CN107275513B - Manufacturing method of O L ED device cathode and display panel, display panel and display device - Google Patents
Manufacturing method of O L ED device cathode and display panel, display panel and display device Download PDFInfo
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
The invention discloses a manufacturing method of an organic electroluminescent device cathode and a display panel, the display panel and a display device, wherein the manufacturing method of the organic electroluminescent device cathode comprises the following steps: dissolving cathode materials in a solvent containing fluorine compounds to form a dispersion suspension; forming the dispersion suspension on a substrate, and volatilizing the solvent in the dispersion suspension to form a cathode layer. The method for manufacturing the cathode provided by the embodiment of the invention realizes that the cathode is manufactured by adopting a solution method, avoids various adverse effects caused by manufacturing the cathode by adopting a cavity coating method, has lower manufacturing cost, can be suitable for substrate substrates with various sizes or materials, such as glass, plastic, metal or silicon, and the like, and can easily realize the mass production of organic electroluminescent devices because the solvent containing the fluorine compound can not generate adverse effects on the organic layer of the organic electroluminescent device and can be easily butted with the process for manufacturing the organic film layer by adopting the solution method.
Description
Technical Field
The invention relates to the technical field of display, in particular to a method for manufacturing an organic electroluminescent device cathode and a display panel, the display panel and a display device.
Background
In the display field, Organic electroluminescent devices (Organic L light-Emitting diodes, O L ED) have the advantages of self-luminescence, fast response, wide viewing angle, high brightness, bright color, lightness and thinness, and are considered as next generation display technologies.
At present, in a manufacturing process of an O L ED device, an organic layer may be manufactured by a solution method, but a cathode needs to be manufactured by a cavity coating method, for example, vacuum evaporation coating or Physical Vapor Deposition (PVD) method, both of which need to be performed in a vacuum cavity, so that an O L ED device cannot be manufactured by the solution method completely in the prior art, and in a process of manufacturing an O L ED device, it is necessary to first manufacture an organic layer on a substrate by the solution method, and then transfer the substrate after manufacturing the organic layer into the vacuum cavity to manufacture the cathode, and this method for manufacturing an O L ED device may cause various adverse effects, including:
(1) there are limitations on substrate size: the coating by vacuum deposition requires the size of the substrate, and the size of the substrate is generally within G5, and if the size exceeds the size, the problems of glass sagging, uneven film thickness and the like are easy to occur. The PVD method is adopted for coating, and the size of the substrate is limited to be not too large in consideration of the factors such as the size of a cavity, the size of a sputtering target material and the uniformity of the film thickness;
(2) selection of materials: the vacuum evaporation method is generally only used for evaporating materials with the temperature lower than 1300 ℃, and the PVD method is adopted for film coating, although the PVD method can be used for film coating, the target material for film coating by the PVD method needs to be prepared in advance, for example, a cathode with a combination of various substances is needed, and the process is difficult to complete;
(3) damage to O L ED devices, namely, if vacuum evaporation coating or PVD coating is adopted, the O L ED devices can be damaged due to high temperature, mainly represented as crystallization or decomposition;
(4) the manufacturing of a high-precision Metal Mask (FMM) is difficult: whether the film is plated by a vacuum evaporation method or a PVD method, the FMM is difficult to adopt, because the FMM is seriously deformed due to high temperature, the current cathode can only be covered on the whole surface, and an inclined electric field can be generated between the cathode and the anode, so that the transverse leakage of a device is caused;
(5) the process is complex, the flexible O L ED device is a future development trend, the solution method for manufacturing the O L ED device is one of the trends of large-size O L ED devices, if the organic layer in the O L ED device is manufactured by the solution method, and the cathode is manufactured by the cavity coating method, the series connection process is complex, and the process is one of the reasons for poor service life of the device manufactured by the solution method in the prior art.
Therefore, how to overcome the adverse effect caused by using the cavity coating method to manufacture the cathode is a technical problem which needs to be solved urgently.
Disclosure of Invention
The embodiment of the invention provides a method for manufacturing a cathode of an organic electroluminescent device and a display panel, the display panel and a display device, which are used for solving the problem that the cathode manufactured by adopting a cavity coating method in the prior art can cause various adverse effects.
In a first aspect, an embodiment of the present invention provides a method for manufacturing a cathode of an organic electroluminescent device, including:
dissolving cathode materials in a solvent containing fluorine compounds to form a dispersion suspension;
and forming the dispersion suspension on a substrate, and volatilizing the solvent in the dispersion suspension to form the cathode layer.
In a second aspect, an embodiment of the present invention further provides a method for manufacturing an organic electroluminescent display panel, including:
forming an anode layer on a substrate, and forming organic film layers on the anode layer;
forming a protective layer on the organic film layer, and forming a photoresist layer on the protective layer;
processing the protective layer and the photoresist layer to form a pattern complementary to a pattern of a cathode layer to be formed;
the cathode layer is manufactured by adopting the manufacturing method of the cathode of the organic electroluminescent device;
and stripping the protective layer and the photoresist layer.
In a third aspect, an embodiment of the present invention further provides an organic electroluminescent display panel, where the organic electroluminescent display panel is manufactured by using the manufacturing method of the organic electroluminescent display panel.
In a fourth aspect, an embodiment of the present invention further provides a display device, including: the organic electroluminescent display panel is provided.
The invention has the following beneficial effects:
the embodiment of the invention provides a manufacturing method of an organic electroluminescent device cathode and a display panel, the display panel and a display device, wherein the manufacturing method of the organic electroluminescent device cathode comprises the following steps: dissolving cathode materials in a solvent containing fluorine compounds to form a dispersion suspension; forming the dispersion suspension on a substrate, and volatilizing the solvent in the dispersion suspension to form a cathode layer. The method for manufacturing the cathode provided by the embodiment of the invention realizes the purpose of manufacturing the cathode by adopting a solution method, avoids various adverse effects caused by manufacturing the cathode by adopting a vacuum coating method, has low manufacturing cost, can be suitable for substrate substrates with various sizes or materials, such as glass, plastic, metal or silicon, and the like, and can easily realize the mass production of organic electroluminescent devices because the solvent containing the fluorine compound can not generate adverse effects on the organic layer of the organic electroluminescent device and can be easily butted with the process for manufacturing the organic film layer by adopting the solution method.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a cathode of an organic electroluminescent device according to an embodiment of the present invention;
fig. 2a is a second flowchart of a method for manufacturing a cathode of an organic electroluminescent device according to an embodiment of the present invention;
fig. 2b is a third flowchart of a method for manufacturing a cathode of an organic electroluminescent device according to an embodiment of the present invention;
FIGS. 3a and 3b are schematic diagrams of the chemical structures of two fluorine-containing compounds provided by the embodiment of the present invention;
fig. 4 is a fourth flowchart of a method for manufacturing a cathode of an organic electroluminescent device according to an embodiment of the present invention;
fig. 5 is a flowchart of a method for manufacturing a display panel of an organic electroluminescent device according to an embodiment of the present invention;
fig. 6a to 6h are schematic structural diagrams corresponding to steps of a method for manufacturing a display panel of an organic electroluminescent device according to an embodiment of the present invention;
FIG. 7 is a schematic diagram of the molecular formula of the chemical structure for making a protective layer;
fig. 8 is a schematic structural diagram of an organic electroluminescent display panel according to an embodiment of the present invention;
fig. 9 is a schematic structural diagram of a display device according to an embodiment of the present invention;
401, a substrate base plate; 402. an anode layer; 403. an organic film layer; 404. a protective layer; 405. a photoresist layer; 406. a mask plate; 407. a cathode layer.
Detailed Description
Aiming at the problem that the cathode manufactured by adopting a cavity coating method in the prior art can cause various adverse effects, the embodiment of the invention provides a manufacturing method of an organic electroluminescent device cathode and a display panel, the display panel and a display device.
The following describes in detail specific embodiments of a method for manufacturing a cathode of an organic electroluminescent device and a display panel, and a display device according to embodiments of the present invention, with reference to the accompanying drawings. The thicknesses and shapes of the various film layers in the drawings are not to be considered true proportions, but are merely intended to illustrate the present invention.
In a first aspect, an embodiment of the present invention provides a method for manufacturing a cathode of an organic electroluminescent device, as shown in fig. 1, including:
s101, dissolving a cathode material in a solvent containing a fluorine compound to form a dispersion suspension;
and S102, forming the dispersion suspension on the substrate, and volatilizing the solvent in the dispersion suspension to form the cathode layer.
The method for manufacturing the cathode of the organic electroluminescent device provided by the embodiment of the invention realizes that the cathode is manufactured by adopting a solution method, avoids various adverse effects caused by manufacturing the cathode by adopting a cavity coating method, has low manufacturing cost, can be suitable for substrate substrates with various sizes or materials, such as glass, plastic, metal or silicon, and the like, and can easily realize mass production of the organic electroluminescent device because the solvent containing the fluorine compound can not generate adverse effects on an organic layer of the organic electroluminescent device and can be easily butted with a process for manufacturing an organic film layer by adopting the solution method.
In the step S101, the cathode material is dissolved in the solvent containing the fluorine compound to form a dispersion suspension for subsequently manufacturing the cathode layer, the solvent containing the fluorine compound does not damage the organic layer of the organic electroluminescent device, in a specific implementation, the non-encapsulated O L ED device may be placed in the solvent containing the fluorine compound, a part of the O L ED device is soaked in the solvent containing the fluorine compound, another part of the O L ED device is not soaked in the solvent containing the fluorine compound, after soaking for a certain time (for example, 3 days, 5 days, 6 days, or longer), the O L ED device is turned on, the effect of the solvent containing the fluorine compound on the O L ED device is determined by detecting the display effect of the O L ED device, and it is verified that the O L ED device soaked by the solvent containing the fluorine compound does not show an abnormality, that the solvent containing the fluorine compound does not damage the O L ED device.
In practical applications, the cathode material preferably has a particle size of 10nm to 1um, and since the particles of the cathode material are relatively small, the cathode material is dissolved in a solvent containing a fluorine compound, and the cathode material can be dispersed in the solvent containing the fluorine compound and maintained in a suspended state to form a dispersion suspension. Since the cathode material in the dispersion suspension is in a dispersed suspension state, the cathode material in the dispersion suspension is substantially uniform, and therefore, in step S102, the dispersion suspension is formed on the substrate, that is, the cathode material is substantially uniformly distributed on the substrate, and after the solvent in the dispersion suspension is volatilized, a cathode layer with a uniform thickness can be formed.
Specifically, in the method for manufacturing the cathode of the organic electroluminescent device provided by the embodiment of the present invention, the cathode material is preferably one or more of silver, gold, graphite, a carbon nanotube, graphene, a nano metal, indium tin oxide, and indium zinc oxide, and the particle size of the cathode material is preferably 10nm to 1 um. In specific implementation, other materials with better conductivity can be used as the cathode material, and the cathode material is not limited herein.
In practice, some kinds of cathode materials have better dispersion performance in a solvent containing a fluorine compound, for example, when the cathode material is a nano metal, such as nano copper, nano silver and the like, because the nano-metal particles have a nano size, the nano-metal material has better dispersion performance in the fluorine-containing compound, the nano-metal is placed in the solvent of the fluorine-containing compound, the nano metal particles can be dispersed in the solvent and maintain the suspension state, the dispersed suspension can be easily obtained by means of auxiliary dispersion such as ultrasonic oscillation or stirring, the dispersed suspension is formed on the substrate, after the solvent in the dispersed suspension is volatilized, the nano metal particles are gathered together, because of the interaction force among the particles, a layer of compact film can be formed, and the conductivity is good.
In practice, the dispersibility of some cathode materials in the solvent containing fluorine compounds may not be too high, and the following methods can be adopted to improve the dispersibility of the cathode materials in the solvent containing fluorine compounds.
The first method is as follows:
in practical applications, in the method for manufacturing the cathode of the organic electroluminescent device according to the embodiment of the present invention, before the step S101, as shown in fig. 2a, the method may further include:
s100a, wrapping the cathode material with organic matter.
In step S100a, the cathode material is coated with an organic substance, for example, a metal material may be coated with a polymer, a dispersant, or a conductive adhesive, or the cathode material may be coated with another organic substance, which is not limited herein. Specifically, the cathode material may be placed in the organic solvent to wrap the organic solvent around the cathode material, so that in the subsequent step S101, aggregation of particles of the cathode material may be prevented, and particles of the cathode material may be prevented from precipitating after aggregation, that is, the dispersibility of the cathode material is improved, and the viscosity of particles of the cathode material may also be increased, so that the cathode layer formed in the subsequent step S102 has a better flatness.
The second method comprises the following steps:
in practical applications, in the method for manufacturing the cathode of the organic electroluminescent device provided in the embodiment of the present invention, the step S101 may specifically include:
dissolving cathode material, polyvinylidene fluoride and dispersant in solvent containing fluorine compound to form dispersion suspension.
The Polyvinylidene Fluoride (PVDF) can weaken aggregation of the cathode material, prevent the cathode material from precipitating after being aggregated, and the PVDF also has a certain bonding effect, which is beneficial for the cathode material to be suspended in the solvent, and the dispersing agent can improve the dispersing performance of the cathode material in the solvent, so that the cathode material, the PVDF and the dispersing agent are dissolved in the solvent containing the fluorine compound, the dispersing performance of the cathode material in the formed dispersing suspension is good, and aggregation is not easy to occur, in the subsequent step S102, after the solvent containing the fluorine compound is volatilized, the PVDF and the dispersing agent exist, the cathode material can be adhered on the substrate to form the film, and the flatness of the film is good.
Specifically, the mass fractions of the cathode material, polyvinylidene fluoride and the dispersing agent are as follows:
the mass fraction of the cathode material is within the range of 50-100%, the mass fraction of the polyvinylidene fluoride is less than 50%, and the mass fraction of the dispersing agent is less than 5%.
The mass fraction of the cathode material is set to be within the range of 50-100%, so that the cathode layer formed in the step S102 has good conductivity, the mass fraction of the polyvinylidene fluoride is set to be less than 50%, the aggregation of the cathode material in a solvent containing a fluorine compound can be weakened, and the mass fraction of the dispersing agent is set to be 5%, so that the cathode material can be guaranteed to have good dispersing performance.
Specifically, the dispersant may be sodium lauryl sulfate, polyacrylic acid, cellulose, or polyvinyl alcohol. In specific implementation, the dispersant may be other materials, for example, other small molecule compounds or high molecular polymers, as long as the dispersing performance of the cathode material can be improved.
In a specific implementation, the dissolving of the cathode material, the polyvinylidene fluoride and the dispersant in the solvent containing the fluorine compound to form a dispersion suspension may specifically include:
dissolving a cathode material, polyvinylidene fluoride and a dispersing agent in a solvent containing a fluorine compound, and forming a dispersion suspension by adopting an ultrasonic oscillation or stirring mode.
The cathode material can be promoted to be rapidly dispersed in the solvent containing the fluorine compound by adopting an ultrasonic oscillation or stirring mode, when the method is specifically implemented, only the ultrasonic oscillation or only the stirring mode can be adopted, and the ultrasonic oscillation and the stirring (for example, magnetic stirring) can also be combined, as long as the dispersion effect can be achieved, the specific ultrasonic oscillation or stirring time can be set according to actual needs, and the specific ultrasonic oscillation or stirring process is not limited.
Specifically, in the method for manufacturing the cathode of the organic electroluminescent device according to the embodiment of the present invention, the step S102 of forming the dispersion suspension on the substrate may include:
the dispersion suspension is formed on the base substrate by coating or spraying.
The manner of applying a coating film or spraying is a preferred embodiment of the present invention, and when the method is implemented, other manners, such as inkjet printing or screen printing, may also be used, and the specific implementation manner of forming the dispersion suspension on the substrate is not limited herein.
The third method comprises the following steps:
when the cathode material is graphene;
before the step S101, as shown in fig. 2b, the method may further include:
s100b, fluorinating the cathode material.
When the cathode material is graphene, in step S100b, the cathode material is fluorinated to obtain fluorinated graphene, and after the graphene is fluorinated to obtain fluorinated graphene, the conductivity of the fluorinated graphene is not changed much, that is, the fluorinated graphene also has relatively good conductivity, and compared with graphene, the fluorinated graphene is more easily dispersed in a solvent containing a fluorine compound, that is, the dispersibility of the cathode material in the solvent containing a fluorine compound is improved.
Further, in the method for manufacturing a cathode of an organic electroluminescent device according to an embodiment of the present invention, the step S102 may include:
forming the dispersion suspension on a substrate, and volatilizing a solvent in the dispersion suspension to form a cathode layer; or the like, or, alternatively,
the dispersion suspension is formed on a base substrate, and then the solvent in the dispersion suspension is volatilized to form a cathode layer.
In step S102, the solvent in the dispersion suspension may be volatilized at the same time or after the dispersion suspension is formed on the substrate, for example, if the dispersion suspension is formed on the substrate by spraying, the solvent may be volatilized while spraying, or the solvent may be sprayed before volatilizing, in a specific implementation, the substrate may be placed on a heating plate to realize spraying the dispersion suspension while heating the substrate to volatilize the solvent, or the dispersion suspension is sprayed on the substrate and then the substrate is placed in a heating box to volatilize the solvent in the dispersion suspension, and the specific process sequence is not limited herein.
Specifically, in the method for manufacturing the cathode of the organic electroluminescent device according to the embodiment of the present invention, in step S102, volatilizing the solvent in the dispersion suspension may specifically include:
heating the dispersion suspension to volatilize the solvent in the dispersion suspension; wherein the content of the first and second substances,
the heating temperature is 40-60 ℃, and the heating time is 5-30 min.
In the step S102, the solvent in the dispersion suspension is volatilized at a lower temperature, which does not affect the film layer on the organic electroluminescent device, for example, does not affect the performance of the organic layer, and the solvent is volatilized at a lower temperature, which does not cause the positions of the particles of the cathode material in the dispersion suspension to largely float, so that the uniformity of the formed cathode layer is better. The heating temperature of 40 to 60 ℃ is a preferred embodiment of the present invention, and in practical applications, other temperatures may be selected as long as the performance of the organic electroluminescent device is not affected and the formed cathode layer is relatively uniform, and the heating time of 5 to 30min is also a preferred embodiment of the present invention.
Specifically, in the method for manufacturing the cathode of the organic electroluminescent device according to the embodiment of the present invention, the fluorine-containing compound is preferably a polyfluoro or perfluoroalkane, a polyfluoro or perfluoroaromatic compound, a polyfluoro or perfluoroether, or a polyfluoro or perfluoroolefin. In practical applications, the fluorine-containing compound may also be other fluorine-containing compounds, such as two chemical structures shown in fig. 3a and 3b, and the specific material of the fluorine-containing compound is not limited herein.
In the following, referring to fig. 4, a best mode of the embodiment of the present invention is described with the cathode material being graphene as an example, and as shown in fig. 4, a method for manufacturing a cathode of an organic electroluminescent device according to the embodiment of the present invention may include:
s201, dissolving a cathode material, polyvinylidene fluoride and a dispersing agent in a solvent containing a fluorine compound;
s202, dispersing a cathode material, polyvinylidene fluoride and a dispersing agent in a fluorine-containing compound solvent by adopting an ultrasonic oscillation mode to form a dispersion suspension;
s203, spraying the dispersed suspension on a substrate;
and S204, heating the substrate after spraying the dispersion suspension to volatilize the solvent in the dispersion suspension, thereby obtaining the cathode layer.
In practical application, when an O L ED device is manufactured, an anode and each organic layer can be manufactured in a manner in the prior art, a cathode layer is manufactured by using the manufacturing method of the cathode provided by the embodiment of the present invention, the obtained O L ED device is tested, a voltage is applied between the anode and the cathode, and the light emitting efficiency of the O L ED device is detected, and through the test, a voltage of 12V is applied between the anode and the cathode of the O L ED device manufactured by using the manufacturing method of the cathode provided by the embodiment of the present invention, and the light emitting efficiency of the O L ED device can reach 15 Cd/a.
The method for manufacturing the cathode of the organic electroluminescent device provided by the embodiment of the invention realizes that the cathode is manufactured by adopting a solution method, avoids various adverse effects caused by manufacturing the cathode by adopting a cavity coating method, has lower manufacturing cost, and in addition, the solvent containing the fluorine compound can not generate adverse effects on an organic layer of the organic electroluminescent device, is easier to butt joint with a process for manufacturing an organic film layer by adopting the solution method, and is easy to realize the mass production of the organic electroluminescent device. In the embodiment of the invention, various modes for improving the dispersion performance of the cathode material in the solvent containing the fluorine compound are provided, so that the cathode material in the obtained cathode layer is ensured to be distributed uniformly, and the flatness of the cathode layer is better.
In a second aspect, an embodiment of the present invention provides a method for manufacturing an organic electroluminescent display panel, as shown in fig. 5 and fig. 6a to 6h, including:
s301, forming an anode layer 402 on the substrate 401 (as shown in fig. 6 a), and forming organic film layers 403 on the anode layer 402 (as shown in fig. 6 b);
s302, forming a protection layer 404 on the organic film 403 (as shown in fig. 6 c), and forming a photoresist layer 405 on the protection layer 404 (as shown in fig. 6 d);
s303, processing the protective layer 404 and the photoresist layer 405 to form a pattern complementary to the pattern of the cathode layer 407 to be formed (refer to fig. 6e, 6 e', and 6 f);
s304, manufacturing a cathode layer 407 by adopting the manufacturing method of the organic electroluminescent device cathode (as shown in FIG. 6 g);
s305, stripping the protective layer 404 and the photoresist layer 405 (as shown in fig. 6 h).
In the method for manufacturing the organic electroluminescent display panel according to the embodiment of the present invention, the protective layer 404 is formed on the organic film layer 403, the photoresist layer 405 is formed on the protective layer 404, the protective layer 404 and the photoresist layer 405 are processed to form a pattern complementary to a pattern of the cathode layer 407 to be formed, and after the cathode layer 407 is obtained by using the method for manufacturing the cathode, the protective layer 404 and the photoresist layer 405 are peeled off to obtain the pattern of the cathode layer 407. In the prior art, the entire cathode layer 407 is directly fabricated on the organic film layer 403, and the pattern of the cathode layer 407 is obtained by etching with an etching solution, which generally contains acidic substances and may damage the organic film layer 403.
In specific implementation, in step S301, the anode layer 402 is formed on the substrate 401 by a chamber coating method (for example, vacuum evaporation coating or physical vapor deposition), or a solution method similar to the method for manufacturing the cathode provided in the embodiment of the present invention, preferably a chamber coating method. The anode layer 402 may be made of transparent Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO), or may be made of other materials, and the manner and material of the anode layer 402 are not limited herein. Each organic film layer 403 may be formed over the anode layer 402 by evaporation or a solution method, and the organic film layer 403 includes at least: the light-emitting layer formed on the anode layer 402 may further include one or more of an anode buffer layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode buffer layer, as required, for example, if the cathode material has a high work function, the electron injection layer may be added to improve the electron transport capability.
Specifically, in the method for manufacturing the organic electroluminescent display panel according to the embodiment of the present invention, in the step S302, forming the protective layer 404 on the organic film layer 403 includes:
a protective layer 404 is formed on the organic film 403 by spin coating or ink jet printing.
In the embodiment of the invention, the protective layer 404 is manufactured on the organic film 403 by adopting a spin coating or ink jet printing mode, the protective layer 404 does not need to be manufactured by adopting a cavity coating method, and various adverse effects of manufacturing the cathode layer 407 on the organic film 403 by adopting the cavity coating method in the background art can be avoided.
In the step S302, the protective layer 404 is disposed between the organic film layer 403 and the photoresist layer 405, so that the photoresist layer 405 can be removed after the cathode layer 407 is subsequently fabricated, if the protective layer 404 is not disposed, that is, the photoresist layer 405 is directly fabricated on the organic film layer 403, after the photoresist layer 405 is exposed and developed, the photoresist layer 405 is cured, a portion of the photoresist layer 405 that is insoluble in a developing solution is not removed, taking a negative photoresist as an example, a portion of the photoresist layer 405 corresponding to a light-transmitting region of the mask plate 406 has changed solubility after exposure, and is insoluble in a corresponding developing solution and cannot be removed. In the embodiment of the present invention, the protective layer 404 is disposed between the organic film layer 403 and the photoresist layer 405, so that after the cathode layer 407 is fabricated, the protective layer 404 can be removed by using a solvent that can dissolve the protective layer 404, and thus the photoresist layer 405 and the cathode layer 407 on the photoresist layer 405 are also removed together, thereby obtaining the pattern of the cathode layer 407. In practical applications, the solvent for removing the protective layer 404 is preferably selected to have no influence on the organic film layer 403 and the cathode layer 407.
Specifically, in the method for manufacturing an organic electroluminescent display panel according to an embodiment of the present invention, the step S303 may include:
the photoresist layer 405 is processed by a photolithography process to form a pattern complementary to the pattern of the cathode layer 407 (as shown in fig. 6e or fig. 6 e');
the protective layer 404 is treated with an etching process to form a pattern that conforms to the pattern of the photoresist layer 405 (as shown in figure 6 f).
It should be noted that the "complementary patterns" mentioned in the embodiments of the present invention may refer to absolute complementary patterns, or may refer to substantially complementary patterns obtained due to inevitable process reasons or other reasons. The "uniform pattern" mentioned in the embodiments of the present invention may refer to an absolutely uniform pattern, or may refer to a substantially uniform pattern obtained due to inevitable process reasons or other reasons.
The photoresist layer 405 is a film layer made of a photoresist material, the photoresist is also called a photoresist, and is a light-sensitive mixed liquid composed of three main components of photosensitive resin, sensitizer and solvent, after the photosensitive resin is illuminated, the photo-curing reaction can be quickly carried out, so that the physical properties of the photoresist, particularly the solubility, the affinity and the like are obviously changed, and the soluble part can be dissolved by proper solvent treatment to obtain the required image. Photoresists can be classified into negative photoresists, which become developer-insoluble materials after exposure and curing, and positive photoresists, which become developer-soluble materials after exposure and curing.
Fig. 6e is a schematic illustration of a photolithographic process of the photoresist layer 405 using a negative photoresist, in order to obtain a pattern of the cathode layer 407, in exposing the photoresist layer 405, it is necessary to irradiate light onto the photoresist layer 405 through the mask plate 406, the photoresist layer 405 corresponding to the light-transmitting region of the mask plate 406 is irradiated with light, to form a substance insoluble in a developing solution, while the photoresist layer 405 corresponding to the non-light-transmitting region of the mask plate 406 is not irradiated with light, the solubility of which is unchanged and which is soluble in a developing solution, and after exposure, the exposed photoresist layer 405 is treated with a developing solution corresponding to the negative photoresist, so that the photoresist layer 405 corresponding to the non-light-transmitting area is soluble in the developing solution to obtain a pattern corresponding to the light-transmitting area of the mask plate 406, as shown in figure 6e, it can be seen that the pattern of the masking plate 406 of negative photoresist is complementary to the pattern of the cathode layer 407 to be formed.
Fig. 6 e' is a schematic illustration of a photolithographic process of the photoresist layer 405 using a positive photoresist, similar to fig. 6e, in order to obtain a pattern of the cathode layer 407, in exposing the photoresist layer 405, it is necessary to irradiate light onto the photoresist layer 405 through the mask plate 406, after the photoresist layer 405 corresponding to the light-transmitting region of the mask plate 406 is irradiated with light, a substance soluble in a developing solution is formed, while the photoresist layer 405 corresponding to the non-light-transmitting region of the mask plate 406 is not irradiated with light, the solubility of which is unchanged and insoluble in the developer, and after exposure, the exposed photoresist layer 405 is treated with a developer corresponding to the positive photoresist, so that the photoresist layer 405 corresponding to the clear region is dissolved in the developer to obtain a pattern complementary to the clear region of the mask 406, as shown in figure 6 e', it can be seen that the pattern of the mask 406 of positive photoresist coincides with the pattern of the cathode layer 407 to be formed.
Therefore, in the step S303, the photoresist layer 405 may be made of a positive photoresist or a negative photoresist, and the pattern of the cathode layer 407 may be made of both the positive photoresist and the negative photoresist, but the patterns of the mask plate 406 used by the positive photoresist and the negative photoresist are complementary, as is apparent from comparing fig. 6e and 6 e'.
Referring to fig. 6f, in step S303, the protective layer 404 needs to be processed by an etching process to form a pattern consistent with the pattern of the photoresist layer 405, and the physical properties of the protective layer 404 are not changed by the etching process, so that the protective layer 404 can be subsequently removed by a corresponding solvent.
In step S304, referring to fig. 6g, the cathode layer 407 is formed by the method for forming the cathode of the organic electroluminescent device, that is, the cathode layer 407 is formed by a solution method, the cathode material is dissolved in a solvent containing a fluorine compound to form a dispersion suspension, the dispersion suspension is formed on the photoresist layer 405, and the solvent in the dispersion suspension is heated and volatilized, so that the photoresist layer 405 and the protective layer 404 have a pattern complementary to the pattern of the cathode layer 407, and thus, after the photoresist layer 405 and the protective layer 404 are removed, the pattern of the cathode layer 407 can be obtained.
In the step S305, the stripping the protective layer 404 and the photoresist layer 405 may specifically include: after the cathode layer 407 is formed, the substrate 401 (shown in fig. 6 g) is placed in a solvent capable of dissolving the protective layer 404, and is kept for a period of time (e.g. 30min), and after the protective layer 404 is completely or mostly dissolved, the photoresist layer 405 and the cathode layer 407 on the photoresist layer 405 are removed together, so as to obtain a pattern of the cathode layer 407 (shown in fig. 6 h).
In the step S302, the material for forming the protection layer 404 preferably has a chemical structure as shown in fig. 7, wherein R is1Semi-perfluoroalkyl radical, R2The chemical structure can be dissolved in a solvent containing a fluorine-containing compound, such as a fluorine-containing ether, for example, hydrofluoroether(HFE) may be a fluorine-containing compound as shown in FIG. 3a or FIG. 3b, or other fluorine-containing compounds, or other materials may be used to dissolve the passivation layer, such as alkyl ether or ethyl tert-butyl ether, for example, but not limited thereto, in practical applications, the material used to form the passivation layer 404 may also be other materials. In step S305, the protective layer 404 and the photoresist layer 405 may be stripped using a solvent containing a fluorine compound. The fluorine-containing compound used in the stripping process may be the same as or different from the fluorine-containing compound used in the process of producing the cathode layer 407, and is not limited herein.
In practical implementation, since the material of the protection layer 404 may be dissolved in the fluorine-containing compound, in step S304, during the process of manufacturing the cathode layer 407, the fluorine-containing compound may have a certain effect on the protection layer 404, and the effect on the protection layer 404 may be alleviated by increasing the concentration of the cathode material, adjusting the process parameters of the spraying or coating process, and adjusting the heating time during the volatilization process.
In practical application, in the step S304, the cathode material is dissolved in the solvent containing the fluorine compound to form a dispersion suspension, and the cathode material is suspended in the solvent containing the fluorine compound by means of ultrasonic oscillation or stirring, a dispersant may be further added to the cathode material with poor dispersibility, the cathode material is only dispersed in the solvent containing the fluorine compound, the cathode material and the fluorine compound do not chemically react, the dispersion suspension is formed on the photoresist layer 405, and after the solvent in the dispersion suspension is heated and volatilized, the cathode material in the solvent containing the fluorine compound aggregates and precipitates, due to the interaction force between the particles of the cathode material, and the dispersant also has a certain binding effect, so that the cathode material forms a dense thin film, when the protective layer 404 is peeled off in the subsequent step S305, the substrate base 401 after the cathode layer 407 is fabricated is placed in the solvent containing the fluorine compound, at this time, the particles of the cathode material in the cathode layer 407 are in a state of being aggregated, and in the stripping process in step S305, the substrate base 401 is simply immersed in the solvent containing the fluorine compound, and the substrate base 401 is not subjected to ultrasonic oscillation or stirring, and the interaction force between the particles in the cathode layer 407 is not destroyed, so that the cathode material in the cathode layer 407 is not re-dissolved in the fluorine compound, that is, the stripping process does not have an adverse effect on the cathode layer 407.
According to the manufacturing method of the organic electroluminescence display panel, the protective layer is formed between the organic film layer and the photoresist layer, the pattern complementary to the pattern of the cathode layer to be formed is formed, and after the cathode layer is manufactured, the protective layer and the photoresist layer are removed in a stripping mode, so that the patterning of the cathode layer is realized under the condition that the performance of the organic film layer is not influenced. Further, since the cathode layer is formed by the solution method, it can be applied to substrate boards of various sizes and materials, for example, substrate boards of materials such as glass, plastic, metal, or silicon, and the solvent containing a fluorine compound used for forming the cathode layer does not adversely affect the organic layer of the organic electroluminescent device, and can be easily connected to the process for forming the organic film layer by the solution method, thereby facilitating mass production of the organic electroluminescent device.
In a third aspect, based on the same inventive concept, an embodiment of the present invention further provides an organic electroluminescent display panel, where the organic electroluminescent display panel is manufactured by using the manufacturing method of the organic electroluminescent display panel. The schematic structural diagram of the organic electroluminescent display panel is shown in fig. 8, where DATA represents a DATA line, SCAN represents a SCAN line, VDD represents a power supply end, and four rows and five columns of pixels arranged in an array are illustrated in the figure without limiting the number of pixels.
In a fourth aspect, an embodiment of the present invention further provides a display device, including: the organic electroluminescent display panel is provided. The display device can be applied to any product or component with a display function, for example, a mobile phone, as shown in fig. 9, a display panel of the mobile phone can adopt the organic electroluminescent display panel provided by the embodiment of the present invention, a schematic cross-sectional view at AA' in the figure can be as shown in fig. 6h, and in addition, the display device can also be applied to products or devices such as a tablet computer, a television, a display, a notebook computer, a digital photo frame, a navigator, and the like. Since the principle of the display device to solve the problem is similar to that of the organic electroluminescent display panel, the implementation of the display device can be referred to the implementation of the organic electroluminescent display panel, and repeated details are not repeated.
The embodiment of the invention provides a manufacturing method of an organic electroluminescent device cathode and a display panel, the display panel and a display device, wherein the manufacturing method of the organic electroluminescent device cathode comprises the following steps: dissolving cathode materials in a solvent containing fluorine compounds to form a dispersion suspension; forming the dispersion suspension on a substrate, and volatilizing the solvent in the dispersion suspension to form a cathode layer. The method for manufacturing the cathode provided by the embodiment of the invention realizes that the cathode is manufactured by adopting a solution method, avoids various adverse effects caused by manufacturing the cathode by adopting a cavity coating method, has lower manufacturing cost, can be suitable for substrate substrates with various sizes or materials, such as glass, plastic, metal or silicon, and the like, and can easily realize the mass production of organic electroluminescent devices because the solvent containing the fluorine compound can not generate adverse effects on the organic layer of the organic electroluminescent device and can be easily butted with the process for manufacturing the organic film layer by adopting the solution method.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (16)
1. A method for manufacturing an organic electroluminescent display panel, comprising:
forming an anode layer on a substrate, and forming organic film layers on the anode layer;
forming a protective layer on the organic film layer, and forming a photoresist layer on the protective layer;
processing the protective layer and the photoresist layer to form a pattern complementary to a pattern of a cathode layer to be formed;
dissolving cathode materials in a solvent containing fluorine compounds to form a dispersion suspension;
forming the dispersion suspension on a substrate, and volatilizing a solvent in the dispersion suspension to form a cathode layer;
and stripping the protective layer and the photoresist layer.
2. The method of claim 1, wherein said processing the protective layer and the photoresist layer to form a pattern complementary to a pattern of a cathode layer to be formed comprises:
processing the photoresist layer by adopting a photoetching process to form a pattern complementary to the pattern of the cathode layer;
and processing the protective layer by adopting an etching process to form a pattern consistent with the pattern of the photoresist layer.
3. The method of claim 1 or 2, wherein forming a protective layer over the organic film layer comprises:
and forming a protective layer on the organic film layer by adopting a spin coating or ink-jet printing mode.
4. The method of claim 1, wherein prior to dissolving the cathode material in the solvent comprising the fluorine-containing compound to form the dispersion suspension, the method further comprises:
and coating the cathode material with organic matters.
5. The method of claim 1, wherein dissolving the cathode material in a solvent comprising a fluorine-containing compound to form a dispersion suspension comprises:
dissolving cathode material, polyvinylidene fluoride and dispersant in solvent containing fluorine compound to form dispersion suspension.
6. The method according to claim 5, wherein the cathode material is in a range of 50 to 100% by mass, the polyvinylidene fluoride is less than 50% by mass, and the dispersant is less than 5% by mass.
7. The method of claim 5, wherein the dispersant is sodium lauryl sulfate, polyacrylic acid, cellulose, or polyvinyl alcohol.
8. The method of claim 5, wherein dissolving the cathode material, polyvinylidene fluoride and the dispersing agent in a solvent comprising a fluorine compound to form a dispersion suspension comprises:
dissolving the cathode material, the polyvinylidene fluoride and the dispersing agent in a solvent containing a fluorine compound, and forming the dispersed suspension by adopting an ultrasonic oscillation or stirring mode.
9. The method of claim 1, wherein said forming said dispersion suspension on a substrate comprises:
and forming the dispersion suspension on the substrate by adopting a coating or spraying mode.
10. The method of claim 1, wherein the forming the dispersion suspension on a substrate and volatilizing a solvent in the dispersion suspension to form a cathode layer comprises:
forming the dispersion suspension on the substrate base plate, and volatilizing the solvent in the dispersion suspension to form a cathode layer; or the like, or, alternatively,
and forming the dispersion suspension on the substrate base plate, and then volatilizing the solvent in the dispersion suspension to form the cathode layer.
11. The method according to any one of claims 4 to 10, wherein the volatilizing the solvent in the dispersion suspension specifically comprises:
heating the dispersion suspension to volatilize the solvent in the dispersion suspension; wherein the content of the first and second substances,
the heating temperature is 40-60 ℃, and the heating time is 5-30 min.
12. The method according to any one of claims 4 to 10, wherein the fluorine-containing compound is a polyfluoro or perfluoroalkane, a polyfluoro or perfluoroaromatic compound, a polyfluoro or perfluoroether, or a polyfluoro or perfluoroolefin.
13. The method according to any one of claims 4 to 10, wherein the cathode material is one or more of silver, gold, graphite, carbon nanotubes, graphene, nanometal, indium tin oxide, or indium zinc oxide.
14. The method of claim 13, wherein the cathode material is graphene;
before the cathode material is dissolved in the solvent containing the fluorine compound to form the dispersion suspension, the method further comprises the following steps:
fluorinating the cathode material.
15. An organic electroluminescent display panel, characterized in that the organic electroluminescent display panel is manufactured by the method for manufacturing an organic electroluminescent display panel according to any one of claims 1 to 14.
16. A display device, comprising: the organic electroluminescent display panel according to claim 15.
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