JP6565321B2 - Laminated structure, organic EL element using the same, and manufacturing method thereof - Google Patents

Description

  The present invention relates to a laminated structure including a partition for coating a liquid functional coating material in an arbitrary compartment, a manufacturing method thereof, an organic EL element using the laminated structure, and a manufacturing method thereof.

  In recent years, a printed electronics technology has been developed in which a functional coating material in a liquid state is formed on a substrate by an inkjet method, a nozzle printing method, or other printing methods. Examples of functional coating materials include organic light emitting materials for organic electroluminescent elements (hereinafter abbreviated as organic EL elements), organic semiconductor materials for organic thin film transistors, conductive nano inks for forming electrical wiring, conductive nano pastes, and the like.

Conventionally, a functional material pattern has been formed by forming a thin film of a functional material on the entire surface of the substrate and performing an etching process after forming a resist pattern by photolithography. However, by directly patterning functional materials with printed electronics technology, cost reduction effects such as shortening of the manufacturing process and improvement of material usage efficiency are expected.
However, when the liquid functional coating material is applied onto the substrate, the functional material may be formed in a different site from the originally desired location due to the wetting and spreading of the liquid, which may cause malfunction of the functional device. . Therefore, a structure is widely adopted in which partition walls are formed at both ends or upper and lower ends of a region where the functional material is to be formed so that the functional coating material does not spread outside the partition wall.

  For example, full-color organic EL elements enable full-color display by arranging three colors of organic EL light-emitting pixels of red, green, and blue in the display area. However, organic EL light-emitting materials are formed by a printing method. In the case of forming a film, a structure is employed in which partitioning is performed in advance between display areas and then printing of each color is performed, so that mixing into an adjacent area due to wet spreading of the light emitting material does not occur (Patent Document 1).

However, even if the partition walls are provided between the display areas, if the partition walls themselves have wettability to the functional coating material, the applied functional coating material does not stay on the base substrate, but wets the side surfaces and top surface of the partition walls. There is a risk that.
As an illustration, for example, when a full color type organic EL device is manufactured, if the wetting of the side wall of the partition occurs, a part of the functional coating material that should be originally formed on the base substrate is wetted by the partition. Since it adheres, the use efficiency of material will fall. In addition, when the amount of wetting differs for each partition wall, uneven printing occurs, which may lead to uneven light emission when EL light is emitted. Further, when the wetting reaches the upper surface of the partition wall, for example, EL light emitting material of a different color is mixed in the region where the EL light emitting layer of a certain color is formed, thereby causing poor light emission characteristics. Therefore, in order to solve the problem due to the conductive material wetting on the partition wall, it is necessary to impart liquid repellency to the functional coating material to the partition wall.

  As means for imparting liquid repellency, there is a method of performing surface treatment such as chemical treatment or plasma treatment after the formation of the partition walls (Patent Document 2). This method has an advantage that the liquid repellency can be controlled depending on the chemical solution and plasma conditions to be used. However, since the treatment is performed on the entire substrate, there is a possibility of changing not only the partition walls but also the characteristics of the base substrate surface.

  There is also a method of forming a partition using a material having liquid repellency before the partition is formed (Patent Document 3). With this method, the step of imparting liquid repellency after the formation of the partition walls is unnecessary, and there is no possibility of changing the characteristics of the surface of the base substrate.

  However, even if the liquid repellency is imparted by these methods, the liquid repellency may be lowered when the substrate is washed in the subsequent process, or is subjected to heating or plasma surface treatment. Further, even if a surface treatment is performed or a partition material having liquid repellency is used, it is insufficient to obtain a liquid repellency effect with little wetting with respect to a liquid having a low surface tension such as an organic solvent.

In addition to the above method, there is a method of imparting liquid repellency to the partition wall by providing a nano liquid repellent structure on the partition wall surface and reducing the surface energy. For example, the phenomenon of lotus leaves and flowers splashing water droplets is called the Lotus effect. It is thought that water droplets are less likely to adhere due to the fine structure on the surface of lotus leaves and flowers, but by artificially forming a nanometer-order uneven structure on the surface of the substance It is known that the same liquid repellent effect can be imparted.
Examples of means for providing a nano-repellent structure include laser processing and nanoimprinting. The nanoimprint method is attracting attention as a technique for realizing an ultrafine structure in place of conventional photolithography. Although it takes time and cost to create a mold, once the mold is created, the mold can be used repeatedly, which facilitates mass production of devices.

  A method of providing a nano uneven structure on the surface of a resin by a nanoimprint method and controlling the liquid repellency of the surface is known (Patent Document 4). When a nano liquid-repellent structure is provided on the barrier ribs by the nanoimprint method, for example, after the barrier rib material is applied to the base substrate in a batch, a nano liquid repellent pattern is formed on the surface by pressing a mold having a nano liquid-repellent pattern before curing. Then, after forming a partition pattern by photolithography or the like, a nano-liquid-repellent structure can be imparted to the partition by performing a curing process.

However, in this method, since the nano liquid-repellent structure is formed only on the upper surface of the partition wall, it is impossible to prevent the wetting to the side surface. For this reason, there still remains a problem of reduction in material use efficiency due to the functional coating material getting wet on the side wall of the partition wall and uneven printing.
It is possible to provide a nano-liquid-repellent structure only on the upper surface of the partition wall by processing from the upper surface of the substrate. It is extremely difficult to provide a liquid repellent structure.

JP 2002-305077 A JP 2004-55159 A JP 2006-216297 A JP 2011-53334 A

  The present invention has been proposed in order to solve the above problems, and includes a laminated structure including a partition wall having a nano-liquid-repellent structure on an upper surface and a side surface, an organic EL element using the laminated structure, and those An object is to provide a manufacturing method.

  One aspect of the present invention for solving the above problems includes a step of applying a material resin for a partition wall to a base substrate and a mold for forming a nano-water-repellent structure having a convex surface on the material resin. A step of placing the surface on which the shape is formed facing the material resin, and a partition wall structure forming mold having a partition wall structure on the mold for forming the nano liquid repellent structure, and the surface on which the partition wall structure is formed is nano repellent. A step of placing the liquid structure forming mold so as to face the mold, and pressing the partition structure forming mold toward the base substrate to pressurize the material resin to form a partition wall having a nano liquid repellent structure on the side surface and the upper surface. A method for manufacturing a laminated structure.

  Moreover, the above-mentioned mold for forming a nano-liquid-repellent structure may have flexibility.

  Moreover, the above-mentioned mold for forming a nano-liquid-repellent structure may have a thickness of 5 μm or more and 15 μm or less.

  Still another aspect of the present invention is an organic method including a step of manufacturing a laminated structure by the above-described manufacturing method and a step of applying an organic EL light emitting material to a region on the base substrate that is partitioned by a partition wall. This is a method for manufacturing an EL element.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated structure provided with the partition which has a nano liquid repellent structure on an upper surface and a side surface, the organic EL element using the laminated structure, and those manufacturing methods can be provided.

The schematic diagram which shows schematic structure of the laminated structure which concerns on one Embodiment of this invention The schematic diagram for demonstrating the manufacturing process of the laminated structure which concerns on one Embodiment of this invention. The schematic diagram for demonstrating the manufacturing process of the laminated structure which concerns on one Embodiment of this invention. The schematic diagram for demonstrating the manufacturing process of the mold for nano repellent structure formation which concerns on one Embodiment of this invention. The schematic diagram for demonstrating the manufacturing process of the laminated structure which concerns on one Embodiment of this invention. The schematic diagram for demonstrating the manufacturing process of the mold for partition structure formation which concerns on one Embodiment of this invention. The schematic diagram for demonstrating the manufacturing process of the laminated structure which concerns on embodiment of this invention The schematic diagram for demonstrating the manufacturing process of the laminated structure which concerns on embodiment of this invention The schematic diagram for demonstrating the manufacturing process of the laminated structure which concerns on embodiment of this invention Schematic of the state which apply | coated the functional coating material to the area | region enclosed by the partition in the laminated structure which concerns on Example 1 of this invention. Schematic of a state in which a functional coating material is applied to a region surrounded by partition walls in the laminated structure according to Comparative Example 1 Schematic of a state in which a functional coating material is applied to a region surrounded by partition walls in the laminated structure according to Comparative Example 2

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings. However, the present invention is not limited to this embodiment.

  FIG. 1 is a schematic cross-sectional view showing a schematic structure of a laminated structure according to an embodiment of the present invention. The laminated structure includes a partition wall 1 and a base substrate 2, and the partition wall 1 is provided on the upper surface of the base substrate 2. In addition, a nano liquid repellent structure in which convex shapes are arranged on the surface in a two-dimensional cycle is provided on the side surface and the upper surface of the partition wall 1.

  Next, the manufacturing method of the laminated structure according to this embodiment will be described with reference to FIGS. However, the present invention is not limited to this manufacturing method. 2, 3, 5, 7, 8, and 9 are schematic cross-sectional views for explaining the manufacturing process of the laminated structure according to the embodiment, and FIG. 4 shows the manufacturing process of the mold for forming the nano-liquid-repellent structure. FIG. 6 is a schematic cross-sectional view for explaining, and FIG. 6 is a schematic cross-sectional view for explaining a manufacturing process of a partition wall structure forming mold.

  First, as shown in FIG. 2, a material resin for the partition walls 1 is applied on the base substrate 2. As the material resin for the partition wall 1, a material capable of forming a liquid repellent structure on the surface is selected by a nanoimprint method. For example, a fluorine resin, an acrylic resin, or the like can be used, but is not limited thereto. When a UV curable resin is used as the material resin for the partition wall 1, a cationic polymerization type resin or a radical polymerization type resin may be selected.

  Moreover, the coating method of the material resin of the partition wall 1 may be applied collectively by using a coating method such as a spin coater, a bar coater, a roll coater, a die coater, a gravure coater, an inkjet printer, a nozzle coater, a flexographic printing machine, etc. It may be used and printed only at a location where the partition wall 1 is desired to be formed. The base substrate 2 is a device substrate for applying a functional coating material on the upper surface. For example, in the case of an organic EL element, a glass substrate having a transparent oxide conductive film electrode such as ITO formed on the surface serves as a base substrate. However, the present embodiment is not limited thereto.

  Next, as shown in FIG. 3, the nano-liquid-repellent structure forming mold 10 is placed on the material resin of the uncured partition wall 1 with the surface on which the nano-liquid-repellent structure is formed facing down, that is, the nano-repellent structure. It is installed so that the surface on which the liquid structure is formed faces the material resin. The mold 10 for forming a nano liquid repellent structure may be manufactured by directly forming a nano liquid repellent structure on a flexible substrate, or a resin is applied to the flexible substrate, and the nano liquid repellent structure is applied to the resin surface. It may be manufactured by forming a structure. The base material of the mold 10 for forming the nano-liquid-repellent structure may be insulative or conductive, and need not have transparency. However, when the partition wall 1 is formed by the nanoimprint method using the nano liquid repellent structure forming mold 10, the material resin of the partition wall 1 is a UV curable resin, and the material of the partition wall 1 is passed through the nano liquid repellent structure forming mold 10. When UV irradiation is performed on the resin, the material needs to be transparent.

  Examples of the material for the base material of the mold 10 for forming a nano-liquid repellent structure include plastic films such as polypropylene, polyethersulfone, polycarbonate, cycloolefin polymer, polyarylate, polyamide, polymethyl methacrylate, polyethylene terephthalate, and polyethylene naphthalate. Sheets can be used. Further, a silicone resin such as dimethylpolysiloxane may be used as the material. However, when the partition wall 1 is formed by the thermal nanoimprint method, the material of the base material of the mold 10 for forming the nano-liquid-repellent structure is preferably a material that does not denature before and after the thermal nanoimprint process temperature. When a resin is applied to a flexible substrate and a nano liquid-repellent structure forming mold 10 is produced by forming a nano liquid-repellent structure on the resin surface, the resin material applied to the resin surface is the material of the partition wall 1. As with the resin, a material capable of forming a liquid repellent structure on the surface is selected by nanoimprinting.

  Further, the base material of the mold 10 for forming the nano-liquid-repellent structure is flexible so as to follow the concavo-convex shape of the mold 11 for forming the partition wall structure when pressed using the mold 11 for forming the partition wall structure in a later step. It is preferable to have properties. For this purpose, it is preferable that the nano-liquid repellent structure forming mold 10 is thinner because it can easily follow the uneven shape. Specifically, the thickness of the nano-liquid repellent structure forming mold 10 is desirably 15 μm or less. However, if the thickness is too thin, the handleability may be reduced, or it may be damaged when pressurized in the imprint process. Therefore, it is desirable that the thickness is at least 5 μm.

  As shown in FIG. 4, the nano liquid repellent structure of the mold 10 for forming the nano liquid repellent structure is formed by nanoimprint transfer. The master mold to be used is for a substrate on which a resist pattern is formed by applying a resist for electron beam lithography (hereinafter referred to as EB lithography) on a substrate such as silicon or quartz glass, and then performing EB lithography and resist development. It is manufactured by performing a dry etching process and forming a pattern on the substrate.

  The base material of the mold 10 for forming the nano-liquid-repellent structure or the base material of the mold 10 for forming the nano-liquid-repellent structure coated with the resin for nano-imprinting is placed on a stage with a temperature control mechanism to a temperature at which thermal nano-imprinting is possible. After heating, the nano liquid-repellent structure forming mold 10 can be formed by performing thermal nanoimprint transfer using the master mold manufactured in the above process. Alternatively, it is also possible to apply the UV curable nanoimprint resin to the base of the mold 10 for forming the nano-liquid-repellent structure and form the nano-liquid-repellent structure-forming mold 10 by UV-curing nanoimprint transfer.

Hereinafter, the design of the nano liquid-repellent structure formed on the partition wall 1 will be described. The apparent contact angle θ of the liquid on the coated surface having irregularities is expressed by the following Cassie-Baxter equation.
cos θ = F (cos θ ₁ +1) −1
Here, θ ₁ is a true contact angle when the liquid is dropped on a flat surface to be coated without unevenness, and F is a rate at which the surface material is in point contact with the droplet. As F is closer to 0, θ is closer to 180 °, which is desirable because higher liquid repellency can be obtained.

  In order to reduce F, it is necessary to reduce the rate at which the surface material is in point contact with the droplet, that is, to reduce the area of the convex portion of the concavo-convex structure. That is, when forming a periodic concavo-convex structure, the width of the convex portion may be designed to be narrower than the width of the concave portion. In the partition wall 1, the nano liquid repellent structure formed on the nano liquid repellent structure forming mold 10 and the nano liquid repellent structure formed on the partition wall 1 have inverted structures, but the nano liquid repellent structure forming mold 10 has a nano structure. The uneven structure of the master mold for forming the liquid repellent structure is the same as the uneven structure of the partition wall 1. Therefore, if a master mold for forming the nano-liquid-repellent structure of the mold 10 for forming the nano-liquid-repellent structure is manufactured with the design described below, when the partition wall 1 is manufactured, the nano-liquid-repellent structure with the same uneven structure design. Can be formed.

  The mold for forming a nano liquid-repellent structure has a structure in which convex shapes are arranged on the surface in a two-dimensional cycle. The shape of the convex portion may be designed in a prismatic shape, a cylindrical shape, or the like, but is not limited thereto. The width or diameter of the convex portion is 300 nm or less and is preferably narrower, but it is difficult to make it 100 nm or less in consideration of the processing accuracy of the EB lithography apparatus and the durability of the mold during nanoimprint transfer. Further, if the pitch between the convex centers is too narrow, processing defects may occur during EB lithography, so the thickness is set to 200 nm or more and 500 nm or less. The deeper the groove of the concavo-convex pattern is, the easier it is to maintain the liquid repellency because the droplets are less likely to contact the bottom.

  Next, as shown in FIG. 5, the partition structure forming mold 11 is placed on the nano-liquid-repellent structure forming mold 10 so that the groove structure pattern for forming the partition structure is on the bottom, that is, the groove structure forming partition structure. The surface on which the pattern is formed is installed so as to face the mold 10 for forming the nano-liquid-repellent structure. The partition wall structure forming mold 11 is manufactured by forming a groove pattern for partition wall structure formation on a hard substrate such as glass, ceramics, or metal. The base material of the partition wall structure forming mold 11 is formed using a glass-based material such as quartz or sapphire, or a metal-based material such as stainless steel or titanium, but is not limited thereto.

  Formation of the groove-shaped pattern for forming the partition wall structure is performed by a method suitable for the base material of the mold 11 for forming the partition wall structure. For example, when the substrate is a glass-based material, as shown in FIG. 6, after applying a photoresist to the substrate surface and patterning the resist by photolithography, the groove pattern is formed by wet etching or sandblasting. Can be formed. On the other hand, in the case of a metal-based material, it is possible to form a groove pattern directly on the surface not only by etching using photolithography but also by cutting or laser processing.

  The partition wall structure forming mold 11 has a structure in which a groove pattern is formed on the surface. The pattern shape and size of the partition wall 1 to be formed in a later process are determined by the shape and size of the groove pattern formed in the partition wall structure forming mold 11. When the partition wall 1 is desired to have a stripe structure in which the linear partition walls 1 are arranged in parallel, the pattern formed on the partition structure forming mold 11 has a structure in which linear grooves are arranged in parallel. Further, when it is desired to make the partition wall 1 have a box structure in which the partition walls are formed in a cross-beam shape, a cross-shaped groove is formed in the partition structure forming mold 11.

  The width of the groove pattern may be the same as that of the partition wall 1. On the other hand, during the nanoimprint transfer for manufacturing the partition wall 1, the partition wall 1 and the nano liquid-repellent structure forming mold 10 bulge in a convex shape along the shape of the groove pattern. It is formed to have a depth equal to or higher than the combined depth of the mold and the thickness of the mold 10 for forming the nano-liquid-repellent structure, preferably 1.5 times or more.

  For example, when the stripe-shaped partition wall 1 having a width of 20 μm and a height of 2 μm is to be formed using the nano-liquid repellent structure forming mold 10 having a thickness of 10 μm, the partition wall structure forming mold 11 has a width of 20 μm and a height of 18 μm. A striped groove pattern may be formed. A method of forming the partition wall 1 by nanoimprint transfer will be described with reference to FIGS. As apparatuses for performing nanoimprint transfer, there are a roll type nanoimprint type transfer machine that moves a roller linearly and a batch transfer type nanoimprint transfer machine that transfers using a parallel lithographic plate. In the present embodiment, transfer using a roll-type nanoimprint transfer machine will be described, but the transfer method is not limited thereto, and transfer may be performed using a batch transfer nanoimprint transfer machine.

  FIG. 7 is a schematic diagram for explaining an example of a schematic structure of the roll-type nanoimprint transfer machine 100. The roll type nanoimprint transfer machine 100 includes a substrate stage 101, a roller 102, and a UV irradiation unit 103. The substrate stage 101 is an electric stage that can move in the front-rear direction (the arrow direction in FIG. 7) with respect to the roller 102. Further, the substrate stage 101 has a stage temperature adjustment function, and nanoimprint transfer can be performed at a specified temperature.

  Hereinafter, the nanoimprint transfer process will be described. First, as shown in FIG. 5, with respect to the base substrate 2 to which the material resin of the partition wall 1 is applied, the mold 10 for forming the nano liquid repellent structure is arranged so that the surface on which the nano liquid repellent structure is formed faces the material resin of the partition wall 1. Then, a transfer structure in which the partition structure forming mold 11 is placed so that the surface on which the groove-like pattern is formed faces the nano liquid repellent structure forming mold 10 is placed on the substrate stage 101. Alternatively, the substrate 2 coated with the material resin for the partition walls 1 may be installed in advance on the substrate stage 101, and the nano-liquid-repellent structure forming mold 10 and the partition structure forming mold 11 may be installed thereon.

  The substrate stage 101 is moved to a position where the upper end surface of the partition wall structure forming mold 11 is in contact with the lower portion of the roller 102, and then the roller 102 is lowered and pressurized toward the substrate 2. By moving the substrate stage 101 in the direction in which the roller 102 rotates (in the direction of the arrow in FIG. 7) while the partition wall structure forming mold 11 is being pressed by the roller 102, A nano liquid repellent structure can be imparted simultaneously.

  FIG. 8 is an enlarged view for explaining the behavior of the partition wall 1, the nano-liquid-repellent structure forming mold 10, and the partition wall structure forming mold 11 during roll transfer. By pressing the partition wall structure forming mold 11 toward the substrate 2 with the roller 102, pressure is applied so as to crush the material resin of the partition wall 1 through the partition wall structure forming mold 11 and the nano liquid repellent structure forming mold 10.

  Since the material resin of the partition wall 1 under the convex part of the partition structure forming mold 11 is uncured and has fluidity, it moves so as to be pressed by the pressure of the roller 102. Since no pressure is applied from the concave portion of the partition wall structure forming mold 11, the material of the partition wall 1 pressed by the pressure of the convex portion of the partition wall structure forming mold 11 is a material remaining in the concave portion of the nano liquid repellent structure forming mold 10. Except for this, it is pushed and gathered under the concave portion of the partition structure forming mold 11.

  The nano liquid-repellent structure forming mold 10 under the concave portion of the partition wall structure forming mold 11 is bent to trace the groove pattern by being pushed up by the material resin of the partition wall 1 gathered from the peripheral convex portion lower portion. Since the liquid repellent structure forming mold 10 itself has a thickness, the shape of the partition wall structure forming mold 11 is not completely traced, and a curved convex shape is formed.

  The nano liquid repellent structure forming mold 10 below the concave portion of the partition wall structure forming mold 11 shown in FIG. 8 bends in a convex shape, and the material resin of the partition wall 1 below the convex nano-liquid repellent structure forming mold 10. By curing the material resin of the partition wall 1 in the presence of the partition wall 1, the partition wall 1 having a nano-liquid-repellent structure on the side surface and the upper surface can be formed.

  When the material of the partition wall 1 is a UV curable resin, when the material of the partition wall 1 is irradiated with UV light from the UV irradiation unit 103, the resin material is cured and nanoimprint transfer can be performed. On the other hand, when the material of the partition wall 1 is a thermoplastic resin, the stage temperature is raised, and the resin is softened until nanoimprint transfer is possible, and then roll transfer is performed. Nanoimprint transfer can be performed by lowering the stage temperature after the roll transfer is completed and cooling the material resin of the partition wall 1.

  After the nanoimprint transfer, as shown in FIG. 9, not only the partition walls 1 but also a remaining film between the partition walls exists on the base substrate 2. When an electronic device such as an organic EL element is formed in a later process, the remaining film between the barrier ribs prevents pixel light emission and causes a display defect. Therefore, dry etching treatment is performed to leave a portion where the barrier rib 1 is not formed. Remove the membrane. The gas used for dry etching is selected from oxygen, fluorocarbon, chlorine, or a combination thereof in accordance with the dry etching rate of the material resin of the partition wall 1.

  When oxygen gas is used at the time of dry etching, the surface energy of the partition wall 1 may be reduced due to the oxygen plasma treatment, and the liquid repellency may be lowered. Therefore, plasma surface modification treatment with fluorocarbon gas is performed after the remaining film is removed. It is preferable.

  A laminated structure can be manufactured by the above process. After manufacturing the laminated structure, a functional coating material such as an organic EL light-emitting material is applied to the base substrate 2 in the region separated by the partition wall 1 by printing or the like, and then undergoes a subsequent manufacturing process. Functional devices such as organic EL elements are completed.

  As described above, according to the multilayer structure manufactured using the method for manufacturing the multilayer structure according to the present invention, the functional coating material is applied to the base substrate 2 in the region surrounded by the partition wall 1. It is possible to prevent the wetting and rising to the side wall and upper surface of the partition wall that occurs when applied. Since wetting up to the partition wall 1 can be prevented, the functional coating material can be applied without causing the functional coating material to be mixed into an adjacent region or coating unevenness. In addition, since the functional coating material can be applied to the base substrate 2 without waste, it is also effective in reducing the device production cost.

  Also, the method for producing a laminated structure according to the present invention is another method, for example, producing a mold having a nano pattern on the bottom and side surfaces of a concave shape, and nanoimprinting the mold on the partition wall material applied to the base substrate The following advantages exist even when compared with the transfer method. That is, when continuous transfer is performed for mass production of partition walls, the pattern of the nano-liquid-repellent structure gradually deforms and wears as the number of transfers increases. In the case of a manufacturing method in which transfer is performed using a mold having a nano pattern on the bottom and side surfaces of the concave shape, when the pattern of the nano-liquid-repellent structure is worn, it is necessary to newly manufacture the entire mold. On the other hand, in the method for manufacturing a laminated structure according to the embodiment, even when the pattern of the nano-liquid repellent structure is worn, the liquid repellency imparted to the partition wall can be regenerated only by replacing the nano-liquid repellent structure forming mold. it can. Since the nano-liquid-repellent structure forming mold itself can be easily manufactured, the manufacturing method of the laminated structure according to the embodiment is excellent in maintainability when continuous transfer is performed.

Hereinafter, although the Example and comparative example of this invention are shown, this invention is not limited to this Example.
<Example 1>
(Manufacturing process of partition wall 1)
The material resin of the partition wall 1 was applied to the organic EL element substrate which is the base substrate 2 with a spin coater at a rotation speed of 0.5 μm. The material resin for the partition wall 1 was an acrylic resin having UV curing properties.

  Next, the mold 10 for forming the nano-liquid repellent structure was placed on the resin material of the uncured partition wall 1 with the surface on which the nano-liquid repellent structure was formed facing down. The mold 10 for forming a nano liquid repellent structure was formed by providing a nano liquid repellent pattern on the surface of a 10 μm thick polyethylene terephthalate film by thermal nanoimprint transfer. The master mold used for nanoimprint transfer was formed by drawing a nano-repellent pattern on a quartz substrate by EB lithography.

  The nano-liquid-repellent pattern formed on the master mold used for nanoimprint transfer is a concavo-convex structure with prisms arranged in a two-dimensional cycle on the surface, and the width, pitch, and height of the prisms with a scanning probe microscope SPI3800N (manufactured by Seiko Instruments Inc.) When the height was measured, the width of the prism was 200 nm, the pitch between the centers of the prisms was 400 nm, and the height of the prism was 500 nm.

  Next, the partition wall structure forming mold 11 was placed on the nano liquid repellent structure forming mold 10 so that the concavo-convex surface was down. The partition wall structure forming mold 11 was manufactured by applying a photoresist on a quartz substrate, exposing and developing the photoresist, and patterning the quartz by wet etching to provide a groove-like stripe pattern on the surface.

  When the groove width and depth were measured with a stylus type step gauge P-11 (manufactured by KLA-Tencor), the groove width was 20 μm and the groove depth was 18 μm. Next, nanoimprint transfer was performed using a roll-type nanoimprint transfer machine 100. An object to be transferred, in which a nano-liquid-repellent structure forming mold 10 and a partition wall structure forming mold 11 were stacked on the substrate 2, was placed on the substrate stage 101.

  After the substrate stage 101 was moved to a position where the upper end surface of the partition wall structure forming mold 11 was in contact with the lower part of the roller 102, the roller 102 was lowered and pressure was applied between the partition wall structure forming mold 11 and the substrate 2.

Next, with the pressure of 175 (N / m ² ) being applied to the roller 102, the substrate stage 101 was moved to the side where the roller 102 was rotated at a speed of 10 (mm / second). During the roll transfer, the material resin of the partition wall 1 is cured by irradiating the material resin of the partition wall 1 with UV through the partition wall structure forming mold 11 and the nano liquid repellent structure forming mold 10 from the UV irradiation unit 103, The structure of the partition 1 was formed.

  After the nanoimprint transfer of the partition wall 1, an ICP dry etching apparatus was used to remove the remaining film where the partition wall 1 was not formed. The remaining film removal conditions were as follows: oxygen used at 40 sccm, helium at 60 sccm, pressure set at 5 mTorr, Rf power set at 300 W, and plasma treatment was performed for 25 seconds. After the residual film was removed, in order to perform plasma surface modification treatment, the gas used was trifluoromethane 40 sccm, helium 60 sccm, pressure 5 mTorr, Rf power 300 W, and plasma treatment was performed for 10 seconds. After the partition wall 1 was formed, the width and height of the partition wall 1 were measured with a stylus type step gauge P-11 (manufactured by KLA-Tencor). As a result, the width was 20 μm and the height was 2 μm.

(Printing process of functional coating material 3 on base substrate 2)
An organic EL light-emitting material, which is a functional coating material 3, was applied to the base substrate 2 on which the partition walls 1 were formed and the regions were partitioned using an ink jet printer. FIG. 10 shows a schematic view of the laminated structure according to Example 1 in a state where the functional coating material 3 is applied to the region surrounded by the partition walls 1.

  First, a red light emitting material was applied, then a green light emitting material, and finally a blue light emitting material. Each color region is separated by the partition wall 1, and a nano-liquid-repellent structure is formed on the side surface and the upper surface of the partition wall 1, so that the applied organic EL light emitting material stays in the region separated by the partition wall 1. No color mixing occurred due to the wet and spreading of the luminescent material in different color areas. Further, since the applied organic EL light emitting material did not wet onto the side surfaces of the partition wall 1, the light emitting material could be applied to the base substrate 2 with a minimum liquid amount without uneven printing.

<Comparative Example 1>
In Comparative Example 1, an example of manufacturing an organic EL element using a partition wall 5 without a nano-repellent structure is shown. The material resin for the partition walls 5 was applied to the organic EL element substrate as the base substrate 2 with a spin coater at a rotation speed of 1 μm. A positive photosensitive polyimide resin was used as a material resin for the partition walls 5. The material resin of the partition wall 5 was exposed and developed by photolithography to pattern the partition wall 5. After post-baking and curing the polyimide resin, the organic EL light-emitting material, which is the functional coating material 3, is applied to the base substrate 2 on which the partition walls 5 are formed using an ink jet printer. It applied in order. FIG. 11 shows a schematic view of a laminated structure according to Comparative Example 1 in a state where the functional coating material 3 is applied to a region surrounded by the partition walls 5.

  Although the regions of the respective colors were separated by the partition walls 5, the luminescent material wets up to the side surfaces of the partition walls 5. Further, uneven printing occurred because the amount of wetting was different within the surface. Further, in the portion where the wet-up is intense, the light-emitting material gets over the upper surface of the partition wall 5 and spreads to a different color region, so that the light-emitting material is mixed in color.

  The display quality of the organic EL device manufactured according to the manufacturing method of Comparative Example 1 was greatly deteriorated compared to the organic EL device manufactured according to the manufacturing method of Example 1 because printing unevenness and color mixing occurred.

<Comparative Example 2>
In Comparative Example 2, an example of manufacturing an organic EL element using a partition wall 6 provided with a nano-liquid-repellent structure only on the upper surface is shown. The material resin for the partition walls 6 was applied to the organic EL element substrate as the base substrate 2 with a spin coater at a rotation speed of 1 μm. As the material resin for the partition wall 6, a positive photosensitive acrylic resin was used.

  The nano liquid-repellent structure was nano-imprint transferred onto the material resin surface of the partition wall 6 using the nano liquid-repellent structure forming mold 10. For the nanoimprint transfer, a roll type nanoimprint transfer machine 100 was used. In Example 1, nanoimprint transfer was performed using a UV curable resin. In Comparative Example 2, the stage was heated to a temperature at which the material resin of the partition wall 6 was softened during nanoimprinting, and thermal nanoimprint transfer was performed to cool the stage after completion of transfer.

  The partition wall 6 was formed by patterning the material resin of the partition wall 6 having the nano-liquid-repellent structure transferred onto the surface by photolithography. The organic EL light emitting material as the functional coating material 3 was applied to the base substrate 2 on which the partition walls 6 were formed in the order of red, green, and blue using an ink jet printer. FIG. 12 shows a schematic diagram of a laminated structure according to Comparative Example 2 in a state where the functional coating material 3 is applied to a region surrounded by the partition walls 6.

  Each color region is separated by a partition wall 6, and a nano liquid repellent structure is formed on the upper surface of the partition wall 6. Therefore, the mixed color of the luminescent material that the luminescent material gets over the upper surface of the partition wall 6 and spreads to different color regions is Did not occur. However, since the nano liquid-repellent structure was not formed on the side surface of the partition wall 6, the light emitting material wets up to the side surface of the partition wall 6. Further, uneven printing occurred because the amount of wetting was different within the surface.

  The display quality of the organic EL device manufactured according to the manufacturing method of Comparative Example 2 was good compared with the display quality of the organic EL device of Comparative Example 1 because there was no color mixing. Therefore, the display quality was deteriorated as compared with the display quality of the organic EL element manufactured according to the manufacturing method of Example 1.

  From the above results, partition walls having a nano-liquid-repellent structure on the upper surface and side surfaces can be manufactured by the manufacturing method of the laminated structure according to the embodiment, and color mixing and printing unevenness do not occur in an organic EL element using the same. It could be confirmed.

  INDUSTRIAL APPLICABILITY The present invention is useful for printed electronics technology for patterning a functional coating material on a substrate.

DESCRIPTION OF SYMBOLS 1, 5, 6 Partition 2 Base substrate 3 Functional coating material 10 Nano liquid repellent structure forming mold 11 Partition structure forming mold 100 Roll type nanoimprint transfer machine 101 Substrate stage 102 Roller 103 Ultraviolet irradiation unit

Claims (4)

Applying a partition wall material resin to the base substrate;
On the material resin, a step of installing a mold for forming a nano-liquid-repellent structure having a convex surface so that the convex surface is facing the material resin;
On the nano liquid repellent structure forming mold, a step of installing a partition wall structure forming mold having a partition structure so that the surface on which the partition wall structure is formed faces the nano liquid repellent structure forming mold;
Pressing the material mold for forming the partition wall structure toward the base substrate to pressurize the material resin to form a partition wall having a nano-liquid-repellent structure on the side surface and the upper surface. Method.   The manufacturing method of the laminated structure of Claim 1 with which the said mold for nano liquid repellent structure formation has flexibility. The manufacturing method of the laminated structure of Claim 1 or 2 with which the said mold for nano liquid-repellent structure formation has thickness of 5 micrometers or more and 15 micrometers or less. A step of producing a laminated structure by the method for producing a laminated structure according to claim 1;
A method of manufacturing an organic EL element, comprising: applying an organic EL light emitting material to a region on the base substrate and partitioned by the partition.

Images