CN112186127B - Organic electroluminescent display panel, manufacturing method thereof and display device - Google Patents
Organic electroluminescent display panel, manufacturing method thereof and display device Download PDFInfo
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- CN112186127B CN112186127B CN202011052883.2A CN202011052883A CN112186127B CN 112186127 B CN112186127 B CN 112186127B CN 202011052883 A CN202011052883 A CN 202011052883A CN 112186127 B CN112186127 B CN 112186127B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 44
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- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 82
- 239000010410 layer Substances 0.000 claims description 70
- 238000007641 inkjet printing Methods 0.000 claims description 12
- 239000002096 quantum dot Substances 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 230000005525 hole transport Effects 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 3
- QSSDFXGXUGCLSY-UHFFFAOYSA-N 3-[3-(3-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOCCCOCCCOCCCO QSSDFXGXUGCLSY-UHFFFAOYSA-N 0.000 claims description 3
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- 238000007639 printing Methods 0.000 abstract description 29
- 238000001879 gelation Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 13
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- 239000007787 solid Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
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- 230000033001 locomotion Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an organic electroluminescent display panel, a manufacturing method thereof and a display device, wherein a mode of introducing a stimulus-responsive gel factor into a printed ink solution is adopted, so that after the ink solution is printed to a pixel opening through a nozzle, a certain external stimulus-driven gel factor is applied to enable the ink solution in the pixel opening to be in a gelation state, the ink solvent is prevented from being volatilized in advance, and the uniformity of ink drops in the pixel opening before a substrate is dried to form a film is maintained. In the drying treatment process after printing, due to the fixation effect of the gel factor on the solute and the solvent, the marangoni effect can be effectively inhibited, the coffee ring and climbing phenomenon are prevented from being formed in the solute drying process, the solvent can be uniformly spread into a film in the pixel openings, the uniformity of the integral film forming of the luminous functional layer of the whole panel in each pixel opening is effectively improved, the printing defect is reduced, the pixels are uniformly luminous after being lightened, the electric leakage phenomenon is reduced, and the device performance is further improved.
Description
Technical Field
The present invention relates to the field of display technologies, and in particular, to an organic electroluminescent display panel, a method for manufacturing the same, and a display device.
Background
At present, the efficiency and the service life of the organic electroluminescent display panel manufactured by the solution spin coating method such as the quantum dot light emitting diode are greatly developed. The ink-jet printing technology can well realize the patterning process requirement of the quantum dot light emitting diode in the display field, and is expected to be applied to manufacturing of large-size full-color display panels.
Ink jet printing of large-size display panels often takes a long time from the beginning to the end, which is sufficient to cause volatilization of the solvent of the ink droplets for early printing, and simultaneously, marangoni (Marangoni) effect and solute drying climbing effect occur in the drying process, so that the solute in the pixel pits (pixel openings) forms coffee rings and climbs, and film formation uniformity is poor, and printing defects are formed. The film formation uniformity of the light-emitting functional layer in the ink-jet printing process is poor, and the device performance is reduced.
Disclosure of Invention
The embodiment of the invention provides an organic electroluminescent display panel, a manufacturing method thereof and a display device, which are used for solving the problem of poor film forming uniformity of a film layer formed by ink-jet printing in the prior art.
In one aspect, an embodiment of the present invention provides a method for manufacturing an organic electroluminescent display panel, including:
Forming a light emitting function layer in a pixel opening by adopting an ink jet printing mode on a substrate base plate provided with a pixel limiting layer comprising a plurality of pixel openings; wherein, at least one layer of luminous functional layer adopts the following mode to make:
Ink-jet printing an ink solution containing a stimulus-responsive gel factor within the pixel opening;
Applying external stimulus conditions to the ink solution that match the stimulus-responsive gel factor to gel the ink solution;
The gelled ink solution is dried to form a light-emitting functional layer containing a gelator.
In a possible implementation manner, in the above manufacturing method provided by the embodiment of the present invention, the method further includes:
Forming a gel factor solution after heating using the stimulus-responsive gel factor and an ink solvent of the ink solution;
The gel factor solution is added to the ink solution in a proportion not greater than the gel critical concentration of the stimulus-responsive gel factor and kept heated to form the ink solution containing the stimulus-responsive gel factor.
In a possible implementation manner, in the above manufacturing method provided by the embodiment of the present invention, the stimulus-responsive gel factor includes one of the following:
the external stimulus condition matched with the temperature responsive gel factor is cooling to room temperature, and the molecular formula is as follows:
The external stimulus condition matched with the light-responsive gel factor is ultraviolet irradiation, and the molecular formula is as follows:
The external stimulus condition matched with the ultrasonic response gel factor is loading ultrasonic wave, and the molecular formula is as follows:
The external stimulus condition matched with the electric response gel factor is loading electric signals, and the molecular formula is as follows:
In one possible implementation manner, in the above manufacturing method provided by the embodiment of the present invention, the first chemical and the second compound are added into the solvent, and then heated and reflowed to form the third compound:
In a possible implementation manner, in the above manufacturing method provided by the embodiment of the present invention, the light-emitting functional layer includes a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, and an electron transport layer;
The ink solvent for manufacturing the quantum dot luminescent layer comprises the following components: 30% -50% of cyclohexane and 40% -60% of tetradecane;
The ink solvent for manufacturing the hole injection layer comprises: diethylene glycol with the content of 30-50%, triethylene glycol with the content of 30-40% and triethylene glycol dimethyl ether with the content of 10-20%;
The ink solvent for manufacturing the hole transport layer comprises: anisole with the content of 80-90%, cyclohexylbenzene with the content of 10-20% and pyrrolidone with the content of 1-5%;
The ink solvent for manufacturing the electron transport layer comprises: 2-methylpentane-2, 4-diol with the content of 5% -10%, 2, 4-pentanediol with the content of 5% -10%, tripropylene glycol monomethyl ether with the content of 50% -70% and tri (propylene glycol) butyl ether with the content of 10% -20%.
In one possible implementation manner, in the above manufacturing method provided by the embodiment of the present invention, the drying treatment of the gelled ink solution includes:
In a reduced pressure drying film forming system, carrying out vacuum drying on the gelled ink solution for a set period of time;
in a hot plate baking system, the dried gelled ink solution is subjected to a heat-baking treatment at a set temperature.
In another aspect, an embodiment of the present invention further provides an organic electroluminescent display panel, including: a substrate, a pixel defining layer comprising a plurality of pixel openings on the substrate, and a light emitting functional layer within the pixel openings;
the material of at least one of the light-emitting functional layers comprises a stimulus-responsive gel factor.
In one possible implementation manner, in the above organic electroluminescent display panel provided by the embodiment of the present invention, the light-emitting functional layer includes a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, and an electron transport layer.
In a possible implementation manner, in the above organic electroluminescent display panel provided by the embodiment of the present invention, the stimulus-responsive gel factor includes one of the following:
a temperature responsive gel factor having the formula:
A light responsive gelator having the formula:
an ultrasound responsive gel factor having the formula:
an electrically responsive gelator having the formula:
in another aspect, an embodiment of the present disclosure further provides a display apparatus, including: the embodiment of the invention provides the organic electroluminescent display panel.
The invention has the following beneficial effects:
According to the organic electroluminescent display panel, the manufacturing method and the display device provided by the embodiment of the invention, after the ink solution is printed to the pixel opening through the nozzle by introducing the stimulus-responsive gel factor into the printed ink solution, a certain external stimulus-driven gel factor is applied to generate a solvent and a solute for self-assembling and fixing the ink solution through a non-covalent bond, so that the ink solution in the pixel opening forms a soft material similar to a solid, namely the ink solution is in a gelation state, the early volatilization of the ink solution is prevented, the solute and the solvent in the ink solution can be fixed in the gelation state, and the uniformity of ink drops in the pixel opening before the substrate is dried to form a film is maintained. In the drying treatment process after printing, the marangoni effect can be effectively inhibited due to the fixation effect of the gel factor on the solute and the solvent, and the coffee ring and climbing phenomenon formed in the solute drying process are prevented, so that the solvent can be uniformly spread into a film in the pixel opening. The manufacturing method can effectively improve the uniformity of the whole film forming of the luminous functional layer of the whole panel in each pixel opening, reduce printing defects, enable the pixels to uniformly emit light after being lightened, reduce uneven brightness after the printed panel is lightened, inhibit the occurrence of printing defects such as bright middle and dark edges, dark middle and bright edges, black spots and the like of the edges of the pixels, reduce electric leakage caused by uneven printing film forming, and further improve the performance of devices.
Drawings
Fig. 1 is a flowchart of a method for manufacturing an organic electroluminescent display panel according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of gelation of an ink solution;
FIG. 3a is a schematic diagram of a white light test result of a film layer manufactured by the prior art manufacturing method;
FIG. 3b is a schematic diagram of a white light test result of a film layer manufactured by the manufacturing method according to the embodiment of the present invention;
FIG. 4 is a flowchart illustrating a method for fabricating an organic electroluminescent display panel according to an embodiment of the present invention;
FIG. 5 is a flowchart showing another embodiment of a method for fabricating an organic electroluminescent display panel according to the present invention;
fig. 6 is a schematic structural diagram of an organic electroluminescent display panel according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The manufacturing method of the organic electroluminescent display panel provided by the embodiment of the invention comprises the following steps:
forming a light emitting function layer in a pixel opening by adopting an ink jet printing mode on a substrate base plate provided with a pixel limiting layer comprising a plurality of pixel openings; as shown in fig. 1, at least one light-emitting functional layer is manufactured by the following method:
S101, ink solution containing stimulus-responsive gel factors is subjected to ink jet printing in pixel openings;
s102, applying external stimulus conditions matched with stimulus-responsive gel factors to the ink solution to gel the ink solution;
s103, drying the gelled ink solution to form a luminous functional layer containing the gel factor.
In the method for manufacturing the organic electroluminescent display panel provided by the embodiment of the invention, the stimulus-responsive gel factor is introduced into the printed ink solution, after the ink solution is printed to the pixel opening through the nozzle, a certain external stimulus (such as external stimulus of temperature, light, electricity, ultrasound and the like) is applied, the gel factor is driven to generate a solvent and a solute of the self-assembled 'fixed' ink solution through non-covalent bonds (such as hydrogen bonds, pi-pi interactions, van der Waals forces, solvophobic effects and the like), so that the ink solution in the pixel opening forms a soft material similar to solid, namely the ink solution is in a gelation state, the early volatilization of the ink solution is prevented, and the gelation state can fix the solute and the solvent in the ink solution, so that the uniformity of ink drops in the pixel opening is maintained before the substrate is dried to form a film. In the drying treatment process after printing, the marangoni effect can be effectively inhibited due to the fixation effect of the gel factor on the solute and the solvent, and the coffee ring and climbing phenomenon formed in the solute drying process are prevented, so that the solvent can be uniformly spread into a film in the pixel opening. The manufacturing method can effectively improve the uniformity of the whole film forming of the luminous functional layer of the whole panel in each pixel opening, reduce printing defects, enable the pixels to uniformly emit light after being lightened, reduce uneven brightness after the printed panel is lightened, inhibit the occurrence of printing defects such as bright middle and dark edges, dark middle and bright edges, black spots and the like of the edges of the pixels, reduce electric leakage caused by uneven printing film forming, and further improve the performance of devices.
Specifically, fig. 2 illustrates a schematic diagram of gelation of an ink solution containing a stimulus-responsive gel factor, and fig. 2 illustrates an example of applying a temperature stimulus, in which the gel factor is in a solution state in a heated state, and solutes, solvents, and gel molecules are in a free motion state; after cooling, the gel factors self-assemble to form a space net structure, the solute and the solvent are fixed, and the movement state of the space net structure is limited to form a solid-like soft material.
Fig. 3a shows the result of white light test of the prior art after the film is dried by printing with the ink solution without added gel factor, and the data shows that the film has serious climbing phenomenon in the drying process, the dried bottom is V-shaped, no effective flat area exists, and the printing of the following functional layer and the final device performance are seriously affected.
Fig. 3b shows the white light test result of the ink solution added with the gel factor after printing and drying to form a film, and the data shows that the film layer after drying is uniform, and the bottom of the film layer after drying is flat, so that the printing of the following functional layers and the performance of the final device are facilitated.
Optionally, in the foregoing manufacturing method provided by the embodiment of the present invention, the light-emitting functional layer may include a film layer such as a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, and an electron transport layer. All the light-emitting functional layers can be manufactured by adopting the steps S101-S103, namely, when a hole injection layer, a hole transmission layer, a quantum dot light-emitting layer and an electron transmission layer are manufactured, the stimulus-responsive gel factors can be added into the corresponding ink solutions to enable the film layers to be in a gelation state before drying and film forming, or the stimulus-responsive gel factors can be added into the corresponding ink solutions only when a certain film layer or certain film layers are manufactured to enable the film layers to be in a gelation state before drying and film forming, and the method is not limited.
Optionally, in the above manufacturing method provided by the embodiment of the present invention, the stimulus-responsive gel factor includes one of the following:
the external stimulus condition of the temperature responsive gel factor matched with the temperature responsive gel factor is cooling to room temperature, and the molecular formula is:
the external stimulus condition of the light-responsive gel factor matched with the light-responsive gel factor is ultraviolet irradiation, and the molecular formula is as follows:
the external stimulus condition matched with the ultrasonic response gel factor is loading ultrasonic wave, and the molecular formula is:
the external stimulus condition matched with the electric response gel factor is loading electric signals, and the molecular formula is as follows:
Specifically, taking a temperature-responsive gel factor as an example, a substrate to be printed may be first cleaned and dried each time inkjet printing is performed; then loading the cleaned and dried substrate into a printer; then, the prepared ink solution containing the temperature responsive gel factor is poured into printer equipment, and parameters such as the printing volume, the printing speed and the like of the ink are adjusted; then printing ink, naturally cooling the ink to room temperature after printing to form gelation, and applying corresponding stimulation conditions, such as ultraviolet irradiation, electric signals, ultrasonic signals and the like, to other types of gel factors to induce gelation; the gelled ink was then dried and inspected for film layers. And repeating the above processes to manufacture other film layers, and finally vacuum evaporating cathodes with matched work functions, such as Al, ag and the like.
Optionally, in the above manufacturing method provided by the embodiment of the present invention, a specific process of forming an ink solution containing a stimulus-responsive gel factor may be further included, as shown in fig. 4, including the following steps:
S401, forming a gel factor solution after heating by adopting a stimulus-responsive gel factor and an ink solvent of the ink solution. Specifically, a certain mass of gel factor can be weighed and put into a round-bottom flask, a proper amount of ink solvent is added, and the gel factor is heated to be completely dissolved, so that a gel factor solution is obtained.
Specifically, the ink solvent is the same as the ink solution for producing the light-emitting functional layer. For example, the ink solvents for making the quantum dot light emitting layer include: 30% -50% of cyclohexane and 40% -60% of tetradecane; the ink solvent for manufacturing the hole injection layer includes: diethylene glycol with the content of 30-50%, triethylene glycol with the content of 30-40% and triethylene glycol dimethyl ether with the content of 10-20%; the ink solvent for making the hole transport layer includes: anisole with the content of 80-90%, cyclohexylbenzene with the content of 10-20% and pyrrolidone with the content of 1-5%; the ink solvent for making the electron transport layer includes: 2-methylpentane-2, 4-diol with the content of 5% -10%, 2, 4-pentanediol with the content of 5% -10%, tripropylene glycol monomethyl ether with the content of 50% -70% and tri (propylene glycol) butyl ether with the content of 10% -20%.
S402, adding a gel factor solution into the ink solution in a proportion of not more than the gel critical concentration of the stimulus-responsive gel factor, and keeping the ink solution heated to form the ink solution containing the stimulus-responsive gel factor. Specifically, the prepared gel factor solution can be proportionally added into the ink solution, and the gel concentration is adjusted to be proper, specifically, the gel critical concentration is different according to the difference of the gel factors, specifically, taking the temperature responsive gel factor as an example, the gel critical concentration is 4mg/mL, and the concentration of the gel factor in the ink solution which is finally prepared is 4mg/mL. Then, the prepared ink solution is kept warm to be in a solution state for standby, the temperature of the thermal insulation is generally 40-45 ℃, the temperature is also kept in the inkjet printing process, and the current printer supports a nozzle heating printing process.
Optionally, in the above manufacturing method provided by the embodiment of the present invention, the temperature-responsive gel factor may be synthesized by:
Firstly, according to the feeding proportion 1:1, 2.73g of compound (1) and 3.36g of compound (2) were weighed into a 100mL round-bottomed flask, 60mL of absolute ethanol was then added as a solvent to the round-bottomed flask, heated to reflux with magnetic stirring, the reaction was terminated after 12 hours of reflux, concentrated and purified by column chromatography to give a crude product (3), and the crude product (3) was purified by ethyl acetate/cyclohexane (v: v=3:
1) And (5) repeatedly recrystallizing and purifying. The nuclear magnetic hydrogen spectrum of the compound (3) is 1H NMR(300MHz,DMSO-d6):δppm11.61(s,1H),8.43(s,1H),7.62(d,2H),7.53(t,2H),7.36(m,4H),7.15(m,7H),7.01(d,2H),4.04(m,4H),1.45(m,16H),0.89(m,6H).
Specifically, the synthesis method of the temperature responsive gel factor can be summarized as follows: the first chemical compound (1) and the second chemical compound (2) are added into a solvent, and then are subjected to heating reflux reaction to form a third chemical compound, wherein the formula is as follows:
Optionally, in the above manufacturing method provided by the embodiment of the present invention, the step S103 may be performed to dry the gelled ink solution, as shown in fig. 5, and specifically may include:
S501, in a vacuum drying film forming system (VCD), performing vacuum drying on the gelled ink solution for a set period of time, for example, for 30 minutes;
S502, in a hot plate baking system (HPB), performing heat baking treatment on the dried gelled ink solution at a set temperature, for example, performing heat baking at 200 ℃ to remove residual trace solvent, so that a film layer forms a compact and flat film at the bottom of the pixel opening.
Based on the same inventive concept, the embodiment of the invention also provides an organic electroluminescent display panel which is manufactured by adopting the manufacturing method. Specifically, as shown in fig. 6, the organic electroluminescent display panel includes: a substrate 100, a pixel defining layer 200 including a plurality of pixel openings 201 on the substrate 100, and a light emitting function layer 300 within the pixel openings 201;
the material of at least one of the light-emitting functional layers 300 comprises a stimulus-responsive gel factor.
In the organic electroluminescent display panel provided by the embodiment of the invention, at least one light-emitting functional layer 300 contains the stimulus-responsive gel factor, the gel factor can enable the ink solution for preparing the film layer to be printed to the pixel opening through the nozzle, and under the condition of applying a certain external stimulus (such as external stimulus of temperature, light, electricity, ultrasound and the like), the gel factor is driven to generate a solvent and a solute for 'fixing' the ink solution through non-covalent bonds (such as hydrogen bonds, pi-pi interactions, van der Waals force, solvophobic effect and the like) so that the ink solution in the pixel opening forms a soft material similar to a solid, namely the ink solution is in a gelation state, the early volatilization of the ink solution is prevented, and the gelation state can fix the solute and the solvent in the ink solution, so that the uniformity of ink drops in the pixel opening is kept before the substrate is dried to form a film. In the drying treatment process after printing, the marangoni effect can be effectively inhibited due to the fixation effect of the gel factor on the solute and the solvent, and the coffee ring and climbing phenomenon formed in the solute drying process are prevented, so that the solvent can be uniformly spread into a film in the pixel opening. The gel factor can effectively improve the uniformity of the whole film formation of the luminous functional layer of the whole panel in each pixel opening, reduce printing defects, enable pixels to uniformly emit light after being lightened, reduce uneven brightness after the printed panel is lightened, inhibit the occurrence of printing defects such as bright middle and dark edges, dark middle and bright edges, black spots and the like of the edges of the pixels, reduce electric leakage caused by uneven printing film formation, and further improve the performance of devices.
Alternatively, in the above-described organic electroluminescent display panel provided by the embodiment of the present invention, the light emitting functional layer 300 may include a hole injection layer, a hole transport layer, a quantum dot light emitting layer, and an electron transport layer. All of the light-emitting functional layers may contain the stimulus-responsive gel factor so that the film layers thereof are in a gelled state before being dried to form a film, or only one or some of the film layers may contain the stimulus-responsive gel factor so that the film layers thereof are in a gelled state before being dried to form a film, which is not limited herein. The material of the stimulus-responsive gel factor contained in each film layer may be the same or different, and is not limited herein.
Optionally, in the above organic electroluminescent display panel provided by an embodiment of the present invention, the stimulus-responsive gel factor includes one of:
a temperature responsive gel factor having the formula:
A light responsive gelator having the formula:
an ultrasound responsive gel factor having the formula:
an electrically responsive gelator having the formula:
Based on the same inventive concept, the embodiment of the present invention further provides a display device, including the above organic electroluminescent display panel provided by the embodiment of the present invention, where the display device may be: any product or component with display function such as a mobile phone, a tablet computer, a television, a display, a notebook computer, a digital photo frame, a navigator and the like. The implementation of the display device can be referred to the embodiment of the organic electroluminescent display panel, and the repetition is not repeated.
According to the organic electroluminescent display panel, the manufacturing method and the display device thereof provided by the embodiment of the invention, through a mode of introducing the stimulus-responsive gel factor into the printed ink solution, after the ink solution is printed to the pixel opening through the nozzle, a certain external stimulus-driven gel factor is applied to generate a solvent and a solute for self-assembling and fixing the ink solution through a non-covalent bond, so that the ink solution in the pixel opening forms a soft material similar to a solid, namely the ink solution is in a gelation state, the early volatilization of the ink solution is prevented, the solute and the solvent in the ink solution can be fixed in the gelation state, and the uniformity of ink drops in the pixel opening before the substrate is dried to form a film is maintained. In the drying treatment process after printing, the marangoni effect can be effectively inhibited due to the fixation effect of the gel factor on the solute and the solvent, and the coffee ring and climbing phenomenon formed in the solute drying process are prevented, so that the solvent can be uniformly spread into a film in the pixel opening. The manufacturing method can effectively improve the uniformity of the whole film forming of the luminous functional layer of the whole panel in each pixel opening, reduce printing defects, enable the pixels to uniformly emit light after being lightened, reduce uneven brightness after the printed panel is lightened, inhibit the occurrence of printing defects such as bright middle and dark edges, dark middle and bright edges, black spots and the like of the edges of the pixels, reduce electric leakage caused by uneven printing film forming, and further improve the performance of devices.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. A method for manufacturing an organic electroluminescent display panel, comprising:
Forming a light emitting function layer in a pixel opening by adopting an ink jet printing mode on a substrate base plate provided with a pixel limiting layer comprising a plurality of pixel openings; wherein, at least one layer of luminous functional layer adopts the following mode to make:
Ink-jet printing an ink solution containing a stimulus-responsive gel factor within the pixel opening; wherein the stimulus-responsive gel factor comprises one of: a temperature responsive gel factor, a light responsive gel factor, an ultrasound responsive gel factor, and an electrical responsive gel factor; the molecular formula of the temperature responsive gel factor is: The molecular formula of the light-responsive gel factor is: /(I) The molecular formula of the ultrasound responsive gel factor is: /(I)The formula of the electro-responsive gel factor is: /(I)
Applying external stimulus conditions to the ink solution that match the stimulus-responsive gel factor to gel the ink solution; the external stimulus condition matched with the temperature responsive gel factor is cooled to room temperature, the external stimulus condition matched with the light responsive gel factor is ultraviolet irradiation, the external stimulus condition matched with the ultrasonic responsive gel factor is loading ultrasonic waves, and the external stimulus condition matched with the electric responsive gel factor is loading electric signals;
The gelled ink solution is dried to form a light-emitting functional layer containing a gelator.
2. The method of manufacturing of claim 1, further comprising:
Forming a gel factor solution after heating using the stimulus-responsive gel factor and an ink solvent of the ink solution;
The gel factor solution is added to the ink solution in a proportion not greater than the gel critical concentration of the stimulus-responsive gel factor and kept heated to form the ink solution containing the stimulus-responsive gel factor.
3. The method of claim 2, wherein the first chemical and the second chemical are added to the solvent and heated to reflux to form the third chemical:
4. the method of claim 2, wherein the light-emitting functional layer comprises a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, and an electron transport layer;
The ink solvent for manufacturing the quantum dot luminescent layer comprises the following components: 30% -50% of cyclohexane and 40% -60% of tetradecane;
The ink solvent for manufacturing the hole injection layer comprises: diethylene glycol with the content of 30-50%, triethylene glycol with the content of 30-40% and triethylene glycol dimethyl ether with the content of 10-20%;
The ink solvent for manufacturing the hole transport layer comprises: anisole with the content of 80-90%, cyclohexylbenzene with the content of 10-20% and pyrrolidone with the content of 1-5%;
The ink solvent for manufacturing the electron transport layer comprises: 2-methylpentane-2, 4-diol with the content of 5% -10%, 2, 4-pentanediol with the content of 5% -10%, tripropylene glycol monomethyl ether with the content of 50% -70% and tri (propylene glycol) butyl ether with the content of 10% -20%.
5. The method of claim 1, wherein the drying the gelled ink solution comprises:
In a reduced pressure drying film forming system, carrying out vacuum drying on the gelled ink solution for a set period of time;
in a hot plate baking system, the dried gelled ink solution is subjected to a heat-baking treatment at a set temperature.
6. An organic electroluminescent display panel, comprising: a substrate, a pixel defining layer comprising a plurality of pixel openings on the substrate, and a light emitting functional layer within the pixel openings;
The material of at least one of the light-emitting functional layers comprises a stimulus-responsive gel factor; the stimulus-responsive gel factor includes one of: a temperature responsive gel factor, a light responsive gel factor, an ultrasound responsive gel factor, and an electrical responsive gel factor; the molecular formula of the temperature responsive gel factor is: The molecular formula of the light-responsive gel factor is: /(I) The molecular formula of the ultrasound responsive gel factor is: /(I)The formula of the electro-responsive gel factor is: /(I)
7. The organic electroluminescent display panel according to claim 6, wherein the light-emitting functional layer comprises a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, and an electron transport layer.
8. A display device, comprising: the organic electroluminescent display panel according to claim 6 or 7.
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| CN108389979A (en) * | 2018-03-07 | 2018-08-10 | 京东方科技集团股份有限公司 | A kind of electroluminescence display panel, preparation method and display device |
| CN110518112A (en) * | 2019-08-26 | 2019-11-29 | 纳晶科技股份有限公司 | A kind of aeroge quantum dot film, preparation method and the display device comprising it |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108389979A (en) * | 2018-03-07 | 2018-08-10 | 京东方科技集团股份有限公司 | A kind of electroluminescence display panel, preparation method and display device |
| CN110518112A (en) * | 2019-08-26 | 2019-11-29 | 纳晶科技股份有限公司 | A kind of aeroge quantum dot film, preparation method and the display device comprising it |
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