CN109742257B - Electroluminescent device, preparation method thereof and display device - Google Patents
Electroluminescent device, preparation method thereof and display device Download PDFInfo
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- CN109742257B CN109742257B CN201910008690.8A CN201910008690A CN109742257B CN 109742257 B CN109742257 B CN 109742257B CN 201910008690 A CN201910008690 A CN 201910008690A CN 109742257 B CN109742257 B CN 109742257B
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Abstract
Provided is a method for manufacturing an electroluminescent device, including: providing a substrate and forming a light emitting unit on the substrate; immersing the substrate base plate formed with the light-emitting unit into the solution in a direction that a plane where the light-emitting unit is located is vertical to the liquid level of the solution, and then pulling out the substrate base plate at a uniform speed in a direction opposite to the immersion direction, wherein solutes of the solution comprise an organic semiconductor material and a high molecular polymer, and a solvent of the solution is an organic solvent capable of dissolving the organic semiconductor material and the high molecular polymer; the organic semiconductor material and the high molecular polymer have different solubilities in the organic solvent. An electroluminescent device is also provided. The invention realizes high-stability and functionalized organic film encapsulation by utilizing different solubilities of the organic semiconductor material and the high molecular polymer in the same solvent in the dip-coating process. The technology can be applied to the fields of transparent flexible displays, logic circuits, medical sensing and the like.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to an electroluminescent device, a preparation method thereof and a display device.
Background
In the fields of display and the like, extremely-sophisticated experiences such as lightness, thinness, flexibility and the like are continuously pursued. The organic functional material integrates the advantages of light weight, flexibility, stretchability, adjustable spectrum, large-area preparation and the like, and becomes an artificial material with the greatest development prospect. Related research relates to a plurality of fields, and attracts the interest of researchers of different subjects such as physics, chemistry, materials, information, biology, medicine and the like, so that the market share of electronic devices based on organic semiconductor materials is continuously expanded.
However, organic semiconductor materials and metal electrode materials have high sensitivity to external environments such as water, oxygen, light, temperature and the like, and poor environmental stability also restricts the application of organic materials in various fields. Water molecules (H) abundantly present in the air under atmospheric environment2O) and oxygen molecules (O)2) Direct contact with the organic material occurs. Therefore, in order to maintain the performance stability of the organic electronic device, an encapsulation process for encapsulating the organic thin film after the device is fabricated is generally required.
The currently used packaging methods are mainly classified into the following three methods: firstly, the metal cover plate is used for packaging, the metal cover plate can not only prevent components such as water, oxygen and the like from permeating the device package, but also enable the device to be firm, but the problems of flexibility, light tightness, larger weight and higher cost can be realized, and the application of the packaging method is also limited; the glass cover plate is packaged, has chemical stability, electrical insulation and compactness, but has poor mechanical strength and is easy to generate micro cracks; and thirdly, thin film packaging, namely forming films of organic or inorganic materials one by one to form stacked units to form a thin film packaging layer, wherein the thin film packaging layer has the advantages of light weight, thin thickness and the like. At present, the process cost is higher by using inorganic packaging technologies such as ALD, sputtering, PECVD and the like and organic thin film packaging technologies of ink jet printing.
Disclosure of Invention
In order to overcome the defects, the invention provides a preparation method of an electroluminescent device, the electroluminescent device formed by the method and a display device comprising the electroluminescent device.
One aspect of the present invention provides a method for manufacturing an electroluminescent device, including: providing a substrate and forming a light emitting unit on the substrate; immersing the substrate base plate formed with the light-emitting unit into the solution in a direction that a plane where the light-emitting unit is located is vertical to the liquid level of the solution, and then pulling out the substrate base plate at a uniform speed in a direction opposite to the immersion direction, wherein solutes of the solution comprise an organic semiconductor material and a high molecular polymer, and a solvent of the solution is an organic solvent capable of dissolving the organic semiconductor material and the high molecular polymer; the organic semiconductor material and the high molecular polymer have different solubilities in the organic solvent.
According to an embodiment of the present invention, the solubility of the organic semiconductor material in the organic solvent is two times or more the solubility of the high molecular polymer in the organic solvent or the solubility of the high molecular polymer in the organic solvent is two times or more the solubility of the organic semiconductor material in the organic solvent.
According to another embodiment of the present invention, the organic semiconductor material is an organic small molecule semiconductor material; the high molecular polymer has a relative molecular weight of 1 × 103The above polymers.
According to another embodiment of the present invention, the organic semiconductor material is selected from one or more of pentacene, triphenylamine, 2, 7-dioctyl [1] benzothieno [3,2-b ] benzothiophene, fullerene, phthalocyanine, perylene derivative, and cyanine; the high molecular polymer is selected from one or more of Polystyrene (PS), polymethyl methacrylate (PMMA) and poly (4-vinylphenol).
According to another embodiment of the invention, the boiling point of the organic solvent is between 35 ℃ and 125 ℃.
The invention provides an electroluminescent device which comprises a substrate, a light-emitting unit and an encapsulation layer, wherein the encapsulation layer comprises an organic semiconductor material film layer and a high molecular polymer film layer which are laminated.
According to an embodiment of the invention, the organic semiconductor material film is adjacent to the light emitting unit relative to the high molecular polymer film.
According to another embodiment of the present invention, the polymer film layer is adjacent to the light emitting unit with respect to the organic semiconductor material film layer. According to another embodiment of the present invention, the organic semiconductor material film layer comprises one or more of pentacene, triphenylamine, 2, 7-dioctyl [1] benzothieno [3,2-b ] benzothiophene, fullerene, phthalocyanine, perylene derivative, and cyanine; the high molecular polymer film layer comprises one or more of Polystyrene (PS), polymethyl methacrylate (PMMA) and poly (4-vinylphenol).
In another aspect, the invention also provides a display device comprising the electroluminescent device.
The invention realizes high-stability organic film encapsulation by utilizing different solubilities of the organic semiconductor material and the high molecular polymer in the same solvent in the dip-coating process. The preparation method is simple, the cost is reduced, and due to the crystallization characteristic of the organic semiconductor, the packaging film can be used as a micro-nano light emitting structure on the surface of the organic semiconductor light emitting device, so that the packaging film layer is further functionalized, the light emitting is improved, and the packaging film layer is further functionalized.
Drawings
The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
Fig. 1 is a schematic diagram of a packaging method according to an embodiment of the invention.
Fig. 2 is a cross-sectional electron microscope image of an encapsulation layer prepared by the encapsulation method of example 1 of the present invention.
Fig. 3 is a schematic diagram of forming a functionalized encapsulation layer according to embodiment 2 of the present invention.
Wherein the reference numerals are as follows:
1: substrate base plate
2: solution of organic semiconductor material and high molecular polymer
3: high molecular polymer
4: organic semiconductor material
5: organic semiconductor material film layer
6: high molecular polymer film layer
7: substrate base plate
8: electroluminescent device
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art. In the drawings, the thickness of regions and layers are exaggerated for clarity. The same reference numerals denote the same or similar structures in the drawings, and thus detailed descriptions thereof will be omitted.
It should be noted that the terms "upper", "lower", "inside" and "outside" in the present invention are only relative concepts or reference to the normal use status of the product, and should not be considered as limiting. The term substrate encompasses all forms of semiconductor structures.
The present invention will be described in detail with reference to the following embodiments.
As shown in fig. 1, a method for manufacturing an electroluminescent device according to an embodiment of the present invention includes providing a substrate 1, and forming a light emitting unit on the substrate 1. The substrate 1 with the light-emitting unit is immersed into the solution 2 in a direction that a plane where the light-emitting unit is located is vertical to the liquid level of the solution 2, then the substrate 1 is pulled out at a uniform speed in a direction opposite to the immersion direction, the solute of the solution comprises an organic semiconductor material 4 and a high molecular polymer 3, and the solvent of the solution 2 is an organic solvent capable of dissolving the organic semiconductor material 4 and the high molecular polymer 3. The organic semiconductor material 4 and the high molecular polymer 3 have different solubilities in an organic solvent.
After the substrate 1 with the light emitting unit formed thereon is immersed in the solution 2 of the organic semiconductor material 4 and the high molecular polymer 3 in a vertical direction, the solution 2 forms a meniscus mechanism near a three-phase contact line of the substrate 1 (including the light emitting unit on the substrate 1) -liquid level-air under the action of surface tension and gravity. When the solubility of the organic semiconductor material 4 in the organic solvent is greater than that of the high molecular polymer 3 in the organic solvent, the solvent evaporates near the three-phase contact line, the high molecular polymer 3 with low solubility preferentially precipitates and attaches to the surface of the film, and the organic semiconductor material 4 with high solubility delays precipitating and is positioned in the inner layer of the film, so that when the substrate 1 is pulled upwards at a certain speed, the organic semiconductor material 4 and the high molecular polymer 3 are continuously conveyed near the contact line by the capillary force and the concentration gradient action along with the rising of the substrate 1 and are deposited to form a patterned composite film with the surface being a high molecular polymer film layer and the bottom layer (adjacent to the substrate 1) being an organic semiconductor material film layer. On the contrary, if the solubility of the high molecular polymer 3 in the organic solvent is higher than that of the organic semiconductor material 4 in the organic solvent, a patterned composite film having a surface of the organic semiconductor material film layer and a bottom of the high molecular polymer film layer is formed.
The difference in solubility between the organic semiconductor material 4 and the high molecular polymer 3 in the organic solvent determines the formation of different film layers during the film formation, and the material with high solubility is formed on the inner side with respect to the substrate 1 and the material with low solubility is formed on the outer side. Preferably, the difference in solubility of the organic semiconductor material 4 and the high molecular polymer 3 in the organic solvent is two times or more, that is, the solubility of the organic semiconductor material 4 in the organic solvent is two times or more the solubility of the high molecular polymer 3 in the organic solvent; or the solubility of the high molecular polymer 3 in the organic solvent is more than twice as high as that of the organic semiconductor material 4 in the organic solvent.
The preparation method of the invention is suitable for any organic semiconductor material and high molecular polymer which can be used for film formation, and preferably, in the embodiment, the organic semiconductor material 4 is an organic small molecular semiconductor material, and the high molecular polymer 3 is an organic small molecular semiconductor material with a relative molecular weight of 1 × 103The above polymers. The organic small molecule semiconductor material has no structural fragments which exist alternately in a chain shape in the molecule, and generally only consists of one relatively large structural fragment
A conjugated system. Common organic small molecule semiconductor materials such as, but not limited to, pentacene, triphenylamine, 2, 7-dioctyl [1]]Benzothieno [3,2-b ]]One or more of benzothiophenes, fullerenes, phthalocyanines, perylene derivatives, and cyanines; the high molecular polymer is selected from one or more of Polystyrene (PS), polymethyl methacrylate (PMMA), poly (4-vinylphenol) and the like.
The organic semiconductor material and the high molecular polymer form an encapsulation layer after the organic solvent in the solution is volatilized, and the boiling point of the organic solvent used in the solution is preferably between 35 and 125 ℃. The organic solvent may be, for example, but not limited to, dichloromethane, chloroform, toluene, and the like.
The concentration of the solute in the solution, the dipping rate, and the pulling rate are not essential factors for film formation, and therefore, those skilled in the art can appropriately select the concentration, dipping rate, and pulling rate according to the thickness of the film to be formed, the type of the solute and the solvent in the solution, and the like.
In addition to the above necessary steps, other auxiliary steps may be included, such as, but not limited to, surface treatment of the substrate surface of the substrate, removal of impurities from the surface, or modification of surface roughness to enhance the bonding force between the encapsulation layer and the substrate.
The electroluminescent device formed by the preparation method comprises a substrate, a light-emitting unit and a packaging layer, wherein the packaging layer comprises an organic semiconductor material film layer and a high molecular polymer film layer which are stacked. As described above, the encapsulation layer may be formed by forming the organic semiconductor material film layer adjacent to the substrate and forming the high molecular polymer film layer on the outer side of the encapsulation layer, or by forming the high molecular polymer film layer adjacent to the substrate and forming the organic semiconductor material film layer on the outer side of the encapsulation layer. That is, the organic semiconductor material film layer is adjacent to the light emitting unit relative to the high molecular polymer film layer; or the high molecular polymer film layer is adjacent to the light-emitting unit relative to the organic semiconductor material film layer.
When the organic semiconductor material film layer is formed on the inner side with respect to the substrate base plate 1, it is advantageous to form a highly stable encapsulation layer. When the solubility of the organic semiconductor material is higher than that of the high molecular polymer, when the solvent near the three-phase contact line of the substrate, the solution and the air is evaporated, the high molecular polymer with low solubility is preferentially precipitated on the surface of the film layer, and the organic semiconductor material with high solubility is fully covered by the high molecular polymer precipitated first, so that a stable encapsulation layer is formed due to the high stability of the high molecular polymer. When the organic semiconductor material film layer is formed outside the substrate 1, it is advantageous to form a light-emitting layer having a high transmittance. When the solubility of the organic semiconductor material is lower than that of the high molecular polymer, a high molecular polymer film layer on the inner side and a crystalline layer of the organic semiconductor on the outer layer can be obtained. At this time, due to the fluid property of the high molecular polymer (the high molecular polymer is generally widely used for preparing each thin film device as an interface modification layer), the gap on the surface of the substrate can be filled, so that the light-emitting surface of the substrate is smoother, the light refraction loss is reduced, the crystallization quality of the organic semiconductor material is improved, the organic semiconductor material can be used as a micro-nano structure functional layer, the light-emitting of the organic semiconductor light-emitting device is improved, and the encapsulation film layer is further functionalized. The type of the organic semiconductor material and the environment of the film during growth determine the crystallization characteristics, and different crystallization characteristics generate different light emitting effects, so that those skilled in the art can select different types of organic semiconductor materials according to specific light emitting requirements.
The following examples respectively illustrate the two encapsulation layers, and those skilled in the art will appreciate that the following examples are only for illustrating the inventive concept of the present invention and are not intended to limit the present invention.
EXAMPLE 1 formation of high stability encapsulation layer
The organic semiconductor material is 6, 13-bis (triisopropylsilylethynyl) pentacene (TIPS-pentacene), the high molecular polymer is Polystyrene (PS), and the solvent is dichloromethane. Preparing TIPS-pentacene/dichloromethane solution and PS/dichloromethane solution, wherein the concentration is 10mg/ml, and the weight ratio of the TIPS-pentacene/dichloromethane solution is as follows: the PS/dichloromethane solution is mixed at a volume ratio of 3:1, and the substrate used is a heavily N-doped Si substrate (containing light-emitting units thereon). The dipping speed of the substrate base plate is 18mm/min, the dipping time is 2min, and the pulling speed is 10 mm/min.
Fig. 2 is a cross-sectional electron microscope cross-sectional view of the formed encapsulation layer, showing that the structure of the encapsulation layer is a PS/TIPS-pentacene laminated structure. The PS film layer is positioned on the upper layer (namely the outer side of the packaging layer) of the organic semiconductor material film layer, and because the PS film layer has excellent heat insulation, chemical corrosion resistance and transparency, the light transmittance can reach more than 90 percent, the capability of resisting the external water and oxygen erosion of the electroluminescent device can be improved, and the PS film layer can be particularly applied to the packaging of transparent flexible devices.
Example 2 implementation of encapsulation layer functionalization
Fig. 3 shows a schematic view of an organic semiconductor material film layer 5 having crystalline characteristics formed on the outer side of the encapsulation layer. As can be seen from the figure, the encapsulation layer of the electroluminescent device 8 is formed on the base substrate 7, and includes the high molecular polymer film layer 6 and the organic semiconductor material film layer 5 formed on the sides. Due to the crystallization characteristic of the organic semiconductor material film layer 6, the packaging layer can be used as a micro-nano structure functional layer, the light emitting of the electroluminescent device 8 is improved, and the packaging film layer is further functionalized.
Optionally, an embodiment of the present invention further provides a display apparatus, which may include the OLED device described above, where the display apparatus may be: the display device comprises any product or component with a display function, such as a liquid crystal panel, electronic paper, a mobile phone, a tablet personal computer, a television, a display, a notebook computer, a digital photo frame, a navigator and the like.
Compared with the prior art which requires at least two times of packaging, the method for forming the packaging layer through one-step molding avoids the possibility that impurities are introduced into the interface between the film layers due to multiple film forming in the prior art, so that the high-stability packaging layer is easier to form. Meanwhile, the crystallization characteristic of the organic semiconductor material enables the packaging layer to be used as a micro-nano structure functional layer, and the light emitting of the device is improved.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for manufacturing an electroluminescent device, comprising:
providing a substrate and forming a light emitting unit on the substrate; and
immersing the substrate base plate formed with the light-emitting unit into the solution in a direction that the plane where the light-emitting unit is located is vertical to the liquid level of the solution, and then pulling out the substrate base plate at a uniform speed in a direction opposite to the immersion direction;
the solute of the solution comprises an organic semiconductor material and a high molecular polymer, and the solvent of the solution is an organic solvent capable of dissolving the organic semiconductor material and the high molecular polymer; the organic semiconductor material and the high molecular polymer have different solubilities in the organic solvent;
wherein the organic semiconductor material is selected from one or more of pentacene, triphenylamine, 2, 7-dioctyl [1] benzothieno [3,2-b ] benzothiophene, fullerene, phthalocyanine, perylene derivative and cyanine.
2. The method for producing an electroluminescent device according to claim 1, wherein the organic semiconductor material has a solubility in the organic solvent which is two times or more the solubility of the high molecular polymer in the organic solvent; or the solubility of the high molecular polymer in the organic solvent is more than twice of the solubility of the organic semiconductor material in the organic solvent.
3. The method of claim 1, wherein the high molecular weight polymer has a relative molecular weight of 1 x 103The above polymers.
4. The method of claim 3, wherein the high molecular weight polymer is selected from one or more of polystyrene, polymethyl methacrylate, and poly (4-vinylphenol).
5. The method of claim 1, wherein the organic solvent has a boiling point of 35-125 ℃.
6. An electroluminescent device comprises a substrate, a light-emitting unit and an encapsulation layer, wherein the encapsulation layer comprises an organic semiconductor material film layer and a high molecular polymer film layer which are laminated;
the organic semiconductor material film layer comprises one or more of pentacene, triphenylamine, 2, 7-dioctyl [1] benzothieno [3,2-b ] benzothiophene, fullerene, phthalocyanine, perylene derivative and cyanine.
7. The electroluminescent device of claim 6, wherein the layer of organic semiconductor material is adjacent to the light-emitting unit relative to the layer of high molecular polymer film.
8. The electroluminescent device of claim 6, wherein the high molecular polymer film layer is adjacent to the light-emitting unit relative to the organic semiconductor material film layer.
9. The electroluminescent device of claim 6, wherein the polymer film layer comprises one or more of polystyrene, polymethylmethacrylate, and poly (4-vinylphenol).
10. A display device comprising an electroluminescent device as claimed in any one of claims 6 to 9.
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