated, which includes h1:h2=47:47 (the mass ratio of H1 to H2 is 47:47 as the main material), GD-1 as the doping material, the doping material doping ratio is 6% by weight, and the light emitting layer film thickness is 40nm. After the light-emitting layer 6, vacuum evaporation of the compound 268 was continued as the hole blocking layer 7 with a film thickness of 5nm; then, ET-1 and Liq were vacuum-evaporated, the mass ratio of ET-1 to Liq was 1:1, the film thickness was 30nm, and this layer was the electron transport layer 8. On the electron transport layer 8, a Yb layer having a film thickness of 1nm was formed by a vacuum vapor deposition apparatus, and this layer was an electron injection layer 9. On the electron injection layer 9, an Mg/Ag electrode layer having a film thickness of 13nm was prepared by a vacuum vapor deposition apparatus, and the mass ratio of Mg to Ag was 1:9, which layer was the second electrode layer (cathode) 10. Then, 65nm CPL-1 was vapor deposited as the light extraction layer 11.
Device examples 2-20 and device comparative examples 1-11 were prepared in a similar manner to device example 1, and the substrates each used a transparent PI film, and the first electrode layers (anodes) each used ITO (15 nm)/Ag (150 nm)/ITO (15 nm), except that the parameters in table 4 below were used.
TABLE 4 Table 4
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Device test examples
The prepared device was tested for driving voltage, current efficiency and LT95 lifetime. The voltage and current efficiency were measured using an IVL (Current-Voltage-Brightness) test system (Freund's scientific instruments, st. Co., ltd.) with a current density of 10mA/cm 2. LT95 refers to the time taken for the device brightness to decay to 95% of the initial brightness, and the current density at the time of testing is 50mA/cm 2; the life test system is an EAS-62C type OLED device life tester of Japanese systems research company. The test results are shown in Table 5 below.
TABLE 5
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As can be seen from the device test data results of table 5 above, the device driving voltage prepared using the compounds of the present invention as hole blocking layer materials is significantly reduced while the current efficiency is significantly improved, and unexpectedly and greatly prolongs the device lifetime, for example, the lifetime is substantially 1.30 times or more that of the device comparative examples 1 to 11, as compared to the comparative devices using M1 to M11 as hole blocking layer materials.
The comparative compounds M1 to M11 used in the comparative examples have structures similar to the present invention, and only differences in bridging groups between pyrimidine and pyrimidine groups or differences in linking groups, such as only differences in the way of linking the bridging groups, differences in the specific structures of the bridging groups, however, unexpectedly, the compounds of the present invention have better technical effects as hole blocking materials, whether they are driving voltages, current efficiencies or lifetimes, than the comparative compounds.
The effect of the compound synthesized according to the present invention on the use as an electron transport layer in a device is described in detail below by device examples 1-1 to 1-20 and device comparative examples 1-1 to 11, and the device structure is shown in fig. 2. The device examples 1-1 to 1-20 and the device comparative examples 1-1 to 1-11 were identical in the manufacturing process and the film thickness of the electrode material was kept uniform by using the same substrate material and electrode material, except that the electron transport material in the device was changed, as compared with the device example 1-1. The device stack structure is shown in table 6, and the performance test results of each device are shown in table 7.
The molecular structural formula of the related material is shown as follows:
Device example 1-1
The preparation process comprises the following steps:
As shown in fig. 2, the transparent substrate layer 1 is a transparent PI film, the anode is ITO (15 nm)/Ag (150 nm)/ITO (15 nm), and the first electrode layer (anode) 2 is washed, i.e., alkali washing, pure water washing, drying are sequentially performed, and then ultraviolet-ozone washing is performed to remove organic residues on the surface of the anode layer. On the first electrode layer (anode) 2 after the above washing, HT-1 and P-1 having film thicknesses of 10nm were vapor deposited as hole injection layers 3 by a vacuum vapor deposition apparatus, and the mass ratio of HT-1 and P-1 was 97:3. Subsequently, HT-1 having a thickness of 135nm was evaporated as a hole transport layer 4. Subsequently EB-1 was evaporated to a thickness of 40nm as an electron blocking layer 5. After the evaporation of the electron blocking material is completed, a light emitting layer 6 of the OLED light emitting device is fabricated, which includes h1:h2=47:47 (the mass ratio of H1 to H2 is 47:47 as the main material), GD-1 as the doping material, the doping material doping ratio is 6% by weight, and the light emitting layer film thickness is 40nm. After the light-emitting layer 6 was deposited by vacuum deposition, the mass ratio of the compound 268 to the Liq was 1:1, the film thickness was 35nm, and the layer was the electron transport layer 7. On the electron transport layer 7, a Yb layer having a film thickness of 1nm was formed by a vacuum vapor deposition apparatus, and this layer was the electron injection layer 8. On the electron injection layer 8, an Mg/Ag electrode layer having a film thickness of 13nm was prepared by a vacuum vapor deposition apparatus, and the mass ratio of Mg to Ag was 1:9, which was the second electrode layer (cathode) 9. Then, 65nm CPL-1 was evaporated as the light extraction layer 10.
Device examples 1-1 to 1-20 and device comparative examples 1-1 to 1-11 were prepared in a similar manner to device example 1-1, and the substrates were each made of a transparent PI film, and the anodes were each made of ITO (15 nm)/Ag (150 nm)/ITO (15 nm), except that the parameters in table 6 below were used.
TABLE 6
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The prepared device was tested for driving voltage, current efficiency and LT95 lifetime. The voltage and current efficiency were measured using an IVL (Current-Voltage-Brightness) test system (Freund's scientific instruments, st. Co., ltd.) with a current density of 10mA/cm 2. LT95 refers to the time taken for the device brightness to decay to 95% of the initial brightness, and the current density at the time of testing is 50mA/cm 2; the life test system is an EAS-62C type OLED device life tester of Japanese systems research company. The test results are shown in Table 7 below.
TABLE 7
As can be seen from the device test data results of table 7 above, the device driving voltage prepared using the compound of the present invention as an electron transport layer material was significantly reduced while the current efficiency was significantly improved, as compared to the comparative devices using M1 to M11 as an electron transport layer material, and unexpectedly and greatly prolonged the device lifetime, for example, by substantially 1.20 times or more of that of the device comparative examples 1-1 to 1-11.
The comparative compounds M1 to M11 used in the comparative examples have structures similar to the present invention, and only differences in bridging groups between pyrimidine and pyrimidine groups or differences in linking groups, such as only differences in the way of linking the bridging groups, differences in the specific structures of the bridging groups, however, unexpectedly, the compounds of the present invention have better technical effects as electron transport materials, whether they are driving voltages, current efficiencies or lifetimes, than the comparative compounds.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (9)
1. The pyrimidine structure-containing compound is characterized in that the structure of the compound is shown as a general formula (1):
in the general formula (1), L is represented by a structure shown in a general formula (C-1), a general formula (C-2), a general formula (C-3) or a general formula (C-4);
Ar1 and Ar2 are respectively and independently represented by a structure shown in a general formula (a) or a general formula (b);
Ra, rb, rc are each independently represented by phenyl, naphthyl, or biphenyl, and at most only one of Ra, rb, rc may be represented by naphthyl or biphenyl.
2. The compound according to claim 1, wherein the structure of the compound is represented by any one of the general formulae (1-1) to (1-36):
in the general formulae (1-1) to (1-36), R 1、R2 each independently represents a phenyl group, a naphthyl group or a biphenyl group, and at most only one of R 1、R2 may represent a naphthyl group or a biphenyl group.
3. The compound of claim 1, wherein the general formula (a) is represented by any one of the following structures:
The general formula (b) is represented by any one of the following structures:
The general formula (b) is represented by any one of the following structures:
4. The compound according to claim 1, wherein the structure of the compound is represented by any one of the general formulae (2-1) to (2-16):
in the general formulae (2-1) to (2-16), ra, rb, rc are each independently represented by phenyl, naphthyl or biphenyl, and at most only one of Ra, rb, rc may be represented by naphthyl or biphenyl.
5. The compound according to claim 1, wherein the specific structure of the compound is any one of the following structures:
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6. An organic electroluminescent device comprising a first electrode and a second electrode, wherein a plurality of organic thin film layers are provided between the first electrode and the second electrode of the organic electroluminescent device, characterized in that at least one organic thin film layer contains the pyrimidine structure-containing compound according to any one of claims 1 to 5.
7. The organic electroluminescent device according to claim 6, wherein the multi-layered organic thin film layer comprises a hole blocking layer containing the pyrimidine structure-containing compound according to any one of claims 1 to 5.
8. The organic electroluminescent device according to claim 7, wherein the multi-layered organic thin film layer comprises an electron transport layer containing the pyrimidine structure-containing compound according to any one of claims 1 to 5.
9. The organic electroluminescent device of claim 8, wherein the electron transport layer further comprises lithium octahydroxyquinoline.
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| CN111406052A (en) * | 2017-11-15 | 2020-07-10 | 斗山索如始株式会社 | Organic compound and organic electroluminescent element using same |
| CN112409276A (en) * | 2019-08-20 | 2021-02-26 | 北京鼎材科技有限公司 | Compound and application thereof |
| JP2021031463A (en) * | 2019-08-27 | 2021-03-01 | 東ソー株式会社 | Bisazine compound |
| WO2021086143A1 (en) * | 2019-10-31 | 2021-05-06 | 솔브레인 주식회사 | Organic compound, organic light-emitting diode comprising same, and display device comprising organic light-emitting diode |
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