CN116376361A - Electronic ink with luminous layer, preparation method thereof and organic electroluminescent device - Google Patents
Electronic ink with luminous layer, preparation method thereof and organic electroluminescent device Download PDFInfo
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- CN116376361A CN116376361A CN202310098597.7A CN202310098597A CN116376361A CN 116376361 A CN116376361 A CN 116376361A CN 202310098597 A CN202310098597 A CN 202310098597A CN 116376361 A CN116376361 A CN 116376361A
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- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 103
- 239000002904 solvent Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000007641 inkjet printing Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 150000003384 small molecules Chemical class 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 20
- -1 small molecule compound Chemical class 0.000 claims description 17
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 238000004020 luminiscence type Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000006184 cosolvent Substances 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 150000003918 triazines Chemical class 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
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- 238000007738 vacuum evaporation Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PFYHAAAQPNMZHO-UHFFFAOYSA-N Methyl 2-methoxybenzoate Chemical group COC(=O)C1=CC=CC=C1OC PFYHAAAQPNMZHO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical group COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 1
- ACSHDTNTFKFOOH-UHFFFAOYSA-N 3-[4-[3,5-bis(4-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=CC(=CC=2)C=2C=C(C=C(C=2)C=2C=CC(=CC=2)C=2C=NC=CC=2)C=2C=CC(=CC=2)C=2C=NC=CC=2)=C1 ACSHDTNTFKFOOH-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- NWPWRAWAUYIELB-UHFFFAOYSA-N ethyl 4-methylbenzoate Chemical group CCOC(=O)C1=CC=C(C)C=C1 NWPWRAWAUYIELB-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- 238000004528 spin coating Methods 0.000 description 1
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- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
Abstract
The invention relates to the field of electroluminescent display, in particular to luminescent layer electronic ink, a preparation method thereof and an organic electroluminescent device. The luminous layer electronic ink comprises the following components: 0.5% -30% of organic micromolecular host material, 0.05% -10% of organic micromolecular sensitizer material, 0.01% -5% of organic micromolecular luminescent material, 0.1% -5% of surface tension regulator, 0.1% -5% of viscosity regulator and 60% -98% of first solvent. The organic micromolecule material selected by the invention can effectively improve the overall luminous efficiency of the luminous layer, reduce the efficiency roll-off of the organic electroluminescent device, and is favorable for preparing the ink-jet printing type organic electroluminescent material into the electronic ink applicable to the ink-jet printing process, thereby obtaining the high-level organic electroluminescent device.
Description
Technical Field
The invention relates to the field of electroluminescent display, in particular to luminescent layer electronic ink, a preparation method thereof and an organic electroluminescent device.
Background
The display device can convert various data collected and processed by the computer into various visual forms for display, and plays an essential role in various aspects of life, work, study and the like along with development of technology and popularization of computer technology in various industries. In order to pursue better visual experience and display requirements, researchers have prepared various display devices including cathode ray tube displays, liquid crystal displays, organic electroluminescent devices, etc. according to different light-emitting principles. The Organic Light-Emitting Diode is a novel high-quality display technology, wherein the English name of the Organic Light-Emitting Diode is OLED. Compared with the conventional liquid crystal display, the organic electroluminescent display has the advantages of low voltage requirement, high power saving efficiency, quick response, light weight, thin thickness, simple structure, low cost, wide viewing angle, almost infinite contrast, low power consumption, extremely high response speed and the like, so that the organic electroluminescent display is deeply favored by consumers and has wide market development prospect.
The common production process of the organic electroluminescent display screen is vacuum evaporation, however, the cost of the vacuum evaporation production process is higher, the size of the produced display screen is affected by the vacuum evaporation process, the size of the display screen is difficult to be larger than 80 inches, and the application of the organic electroluminescent display in the display field is greatly limited. Compared with the vacuum evaporation method, the solution processing method, in particular to the technology of ink-jet printing organic electroluminescent devices, has the advantages of high material utilization rate, low equipment and environment requirements, suitability for large-area processing and the like. The technology of ink-jet printing organic electroluminescent devices realizes the high utilization of materials by accurately dripping electronic ink prepared from organic materials into pixel pits, and does not need a fine metal mask plate required in a vacuum evaporation process, thereby becoming a main stream process for the production of display screens of next-generation organic electroluminescent devices.
However, how to obtain high-performance electronic ink with luminous layer capable of being printed by ink jet is a problem to be solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a luminescent layer electronic ink, which comprises the following components:
the organic micromolecular main body material comprises the following components in percentage by mass in a range of 0.5% -30%;
the organic small molecule sensitizer material comprises the following components in percentage by mass in a range of 0.05% -10%;
an organic small molecule luminescent material, wherein the mass fraction content range of the organic small molecule luminescent material is 0.01% -5%;
a surface tension regulator, wherein the mass fraction content range of the surface tension regulator is 0.1% -5%;
a viscosity regulator, wherein the mass fraction content range of the viscosity regulator is 0.1% -5%;
the mass fraction content range of the first solvent is 60% -98%;
the organic micromolecular sensitizer material is used for improving the overall luminous efficiency of the luminous layer electronic ink, the organic micromolecular luminous material is one of three-coordinate boron luminous compounds containing carbazole skeletons, and the luminous peak of the three-coordinate boron luminous compounds containing carbazole skeletons is located at 450-570 nm.
Further, the organic small molecule luminescent material is selected from any one of compounds E1-E79:
further, the organic small molecule host material comprises one or more of carbazole derivatives and triazine derivatives.
Further, the organic small molecule host material is selected from any one of compounds H1-H33:
further, the luminescence peak of the organic small molecule sensitizer material is positioned between 440nm and 560nm, and the organic small molecule sensitizer material comprises any one of phosphorescent materials and thermally activated delayed fluorescent materials.
Further, the small organic molecule sensitizer material is selected from any one of the compounds S1-S79:
further, the surface tension modifier includes one or more of a co-solvent, a surfactant, and a small molecule compound that modifies surface tension;
the small molecular compound for regulating the surface tension comprises one or more of imidazole and derivatives thereof, phenol, hydroquinone and isopropyl toluene.
Further, the viscosity modifier comprises one or more of alcohol, ether, ester, phenol and amine compounds.
Further, the luminescent layer electronic ink further comprises a second solvent, and the mass fraction content of the second solvent ranges from 0.1% to 30%.
Further, the first solvent comprises any one of a liquid organic compound and a liquid naphthalene compound containing benzene ring structures; the second solvent is one or more of alcohols, ketones, ethers, esters, amides and aromatic compounds.
Further, the viscosity of the electronic ink of the luminous layer is 1cps to 20cps; the surface tension is 20dyne/cm-60dyne/cm.
The invention also provides a preparation method of the luminescent layer electronic ink, which comprises the following steps:
s1, weighing the components of the electronic ink with the luminous layer according to the proportion;
s2, whether the electronic ink component of the luminescent layer comprises the second solvent or not, if yes, uniformly mixing the weighed first solvent and the second solvent to obtain a solvent; if not, the first solvent is used as the solvent;
s3, dissolving the weighed organic micromolecular host material, the weighed organic micromolecular sensitizer material and the weighed organic micromolecular luminescent material in the solvent, and uniformly mixing to obtain a first mixed solution;
s4, adding the weighed surface tension regulator and the weighed viscosity regulator into the first mixed solution, and stirring for 0.5-24 hours at the temperature of 20-80 ℃ until the surface tension regulator and the viscosity regulator in the mixed solution are completely dissolved, so as to obtain a second mixed solution;
and S5, filtering the second mixed liquid to obtain the luminescent layer electronic ink.
The invention also provides an organic electroluminescent device, wherein the luminescent layer of the organic electroluminescent device is prepared from the luminescent layer electronic ink through an inkjet printing process.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a luminescent layer electronic ink, which comprises an organic small molecule main body material, an organic small molecule sensitizer material, an organic small molecule luminescent material, a surface tension regulator, a viscosity regulator and a first solvent, wherein the organic small molecule luminescent material has the advantages of narrow spectrum, pure light color, high luminous efficiency and long luminescent life; the organic small molecule sensitizer material can effectively improve the overall luminous efficiency and reduce the efficiency roll-off of the luminous device; the viscosity and the surface tension of the electronic ink of the luminous layer can be adjusted by adding the surface tension regulator and the viscosity regulator and adjusting the proportion of the components of each solvent; the electronic ink of the luminescent layer also comprises a second solvent, and the addition of the second solvent can effectively assist in dissolving the organic compound and adjusting the physical parameters of the electronic ink of the luminescent layer;
the preparation method of the luminescent layer electronic ink provided by the invention is simple, and the components of the luminescent layer electronic ink are uniformly mixed and stirred at a certain temperature; the luminescent layer electronic ink is prepared by adopting small molecular substances, and is beneficial to being applied to an ink-jet printing type organic electroluminescent device.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated below. In the description of the present invention, the terms "first", "second" are used for descriptive purposes only and are not to be construed as indicating relative importance or implicitly indicating the number of technical features indicated. Thus, unless otherwise indicated, features defining "first", "second" may include one or more such features either explicitly or implicitly; the meaning of "plurality" is two or more. The terms "comprises," "comprising," and any variations thereof, are intended to cover a non-exclusive inclusion, such that one or more other features, integers, steps, operations, elements, components, and/or groups thereof may be present or added.
All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items.
In addition, the technical features mentioned in the different embodiments of the invention described below can be combined with one another as long as they do not conflict with one another.
The invention provides a luminescent layer electronic ink, which comprises an organic micromolecule main body material, an organic micromolecule sensitizer material, an organic micromolecule luminescent material, a surface tension regulator, a viscosity regulator and a first solvent.
Further, the organic micromolecular main body material is selected from one or more of carbazole derivatives and triazine derivatives, and the weight percentage of the organic micromolecular main body material is 0.5-30%.
Preferably, the organic small molecule host material is selected from any one of the compounds H1-H33:
further, the organic small molecular sensitizer material is selected from any one of phosphorescent materials with luminescence peaks at 440-560 nm or thermal activation delay fluorescent materials, the weight percentage range of the organic small molecular sensitizer material is 0.05-10%, the organic small molecular sensitizer can effectively improve the overall luminous efficiency of the electronic ink of the luminous layer, and the efficiency roll-off of the luminous device is reduced.
Preferably, the small organic molecule sensitizer material is selected from any one of the compounds S1-S79:
further, the organic small molecular luminescent material is selected from three-coordinate boron luminescent compounds containing carbazole skeletons with luminescence peaks at 450-570 nm, the weight percentage range of the three-coordinate boron luminescent compounds is 0.01% -5%, and the organic small molecular luminescent material has the advantages of narrow spectrum, pure light color, high luminous efficiency and excellent luminescence life.
Preferably, the organic small molecule luminescent material is selected from any one of the compounds E1-E79:
further, the weight percentage of the surface tension regulator ranges from 0.1% to 5%; the surface tension regulator comprises one or more of cosolvent, surfactant and small molecular compound for regulating surface tension; wherein the small molecule compound for regulating surface tension comprises one or more of imidazole and its derivatives, phenol and hydroquinone.
Further, the viscosity modifier is one or more of alcohol, ether, ester, phenol and amine compounds, and the weight percentage of the viscosity modifier is 0.1-5%.
Further, the first solvent is any one of a liquid organic compound or a liquid naphthalene compound containing a benzene ring structure; the first solvent is present in an amount ranging from 60% to 98% by weight.
Further, the organic solvent can also comprise a second solvent, wherein the second solvent is selected from one or more of alcohols, ketones, ethers, esters, amides and aromatic compounds, and the weight percentage of the second solvent is in the range of 0.1-30%. The second solvent is effective to assist in dissolving the organic compound.
The added surface tension regulator and viscosity regulator can regulate the viscosity and surface tension of the electronic ink of the luminous layer, so that the viscosity of the electronic ink of the luminous layer is 1cps-20cps, and the surface tension is 20dyne/cm-60dyne/cm.
From the above, the main material, sensitizer material and luminescent material of the luminescent layer electronic ink of the invention all adopt small molecular substances, which is beneficial to the dissolution in solvent, and can effectively prevent the ink from blocking the nozzle during the inkjet printing; and the surface tension and viscosity of the electronic ink with the luminescent layer are regulated within a set range by adding the surface tension regulator and the viscosity regulator, which is beneficial to expanding the application range of the electronic ink in ink-jet printing.
The invention also discloses a preparation method of the luminescent layer electronic ink, which comprises the following steps:
s1, weighing the components according to the proportion of any one of the luminous layer electronic ink;
s2, whether the electronic ink component of the luminescent layer comprises the second solvent or not, if yes, uniformly mixing the weighed first solvent and the second solvent to obtain a solvent; if not, the first solvent is used as the solvent;
s3, dissolving the weighed organic micromolecular host material, the weighed organic micromolecular sensitizer material and the weighed organic micromolecular luminescent material in a solvent, stirring or uniformly mixing by using other modes to obtain a first mixed solution;
s4, adding the weighed surface tension regulator and viscosity regulator into the first mixed solution, and stirring for 0.5-24 hours at the temperature of 20-80 ℃ until the surface tension regulator and viscosity regulator in the mixed solution are completely dissolved, so as to obtain a second mixed solution;
and S5, filtering the second mixed liquid to obtain the electronic ink with the luminous layer.
According to the method steps, when the electronic ink with the luminous layer is prepared, the temperature is controlled to be only 20-80 ℃, and all the components are mixed and stirred uniformly, so that the preparation method is simple, the energy consumption is low, and the preparation cost is greatly reduced.
The invention also discloses an organic electroluminescent device, wherein the luminescent layer of the organic electroluminescent device is prepared from any one of the luminescent layer electronic ink through an inkjet printing process.
Specifically, in the embodiment of the organic electroluminescent device, a substrate layer, an anode layer, a hole injection layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer are sequentially arranged respectively, wherein the substrate layer is positioned at the lowest end of the hierarchical structure, and the cathode layer is positioned at the uppermost end of the hierarchical structure; when power is supplied to a proper voltage, anode holes and cathode charges are combined in the luminescent layer to form excitons (electron-hole pairs) in an excited state, the excitons in the excited state are recombined and transfer energy to the luminescent material, so that the energy is transited from a ground state energy level to an excited state, photons are generated by the excited state energy through the radiation relaxation process, light energy is released, and light is emitted, wherein the luminescent layer is prepared from luminescent layer electronic ink through an ink-jet printing process.
In one embodiment, the hole injection layer is located in the organic electroluminescent device as a hole transport layer.
The preparation method of the light-emitting layer comprises the steps of firstly carrying out ink-jet printing and depositing on a hole injection layer or a hole transport layer on the light-emitting layer electronic ink, then carrying out vacuum drying for 5-30min under the vacuum degree of 0.01Pa-50000Pa, then carrying out heating and drying for 5-120min under the vacuum degree of 80-180 ℃, and after the heating and drying is finished, forming the light-emitting layer on the hole injection layer or the hole transport layer on the light-emitting layer electronic ink. The luminous layer is prepared by using an ink-jet printing process, and the preparation method is simple and has wide application range.
In order to further illustrate the present invention, the following embodiments are used to describe a luminescent layer electronic ink and a preparation method thereof.
Example 1
Embodiment 1 provides a luminescent layer electronic ink, wherein the organic small molecule main body material adopts the H10, the weight percentage thereof is 4%, the organic small molecule sensitizer material adopts the S69, the weight percentage thereof is 0.8%, the organic small molecule luminescent material adopts the E43, and the weight percentage thereof is 0.1%; the total weight percentage of the surface tension regulator is 0.3 percent, wherein the cosolvent in the surface tension regulator is cyclohexane, and the small molecular compound for regulating the surface tension is hydroquinone; the viscosity modifier is an ester compound, and the weight percentage of the viscosity modifier is 0.2 percent; the first solvent is methyl benzoate, and the weight percentage of the first solvent is 94.6 percent.
The first solvent is used as a solvent, and the organic micromolecular host material, the organic micromolecular sensitizer material and the organic micromolecular luminescent material are added into the solvent, dissolved and uniformly mixed to obtain a first mixed solution;
adding a surface tension regulator and a viscosity regulator into the first mixed solution, and stirring for 0.5-24 hours at the temperature of 20-80 ℃ until the surface tension regulator and the viscosity regulator are completely dissolved, so as to obtain a second mixed solution;
and filtering the second mixed solution by using a needle filter with a filter diameter of 0.22 mu m to obtain the electronic ink with the luminous layer.
The surface tension regulator is added into the electronic ink of the luminous layer to regulate the surface tension of the electronic ink of the luminous layer, wherein the surface tension is 35dyne/cm; the viscosity modifier is added to adjust the viscosity of the electronic ink of the luminescent layer to 3.3cps.
Example 2
Embodiment 2 provides an electronic ink with a luminescent layer, wherein the organic micromolecule main body material adopts the H3, and the weight percentage of the H3 is 0.5%; the organic micromolecular sensitizer material adopts the S6, and the weight percentage of the organic micromolecular sensitizer material is 0.15 percent; the organic small molecule luminescent material adopts the E53, and the weight percentage of the organic small molecule luminescent material is 0.01 percent; the total weight percentage of the surface tension regulator is 0.1 percent, wherein the surface tension regulator is isopropyl toluene; the viscosity modifier is an ether compound, and the weight percentage of the viscosity modifier is 1 percent; the first solvent is diphenyl ether with the weight percentage of 94.1 percent, and the second solvent is ether compound with the weight percentage of 4.14 percent.
Stirring and mixing the first solvent and the second solvent uniformly to obtain a solvent;
adding the organic micromolecular host material, the organic micromolecular sensitizer material and the organic micromolecular luminescent material into a solvent, dissolving and uniformly mixing to obtain a first mixed solution;
adding a surface tension regulator and a viscosity regulator into the first mixed solution, and stirring for 0.5-24 hours at the temperature of 20-80 ℃ until the surface tension regulator and the viscosity regulator are completely dissolved, so as to obtain a second mixed solution;
and filtering the second mixed solution by using a needle filter with a filter diameter of 0.22 mu m to obtain the electronic ink with the luminous layer.
The surface tension regulator is added into the electronic ink of the luminous layer to regulate the surface tension of the electronic ink of the luminous layer, wherein the surface tension is 42dyne/cm; the viscosity modifier is added to adjust the viscosity of the electronic ink of the luminescent layer to 5.8cps.
Example 3
Embodiment 3 provides another luminescent layer electronic ink, wherein the organic small molecule host material adopts the above H12, the weight percentage thereof is 2%, the organic small molecule sensitizer material adopts the above S67, the weight percentage thereof is 1%, the organic small molecule luminescent material adopts the above E37, the weight percentage thereof is 0.08%, the weight percentage of the surface tension regulator is 2.5%, wherein the surface tension regulator is benzimidazole; the viscosity modifier is an ether compound, and the weight percentage of the viscosity modifier is 2.5 percent; the first solvent is methyl o-methoxybenzoate, the second solvent is naphthalene compound, and the weight percentage of the first solvent and the second solvent is 91.92 percent.
Stirring and mixing the first solvent and the second solvent uniformly to obtain a solvent;
adding an organic micromolecular host material, an organic micromolecular sensitizer material and an organic micromolecular luminescent material into a solvent, dissolving and uniformly mixing to obtain a first mixed solution;
adding the surface tension regulator and the viscosity regulator into the first mixed solution, and stirring for 0.5-24 hours at the temperature of 20-80 ℃ until the surface tension regulator and the viscosity regulator in the mixed solution are completely dissolved to obtain a second mixed solution;
and filtering the second mixed solution by using a needle filter with a filter diameter of 0.22 mu m, thus obtaining the electronic ink with the luminous layer.
The surface tension regulator is added into the electronic ink of the luminous layer to regulate the surface tension of the electronic ink of the luminous layer, wherein the surface tension is 26dyne/cm; the viscosity modifier is added to adjust the viscosity of the electronic ink of the luminescent layer to 12.1cps.
Example 4
Embodiment 4 provides another luminescent layer electronic ink, wherein the organic small molecule main body material adopts the above-mentioned H6, its weight percentage is 5%, the organic small molecule sensitizer material adopts the above-mentioned S13, its weight percentage is 0.25%, the organic small molecule luminescent material adopts the above-mentioned E55, its weight percentage is 0.1%, the weight percentage of the surface tension regulator is 2%, wherein the cosolvent in the surface tension regulator is dimethylformamide, the surfactant is sodium alkylbenzenesulfonate, hydroquinone, the small molecule compound for regulating surface tension is imidazole and its derivative; the viscosity modifier is an ester compound, and the weight percentage of the viscosity modifier is 5%; the first solvent is o-xylene, and the total weight percentage is 87.65%.
Adding an organic micromolecular host material, an organic micromolecular sensitizer material and an organic micromolecular luminescent material into a mixed solvent, dissolving and uniformly mixing to obtain a first mixed solution;
adding a surface tension regulator and a viscosity regulator into the first mixed solution, and stirring for 0.5-24 hours at the temperature of 20-80 ℃ until the surface tension regulator and the viscosity regulator in the mixed solution are completely dissolved to obtain a second mixed solution;
and filtering the second mixed solution by using a needle filter with a filter diameter of 0.22 mu m, thus obtaining the electronic ink with the luminous layer.
The surface tension regulator is added into the electronic ink of the luminous layer to regulate the surface tension of the electronic ink of the luminous layer, wherein the surface tension is 31dyne/cm; the viscosity modifier is added to adjust the viscosity of the electronic ink of the luminescent layer to 2.8cps.
Example 5
Embodiment 5 provides another luminescent layer electronic ink, wherein the organic small molecule host material adopts the above H6, the weight percentage thereof is 5%, the organic small molecule sensitizer material adopts the above S67, the weight percentage thereof is 1.5%, the organic small molecule luminescent material adopts the above E43, the weight percentage thereof is 0.1%, the weight percentage of the surface tension regulator is 0.5%, the surface tension regulator is benzimidazole, the viscosity regulator is an ether compound, the weight percentage thereof is 1%, the first solvent is ethyl p-methylbenzoate, the weight percentage thereof is 68.9%, the second solvent is chlorobenzene, and the weight percentage thereof is 23%.
Stirring and mixing the first solvent and the second solvent uniformly to obtain a solvent;
adding an organic micromolecular host material, an organic micromolecular sensitizer material and an organic micromolecular luminescent material into a mixed solvent, dissolving and uniformly mixing to obtain a first mixed solution;
adding a surface tension regulator and a viscosity regulator into the first mixed solution, and stirring for 0.5-24 hours at the temperature of 20-80 ℃ until the surface tension regulator and the viscosity regulator in the mixed solution are completely dissolved to obtain a second mixed solution;
and filtering the second mixed solution by using a needle filter with a filter diameter of 0.22 mu m, thus obtaining the electronic ink with the luminous layer.
The surface tension regulator is added into the electronic ink of the luminous layer to regulate the surface tension of the electronic ink of the luminous layer, wherein the surface tension is 36dyne/cm; the viscosity modifier is added to adjust the viscosity of the electronic ink of the luminescent layer to 3.3cps.
Example 6
The electronic ink of the luminous layer is prepared into the luminous layer in the electroluminescent device for preparing the electroluminescent device, and the photoelectric property of the electroluminescent device is tested. The following is a solution processing OLED device preparation process:
ultrasonically cleaning the prepared ITO glass for 15 minutes sequentially by using cleaning liquid, deionized water and isopropanol, and putting the ITO glass into a 70 ℃ oven for drying; treating the dried ITO glass by using an ultraviolet ozone cleaning machine for 15 minutes; then 200 microliters of PSS solution is dripped on the ITO glass, spin coating is carried out for 40 seconds by using the rotating speed of 2000rpm/min, and annealing drying is carried out on the ITO glass for 15 minutes by using the temperature of 150 ℃ to form a hole injection layer with the thickness of 40 nm; selectingThe electronic ink for luminescent layer described in example 4 was deposited on the hole injection layer by means of ink jet printing (type of ink jet printer is Fujifilm DMP 2850), then treated under a pressure of 50000Pa for 10 minutes by a vacuum film forming process, then treated under a pressure of 1Pa for 5 minutes, dried and formed into a film, and then baked at 120 ℃ for 20 minutes to form a luminescent layer with a thickness of 50 nm; transferring unfinished devices into evaporation chamber at 3×10 -5 Forming an electron transport layer at a rate of 0.05nm/s under Pa vacuum atmosphere and a thickness of 30nm, wherein the electron transport layer is made of 1,3, 5-tris (3-pyridyl-3-phenyl) benzene TmPyPB; forming an electron injection layer at a rate of 0.01nm/s and a thickness of 2nm, wherein the electron injection layer is made of (8-hydroxyquinoline) lithium; the cathode layer was formed using a rate of 0.02nm/s, where the cathode layer was selected from metallic aluminum. An organic electroluminescent device was obtained.
Example 7
Other experimental procedures were the same as in example 6, except that the luminescent layer electronic ink was replaced with the luminescent layer electronic ink described in example 3.
Example 8
Other experimental procedures were the same as in example 6, except that the luminescent layer electronic ink was replaced with the luminescent layer electronic ink described in example 6.
Comparative example 1
Other experimental processes were the same as example 6, except that the luminescent layer electronic ink did not contain small molecule sensitizer materials.
Comparative example 2
Other experimental processes were the same as example 7 except that the luminescent layer electronic ink did not contain small molecule sensitizer materials.
Comparative example 3
Other experimental processes were the same as example 8 except that the luminescent layer electronic ink did not contain small molecule sensitizer materials.
The current, voltage, brightness, luminescence spectrum and other characteristics of the device were synchronously tested using a Photo Research PR 655 spectral scanning luminance meter and a Keithley K2400 digital source meter system. The performance test of the device was performed at room temperature under ambient atmosphere. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, in the present application, the organic electroluminescent device with luminescent layer prepared from the luminescent layer electronic ink has greatly improved maximum current efficiency, maximum external quantum and efficiency roll-off due to synergistic effect of the components by adding appropriate proportion of organic small molecule sensitive Hua Ji into the luminescent layer electronic ink.
The organic micromolecular luminescent material in the luminescent layer electronic ink is defined to be the three-coordinate boron luminescent compound containing the carbazole skeleton with the luminescence peak at 450-570 nm by screening and proportioning the components, and the prepared luminescent layer electronic ink has good luminescence property and proper viscosity and surface tension by cooperative coordination among different components, so that the luminescent layer electronic ink can be widely applied to an inkjet printing process.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the invention, the steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (13)
1. A luminescent layer electronic ink, wherein the luminescent layer electronic ink comprises:
the organic micromolecular main body material comprises the following components in percentage by mass in a range of 0.5% -30%;
the organic small molecule sensitizer material comprises the following components in percentage by mass in a range of 0.05% -10%;
an organic small molecule luminescent material, wherein the mass fraction content range of the organic small molecule luminescent material is 0.01% -5%;
a surface tension regulator, wherein the mass fraction content range of the surface tension regulator is 0.1% -5%;
a viscosity regulator, wherein the mass fraction content range of the viscosity regulator is 0.1% -5%;
the mass fraction content range of the first solvent is 60% -98%;
the organic micromolecular sensitizer material is used for improving the overall luminous efficiency of the luminous layer electronic ink, the organic micromolecular luminous material is one of three-coordinate boron luminous compounds containing carbazole skeletons, and the luminous peak of the three-coordinate boron luminous compounds containing carbazole skeletons is located at 450-570 nm.
2. The electronic ink of claim 1, wherein the small organic molecule luminescent material is selected from any one of compounds E1-E79:
3. the electronic ink of claim 1, wherein the organic small molecule host material comprises one or more of carbazole derivatives and triazine derivatives.
4. The electronic ink of claim 1, wherein the organic small molecule host material is selected from any one of compounds H1-H33:
5. the electronic ink of claim 1, wherein the luminescence peak of the small organic molecule sensitizer material is 440nm-560nm, and the small organic molecule sensitizer material comprises any one of phosphorescent material and thermally activated delayed fluorescence material.
6. The electronic ink of claim 1, wherein the small organic molecule sensitizer material is selected from any one of the compounds S1-S79:
7. the electronic ink of claim 1, wherein the surface tension modifier comprises one or more of a co-solvent, a surfactant, and a small molecule compound that modifies surface tension;
the small molecular compound for regulating the surface tension comprises one or more of imidazole and derivatives thereof, phenol, hydroquinone and isopropyl toluene.
8. The electronic ink of claim 1, wherein the viscosity modifier comprises one or more of an alcohol, an ether, an ester, a phenol, and an amine compound.
9. The electronic ink of claim 1, further comprising a second solvent, wherein the second solvent is present in an amount ranging from 0.1% to 30% by mass.
10. The electronic ink of claim 9, wherein the first solvent comprises any one of a liquid organic compound containing a benzene ring structure and a liquid naphthalene compound; the second solvent is one or more of alcohols, ketones, ethers, esters, amides and aromatic compounds.
11. The luminescent layer electronic ink of claim 1, wherein the luminescent layer electronic ink has a viscosity of 1cps to 20cps; the surface tension is 20dyne/cm-60dyne/cm.
12. The method for preparing the electronic ink with the luminescent layer according to any one of claims 1 to 11, wherein the method for preparing the electronic ink with the luminescent layer comprises the following steps:
s1, weighing all components of the electronic ink of the luminous layer according to a proportion;
s2, judging whether the electronic ink component of the luminescent layer comprises the second solvent, if so, uniformly mixing the weighed first solvent and the second solvent to obtain a solvent; if not, the first solvent is used as the solvent;
s3, dissolving the weighed organic micromolecular host material, the weighed organic micromolecular sensitizer material and the weighed organic micromolecular luminescent material in the solvent, and uniformly mixing to obtain a first mixed solution;
s4, adding the weighed surface tension regulator and viscosity regulator into the first mixed solution, and stirring for 0.5-24 hours at the temperature of 20-80 ℃ until the surface tension regulator and viscosity regulator in the mixed solution are completely dissolved, so as to obtain a second mixed solution;
and S5, filtering the second mixed liquid to obtain the luminescent layer electronic ink.
13. An organic electroluminescent device, characterized in that the luminescent layer of the organic electroluminescent device is made of the luminescent layer electronic ink according to any one of claims 1-11 by an inkjet printing process.
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| CN115440903A (en) * | 2021-06-03 | 2022-12-06 | 广东聚华印刷显示技术有限公司 | Organic luminescent material composition, organic luminescent ink, luminescent film and device |
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| CN114373877A (en) * | 2021-12-31 | 2022-04-19 | 昆山国显光电有限公司 | Organic electroluminescent device and display device |
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