CN112864343B - Coating device and ink coating method - Google Patents
Coating device and ink coating method Download PDFInfo
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- CN112864343B CN112864343B CN201911176903.4A CN201911176903A CN112864343B CN 112864343 B CN112864343 B CN 112864343B CN 201911176903 A CN201911176903 A CN 201911176903A CN 112864343 B CN112864343 B CN 112864343B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
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Abstract
The invention provides a coating device and a coating method of ink. The coating device comprises a first substrate with a first surface and a second surface which are opposite, wherein at least one through hole penetrating from the first surface to the second surface is arranged in the first substrate, the surface energy of the first surface is M1, the surface energy of the second surface is M2, the inner surface of the defining through hole is a third surface, at least part of the surface energy of the third surface is M3, M3 is more than M1, and M3 is more than M2. By adjusting the relationship between the surface energies of the upper and lower surfaces of the substrate and the inner surface of the through-hole in the coating apparatus, not only can ink be rapidly loaded into the through-hole, but also ink can be stably held in the through-hole against the action of gravity, so that the ink loading of the through-hole with a smaller volume or opening becomes easy to realize. When the coating device is used for coating ink in the sub-pixel area, the density of the through holes can be adjusted according to the distribution of the sub-pixel area, so that the manufacturing of the pixel substrate with large area and high pixel density is realized.
Description
Technical Field
The invention relates to the technical field of optics, in particular to a coating device and a coating method of ink.
Background
The self-luminous display technology represented by the OLED is receiving more and more attention, and the characteristics of high contrast, light weight, flexibility and the like are that the LCD display technology cannot be achieved, and the main stream manufacturing technology of such display panel is to manufacture three primary colors of RGB by utilizing vacuum evaporation and combining a mask plate (mask), but this mode is not suitable for manufacturing a large-size panel, because the light weight mask plate (mask) is expanded along with the continuous size, sagging deformation is increased, the gap between the mask and a substrate is increased continuously, resulting in poor accuracy of the evaporation position of RGB materials, color distortion, on the other hand, high vacuum equipment and maintenance cost thereof are very high, so the high-efficiency low-cost inkjet printing technology is receiving more and more attention.
When the three-color printing device is manufactured by using the ink printing technology, the substrate is placed on the flat base station, so that the problem of deformation does not exist, and the printing equipment sequentially drives RGB ink into corresponding sub-pixels according to the ink jet requirement to realize three-primary-color manufacturing. However, as pixel density increases, the size of pixels becomes smaller and smaller, such techniques encounter a significant bottleneck, calculated as 300ppi pixel density, with a pixel size of approximately 84.6x84.6 μm, assuming a pixel defining layer height of 1.5 μm, and without considering the limit of aperture ratio, a sub-pixel volume of approximately 3.5pL, which is substantially close to the limit of mass-produced printheads (single sub-pixel volume of approximately 1 pL), and when considering 50% aperture ratio, a print volume of 2pL is obviously not achievable by mass-produced printheads (single sub-pixel volume is much smaller than 1 pL).
Therefore, there is an urgent need to provide a coating technology with low cost, which is not only not affected by the panel size, but also satisfies the image quality requirement of high pixel density.
Disclosure of Invention
The invention mainly aims to provide a coating device and a coating method of ink, which are used for solving the problem that the coating device in the prior art cannot simultaneously meet the requirements of large-area coating and high pixel density.
In order to achieve the above object, according to one aspect of the present invention, there is provided a coating apparatus comprising: the first substrate is provided with a first surface and a second surface which are opposite, at least one through hole penetrating from the first surface to the second surface is arranged in the first substrate, the surface energy of the first surface is M1, the surface energy of the second surface is M2, the inner surface defining the through hole is a third surface, and at least part of the surface energy of the third surface is M3, M3 is more than M1, and M3 is more than M2.
Further, the surface tension of the ink applied by the coating device is M4, and M3 > M4> M2.
Further, the surface energy of the third surface in the extending direction of the through hole is kept constant; or dividing the third surface into a plurality of subareas distributed along the extending direction of the through hole, wherein the surface energy of each subarea gradually increases in the direction of the first surface pointing to the second surface; or the surface energy of the third surface increases in a direction in which the first surface points toward the second surface.
Further, M3 > 70mJ/M 2,M1<30mJ/m2, and M2 < 30mJ/M 2, preferably M1. Ltoreq.20 mJ/M 2,M2<20mJ/m2.
Further, the first substrate has an outer peripheral surface connecting the first surface and the second surface, the surface energy of the outer peripheral surface being M5, M5< M4, preferably M5< 30mJ/M 2, more preferably M5. Ltoreq.20 mJ/M 2.
Further, the pore diameter of the through-hole is not more than 100. Mu.m, preferably not more than 50. Mu.m, more preferably not more than 20. Mu.m.
Further, the length of the through hole is defined as L,1 cm.gtoreq.L.gtoreq.10 μm, preferably 1 mm.gtoreq.L.gtoreq.10 μm, more preferably 100 μm.gtoreq.L.gtoreq.25 μm.
Further, the area of the first surface not in communication with the through-hole is a non-through-hole area, and the coating device further includes a reinforcing member, at least part of which is in contact with the non-through-hole area.
Further, the coating device further comprises a switch structure, wherein the switch structure comprises a shielding plate for closing one end, close to the first surface, of the through hole.
Further, the coating device further comprises a pressure control system, wherein the pressure control system is positioned on one side of the first substrate with the first surface and is used for pressing the through hole.
According to another aspect of the present invention, there is provided a method of applying ink, the ink being applied by the application device described above.
Further, the coating method comprises the following steps: s1, contacting the second surface of the coating device with ink so that the ink enters the through hole of the coating device; s2, providing a second substrate, wherein one side surface of the second substrate is provided with at least one mutually isolated sub-pixel area, the surface energy of the inner surface of the sub-pixel area is M6, M6 is more than M2, the through hole in the coating device and the sub-pixel area are arranged in an aligned mode, the first surface of the coating device is far away from the second substrate relative to the second surface, and pressure is applied to the through hole from one side of the first surface, so that ink in the through hole contacts with the inner surface of the sub-pixel area and enters the sub-pixel area.
Further, the pressure is applied by passing an inert gas.
Further, the inner surface of the sub-pixel region is an electrode surface, or the inner surface of the sub-pixel region is a functional layer surface, and the functional layer is selected from any one of a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, an electron transport layer, and a light emitting layer.
By applying the technical scheme of the invention, the coating device comprises a first substrate with a first surface and a second surface which are opposite, wherein at least one through hole penetrating from the first surface to the second surface is arranged in the first substrate, the surface energy of the first surface is M1, the surface energy of the second surface is M2, at least part of the inner surface of the through hole is defined as a third surface, the surface energy of the third surface is M3, M3 is more than M1, and M3 is more than M2. According to the invention, through adjusting the relation between the upper surface and the lower surface of the substrate and the surface energy of the inner surface of the through hole in the coating device, ink can be rapidly loaded into the through hole, the ink can be stably kept in the through hole against the action of gravity, and the loading capacity of the ink in the through hole is regulated and controlled through designing the volume of the through hole and the surface energy distribution of the inner surface of the through hole, so that the ink loading of the through hole with smaller volume or opening is easy to realize. When the coating device is used for coating ink in the sub-pixel area, the density of the through holes can be adjusted according to the distribution of the sub-pixel area, so that the manufacture of the pixel substrate with large area and high pixel density is realized; in addition, the coating device has simple structure and low maintenance cost, and is easy to clean even if the through hole is blocked.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
Fig. 1 is a schematic cross-sectional view showing a first substrate in a coating apparatus according to an embodiment of the present invention; and
Fig. 2 shows a schematic top view of the first substrate shown in fig. 1 after the reinforcement is provided thereon.
Wherein the above figures include the following reference numerals:
10. A first substrate; 110. a first surface; 120. a second surface; 130. a through hole; 131. a third surface; 20. a reinforcement.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate in order to describe the embodiments of the invention herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
As described in the background art, there is an urgent need to provide a coating technique with low cost, which is not only not affected by the size of the panel, but also satisfies the image quality requirement of high pixel density. The inventor of the present invention studied the above problems and proposed a coating apparatus, as shown in fig. 1, comprising a first substrate 10, the first substrate 10 having a first surface 110 and a second surface 120 opposite to each other, at least one through hole 130 penetrating from the first surface 110 to the second surface 120 being provided in the first substrate 10, the surface energy of the first surface 110 being M1, the surface energy of the second surface 120 being M2, the inner surface defining the through hole 130 being a third surface 131, at least a portion of the surface energy of the third surface 131 being M3, M3 > M1, and M3 > M2.
Unlike the substrate used in the coating device in the prior art, the surface energy of the coated substrate is optimized in the coating device provided by the invention, so that when the coating device is used for coating the ink, specific ink suitable for the coating device needs to be used to prevent the ink from adhering to the surface of the coated substrate, and the surface tension of the ink suitable for the coating device is M4, and M3 > M4> M2.
According to the invention, through adjusting the relation between the upper surface and the lower surface of the substrate and the surface energy of the inner surface of the through hole in the coating device, ink can be rapidly loaded into the through hole, the ink can be stably kept in the through hole against the action of gravity, and the loading capacity of the ink in the through hole is regulated and controlled through designing the volume of the through hole and the surface energy distribution of the inner surface of the through hole, so that the ink loading of the through hole with smaller volume or opening is easy to realize. When the coating device is used for coating ink in the sub-pixel area, the density of the through holes can be adjusted according to the distribution of the sub-pixel area, so that the manufacture of the pixel substrate with large area and high pixel density can be realized; in addition, the coating device has simple structure and low maintenance cost, and is easy to clean even if the through hole is blocked.
In the coating apparatus of the present invention, the first surface 110 of the first substrate 10 may be a flat plane, or may be a curved surface or a convex surface, which is not particularly limited herein; the second surface 120 opposite to the first surface 110 is used as a coating surface of a coating device, and in order to enable the ink to be better coated on the surface of the object after passing through the coating device, preferably, the second surface 120 is a flat and highly flat surface, and the surface of the object may be placed on a flat and shockproof platform as horizontal as possible, and the second surface 120 is in close contact with the surface of the object and enables the ink to be coated.
In the coating apparatus of the present invention, the first surface 110, the second surface 120, and the third surface 131 of the first substrate 10 have surface energies of M1, M2, and M3, respectively, and one skilled in the art may form the first surface 110, the second surface 120, and the third surface 131 using materials having different surface energies, or may perform surface treatments on the first surface 110, the second surface 120, and the third surface 131 formed of the same material to have different surface energies. The above-described surface treatment is more flexible than the manner in which the first surface 110, the second surface 120, and the third surface 131 have different surface energies using materials having different surface energies, and the first surface 110, the second surface 120, and/or the third surface 131 may be further surface-treated to have appropriate surface energies, respectively, according to the surface tension M4 of different inks.
The embodiment of the surface treatment is described by using silicon as the material of the first substrate 10, and the precise porous substrate is obtained by photoetching the silicon material, when the surface treatment is required to reduce the surface energy of the silicon material, a fluorine-containing coupling agent (such as fluorosilicone) can be used for grafting on the surface of the silicon substrate to form a silicon-oxygen bond, and a carbon chain with the fluorine atom substituted for the hydrogen atom brings low surface energy, when different silicon surfaces are required to have different surface energy, such as from small to large, a F atom fully substituted silane coupling agent can be used, and the grafting density is high, so that the surface of the substrate to be treated can be fully covered as far as possible; the surface energy of the substrate is gradually increased as the grafting density is reduced or the number of F atoms substituted for H atoms is small. Since the surface energy of the surface of the silicon substrate is very high, when the surface energy needs to be improved, the surface energy of the inner surface of the through hole can be adjusted by carrying out plasma treatment in the through hole to graft the silane coupling agent with hydroxyl or amino on the surface of the through hole. The surface treatment may be grafted by contact reaction with a solution of the surface treatment agent, or may be grafted to the through-holes (i.e., the third surface 131) or other surfaces (i.e., the first surface 110 and the second surface 120) by gasifying the surface treatment agent and reacting the surface treatment agent with plasma. In addition, the roughness of the walls of the through-holes during etching is also an important factor affecting the spreading of the ink, i.e. the roughness can also affect the surface energy of the walls of the through-holes.
The surface energy of the third surface 131 may be a constant value or may be gradually changed along a certain direction, as long as M3 > M1 and M3 > M2 are satisfied, and the surface energy of the third surface 131 along the extending direction of the through hole 130 is constant; or dividing the third surface 131 into a plurality of sub-areas distributed along the extending direction of the through hole 130, wherein the surface energy of each sub-area gradually increases in the direction that the first surface 110 points to the second surface 120; or the surface energy of the third surface 131 increases in a direction in which the first surface 110 points toward the second surface 120.
In order to ensure that the ink can be rapidly loaded into the through hole of the coating device, it is preferable that the surface energy M3 of the third surface 131 is more than 70mJ/M 2, the surface energy M1 of the first surface 110 is less than 30mJ/M 2, and the surface energy M2 of the second surface 120 is less than 30mJ/M 2; in order to further reduce the possibility of contamination of the coating device with ink, more preferably, M1 is 20mJ/M 2 and M2 is less than 20mJ/M 2.
The first substrate 10 further has an outer peripheral surface connecting the first surface 110 and the second surface 120, and in order to avoid adhesion of ink to the outer peripheral surface, the surface energy of the outer peripheral surface is preferably M5, and M5< M4; more preferably, M5< 30mJ/M 2, still more preferably M5. Ltoreq.20 mJ/M 2.
In the coating apparatus of the present invention, the number of the through holes 130 in the first substrate 10 may be one or more, and when a plurality of through holes are provided, the coating apparatus of the present invention is used to prevent the surface of the substrate from being stained with ink except for the inside of the through holes when the coating apparatus is used to perform coating, so that the same coating apparatus may be used to perform a plurality of cycles of loading and coating ink, thereby realizing the coating of a plurality of ink (e.g., RGB ink) materials in the sub-pixel region.
In order to ensure rapid loading of ink into the through-holes of the coating apparatus, the through-holes 130 preferably have a pore diameter of 100 μm or less, more preferably the through-holes 130 have a pore diameter of 50 μm or less, and still more preferably the through-holes 130 have a pore diameter of 20 μm or less. It should be noted that the cross section of the through hole 130 may be circular, or may be in other patterns, such as oval, polygonal, or irregular patterns, and the aperture of the through hole 130 may be understood as the shortest line length passing through the geometric center of the cross section of the through hole and overlapping with the edge line of the through hole.
Since the smaller the pore diameter of the through-hole 130, the larger the risk of clogging, and the nano particles may be contained in the ink, for example, when the ink is a quantum dot ink, the particle size of the quantum dot in the ink is about 10nm, or when the ink is PEDOT, the particle size of the colloidal particles in the PEDOT is 30nm, in this case, in order to avoid clogging of the ink, the pore diameter of the through-hole 130 is preferably not less than 1 μm.
To ensure that the through holes 130 are filled with sufficient ink to meet the pixel density requirements of different devices, the length of the through holes 130 is preferably defined to be L,1cm, 1mm, 10 μm, 100 μm, 25 μm, or more. For example, a volume of approximately 19.625 picoliters, calculated as a pore size of 50 μm and a length of 10 μm, that completely fills the via 130 can be used to fabricate a 100ppi pixel substrate.
In the coating apparatus of the present invention, the area of the first surface 110 not in communication with the through hole 130 is a non-through hole area, and when the area of the first substrate 10 is large, deformation may occur in the plane direction perpendicular to the through hole 130, and when the deformation is too large, misalignment of the through hole 130 may occur, so that deviation occurs during coating, and in order to avoid deformation caused by the large area of the first substrate 10, preferably, the coating apparatus further includes a stiffener 20, at least part of the stiffener 20 contacts with the non-through hole area, as shown in fig. 2. The person skilled in the art can choose from the prior art a stiffener 20 with a suitable stiffness and thickness according to the actual area of the first substrate 10, as the stiffener 20 described above can be of the same material as the first substrate 10. In order to avoid deformation of the first substrate 10, a force may be applied to maintain the horizontal state of the first substrate 10, in one embodiment, a layer of magnetic material is plated on the first surface 110 of the first substrate 10, and then a magnetic plate is disposed on a side of the first surface 110 away from the through hole 130, so as to maintain the horizontal state of the first substrate 10 through magnetic attraction.
In some embodiments, the coating apparatus of the present invention further includes a switch structure including a shielding plate for closing an end of the through-hole 130 adjacent to the first surface 110, and the switch structure may further include a control member electrically or mechanically connected to the shielding plate for controlling the shielding plate to close an end of the through-hole 130 adjacent to the first surface 110. The shielding plate may be disposed on a side of the first surface 110 away from the first substrate 10, may be disposed on the first surface 110, or may be disposed inside the through hole 130, so long as the purpose of sealing one end of the through hole 130 close to the first surface 110 is achieved.
In some embodiments, the coating apparatus of the present invention further includes a pressure control system disposed on a side of the first substrate 10 having the first surface 110 for applying pressure to the through-hole 130. The pressure control system may include a gas delivery device for delivering gas into the through hole 130, and a pressure controller electrically connected to the gas delivery device for controlling the pressure of the output gas, which is not limited to the above, and may be reasonably selected by a person skilled in the art according to the prior art, so long as the pressure applied to the through hole 130 can be achieved.
According to another aspect of the present invention, there is also provided a method of coating ink using the above-described coating apparatus.
Unlike the coating substrate used in the coating method in the prior art, the surface energy of the coating substrate is optimized in the coating method provided by the invention, so that when the coating substrate is used for coating ink, specific ink suitable for the coating substrate needs to be used to prevent the ink from adhering to the surface of the coating substrate, and the surface tension of the ink suitable for the coating substrate is M4, M4< M3, M4> M2.
According to the invention, through adjusting the relation between the upper surface and the lower surface of the substrate and the surface energy of the inner surface of the through hole in the coating device, ink can be rapidly loaded into the through hole, the ink can be stably kept in the through hole against the action of gravity, and the loading capacity of the ink in the through hole is regulated and controlled through designing the volume of the through hole and the surface energy distribution of the inner surface of the through hole, so that the ink loading of the through hole with smaller volume or opening is easy to realize. When the coating device is used for coating ink in the sub-pixel area, the density of the through holes can be adjusted according to the distribution of the sub-pixel area, so that the manufacturing of the pixel substrate with large area and high pixel density can be realized.
In order to achieve the application of the ink in the subpixel areas using the above-described application device, in a preferred embodiment, the above-described application method includes the steps of: s1, contacting the second surface 120 of the coating device with ink to enable the ink to enter the through hole 130 of the coating device; s2, providing a second substrate, wherein one side surface of the second substrate is provided with at least one sub-pixel area which is isolated from each other, the surface energy of the inner surface of the sub-pixel area is M6, M6 is more than M2, arranging the through hole 130 in the coating device and the sub-pixel area in an alignment mode, arranging the first surface 110 of the coating device far away from the second substrate relative to the second surface 120, and applying pressure to the through hole 130 from one side of the first surface 110 so that ink in the through hole 130 contacts with the inner surface of the sub-pixel area and enters the sub-pixel area.
The surface energy of the inner surface of the sub-pixel region is M6, the surface energy of the inner surface (the third surface 131) of the through hole 130 is M3, and when the ink is loaded in the through hole 130, the liquid surface is concave, gravity cannot make the liquid surface 'bulge' to contact with the inner surface of the sub-pixel region of the second substrate during coating, so that the lower liquid surface 'bulges' by pressing, the lowest edge of the bulge can contact with the inner surface of the sub-pixel region, when M6 is more than M3, the transfer of the ink is easier, and after the ink is pressed, the ink can completely come out into the sub-pixel region even if the ink is not pressed any more; and when M6 < M3, further pressing is required to release the ink from the through hole 130 into the sub-pixel region.
In order to realize the pressing of the through hole 130, a chamber communicated with the through hole 130 is arranged at one side of the first surface 110, and air is introduced into the chamber to increase the air pressure in the chamber, the ink in the through hole 130 is forced to move towards the second surface 120 under the driving of the air pressure, so that hanging liquid drops are slowly formed, and the air pressure in the chamber is further increased to enable the ink to be completely extruded; in order to prevent the pressing gas from being oxidized, the gas is preferably an inert gas, and in order to retard the drying of the ink, the inert gas may be mixed with saturated vapor of the ink main solvent. The pressing method of the through-hole 130 is not limited to the above embodiment, and for example, a voltage may be applied to the through-hole 130, and the ink may be extruded by deforming the inner wall of the through-hole 130 to the center by releasing a small current, or by physical extrusion.
In the process of preparing the light-emitting device, the coating device is used for coating the ink in the sub-pixel region, the inner surface of the sub-pixel region can be an electrode surface or a functional layer surface, any film layer is prepared by the ink coating process in the process of preparing the light-emitting device, and the functional layer can be selected from any one of a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, an electron transport layer and a light-emitting layer.
The above-described coating apparatus of the present invention and a coating method using the same will be further described below with reference to examples.
Example 1
As shown in fig. 1, the coating apparatus provided in this embodiment includes a first substrate 10 with a length of 2.5cm and a width of 1.7cm, where the first substrate 10 has a first surface 110 and a second surface 120 opposite to each other, and at least one through hole 130 penetrating from the first surface 110 to the second surface 120 is disposed in the first substrate 10; the surface energy of the first surface 110 is M1, the surface energy of the second surface 120 is M2, the inner surface of the defining through hole 130 is a third surface 131, the surface energy of the third surface 131 is M3, M3 > M1, and M3 > M2; the aperture of the through holes 130 is 10 μm, the length is 10 μm, and the number is 1920×1080×3; the first substrate 10 further has an outer peripheral surface connecting the first surface 110 and the second surface 120, and the surface energy of the outer peripheral surface is M5, and M5< M4.
The manufacturing process of the first substrate 10: coating photoresist on the whole surface of a cleaned silicon wafer with the thickness of 50 mu m, exposing, developing and acid etching to obtain a groove with the aperture of 50 mu m and the length of 40 mu m (the inner surface of the groove belongs to a part of the first surface 110), immersing the silicon wafer with the photoresist in a treatment liquid for carrying out surface grafting reaction and washing the silicon wafer clean, recoating the photoresist in the groove with the acid etching, exposing the surface of the silicon wafer to be corroded after exposure and development, further etching with acid liquor to obtain through holes 130 with the aperture of 10 mu m, the length of 10 mu m and the number of 1920 x 1080 x 3, removing the photoresist, finishing the manufacture of the first substrate 10, wherein the length of the first substrate 10 is 12.5cm, the width of the first substrate 10 is 6.5cm, and a single time can be used for coating a 5.2 inch display device.
Wherein the treatment solution comprises 2wt% of 1H, 2H-perfluoro decyl triethoxysilane ethanol solution and 0.5wt% of acetic acid as a reaction catalyst; the processing process comprises the following steps: immersing the silicon wafer in the treatment liquid for 5min, taking out, washing with a large amount of ethanol, and baking.
Since M1, M2 and M5 were subjected to the same surface treatment, the surface energies were uniform, and another wafer subjected to a parallel test of grafting a low surface material was tested by an OCA-200 type surface energy tester, and the surface energies were around 28mJ/M 2, i.e., the surface energies of M1, M2 and M5 were about 28mJ/M 2. Because the inner surface of the through hole is difficult to test, a silicon wafer with the thickness of 0.4mm and the diameter of 1cm and the thickness of 10 mu M is removed by etching by selecting a silicon wafer with the thickness of 4 inches, and the surface energy of the etched surface (round bottom surface) is tested to obtain the surface energy value of about 1238mJ/M 2, namely M3 is about 1238mJ/M 2.
Example 2
As shown in fig. 1, the coating apparatus provided in this embodiment includes a first substrate 10 with a length of 2.5cm and a width of 1.7cm, where the first substrate 10 has a first surface 110 and a second surface 120 opposite to each other, and at least one through hole 130 penetrating from the first surface 110 to the second surface 120 is disposed in the first substrate 10; the surface energy of the first surface 110 is M1, the surface energy of the second surface 120 is M2, the inner surface of the through hole 130 is defined as a third surface 131, the third surface 131 is divided into two subareas distributed along the extending direction of the through hole 130, the surface energy of each subarea gradually increases in the direction of the first surface 110 pointing to the second surface 120, the surface energy of the two subareas is M31 and M32 respectively, (M31, M32) > M1, and (M31, M32) > M2; the aperture of the through holes 130 is 50 μm, the length is 25 μm, and the number is 96×64×3; the first substrate 10 further has an outer peripheral surface connecting the first surface 110 and the second surface 120, and the surface energy of the outer peripheral surface is M5, and M5< M4.
The manufacturing process of the first substrate 10: coating Polyimide (PI) photoresist on a cleaned silicon wafer with the thickness of 20 mu m, baking, solidifying and forming, immersing the silicon wafer in a grafting treatment liquid for 5min, taking out the silicon wafer, washing and drying the silicon wafer, exposing and developing the silicon wafer, obtaining a first hole section with the aperture of 50 mu m and the length of 5 mu m (the thickness of a PI dry film is 5 mu m, the bottom silicon wafer is just exposed at a through hole of the PI dry film after exposing and developing), immersing the silicon wafer with the porous polyimide film layer in acid liquid for etching, etching the exposed silicon wafer, further obtaining a second hole section with the aperture of 50 mu m and the length of 20 mu m, taking out, washing and drying the second hole section to obtain a first substrate 10 with the through holes 130, wherein the number of the through holes is 96 times 64 times 3, the aperture of the through holes 130 in the first substrate 10 is 50 mu m, the total length of the first hole Duan Jiadi cm, the total length of the second hole section is 6.5cm, the width of the first substrate 10 is 6.5cm, and a single-time coating of 1.2 display devices can be realized. ,
Wherein the composition of the treatment solution was a 2wt% ethanol solution of 1H, 2H-perfluorooctyl trimethoxysilane (0.5 wt% acetic acid as catalyst). And testing the surface energy of the polyimide film layer and the silicon wafer in a parallel test by using an OCA-200 surface energy tester to obtain the corresponding surface energy as follows: m1 (PI side) was about 29mJ/M 2, M2 (Si wafer side, grafting density was higher, surface energy was lower) was about 22mJ/M 2, M31 (first hole section in PI) was about 43mJ/M 2, M32 (second hole section in Si wafer) was about 1200mJ/M 2, and the outer peripheral surface was composed of two materials, so that the value of M5 was different depending on the position of the outer peripheral surface, and the surface energy was 22mJ/M 2 or 29mJ/M 2.
Example 3
As shown in fig. 1, the coating apparatus provided in this embodiment includes a first substrate 10 with a length of 2.5cm and a width of 1.7cm, where the first substrate 10 has a first surface 110 and a second surface 120 opposite to each other, and at least one through hole 130 penetrating from the first surface 110 to the second surface 120 is disposed in the first substrate 10; the surface energy of the first surface 110 is M1, the surface energy of the second surface 120 is M2, the inner surface of the through hole 130 is defined as a third surface 131, and the surface energy of the third surface 131 increases from M31 to M32, (M31, M32) > M1, and (M31, M32) > M2 in the direction in which the first surface 110 points to the second surface 120; the aperture of the through holes 130 is 20 μm, the length is 100 μm, and the number is 96×64×3; the first substrate 10 further has an outer peripheral surface connecting the first surface 110 and the second surface 120, and the surface energy of the outer peripheral surface is M5, and M5< M4.
The manufacturing process of the first substrate 10: cleaning a silicon wafer with the thickness of 100 mu m, placing the silicon wafer into a plasma cavity, introducing perfluoromethyl cyclohexane gas for carrying out interface grafting reaction, coating photoresist, exposing the surface of the silicon wafer to be corroded after exposure and development, etching the exposed surface of the silicon wafer by using acid liquor to obtain through holes with the aperture of 20 mu m and the length of 100 mu m and the number of 96X 3, washing and drying the through holes, immersing the silicon wafer into ethanol treatment liquid of 3, 3-trifluoropropyl trimethoxysilane, lifting the silicon wafer at the speed of 1 mu m/s in the length direction of the through holes, removing all the silicon wafer from the soaking liquid after about 2min, stripping residual photoresist on the surface of the silicon wafer after washing cleanly, and drying the silicon wafer to obtain a first substrate 10 with the length of 12.5cm and the width of 6.5cm, wherein a 1.2-inch display device can be coated once.
The surface energy of each of the corresponding surfaces in the parallel test was measured using an OCA-200 type surface energy tester, wherein M1, M2 and M5 were about 19mJ/M 2, the grafting speed of the fluorinated siloxane was greatly slowed down due to the lack of the acid catalyst, the surface energy M32 of the part of the inner surface of the through-hole which was first separated from the treatment liquid was about 71mJ/M 2, and the surface energy M31 of the part of the inner surface which was separated from the treatment liquid was about 47mJ/M 2, and it was apparent that the reaction time of 2 minutes was not able to graft the entire surface of the through-hole 130.
Example 4
The coating method provided in this embodiment includes the following steps:
the second surface 120 of the coating device in example 1 was contacted with a PEDOT: PSS ink (solvent composition of water, ethylene glycol, 45 mN/m) to let the ink enter the through-holes 130 of the coating device;
Providing a second substrate, wherein one side surface of the second substrate is provided with at least one sub-pixel area which is isolated from each other, the inner surface of the sub-pixel area is an ITO film layer after being treated by argon-oxygen mixed gas plasma, the surface energy M6 is 79mJ/M 2, the through hole 130 in the coating device is arranged in alignment with the sub-pixel area, the first surface 110 of the coating device is far away from the second substrate relative to the second surface 120, the through hole is pressurized along the direction of the first surface 110 towards the second surface 120, the ink in the through hole is forced to move along the pressurizing direction towards the second surface 120, the ink in the through hole 130 is contacted with the inner surface of the sub-pixel area, and the pressure is further applied to enable the ink in the through hole 130 to enter the sub-pixel area, so as to obtain the display substrate.
The volume filled in each of the through holes 130 was calculated to be about 0.4pL (the columnar through holes 130 are not filled in consideration of the liquid surface shape, and thus the volume of the ink filled in the through holes is calculated to be half of the volume of the through holes, and the same applies to the latter embodiment), and the sub-pixel region is filled one at a time by coating one through hole using the above-mentioned coating device, and the pixel density of the corresponding display substrate is 424ppi.
Example 5
The coating method provided in this embodiment includes the following steps:
The second surface 120 of the coating device in example 2 was contacted with a PEDOT: PSS ink (solvent composition of water, 65 mN/m) to let the ink enter the through-hole 130 of the coating device;
Providing a second substrate, wherein one side surface of the second substrate is provided with at least one sub-pixel area which is isolated from each other, the inner surface of the sub-pixel area is an argon oxygen plasma treated silicon surface, the surface energy M6 is 1305mJ/M 2, the through hole 130 in the coating device is arranged in alignment with the sub-pixel area, the first surface 110 of the coating device is arranged far away from the second substrate relative to the second surface 120, the through hole is pressurized along the direction of the first surface 110 towards the second surface 120 (the applied driving gas is from high-purity nitrogen N 2 mixed with saturated water vapor), the ink in the through hole is forced to move towards the second surface 120 along the pressurizing direction, and the ink in the through hole 130 is contacted with the inner surface of the sub-pixel area, so that the ink in the through hole 130 enters the sub-pixel area, and the display substrate is obtained.
The volume of the filling of each through hole 130 was calculated to be about 20pL, and one sub-pixel region was filled at a time by coating one through hole using the coating apparatus described above, and the pixel density of the corresponding display substrate was 100ppi.
Example 6
The coating method provided in this embodiment includes the following steps:
the second surface 120 of the coating device in example 3 was contacted with a PEDOT: PSS ink (solvent composition of water, ethylene glycol, 45 mN/m) to let the ink enter the through-holes 130 of the coating device;
providing a second substrate, wherein one side surface of the second substrate is provided with at least one sub-pixel area which is isolated from each other, the surface energy of the inner surface of the sub-pixel area is an ITO film layer after being subjected to argon-oxygen mixed gas plasma treatment, the surface energy is M6 and is 79mJ/M 2, a through hole 130 in the coating device is arranged in alignment with the sub-pixel area, the first surface 110 of the coating device is arranged far away from the second substrate relative to the second surface 120, a chamber communicated with the through hole 130 is arranged on one side of the first surface 110, inert gas is introduced into the chamber to increase the air pressure in the chamber, the ink in the through hole 130 is forced to move towards the direction of the second surface 120 under the driving of the air pressure, and the front edge of the ink drop is released from the through hole 130 after being contacted with the inner surface of the sub-pixel area until the ink in the through hole enters the sub-pixel area (at the moment, even if the air pressure is stopped, the ink can enter the sub-pixel area), and is obtained.
The volume of the filling of each through hole 130 was calculated to be about 20pL, and the sub-pixel region was filled one at a time by coating using the coating apparatus described above, and the pixel density of the corresponding display substrate was 100ppi.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
1. according to the invention, by adjusting the relation between the upper surface and the lower surface of the substrate and the surface energy of the inner surface of the through hole in the coating device, not only can the ink be rapidly loaded into the through hole, but also the loading capacity of the ink in the through hole can be improved, so that the ink loading of the through hole with smaller volume or opening is easy to realize;
2. When the coating device is used for coating ink in the sub-pixel area, the density of the through holes can be adjusted according to the distribution of the sub-pixel area, so that the manufacture of the pixel substrate with large area and high pixel density is realized;
3. the coating device has the advantages of simple structure, low maintenance cost and easy cleaning even if the through hole is blocked;
4. When the coating device is provided with a plurality of through holes, the coating device can not only realize the coating of a plurality of ink materials in the sub-pixel area in the preparation process of the light-emitting device by loading the inks with different colors in the different through holes, but also avoid the cross contamination among the inks with different colors, thereby improving the performance of the light-emitting device.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (20)
1. A coating apparatus, characterized by comprising:
A first substrate (10) having a first surface (110) and a second surface (120) opposite to each other, wherein at least one through hole (130) penetrating from the first surface (110) to the second surface (120) is arranged in the first substrate (10), the surface energy of the first surface (110) is M1, the surface energy of the second surface (120) is M2, the inner surface defining the through hole (130) is a third surface (131), at least a part of the surface energy of the third surface (131) is M3, M3 > M1, and M3 > M2;
The coating device further comprises a pressure control system, wherein the pressure control system is positioned on one side of the first substrate (10) with the first surface (110), a chamber communicated with the through hole (130) is arranged on one side of the first surface (110), and inert gas is introduced into the chamber to increase the air pressure in the chamber, so as to press the through hole (130);
wherein the coating device is used for preparing a functional layer of the display device, wherein the functional layer is selected from any one of a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, an electron transport layer and a light emitting layer.
2. The coating device of claim 1, wherein the surface tension of the ink to which the coating device is applied is M4, M3 > M4> M2.
3. The coating apparatus of claim 1, wherein,
The surface energy of the third surface (131) along the extending direction of the through hole (130) is kept constant; or (b)
Dividing the third surface (131) into a plurality of sub-areas distributed along the extending direction of the through hole (130), wherein the surface energy of each sub-area gradually increases in the direction that the first surface (110) points to the second surface (120); or (b)
The surface energy of the third surface (131) increases in a direction in which the first surface (110) points towards the second surface (120).
4. A coating device according to any one of claims 1 to 3, wherein M3 > 70mJ/M 2, M1 < 30mJ/M 2, and M2 < 30mJ/M 2.
5. The coating apparatus of claim 4, wherein M1 is less than or equal to 20mJ/M 2, and M2 is less than 20mJ/M 2.
6. A coating device according to any one of claims 1 to 3, characterized in that the first substrate (10) has an outer peripheral surface connecting the first surface (110) and the second surface (120), the surface energy of the outer peripheral surface being M5, M5< M4.
7. The coating apparatus of claim 6, wherein M5 < 30mJ/M 2.
8. The coating apparatus of claim 7, wherein M5 is less than or equal to 20mJ/M 2.
9. A coating device according to any one of claims 1 to 3, wherein the aperture of the through-holes (130) is ∈100 μm.
10. The coating apparatus according to claim 9, wherein the aperture of the through-hole (130) is 50 μm or less.
11. The coating apparatus according to claim 10, wherein the aperture of the through-hole (130) is 20 μm or less.
12. Coating device according to claim 9, characterized in that the length of the through-hole (130) is defined as L,1cm ≡l ≡10 μm.
13. The coating apparatus of claim 12, wherein 1 mm.gtoreq.L.gtoreq.10 μm.
14. The coating apparatus of claim 13, wherein 100 μm.gtoreq.L.gtoreq.25 μm.
15. A coating device according to any one of claims 1 to 3, wherein the area of the first surface (110) not in communication with the through-hole (130) is a non-through-hole area, the coating device further comprising a reinforcement (20), at least part of the reinforcement (20) being in contact with the non-through-hole area.
16. A coating device according to any one of claims 1 to 3, characterized in that the coating device further comprises a switch structure comprising a shielding plate for closing an end of the through hole (130) adjacent to the first surface (110).
17. A method of applying ink, characterized in that the ink is applied by the application device according to any one of claims 1 to 16.
18. The coating method according to claim 17, characterized in that the coating method comprises the steps of:
S1, contacting a second surface (120) of the coating device with the ink to enable the ink to enter a through hole (130) of the coating device;
S2, providing a second substrate, wherein one side surface of the second substrate is provided with at least one mutually isolated sub-pixel region, the surface energy of the inner surface of the sub-pixel region is M6, M6 is more than M2, a through hole (130) in the coating device is arranged in alignment with the sub-pixel region, a first surface (110) of the coating device is arranged far away from the second substrate relative to the second surface (120), and pressure is applied to the through hole (130) from one side of the first surface (110) so that the ink in the through hole (130) is contacted with the inner surface of the sub-pixel region and enters the sub-pixel region.
19. The coating method according to claim 18, wherein the pressure is applied by passing an inert gas.
20. The coating method according to claim 18, wherein the inner surface of the sub-pixel region is an electrode surface, or the inner surface of the sub-pixel region is a functional layer surface, the functional layer being selected from any one of a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, an electron transport layer, and a light emitting layer.
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CN107150505A (en) * | 2016-03-02 | 2017-09-12 | 松下知识产权经营株式会社 | Cleaning device, clean method and the printing equipment of ink gun |
CN108382092A (en) * | 2018-02-06 | 2018-08-10 | 北京京东方显示技术有限公司 | Deflector, inkjet printing methods, equipment, display base plate and its manufacturing method, device |
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CN108382092A (en) * | 2018-02-06 | 2018-08-10 | 北京京东方显示技术有限公司 | Deflector, inkjet printing methods, equipment, display base plate and its manufacturing method, device |
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