CN111180602B - Display panel and preparation method thereof - Google Patents
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- CN111180602B CN111180602B CN202010009383.4A CN202010009383A CN111180602B CN 111180602 B CN111180602 B CN 111180602B CN 202010009383 A CN202010009383 A CN 202010009383A CN 111180602 B CN111180602 B CN 111180602B
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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
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- 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
- H10K59/12—Active-matrix OLED [AMOLED] displays
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- H—ELECTRICITY
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- 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
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/1201—Manufacture or treatment
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- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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Abstract
The application provides a display panel and a preparation method thereof, wherein the display panel comprises a substrate, and a thin film transistor layer, a light-emitting device layer and a packaging layer which are sequentially stacked on the substrate; the light-emitting device layer comprises a light-emitting layer, the light-emitting layer comprises a main body material and a light-emitting material uniformly distributed in the main body material, and the main body material comprises a cross-linked polymer formed by cross-linking a P-type polymer and an N-type polymer. According to the method, the polymer is subjected to a crosslinking reaction to form the luminescent layer with the solvent resistance characteristic in a heat treatment mode, so that the problem of mutual solubility of an upper layer and a lower layer in a display panel is effectively solved, the selection range of a solvent used by an electronic transmission material in an ink-jet printing technology is increased, and the development progress of a printing type electronic transmission material is accelerated.
Description
Technical Field
The application relates to the technical field of display, in particular to a display panel and a preparation method thereof.
Background
The ink-jet printing type OLED technology has the advantages of low large-area processing cost, no need of a fine metal mask plate, high material utilization rate and the like, is considered as the development direction of future OLEDs, and can obviously reduce the production cost of the OLEDs.
The OLED is generally a multilayer device structure, including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc., and a cross-linking technique is generally used in the industry, and a film formed by cross-linking has a characteristic of solvent resistance to solve the problem of mutual solubility of upper and lower functional layers in the preparation process of an inkjet printing type device, so that the multilayer OLED structure can be prepared by a solution method.
However, in the process of preparing an OLED multilayer device, only three layers of a hole injection layer, a hole transport layer and a light emitting layer can be prepared by inkjet printing at present, and an electron transport layer and the like can still be prepared only by an evaporation method. The difficulty of the printing type electron transport material in research and development of various companies is that the selection of a solvent is very difficult, the selected solvent is required to dissolve the electron transport material, various requirements of printing are met, a lower light emitting layer cannot be damaged, and the research and development progress of the material is limited. Therefore, development of a cross-linkable light-emitting layer ink will accelerate development of a printing type electron transport material and promote development of an OLED to the direction of a full printing process, but cross-linkable light-emitting layer materials are rarely reported in the industry at present.
Disclosure of Invention
The application provides a display panel and a preparation method thereof, which are used for improving the mutual solubility problem among different functional layers, improving the selection range of solvents used by electronic transmission materials in the ink-jet printing technology and accelerating the development progress of the electronic transmission materials.
In order to solve the above problems, the technical solution provided by the present application is as follows:
the application provides a display panel, including:
a substrate;
the thin film transistor layer is arranged on the substrate;
the light-emitting device layer is arranged on the thin film transistor layer and comprises a light-emitting layer;
an encapsulation layer disposed on the light emitting device layer;
the light-emitting layer comprises a main body material and a light-emitting material uniformly distributed in the main body material, wherein the main body material comprises a cross-linked polymer formed by cross-linking a P-type polymer and an N-type polymer.
In the display panel provided by the present application, the P-type polymer includes a homopolymer of a 1, 3-dicarbazole-9-yl benzene derivative, and the N-type polymer includes a homopolymer of a 4, 7-diphenyl-1, 10-phenanthroline derivative.
In the display panel provided by the application, the side chains of the P-type polymer and the N-type polymer both contain at least one crosslinking group, and the crosslinking group comprises one or more of a styrene group, an oxetane group, an amino group and a hydroxyl group.
In the display panel provided by the application, in the main body material, the mass ratio of the P-type polymer to the N-type polymer is 1:9-9: 1.
In the display panel provided by the application, the P-type polymer contains carbazole groups and derivatives thereof, and the N-type polymer contains oxazole, triazole, phenanthroline groups and derivatives thereof.
In the display panel provided by the present application, the light emitting material includes a metal complex and/or an organic fluorescent molecule, and the light emitting material is dispersed and fixed in the cross-linked polymer.
The application also provides a preparation method of the display panel, which is characterized by comprising the following steps:
step S10: sequentially laminating a thin film transistor layer and a pixel definition layer on a substrate, wherein the pixel definition layer comprises a pixel region;
step S20: preparing an anode, a hole injection layer and a hole transport layer in sequence corresponding to the pixel region;
step S30: preparing a luminescent layer ink on the hole transport layer, wherein the luminescent layer ink comprises a main material, a luminescent material and an organic solvent, and the main material comprises a P-type polymer and an N-type polymer;
step S40: heating the luminescent layer ink to enable the luminescent layer ink to generate a cross-linking reaction to form a luminescent layer, wherein the luminescent layer is a polymer film;
step S50: preparing an electron transport layer, an electron injection layer and a cathode on the luminescent layer in sequence;
step S60: an encapsulation layer is prepared on the cathode.
In the manufacturing method of the display panel provided by the application, the preparation method of the luminescent layer ink comprises the following steps:
and dissolving the P-type polymer, the N-type polymer and the luminescent material into an organic solvent, adding a surface tension regulator and a viscosity regulator, and uniformly mixing to form the luminescent layer ink.
In the manufacturing method of the display panel, the side chains of the P-type polymer and the N-type polymer both contain at least one crosslinking group, and the crosslinking group comprises one or more of a styrene group, an oxetane group, an amino group and a hydroxyl group.
In the manufacturing method of the display panel, the mass of the host material in the luminescent layer ink accounts for 0.01 wt% -10 wt% of the concentration of the luminescent layer ink.
The doping concentration of the luminescent material in the main body material is 0.1 wt% -10 wt%.
Has the advantages that: according to the method, the polymer is subjected to a crosslinking reaction to form the luminescent layer with the anti-solvent characteristic in a mode of carrying out heat treatment on the luminescent layer ink, so that the problem of mutual solubility of an upper layer and a lower layer in a display panel is effectively solved, the selection range of a solvent used by an electronic transmission material in an ink-jet printing technology is increased, and the development progress of a printing type electronic transmission material is accelerated.
Drawings
The technical solution and other advantages of the present application will become apparent from the detailed description of the embodiments of the present application with reference to the accompanying drawings.
FIG. 1 is a schematic structural diagram of a display panel according to the present application;
FIG. 2 is a schematic structural diagram of a light-emitting layer of a display panel according to the present application;
FIG. 3A is a chemical structure of a P-type polymer of the present application;
FIG. 3B is a chemical structure of an N-type polymer of the present application;
FIG. 3C is a network of cross-linked polymers of the present application;
fig. 4 is a flowchart of a method for manufacturing a display panel provided in the present application;
fig. 5A to 5D are schematic diagrams illustrating a method for manufacturing a display panel according to the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In the description of the present application, it is to be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the present application and for simplicity in description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed in a particular orientation, and be operated in a particular manner, and are not to be construed as limiting the present application. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", may explicitly or implicitly include one or more of the described features. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
In the description of the present application, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; may be mechanically connected, may be electrically connected or may be in communication with each other; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
In this application, unless expressly stated or limited otherwise, the first feature "on" or "under" the second feature may comprise direct contact of the first and second features, or may comprise contact of the first and second features not directly but through another feature in between. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.
The following disclosure provides many different embodiments or examples for implementing different features of the application. In order to simplify the disclosure of the present application, specific example components and arrangements are described below. Of course, they are merely examples and are not intended to limit the present application. Moreover, the present application may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, examples of various specific processes and materials are provided herein, but one of ordinary skill in the art may recognize applications of other processes and/or use of other materials.
The OLED is generally a multilayer device structure, including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc., and a cross-linking technique is generally used in the industry, and a film formed by cross-linking has a characteristic of solvent resistance to solve the problem of mutual solubility of upper and lower functional layers in the preparation process of an inkjet printing type device, so that the multilayer OLED structure can be prepared by a solution method.
However, in the process of preparing the OLED multilayer device, only three layers of the hole injection layer, the hole transport layer and the light emitting layer can be prepared by inkjet printing at present, and the electron transport layer and the like can still be prepared only by an evaporation method, so that the preparation cost of the photo-OLED device is increased. The application provides a display panel and a preparation method thereof, which can solve the defects.
Referring to fig. 1, the display panel 100 includes a substrate 10, a thin-film transistor layer 20 disposed on the substrate 10, a pixel definition layer 30 disposed on the thin-film transistor layer 20, a light emitting device layer 40 disposed on the pixel definition layer 30, and an encapsulation layer 50 disposed on the light emitting device layer 40.
The light-emitting device layer 40 includes an anode 401, a hole injection layer 402, a hole transport layer 403, a light-emitting layer 404, an electron transport layer 405, an electron injection layer 406, and a cathode 407, which are sequentially stacked.
Referring to fig. 2, the light emitting layer 404 includes a host material 4041 and a light emitting material 4042, and the host material 4041 includes a cross-linked polymer formed by cross-linking a P-type polymer and an N-type polymer.
The P-type polymer and the N-type polymer form a crossed net structure through crosslinking, the volume of the luminescent material 4042 is smaller than the size of a net opening of the net structure, and the luminescent material 4042 is fixed and uniformly distributed in the net main body to form a stable polymer film, so that the film layer phase separation and the corrosion of a subsequent solvent can be effectively inhibited.
In the host material 4041, the mass ratio of the P-type polymer to the N-type polymer is 1:9 to 9: 1.
In this application, host material 4041 has hole transmission ability and electron transmission ability, and still has higher triplet state energy level, forms even stable antisolvent film through the cross-linking reaction, can greatly benefit the selection range that improves printing type electron transport material solvent to and accelerate printing type electron transport material's development progress.
Referring to fig. 3A-3B, the P-type polymer includes, but is not limited to, homopolymers of 1, 3-dicarbazole-9-yl benzene derivatives, carbazole groups, and derivatives thereof.
The N-type polymer includes, but is not limited to, homopolymers of 4, 7-diphenyl-1, 10-diazophenanthrene derivatives, oxazoles, triazoles, thiazoles, thiadiazoles, diazophenanthrene groups, and derivatives thereof.
In the application, the P-type polymer has hole transmission capacity and a high triplet state energy level.
The N-type polymer has electron transmission capability and higher triplet state energy level.
Referring to fig. 3C, in the present application, the side chains of the P-type polymer and the N-type polymer both contain at least one crosslinking group, and the black filled circles in the structure are the crosslinking groups.
The crosslinking group can generate crosslinking reaction under the condition of heating or ultraviolet irradiation, and is used for forming a uniform and stable polymer film by using the main body material.
The crosslinking group comprises one or more of a styrene group, an oxetane group, an amino group and a hydroxyl group.
In the application, the electronic characteristics of the P-type polymer and the N-type polymer cannot be damaged by crosslinking reaction, the two polymers still keep high hole mobility and high electron mobility, and the device performance can be remarkably improved.
In the present application, the light emitting material 4042 includes a metal complex and/or an organic fluorescent molecule.
The metal complex can be one of silver, copper, iridium and platinum, and can also be an alloy formed by silver, copper, iridium and platinum.
The organic fluorescent molecule may be a known polymer light emitting material that emits fluorescence or phosphorescence, and may be one of polythiophene derivatives, polyvinylcarbazole, polysilane-based materials, and the like, which is not limited in any way in the present application.
According to the method, the P-type polymer and the N-type polymer are subjected to a crosslinking reaction to form the light-emitting layer with the solvent resistance, so that the problem of mutual solubility of an upper layer and a lower layer in a display panel is effectively solved, the selection range of a solvent for an electronic transmission material in an ink-jet printing technology is increased, and the development progress is accelerated.
Referring to fig. 4, the present application further provides a process for preparing a display panel, wherein a mixed solution of a host material and a doped luminescent material is used to obtain a thin film with a certain thickness by spin coating, printing or inkjet printing, and the obtained thin film can undergo a cross-linking reaction under ultraviolet irradiation or heating to form a network structure with anti-solvent characteristics, which is beneficial to fixing a dopant and increasing the stability of the thin film, and on the other hand, the thin film can be free from the influence of a selected solvent when the spin coating or inkjet printing is continuously performed on the thin film, thereby improving the range of solvent selection.
In the preparation method of the present application, the display panel is prepared by using an inkjet printing technology, please refer to fig. 5A to 5D, which includes the following steps:
step S10: thin-film transistor layer 20 and pixel defining layer 30 are sequentially stacked on substrate 10.
In the manufacturing method of the present application, the main body of the substrate 10 includes a transparent material such as glass and plastic, which is not limited in this application.
In the manufacturing method of the present application, the pixel defining layer 30 includes a pixel region.
Step S20: an anode 401, a hole injection layer 402, and a hole transport layer 403 are sequentially prepared corresponding to the pixel region.
In the preparation method of the present application, the host material of the anode 401 includes, but is not limited to, indium tin oxide and the like.
In the preparation method of the present application, a hole injection material is prepared on the surface of the anode 401 away from the substrate 10 by an inkjet printing technique, and the hole injection material is subjected to a cross-linking reaction through heat treatment to form a hole injection layer 402 corresponding to the pixel defining region.
On the surface of the hole injection layer 402 far from the anode 401, a hole transport material is prepared by an ink jet printing technology, and the hole transport material is subjected to a crosslinking reaction through heat treatment to form a hole transport layer 403 corresponding to the pixel defining region.
In the preparation method of the present application, the host materials of the hole injection layer 402 and the hole transport layer 403 may be triarylamines, triphenylmethanes, carbazoles, or other similar materials having hole transport properties, which is not limited in this application.
Step S30: a light emitting layer ink 60 is prepared on the hole transport layer 403.
In the preparation method of the present application, the light emitting layer ink 60 includes a host material, a light emitting material, and an organic solvent 601, where the host material includes a P-type polymer and an N-type polymer.
Step S40: and heating the light-emitting layer ink 60 to enable the light-emitting layer ink 60 to generate a cross-linking reaction to form a light-emitting layer 404, wherein the light-emitting layer 404 is a polymer film.
Step S50: an electron transport layer 405, an electron injection layer 406, and a cathode 407 are sequentially prepared on the light emitting layer 404.
In the preparation method of the present application, a mixed solution containing a crosslinking compound is printed onto the light emitting layer 404 by an inkjet printing technique, and vacuum drying treatment is performed to form a crosslinked electron transport material.
The electron transporting material is subjected to heat treatment to form an electron transporting layer 405.
In the manufacturing method of the present application, the manufacturing method of the electron injection layer 406 is the same as or similar to the manufacturing method of the electron transport layer 405, and the description is not repeated here.
In the manufacturing method of the present application, after the electron injection layer 406 is manufactured, the cathode 407 is manufactured by an evaporation method.
In the preparation method of the present application, the material of the electron transport layer 405 is an organic molecular material having a high electron mobility and capable of effectively transferring electrons, which is not limited in this application.
In the preparation method of the present application, the host material of the cathode 407 includes silver, green, platinum, or gold, which is not limited in this application.
Step S60: an encapsulation layer 50 is prepared on the cathode 407.
In the preparation method of the present application, the preparation method of the luminescent layer ink 60 includes: the P-type polymer, the N-type polymer and the light-emitting material 4042 are dissolved in an organic solvent 601, and a surface tension modifier and a viscosity modifier are added and mixed uniformly to form the light-emitting layer ink 60.
In the preparation method of the present application, the material of the organic solvent 601 at least includes one of aromatic hydrocarbon, ether, and alcohol solvents.
The tension regulator comprises one or more of imidazole, imidazole derivatives and phenol, and the viscosity regulator comprises one or more of alcohol, ether, ester, phenol and amine.
In the preparation method, the side chains of the P-type polymer and the N-type polymer both contain at least one crosslinking group, and black solid circles in the structure are the crosslinking groups.
The crosslinking group can generate crosslinking reaction under the condition of heating or ultraviolet irradiation, and is used for forming a uniform and stable polymer film by using the main body material.
The crosslinking group comprises one or more of a styrene group, an oxetane group, an amino group and a hydroxyl group.
In the preparation method of the present application, the light-emitting material 4042 includes a metal complex and an organic fluorescent molecule, and the metal complex may be one of silver, copper, iridium, and platinum, or an alloy formed from silver, copper, iridium, and platinum.
In the preparation method of the present application, the light-emitting material 4042 includes a metal complex of iridium and platinum, and an organic fluorescent molecule.
In the preparation method, the P-type polymer and the N-type polymer are crosslinked to form a cross-mesh structure by means of heat treatment, the volume of the luminescent material 4042 is smaller than the mesh opening size of the mesh structure, and the luminescent material 4042 is fixed and uniformly distributed in the mesh main body to form a uniform polymer film.
In the preparation method of the application, in the luminescent layer ink 60, the mass of the main body material 4041 accounts for 0.01 wt% -10 wt% of the concentration of the luminescent layer ink 60; the doping concentration of the luminescent material 4042 in the main material 4041 is 0.1 wt% to 10 wt%.
The application provides a display panel and a preparation method thereof, wherein the display panel comprises a substrate, and a thin film transistor layer, a light-emitting device layer and a packaging layer which are sequentially stacked on the substrate; the light-emitting device layer comprises a light-emitting layer, the light-emitting layer comprises a main body material and a light-emitting material uniformly distributed in the main body material, and the main body material comprises a cross-linked polymer formed by cross-linking a P-type polymer and an N-type polymer. According to the method, the polymer is subjected to a crosslinking reaction to form the light-emitting layer with the solvent resistance by a heat treatment mode, so that the problem of mutual solubility of an upper layer and a lower layer in the display panel is effectively solved, the selection range of a solvent used by an electronic transmission material in the ink-jet printing technology is increased, and the development progress is accelerated.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
The display panel and the manufacturing method thereof provided by the embodiments of the present application are described in detail above, and the principle and the implementation manner of the present application are explained by applying specific examples herein, and the description of the embodiments above is only used to help understanding the technical scheme and the core idea of the present application; those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present disclosure as defined by the appended claims.
Claims (9)
1. A display panel, comprising:
a substrate;
the thin film transistor layer is arranged on the substrate;
the light-emitting device layer is arranged on the thin film transistor layer and comprises a light-emitting layer;
an encapsulation layer disposed on the light emitting device layer;
the light-emitting layer comprises a main body material and a light-emitting material uniformly distributed in the main body material, wherein the main body material comprises a cross-linked polymer formed by cross-linking a P-type polymer and an N-type polymer;
wherein the P-type polymer comprises a homopolymer of a 1, 3-dicarbazole-9-yl benzene derivative, and the N-type polymer comprises a homopolymer of a 4, 7-diphenyl-1, 10-phenanthroline derivative.
2. The display panel according to claim 1, wherein the side chains of the P-type polymer and the N-type polymer each contain at least one crosslinking group including one or more of a styrene group, an oxetane group, an amino group, and a hydroxyl group.
3. The display panel according to claim 2, wherein the mass ratio of the P-type polymer to the N-type polymer in the host material is 1:9 to 9: 1.
4. The display panel of claim 2, wherein the P-type polymer comprises carbazole groups and derivatives thereof, and the N-type polymer comprises oxazole, triazole, phenanthroline groups and derivatives thereof.
5. The display panel according to claim 1, wherein the light emitting material includes a metal complex and/or an organic fluorescent molecule, and the light emitting material is dispersed and fixed in the cross-linked polymer.
6. A preparation method of a display panel is characterized by comprising the following steps:
step S10: sequentially laminating a thin film transistor layer and a pixel definition layer on a substrate, wherein the pixel definition layer comprises a pixel region;
step S20: preparing an anode, a hole injection layer and a hole transport layer in sequence corresponding to the pixel region;
step S30: preparing a luminescent layer ink on the hole transport layer, wherein the luminescent layer ink comprises a main material, a luminescent material and an organic solvent, and the main material comprises a P-type polymer and an N-type polymer; wherein the P-type polymer comprises a homopolymer of a 1, 3-dicarbazole-9-yl benzene derivative, and the N-type polymer comprises a homopolymer of a 4, 7-diphenyl-1, 10-phenanthroline derivative;
step S40: heating the luminescent layer ink to enable the luminescent layer ink to generate a cross-linking reaction to form a luminescent layer, wherein the luminescent layer is a polymer film;
step S50: preparing an electron transport layer, an electron injection layer and a cathode on the luminescent layer in sequence;
step S60: an encapsulation layer is prepared on the cathode.
7. The method of manufacturing according to claim 6, wherein the method of manufacturing the luminescent layer ink includes: and dissolving the P-type polymer, the N-type polymer and the luminescent material into an organic solvent, adding a surface tension regulator and a viscosity regulator, and uniformly mixing to form the luminescent layer ink.
8. The method according to claim 7, wherein the side chains of the P-type polymer and the N-type polymer each contain at least one crosslinking group comprising one or more of a styrene group, an oxetane group, an amino group and a hydroxyl group.
9. The production method according to claim 8, wherein in the light-emitting layer ink, the mass of the host material accounts for 0.01 wt% to 10 wt% of the concentration of the light-emitting layer ink; the doping concentration of the luminescent material in the main body material is 0.1 wt% -10 wt%.
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| CN114525058A (en) * | 2022-04-21 | 2022-05-24 | 季华恒烨(佛山)电子材料有限公司 | Organic light-emitting layer ink, preparation method and light-emitting layer forming method |
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