JP4695360B2 - Manufacturing method of electronic device - Google Patents

Description

  The present invention relates to an electronic element such as a TFT (Thin Film Transistor), a manufacturing method thereof, a display device including such an electronic element, and an arithmetic device.

  Flat panel displays (display devices) such as liquid crystal display devices, PDPs (plasma display panels), and organic EL (electroluminescence) displays are active elements such as MIM (metal-insulator-metal) elements, TFTs, or light-emitting elements. A portion configured by patterning the thin film layer is provided. These active elements and light emitting elements are made of at least one of an electrode material, an insulating material, and a semiconductor material.

  Particularly, in recent years, an element using an organic material for a part or all of it has been attracting attention because of its merit in manufacturing such as cost reduction and easy area enlargement, and the possibility of function not found in inorganic materials. For example, Patent Document 1 proposes a field effect transistor using an organic semiconductor material whose carrier mobility is changed by a physical external stimulus such as light or heat.

By the way, as a method for patterning the thin film layer, a photolithography method is generally used. The process is as follows.
(1) A photoresist layer is applied on a substrate having a thin film layer (resist application).
(2) The solvent is removed by heating (pre-baking).
(3) Irradiate ultraviolet light through a hard mask drawn using a laser or an electron beam in accordance with pattern data (exposure).
(4) The exposed portion of the resist is removed with an alkaline solution (development).
(5) The unexposed portion (pattern portion) resist is cured by heating (post-bake).
(6) Immersion in an etching solution or exposure to an etching gas to remove the thin film layer where there is no resist (etching).
(7) The resist is removed with an alkali solution or oxygen radical (resist stripping).

  The active element is completed by repeating the above steps after forming each thin film layer. However, the expensive equipment and the length of the steps increase the cost.

  In recent years, pattern formation by a printing method has been attempted in order to reduce manufacturing costs. Patent Document 2 discloses a method in which a part of a patterning process of a thin film layer constituting a TFT is performed by, for example, an intaglio offset printing method instead of a photolithography method. Referring to FIG. 14 showing this method, the transfer body 103 is rotated on the printing plate 101 having the resist 102 in the recesses to transfer the resist 102 to the transfer body 103, and this is transferred to the transfer layer (thin film layer). ) 105 is printed on the substrate 104 formed with a resist pattern on the transfer layer (thin film layer) 105.

  Non-Patent Document 1 describes a method of forming a metal wiring having a width of about 50 μm and a pitch of about 400 μm by an inkjet method using nanoparticle ink.

  According to Non-Patent Document 2, as shown in FIG. 15, TFT electrode layers (110 is a gate electrode layer, 111 is a source electrode layer, and 112 is a drain electrode layer) in which all layers are made of organic materials are inkjet. A method for forming a pattern by a method is described. Here, ribs 113 made of a hydrophobic material (polyimide) are provided on a glass substrate 114 to form source / drain electrode layers 111 and 112 having an interelectrode gap (channel length) of 5 to 10 μm. Reference numeral 115 denotes a semiconductor layer, and 116 denotes a polymer insulator layer.

  According to Patent Document 3, as shown in FIG. 16, an organic molecular film 122 on a substrate 121 is used to decompose and remove a part thereof by ultraviolet rays or the like, thereby comprising a lyophilic portion 121a and a lyophobic portion 121b. A method of forming a conductive film pattern by forming a pattern, selectively applying a liquid 123 containing conductive fine particles to the lyophilic portion 121a, and then performing heat treatment is disclosed.

  According to this method, the pattern consisting of the lyophilic portion 121a and the lyophobic portion 121b can be formed simply by irradiating the organic molecular film 122 with ultraviolet light through a photomask, thereby greatly reducing the process. Can do.

JP-A-7-86600 JP 2002-268585 A JP 2002-164635 A JP 2001-185352 A SOCIETY FOR INFORMATION DISPLAY 2002 INTERNATIONAL SYMPOSIUM DIGEST OF TECHNICAL PAPER / VolumeXXXIII, p.753-755 SOCIETY FOR INFORMATION DISPLAY 2002 INTERNATIONAL SYMPOSIUM DIGEST OF TECHNICAL PAPER / VolumeXXXIII, p.1017-1019, Siencce 290, p.2123-2126 (2000)

  However, in the offset printing method as disclosed in Patent Document 1, even if an extremely accurate method is used, the pattern error including the pattern dimension accuracy and the alignment accuracy is ± 10 μm, and the general-purpose one can reach ± 50 μm. It is not suitable for forming a fine pattern.

  Further, in Non-Patent Document 1, when a normal inkjet head of a level used in a printer is used, it is difficult to form a fine pattern because the resolution is about 30 μm and the alignment accuracy is about ± 15 μm.

Non-Patent Document 2 is excellent in that the wettability with respect to ink is controlled by controlling the surface energy to enable pattern formation exceeding the resolution of the ink jet method, but a rib made of polyimide is produced. (1) Applying a polyimide precursor and baking (polyimide film formation)
(2) Apply a photoresist layer (resist coating)
(3) Remove the solvent by heating (pre-bake)
(4) Irradiate ultraviolet light through a mask (exposure)
(5) Remove resist in exposed area with alkaline solution (development)
(6) Curing the resist of the unexposed part (pattern part) by heating (post-baking)
(7) The polyimide film is removed from the resist-free portion by oxygen plasma (etching).
(8) Remove resist with solvent (resist stripping)
The advantages of the ink jet method are impaired.

  In general, electronic devices are manufactured in a clean room with a high degree of cleanliness. This is because, for example, in the case of a TFT channel part as shown in FIG. 9, even if it is a conductive impurity at the atomic level, it adversely affects the characteristics of the element. It is. However, in the method disclosed in Patent Document 3, when the electrode material is patterned, the wettability is controlled, so that the electrode material is formed in the film forming portion at the final patterning stage. In some cases, the electrode material may once adhere to the non-film forming portion, and most of the electrode material moves to the film forming portion, but a very small amount of electrode material may remain in the non-film forming portion. For example, when the non-film-forming portion is a channel portion of a TFT, the characteristics are very likely to be deteriorated.

  On the other hand, stencil printing is widely studied as another patterning means. In the case of a stencil, since only the film forming part is an opening, even if the coating liquid is applied to the entire surface of the substrate, the coating liquid does not adhere to the non-film forming part, thus degrading the characteristics of the electronic device. It has the great advantage of enabling high-definition patterning to be completed in a short time. FIG. 17 shows a general stencil printing process. That is, as shown in FIG. 17A, the stencil 132 is brought into close contact with the substrate 131 and the ink 134 is applied to the entire surface by the ink supply roller 133, and then the stencil 132 is peeled off as shown in FIG. As a result, the ink 134 remains on the substrate 131 according to the holes of the stencil 132.

  However, for example, a screen printing method generally performed as stencil printing is a technique for forming a thick film of several μm or more. Therefore, the solid content concentration of the coating liquid is very high compared to the above-described inkjet coating, and a coating liquid having a large viscosity is generally used. However, in thin film formation, it is necessary to dilute the coating solution to reduce the solid content concentration. However, when the coating solution is diluted, the viscosity generally decreases and the coating solution tends to flow out to the interface between the substrate and the stencil. In this case, there arises a problem that high-definition patterning cannot be performed.

  On the other hand, Patent Document 4 discloses a thin film patterning method by a screen printing method. This is a method in which a partition layer is formed in advance on a part of a substrate to be formed, and a coating solution is passed therethrough through a screen printing plate. In this case, since the partition wall layer forming step is required, there is a problem that it takes a long time for the entire film forming process.

  Furthermore, for example, when ultraviolet light is used as an energy applying means and exposure is performed with a photomask or laser to control the wettability of the substrate surface, the coating liquid application after the exposure process is applied by an inkjet method. Therefore, it is necessary to align the coating liquid discharge position with the portion where the wettability has changed. Further, when the stencil is brought into close contact with the substrate and the coating liquid is applied instead of the ink jet method, it is necessary to align the stencil pattern with the portion having changed wettability. The site where the wettability has changed is generally difficult to observe with a microscope or the like, and a patterning time loss is caused by the alignment process when using either an inkjet or a printing plate.

  In addition, a major drawback shared by the conventional techniques related to thin film formation as described above is that the material to be patterned is limited. This is because when the coating liquid of the material to be patterned is a solvent having a low surface tension like a general organic solvent, the coating liquid is hardly applied to that part even if a part with different wettability is provided. This is because the solvent needs to be based on water having a large surface tension in order to flow on the substrate surface without being along. One device is generally composed of a plurality of materials. If there is a material that must use a low surface tension solvent, it is applied to the entire surface of the substrate by a method such as spin coating. After that, it is necessary to use other patterning means such as photolithography, and in this case, there is a problem that the manufacturing cost increases. In particular, organic semiconductor materials used for organic TFTs, etc., are many materials that are dissolved and applied in organic solvents, and are the main materials constituting electronic devices, so the development of low-cost patterning technology is an urgent task. Yes.

  An object of the present invention is to apply a low-cost and high-material-use method such as a printing method, easily form a fine pattern, and have an electronic function with high added value in addition to pattern formation. It is providing a device, a manufacturing method thereof, a display device including such an electronic device, and an arithmetic device.

The invention of claim 1 wherein the critical surface tension by applying energy onto the substrate, or to form a surface-variable layer made of an insulating material whose critical surface tension and the surface shape changes, the electronic device to the surface property change layer A method of manufacturing an electronic device for finely patterning a substrate, wherein a stencil having a desired pattern shape is brought into close contact with the surface property change layer formed on the substrate prior to the formation of an electronic device component material, A step of changing the wettability of the surface property change layer by applying energy to the surface property change layer that is in close contact; and the electronic device while the stencil is kept in close contact with the surface property change layer having changed wettability Applying at least one coating liquid of a constituent material on the substrate and performing patterning.

  In the present invention and each of the following inventions, examples of the “electronic element” include semiconductor elements such as transistors and diodes, electric circuit constituent elements such as conductors, resistors, capacitors, and coils, photoelectric conversion elements, thermoelectric conversion elements, and the like. It refers to a display element such as an energy conversion element, EL, liquid crystal, or FED. In the present invention and each of the following inventions, the “electronic element constituent material” refers to a material necessary for manufacturing a target electronic element, such as a conductive material, a semiconductor material, an insulating material, a magnetic material, and a dielectric material. Point to.

  According to a second aspect of the present invention, in the method of manufacturing an electronic device according to the first aspect, the surface property changing layer is made of a polymer material having a hydrophobic group in a side chain.

  According to a third aspect of the present invention, in the method for manufacturing an electronic device according to the first or second aspect, as the stencil, a plurality of stencils having substantially the same pattern are adhered to the surface property change layer formed on the substrate. And stack.

  According to a fourth aspect of the present invention, in the method of manufacturing an electronic device according to the third aspect, the interfacial distance between the stencil plates is made larger than the interfacial distance between the surface property change layer and the stencil plate.

  According to a fifth aspect of the present invention, in the method of manufacturing an electronic device according to the fourth aspect, the surface roughness of the surface where the stencils contact each other with respect to the surface roughness of the surface of the stencil that contacts the surface property changing layer. Increased the size.

  According to a sixth aspect of the present invention, in the method for manufacturing an electronic device according to the fourth aspect, a gap material is interposed at an interface between the stencil plates.

  According to a seventh aspect of the present invention, in the method for manufacturing an electronic device according to any one of the first to sixth aspects, the stencil is made of a material that is adsorbed by magnetic force, and the magnet is used as a substrate contact means using a magnet or an electromagnet. A stencil is brought into close contact with the substrate.

  According to an eighth aspect of the present invention, in the electronic device manufacturing method according to the seventh aspect, the electronic device to be formed on the stencil after energy is applied to change the wettability of the surface property change layer. A step of laminating a mesh plate having a continuous pattern finer than the fine pattern and adsorbed by a magnetic force and placing the mesh plate on the substrate.

  According to a ninth aspect of the present invention, in the method of manufacturing an electronic device according to the eighth aspect, the magnetic attraction force of the substrate contact means on the mesh plate is greater than the magnetic attraction force of the substrate contact means on the stencil. large.

  According to a tenth aspect of the present invention, in the method of manufacturing an electronic device according to any one of the first to sixth aspects, the stencil is made of a material that is adsorbed by static electricity, and the stencil is formed by using static electricity as a substrate adhesion means. Adhere to the substrate.

  An eleventh aspect of the present invention is the electronic device manufacturing method according to the tenth aspect, wherein the electronic device to be formed on the stencil after energy is applied to change the wettability of the surface property changing layer. A step of laminating mesh plates that have a continuous pattern finer than the fine pattern and are electrostatically adsorbed and arranged on the substrate.

  According to a twelfth aspect of the present invention, in the electronic device manufacturing method according to the eleventh aspect, the electrostatic chucking force of the substrate contact means on the mesh plate is greater than the electrostatic chucking force of the substrate contact device on the stencil.

  A thirteenth aspect of the present invention is the electronic device manufacturing method according to any one of the first to twelfth aspects, wherein a static contact angle between the coating liquid and the stencil plate on the surface of the stencil surface is an energy applying portion on the substrate surface. And a step of performing a surface treatment so as to be larger than the contact angle between the coating liquid and the coating liquid.

  A fourteenth aspect of the present invention is the method for manufacturing an electronic device according to the thirteenth aspect, wherein fluorine or a silicone compound is used for the surface treatment.

  A fifteenth aspect of the present invention is the method for manufacturing an electronic element according to any one of the first to fourteenth aspects, wherein the application liquid is applied by a spray coating method.

  According to a sixteenth aspect of the present invention, in the electronic device manufacturing method according to any one of the first to fourteenth aspects, the application liquid is applied by an ink jet coating method.

  According to a seventeenth aspect of the present invention, in the method for manufacturing an electronic device according to any one of the first to fourteenth aspects, the coating liquid is applied by a dubbing coating method.

  The invention according to claim 18 is the method of manufacturing an electronic device according to any one of claims 1 to 14, wherein the coating liquid is applied by using a blade coater, a bar coater, a kiss coater, a gravure coater, a flexo coater, a knife coater, or a curtain coater. , Using at least one means of a spin coater.

  The invention according to claim 19 is the method of manufacturing an electronic device according to any one of claims 1 to 18, wherein after applying the coating liquid, the viscosity of the coating liquid is increased by a predetermined method. Removing the stencil from the substrate.

  According to a twentieth aspect of the present invention, in the electronic device manufacturing method according to the nineteenth aspect, the cross-sectional shape of the hole of the stencil that is in direct contact with the substrate is a tapered shape in which the substrate side is expanded.

  According to a twenty-first aspect of the present invention, in the method of manufacturing an electronic device according to any one of the first to twentieth aspects, energy is applied for changing the wettability of the surface property change layer by ultraviolet irradiation.

  According to a twenty-second aspect of the present invention, in the method for manufacturing an electronic device according to any one of the first to twentieth aspects, the energy application for changing the wettability of the surface property changing layer is performed by plasma irradiation.

  According to the first aspect of the present invention, even when a low-viscosity coating liquid is used, the wettability of only the film forming part of the stencil on the surface property change layer is improved, and the stencil and the substrate are further improved. Due to the close contact, even if the coating liquid is applied to the entire surface of the substrate, problems such as adhesion of the coating liquid to the non-film forming part and outflow of the coating liquid between the substrate and the stencil do not occur. In addition, thin film patterning with a film thickness of about 1 μm or less can be realized in a short time by a simple process. In addition, when applying the coating liquid to the part where the wettability is changed, the wettability is changed by the stencil, so the position of the wettability changed and the patterning means are positioned again using another patterning means. There is no need to match, and the patterning time can be shortened.

  According to the second aspect of the present invention, it becomes possible to increase the difference in critical surface tension between the surface of the energy applying part (film forming part) and the energy non-applying part (non-film forming part). It can be realized in a short time with a simple process.

  According to the invention described in claim 3, since a plurality of stencils having substantially the same pattern as the stencil are laminated on the substrate for patterning, when a coating liquid having low viscosity and low surface tension is used. However, since excess coating liquid escapes to the gap between the stencil plates, it is possible to more reliably prevent the coating liquid from flowing out to the interface between the substrate and the stencil plate, thereby increasing the degree of freedom in selecting the coating solvent. Thus, it is possible to realize high-definition thin film formation of various materials with a film thickness of about 1 μm or less in a short time by a simple process.

  According to the invention described in claim 4, since the interfacial distance between the stencils is larger than the interfacial distance between the substrate and the stencil, when the coating liquid is applied to the entire surface of the substrate on which the stencils are laminated, Thus, the coating liquid does not flow only into the interface between the stencil plates, and the coating liquid does not flow into the interface between the substrate and the stencil, thereby improving the pattern reproducibility and enabling high-definition patterning.

  According to the invention described in claim 5, since the surface roughness of the surface where the stencils come into contact with each other is made larger than the surface roughness of the stencil on the substrate contact surface side, it is larger than the interface distance between the substrate and the stencil. It is possible to easily increase the interface distance between the stencil plates.

  According to the invention described in claim 6, since the gap material is interposed at the interface where the stencils are in contact with each other, the interface distance between the stencils can be easily made larger than the interface distance between the substrate and the stencil. .

  According to the seventh aspect of the present invention, the stencil is made of a material that is adsorbed by magnetic force, and the stencil is brought into close contact using a permanent magnet or an electromagnet as the substrate contact means. In particular, in the case of an electromagnet, since the magnetic plate is turned off and the stencil and the substrate are aligned, the magnetic force is turned on and the stencil and the substrate can be brought into close contact with each other. On the other hand, in the case of a permanent magnet, a small and strong rare earth magnet can be used, so that the stencil and the substrate can be more reliably brought into close contact with each other.

  According to the invention described in claim 8, since the mesh made of a material adsorbed by magnetic force and having a fine continuous pattern is disposed on the stencil as viewed from the substrate, the stencil is fixed more reliably. can do.

  According to the invention of claim 9, since the magnet adsorption force of the mesh plate is larger than the magnet adsorption force of the stencil, the adsorption force to the mesh plate is larger than the force of the stencil to lift, The stencil can be more firmly fixed on the substrate.

  According to the invention described in claim 10, since the stencil is made of a chargeable member that is adsorbed by static electricity and is made to adhere to the substrate using static electricity as a substrate contact means, the entire stencil is firmly and securely fixed onto the substrate. Can be made.

  According to the eleventh aspect of the present invention, the mesh plate made of a chargeable member that is adsorbed by static electricity and having a fine continuous pattern is disposed on the stencil as viewed from the substrate, so that it is more reliable. The stencil can be fixed.

  According to the twelfth aspect of the present invention, since the electrostatic adsorption force on the mesh plate side is larger than the electrostatic adsorption force of the stencil, the adsorption force by the mesh plate is larger than the force that the stencil is trying to lift. The stencil can be fixed on the substrate more reliably.

  According to the invention of claim 13, the stencil surface is such that the static contact angle between the coating liquid and the stencil is larger on the surface of the stencil than the contact angle between the energy applying portion on the substrate surface and the coating liquid. By performing the surface treatment, it is possible to prevent the coating liquid from flowing into the interface between the substrate and the stencil and realize high-definition patterning.

  According to the invention described in claim 14, since a fluorine-based or silicone-based compound is used as the surface treatment, and in general, the fluorine-based and silicone-based compounds are materials having high water repellency. The contact angle can be remarkably increased as compared with the contact angle between the substrate surface and the coating liquid, and thus high-definition and smooth thin film patterning is possible.

  According to the invention described in claim 15, by using the spray coating method for applying the coating liquid, high-definition patterning can be performed in a short time with a small amount of the coating liquid.

  According to the invention described in claim 16, by using the inkjet coating method for applying the coating liquid, high-definition patterning can be performed with the smallest amount of coating liquid as compared with other coating methods.

  According to the invention described in claim 17, by using the dipping coating method for applying the coating liquid, stress is hardly applied to the stencil and the substrate at the time of coating. In addition to being able to float, the patterning can be performed with high precision, and the coating liquid can be applied without causing the coating liquid to fly between the substrates as in the spray method or the inkjet coating method. As a volatile solvent such as acetone, THF, dichloromethane and the like, it is possible to expand the selectivity of the solvent.

  According to the invention of claim 18, the application of the coating liquid is performed by using at least one of a blade coater, a bar coater, a kiss coater, a gravure coater, a flexo coater, a knife coater, a curtain coater, and a spin coater. Coating can be performed without causing the liquid to fly between the substrates, and a volatile solvent can be applied as a solvent for the coating liquid, so that the selectivity of the solvent can be expanded and high-definition patterning can be performed in a short time. Can also be completed.

  According to the invention described in claim 19, since the stencil is removed from the substrate after the coating solution is applied and the viscosity of the coating solution is increased, the coating solution does not flow on the substrate surface after the stencil is removed. It is possible to perform patterning on a predetermined part.

  According to the invention of claim 20, since the cross-sectional shape of the hole of the stencil that is in direct contact with the substrate is a tapered shape that expands on the substrate side, the splashing of the coating liquid at the time of stencil removal is prevented. A thin film with high coating surface uniformity can be formed.

  According to the twenty-first aspect, since ultraviolet irradiation is used for energy application, the surface property changing layer can be processed with high definition.

  According to the invention described in claim 22, since plasma irradiation is used for energy application, it is possible to apply large energy to the surface property change layer, and not only wettability but also surface shape change can be easily performed in a short time. This makes it possible to greatly improve the coating liquid adhesion of the film forming section.

  The best mode for carrying out the present invention will be described with reference to the drawings.

[Method for Manufacturing Electronic Device]
This embodiment includes, for example, semiconductor elements such as transistors and diodes, electric circuit constituent elements such as conductors, resistors, capacitors, and coils, energy conversion elements such as photoelectric conversion elements and thermoelectric conversion elements, EL, liquid crystal, FED, and the like The present invention relates to a method for manufacturing an electronic device including a thin film structure by fine patterning such as the display device of FIG.

  First, the outline of the method for manufacturing an electronic device of the present embodiment will be described. That is, a method of manufacturing an electronic device, wherein a surface property changing layer made of an insulating material whose critical surface tension or surface shape is changed by applying energy is formed on a substrate, and the target electronic device is finely patterned on the surface property changing layer. In addition, prior to the formation of the electronic element constituent material, the stencil having a desired pattern shape is closely attached to the surface property changing layer formed on the substrate, and energy is applied to the surface property changing layer to which the stencil is closely attached. A step of changing the wettability of the surface property changing layer, and applying at least one coating liquid of the electronic element constituent material on the substrate while keeping the stencil in close contact with the surface property changing layer having changed wettability Patterning.

  As the stencil in the present embodiment, the one in which the part to be patterned is completely opened like a metal mask or the one in which the part to be patterned is a mesh like a screen printing plate is applied. Is possible. A metal mask manufactured by electroforming can be easily manufactured with a high-definition pattern having a pitch of 10 μm or less, and thus is suitable for high-definition patterning. In addition, since the energy imparting part and the film forming part completely coincide, the coating liquid uniformly adheres to the film forming part and good film forming properties are obtained. The screen printing plate is highly durable because the opening is supported by a very fine mesh pattern, and there is no deformation of the pattern even during repeated use, and the cost of the film forming process is reduced.

  In the present embodiment, as the electronic element constituent material, for example, a material necessary for manufacturing a target electronic element such as a conductive material, a semiconductor material, an insulating material, a magnetic material, and a dielectric material is used.

  Here, as "conductive material", chromium (Cr), tantalum (Ta), titanium (Ti), copper (Cu), aluminum (Al), molybdenum (Mo), tungsten (W), nickel (Ni) , Gold (Au), palladium (Pd), platinum (Pt), silver (Ag), tin (Sn), or other metals, or (1) polyacetylene conductive polymers, polyparaphenylene and its derivatives, polyphenylene vinylene And polyphenylene conductive polymers such as derivatives thereof, (2) polypyrrole and derivatives thereof, polythiophene, polyethylenedioxythiophene and derivatives thereof, heterocyclic conductive polymers such as polyfuran and derivatives thereof, and (3) polyaniline And at least one conductive polymer selected from the group consisting of ionic conductive polymers such as derivatives thereof. Coating liquid is used which is dispersed or dissolved in.

  “Semiconductor materials” include inorganic semiconductor materials such as CdS, fluorene, polyfluorene derivatives, polyfluorenone, fluorenone derivatives, poly-N-vinylcarbazole derivatives, poly-γ-carbazolylethyl glutamate derivatives, polyvinylphenanthrene. Derivatives, polysilane derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, arylamine derivatives such as monoarylamines, triarylamine derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, styrylanthracene derivatives, pyrazoline derivatives, divinyl Pyrene derivatives such as benzene derivatives, hydrazone derivatives, indene derivatives, indenone derivatives, butadiene derivatives, pyrene-formaldehyde, polyvinylpyrene, etc. α-phenyl stilbene derivative, stilbene derivative such as bis stilbene derivative, at least one organic semiconductor material selected from the group consisting of thiophene derivatives such as enamine derivative, polyalkylthiophene, or pentacene, tetracene, bisazo, trisazo dye, Polyazo dyes, triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, cyanine dyes, styryl dyes, pyrylium dyes, quinacridone dyes, indigo dyes, perylene dyes, polycyclic quinone dyes At least one organic compound selected from the group consisting of dyes, bisbenzimidazole dyes, indanthrone dyes, squarylium dyes, anthraquinone dyes, and phthalocyanine dyes such as copper phthalocyanine and titanyl phthalocyanine Coating liquid is used which the conductive material is dispersed or dissolved in a solvent.

  Furthermore, as the “insulating material”, polyimide resin, styrene resin, polyethylene resin, polypropylene, vinyl chloride resin, polyester alkyd resin, polyamide, polyurethane, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, polyvinyl butyral resin, Photo-curing properties such as polyether resin, polyester resin, acrylic resin, silicone resin, epoxy resin, phenol resin, urea resin, melamine resin, PFA, PTFE, PVDF and other fluorine resins, parylene resin, epoxy acrylate, urethane acrylate, etc. Resin and general formula M (OR) n or MR (OR ′) n−1 [wherein R and R ′ are organic groups such as alkyl groups and phenyl groups, and M is IVA in the periodic table. ~ VIA, VIII or IB ~ VIB It is a metal. ] The coating liquid which melt | dissolved or disperse | distributed the metal alkoxide shown by a solvent is used.

  As the “magnetic material”, rare earth magnetic materials such as Sm—Co—, Nd—Fe—B, and Sm—Fe—N, and magnetic materials such as ferrite and alnico are also applicable.

  The “surface property changing layer” is a layer made of a material whose critical surface tension changes by applying energy such as heat, ultraviolet rays, electron beams, plasma, etc. The amount of change in the critical surface tension before and after the energy application is changed. Larger ones are preferred. In such a case, for example, in the case of a liquid containing a conductive material, a high surface energy is formed by applying energy to a part of the surface property changing layer and forming a pattern including a high surface energy part and a low surface energy part. High surface energy part in which the liquid containing the conductive material is lyophilic according to the pattern shape because it is easy to adhere to the part (lyophilic) and difficult to adhere to the low surface energy part (lyophobic) A conductive layer is formed by selectively adhering to and solidifying it.

  FIG. 1 shows an example of a process related to a method for manufacturing an electronic device according to the present embodiment. First, as shown in FIG. 1A, a surface property change layer 2 is formed on a substrate 1 made of plastic such as glass, polycarbonate, polyarylate, polyethersulfone, polyimide, silicon wafer, metal or the like. The surface property changing layer 2 is made of, for example, a material whose critical surface tension is increased by ultraviolet irradiation as energy application and changes from low surface energy (lyophobic) to high surface energy (lyophilic). A solution in which a polymer containing such a material or a precursor thereof is dissolved or dispersed in an organic solvent or the like is applied onto the substrate 1 by a spin coating method, a dip coating method, a wire bar coating method, a casting method, or the like, and heated. Thus, the surface property change layer 2 is formed.

  Next, as shown in FIG. 1B, a stencil 3 having a predetermined pattern shape is brought into intimate contact with the surface of the surface property changing layer 2 (adhering step), and the surface of the surface property changing layer 2 with which the stencil 3 is in intimate contact. Irradiate with UV light. Thereby, the surface property changing layer 2 is formed with a pattern in which the wettability of the low surface energy part (lyophobic part) 2a and the high surface energy part (lyophilic part) 2b is changed. It is desirable that the ultraviolet rays include light having a relatively short wavelength of 100 nm to 300 nm.

  Next, as shown in FIG. 1C, a semiconductor material, a conductive material, an insulating material, and the like are formed on the surface property changing layer 2 (the entire surface of the substrate 1) on which the pattern having such wettability changed is formed. A magnetic material, a dielectric material or the like is vacuum-deposited, or a solution (at least one coating liquid for electronic component constituent materials) 4 containing these materials is applied, and as shown in FIG. The patterning is completed by removing. Reference numeral 5 denotes a patterned coating solution.

  Therefore, according to the present embodiment, basically, even when a low-viscosity coating solution (solution 4) is used, the film forming part (high surface energy part 2b) of the stencil 3 on the surface property change layer 2 is used. ), And the stencil 3 and the substrate 1 are in close contact with each other, so even if a coating liquid is applied to the entire surface of the substrate 1, the non-film forming portion (low surface energy portion 2a) No problems such as adhesion of the coating liquid and outflow of the coating liquid between the substrate 1 and the stencil 3 occur. Therefore, thin film patterning with a high definition and a film thickness of about 1 μm or less can be realized in a short time with a simple process. It becomes possible. In addition, when applying the coating liquid to the part where the wettability is changed, the wettability is changed by the stencil 3 so that the part having changed wettability and the patterning means are newly used by using another patterning means. There is no need for alignment, and the patterning time can be shortened.

  By the way, the surface property changing layer 2 in the present embodiment is preferably made of a polymer material having a hydrophobic group in the side chain. According to such a polymer material, it becomes possible to increase the difference in critical surface tension between the surface of the energy applying part (film forming part) and the energy non-applying part (non-film forming part), thereby forming a high-definition thin film. This is because the process can be realized in a short time with a simple process.

  This is considered to be due to the wettability (adhesiveness) of the liquid to the solid surface described below. FIG. 2 is a schematic diagram when the droplet 11 is in an equilibrium state at the contact angle θ on the surface of the solid 10, and Young's formula (1) is established.

γ _S = γ _SL + γ _L cos θ (1)
Here, γ _S is the surface tension of the solid 10, γ _SL is the interface tension between the solid 10 and the liquid (droplet 11), and γ _L is the surface tension of the liquid (droplet 11).

The surface tension is substantially synonymous with the surface energy and has exactly the same value. When cos θ = 1, θ = 0 ° and the liquid is completely wetted. The value of γ _L at this time is γ _S −γ _SL , which is called the critical surface tension γ _{C of the} solid. The critical surface tension γ _C is obtained by plotting the relationship between the surface tension of the liquid and the contact angle using several types of liquids with known surface tension, and obtaining the surface tension where θ = 0 ° (cos θ = 1). (Zisman plot). A solid surface with a high critical surface tension γ _C easily wets the liquid (lyophilic), and a solid surface with a low critical surface tension γ _C does not wet easily (lyophobic). In the present embodiment, it is important to make it easy to repel a liquid containing a conductive material, particularly in a region where a conductive layer is not formed. By making the critical surface tension of the lyophobic part 2a of the surface property changing layer 2 be, for example, 30 mN / m or less, the contact angle of water can be made 80 ° or more, and water-based solutions can be easily repelled. can do. More preferably, when the critical surface tension is 25 mN / m or less, the contact angle of water can be 90 ° or more, and a water-based solution can be more reliably repelled.

For such a surface property changing layer 2, it is desirable to use a polymer material having a hydrophobic group in the side chain. Specifically, a main chain having a skeleton such as polyimide or acrylate and a side chain having a strong cohesive force such as an alkyl group (— (CH ₂ ) _× CH ₃ ) are bonded. This alkyl group may contain a halogen atom, a cyano group, a phenyl group, a hydroxyl group, a carboxyl group, or a phenyl group substituted with a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an alkoxy group. Good. It is considered that the more the side chain binding sites, the lower the surface energy (smaller the critical surface tension) and the more lyophobic. It is inferred that, due to energy application, a part of the bond is broken or the orientation state changes, so that the critical surface tension increases and becomes lyophilic.

As another effect that side chains having strong cohesive properties such as long-chain alkyl groups are arranged on the surface, interface characteristics with the semiconductor layer in contact therewith can be improved. When the semiconductor layer is made of an organic semiconductor, the effect is more remarkable. Good interfacial properties
(1) When the semiconductor is crystalline, the crystal grains are enlarged and the mobility is increased.
(2) When the semiconductor is amorphous (polymer), the interface state density decreases and the mobility increases.
(3) If the semiconductor is a polymer and has a side chain such as a long-chain alkyl group, the molecular axis of the π-conjugated main chain can be arranged in almost one direction by regulating its orientation, Mobility increases,
This refers to the appearance of such phenomena.

  In the above description, the number of stencil plates was not mentioned, but as a more preferable form, it is desirable to perform patterning by stacking a plurality of stencil plates having substantially the same pattern in close contact with each other. By laminating a plurality of stencil plates, even when a coating solution with low viscosity and low surface tension is used, excess coating solution escapes to the gap between these stencils, so the basic method described above As described above, it is possible to prevent the coating liquid from flowing out to the interface between the substrate and the stencil. This means that the degree of freedom in selecting a coating solvent is widened, and it is possible to achieve high-definition thin film formation of about 1 μm or less for various materials in a short time with a simple process. .

  In the present embodiment, it is desirable that the viscosity of the coating liquid be 100 cp or less in order to perform thin film patterning with high definition based on the principle described above. This is because when a viscous coating liquid is used like a general printing ink, it is difficult for the coating liquid to escape between the stencil plates, and it is difficult to obtain the effect of laminating the stencil plates.

  In the case of the present embodiment, a plurality of stencils having substantially the same pattern are used, but there is no problem even if they are exactly the same pattern. In the case of substantially the same pattern, the size relationship between the pattern of the substrate side stencil in close contact with the substrate and the pattern of the surface side stencil not in close contact with the substrate is as shown in FIGS. 3 (a) and 3 (b). In any case, it can be used, and it is appropriately used depending on the viscosity of the coating liquid and the coating amount. FIG. 3A shows a case where the hole pattern of the substrate side stencil 3A is smaller than the hole pattern of the surface side stencil 3B, which is suitable when the viscosity of the coating liquid is high or the coating amount is small. On the other hand, FIG. 3B shows a case where the hole pattern of the substrate side stencil 3A is larger than the hole pattern of the surface side stencil 3B, which is suitable when the viscosity of the coating liquid is low or the coating amount is large. is there. Further, when the number of stencil plates to be used is increased, the effect of preventing the coating liquid from flowing out to the interface between the substrate and the stencil plate is further improved.

  When using a plurality of stencil plates in this way, it is preferable to make the interface distance between the stencils larger than the interface distance between the substrate and the stencil plate. According to this, when the coating liquid is applied to the entire surface of the substrate on which the stencil is laminated, the excess coating liquid flows only into the interface between the stencils, and the coating liquid flows into the interface between the substrate and the stencil. This is because pattern reproducibility is improved and high-definition patterning is possible.

For example, when laminating two stencil plates on a substrate, as a part into which the coating liquid flows,
A: Hole of stencil B: Interface between stencils C: Three parts of interface between stencil and substrate can be considered. At this time, if the coating liquid flows into C, dot gain occurs and high-definition patterning cannot be performed. On the other hand, if the coating liquid does not flow into A, patterning itself is impossible. Therefore, the size relationship between the sizes of A, B, and C needs to satisfy AorB> C. Preferably, the relationship of A>B> C is established.

  Here, as a method of making such an interfacial distance different, it is preferable to increase the surface roughness of the surface where the stencils are in contact with each other as compared with the surface roughness of the stencil on the substrate contact surface side. According to this, the interface distance between the stencils can be easily made larger than the interface distance between the substrate and the stencil.

  In addition, the surface roughness in this Embodiment refers to the value when the measurement of Ra prescribed | regulated to JIS B0601-2001 is measured in the pattern formation site | part vicinity 3a of the stencil 3 shown in FIG.

  Further, as another method of changing the interface distance, it is also preferable to interpose a gap material at the interface where the stencils are in contact with each other. This method also makes it possible to easily increase the interfacial distance between the stencils than the interfacial distance between the substrate and the stencil.

  As the gap material in this case, the interface distance between the stencil plates can be maintained at a predetermined value, such as a spherical shape, a flat plate shape, or a mesh shape in which fine holes are formed on the flat plate. And it is suitably designed so that the coating liquid flows in. The gap material is a material that is not damaged by the coating liquid. In the case of a metal material, the coating liquid is not damaged regardless of whether it is aqueous or organic solvent. When the gap material is a resin material, it may be dissolved in an organic solvent. However, when the stencil is made of a material that is more flexible than a metal, such as a resin material, damage to the stencil by rubbing against the gap material may be prevented. It becomes possible.

[Stencil fixing method for stencil]
[Part 1]
In carrying out the manufacturing method of the present embodiment, it is necessary to closely fix the stencil on the substrate. As an example of the method, the stencil is made of a material that can be adsorbed by magnetic force, By using a permanent magnet or an electromagnet, a method of bringing the stencil into close contact with the substrate can be mentioned. According to this method, the entire surface of the stencil can be securely and easily fixed on the substrate. In the case of an electromagnet, the stencil and the substrate can be brought into close contact with each other after the magnetic force is turned off and the stencil and the substrate are aligned. On the other hand, in the case of a permanent magnet, a small and powerful rare earth magnet can be used, so that the stencil and the substrate can be more reliably brought into close contact with each other.

  FIG. 5 shows an example in which the stencils 3A and 3B are made of a material that is attracted by a magnetic force, and the permanent magnet 6 is disposed on the back side of the substrate 1 as the substrate contact means.

  In the case of this substrate contact method, like a stencil, a mesh plate made of a material adsorbed by magnetic force and having a continuous pattern finer than the pattern to be formed is laminated on the stencil when viewed from the substrate. By doing so, it becomes possible to fix the stencil more reliably.

  This is the one that is attracted to the magnet and can move freely in a fine shape, for example, sand iron, does not adhere uniformly to the magnet surface, and usually tries to stand up on the magnet surface along the lines of magnetic force . Also in the case of a stencil, a stencil in which a part to be patterned is completely opened like a metal mask, depending on the pattern shape, the pattern is lifted from the substrate due to the influence of magnetic lines of force. In this case, the coating liquid flows between the substrate and the stencil and high-definition patterning cannot be performed. For example, FIG. 6 shows a pattern example of the stencil 3 that is easily lifted from the substrate 1 (plan view). A portion indicated by 7 is a pattern portion that tends to float. However, even in such a case, the stencil can be reliably fixed on the substrate by covering the stencil 3 with a continuous pattern mesh plate. Therefore, even if it is a stencil plate, a screen printing plate in which the film forming portion is not completely opened does not easily float even with a pattern as shown in FIG.

  In this case, in particular, if the magnitude relationship of the adsorption force is set so that the magnet adsorption force of the mesh plate is larger than the magnet adsorption force of the stencil plate, the substrate by the mesh plate is compared with the force of the stencil floating up Since the suction force is increased, the print can be more securely fixed on the substrate.

[Part 2]
In carrying out the manufacturing method of the present embodiment, as another example of the method of closely fixing the stencil on the substrate, the stencil is made of a chargeable member that is adsorbed by static electricity, and by using static electricity as the substrate contact means, A method for adhering the stencil to the substrate can be mentioned. Also by this method, the entire stencil plate can be securely and easily fixed on the substrate.

  In this case as well as the stencil, a mesh plate made of a charging member that is adsorbed by static electricity and having a continuous pattern finer than the fine pattern of the electronic element to be formed is laminated on the stencil as viewed from the substrate. The stencil can be fixed more securely.

  This is a chargeable member that can move freely in a fine shape, for example, in the case of a resin filler that has numerous holes and is very light and slender with respect to its volume. In some cases, it does not uniformly adhere to the surface and tends to rise on the charged surface along the lines of electric force. Also in the case of a stencil, a stencil in which a part to be patterned is completely opened, the pattern is lifted from the substrate due to the influence of electric lines of force depending on the pattern shape. In this case, the coating liquid flows between the substrate and the stencil and high-definition patterning cannot be performed. However, even in such a case, the stencil can be securely fixed on the substrate by covering the stencil with a continuous pattern mesh plate.

  In this case, in particular, if the magnitude relationship of the adsorption force is set so that the electrostatic adsorption force of the mesh plate is larger than the electrostatic adsorption force of the stencil plate, the substrate by the mesh plate is compared with the force by which the stencil is going to float. Since the adsorption force is increased, the stencil can be more securely fixed on the substrate.

[Surface treatment of stencil]
For the stencil described above, the stencil is subjected to a surface treatment so that the static contact angle between the coating liquid and the stencil is larger than the contact angle between the energy applying portion on the substrate surface and the coating liquid. It is preferable. If such a surface treatment is performed, it is possible to prevent the coating liquid from flowing into the interface between the substrate and the stencil and to realize high-definition patterning.

  In particular, in the cross section of the pattern forming portion of the stencil plate 3 as shown in FIG. 7A, surface treatment is performed so that the contact angle is increased on the surface (part 8) where the plate cross section rises from the substrate 1. It is possible to prevent the coating liquid from rising and to form a smooth thin film 9 having a coating film surface shape after film formation as shown in FIG. Incidentally, when the rising of the coating liquid occurs and the solvent evaporates as it is, the thin film A having the shape shown in FIG.

  In this case, it is desirable to use a fluorine-based or silicone-based compound as the surface treatment of the stencil 3. In general, fluorine-based and silicone-based compounds are highly water-repellent materials. By coating this as a surface treatment agent, the static contact angle between the coating solution and the stencil is compared with the contact angle between the substrate surface and the coating solution. Can be significantly increased. Therefore, high-definition and smooth thin film patterning is possible.

  PTFE (polytetrafluoroethylene), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene) can be used for the surface treatment of the stencil of this embodiment. Copolymer), ETFE (tetrafluoroethylene / ethylene copolymer), PVDF (polyvinylidene fluoride), PCTFE (polychlorotrifluoroethylene) and the like are applicable.

  In addition, a copolymer containing polymer units of the following compounds (monomers) (1) to (7) is also applicable, and in particular, a material obtained by polymerizing the compound (1) is preferable (wherein R is hydrogen). An atom, a methyl group, or a fluorine atom, and Rf is a fluorine atom-containing organic group).

(1) CH2 = CRCOORf,
(2) CH2 = CROCORF,
(3) CH2 = CRC (O) Rf,
(4) CH2 = CRORf,
(5) CH2 = CRCONHRf,
(6) CH2 = C (CH2R) COORf,
(7) CH2 = CR (CH2) nRf

  Further, as a silicone compound applicable to the surface treatment of the stencil of the present embodiment, compounds such as polyalkylsiloxane and polyallylsiloxane and derivatives thereof are used, and in particular, polydimethylsiloxane, polyphenylmethylsiloxane, 3, 3 1,3-trifluoropropylmethylsiloxane and polydiphenylsiloxane are preferred.

  Silane compounds such as silazane such as hexamethyldisilazane, halogenated silane such as methyltrichlorosilane, and alkoxysilane such as tetramethoxysilane are also applicable.

[Coating liquid application method]
In the present embodiment, patterning is performed by applying at least one coating liquid of the target electronic component material while keeping the stencil in close contact with the surface property change layer (substrate) surface. Various methods can be applied as a coating method of the coating liquid.

A. Spray coating method If the spray coating method is used as a coating method of the coating liquid, high-definition patterning can be performed in a short time with a small amount of coating liquid.

  In the case of a coating means such as a bar coater or gravure coater where the coating device and the substrate are in contact, stress is easily applied to the stencil and the substrate during coating liquid application, and the stencil and the substrate may be displaced or floated. In such a case, the coating solution flows between the plate and the substrate, and high-definition patterning cannot be performed. In the case of the spray coating method, the stencil and the substrate hardly move or float, and high-definition patterning is possible. Therefore, even if it is a stencil, a screen printing plate in which the film forming portion is not completely opened, even a pattern as shown in FIG.

B. Inkjet coating method If an inkjet coating method is used as a coating method of the coating solution, high-definition patterning can be performed with the smallest amount of coating solution compared to other coating means. In the case of the ink jet coating method, there is a drawback that patterning takes time compared with other methods, but since the stress is hardly applied to the stencil and the substrate at the time of coating, the stencil and the substrate may be displaced. In addition to being able to float, it is possible to perform high-definition patterning and to supply the coating liquid only to the vicinity of the site where the thin film is to be formed. Patterning is possible.

C. Dipping coating method If the dipping coating method is used as the coating method of the coating liquid, stress is hardly applied to the stencil and the substrate during coating, so the stencil and the substrate may be displaced or floated. Almost no high-definition patterning is possible and coating is performed without causing the coating liquid to fly between the substrates as in the spray coating method and the inkjet coating method. Also, volatile solvents such as dichloromethane can be applied, and the selectivity of the solvent is expanded.

  In the case of this method, a method of casting the coating liquid (dropping the droplet onto the stencil) is also included. When the coating amount of the coating liquid is too large, a method of controlling the coating amount to a desired value by a method such as rotation or air blow while the stencil and the substrate are kept in close contact is also applied.

D. Others As a coating method of the coating solution, at least one of a blade coater, a bar coater, a kiss coater, a gravure coater, a flexo coater, a knife coater, a curtain coater, and a spin coater may be used. In these methods, since the coating liquid is applied without flying between the substrates, a volatile solvent can be applied as the solvent of the coating liquid, the selectivity of the solvent is widened, and high-definition patterning is possible. It can be completed in a short time.

[Removal process]
In the present embodiment, the stencil is used prior to the application of the coating liquid, and it is necessary to finally remove the stencil from the substrate. As the process, after applying the coating liquid, It is desirable that the stencil is removed from the substrate after the viscosity of the coating liquid is increased by the above method (for example, elevating means for evaporating the solvent such as heating or standing at room temperature). According to this, it is possible to perform patterning on a predetermined portion without the coating liquid flowing on the substrate surface after the stencil is removed.

  In taking such a process, it is desirable that the cross-sectional shape of the hole of the stencil 3 that is in direct contact with the substrate 1 is a tapered shape in which the substrate 1 side expands as shown in FIG. That is, if the stencil 3 is removed in a state where the viscosity of the coating liquid has greatly increased, the coating liquid may jump up from the substrate 1 at the edge of the stencil 3 and the uniformity of the coating film at this part may be impaired. As shown in FIG. 3, the cross-sectional shape of the hole of the stencil 3 is a tapered shape that expands on the substrate 1 side, thereby preventing the coating liquid from jumping up at the edge portion of the stencil 3 when the stencil 3 is removed. A thin film with high surface uniformity can be formed.

[Energy application method for forming surface property change layer]
As the energy application method for forming the surface property change layer 2 on the substrate 1, various methods can be adopted as described above. In the case of the present embodiment, the ultraviolet irradiation method and the plasma irradiation method are particularly preferable. It is. According to the ultraviolet irradiation method, the surface property changing layer can be processed with high definition. As the ultraviolet irradiation method, a method of performing entire surface exposure using a photomask, a method of scanning with laser light, or the like is used. In addition, according to the plasma irradiation method, it is possible to apply a large energy to the surface property change layer, and it is possible to easily change not only the wettability but also the surface shape in a short time. It becomes possible to greatly improve the coating liquid adhesion.

[Examples of applicable electronic elements]
A. Electronic element The manufacturing method of the present embodiment includes the above-described semiconductor elements such as transistors and diodes, electric circuit constituent elements such as conductive wires, resistors, capacitors, and coils, energy conversion elements such as photoelectric conversion elements and thermoelectric conversion elements. The present invention can be applied to various electronic elements including a thin film structure by fine patterning such as display elements such as EL, liquid crystal, and FED. As an example, a transistor 21 having a MOS FET structure as shown in FIG. Can be mentioned. In this transistor 21, a source electrode 24 and a drain electrode 25 are formed on a gate electrode 22 via a gate insulating film 23 with a gap of a channel portion 26 portion, and the source electrode 24 including the channel portion 26 portion and A semiconductor layer 27 is formed on the drain electrode 15.

  In addition to this, for example, by applying it to the manufacture of electronic elements such as diodes typified by MIM type and PN junction type diodes, organic EL light emitting elements, capacitors, etc., finely patterned ones can be manufactured at low cost.

B. Display Device FIG. 10 shows a configuration example of a liquid crystal display device (display device) including an electronic element manufactured by the above manufacturing method, for example, a transistor 21 having a MOS FET structure. In this liquid crystal display device 31, a transistor 21 having a MOS FET structure for switching a liquid crystal cell 33 provided with a capacitor 32 for each pixel is connected to each intersection (for each pixel) of a scanning line and a gradation signal line. The desired image is displayed by arranging and turning on / off the liquid crystal cell 33 individually.

  In such a configuration, a voltage is applied from the gradation signal line according to the gradation of each pixel. From the scanning line, an on / off signal voltage is sequentially applied to each line, and after the scanning of one screen is completed, the scanning of the next screen is started. In the case of video support, this interval is preferably 50 Hz or more (1/50 sec or less). The capacitor 32 has a function of charging the voltage of the gradation signal for the time from the transition from one screen to the next screen.

  Since the display device 31 includes the transistor 21 having a MOS FET structure, which is an electronic element manufactured by the above-described manufacturing method, a low-cost and high-definition display device is provided.

C. Arithmetic Device Configuration of an inverter circuit (arithmetic device) 41 including an electronic element manufactured by the above-described manufacturing method, for example, a transistor p-ch using a hole transport material and a transistor n-ch using an electron transport material. An example is shown in FIG.

Here, the source side of the transistor n-ch is connected to the power supply _VDD side of + 5V, the drain side of the transistor n-ch is connected to the ground, and the input voltage Vin is applied to the gate side of the transistors p-ch and n-ch. , And the output voltage Vout is extracted from the connection point between the drain side of the transistor n-ch and the source side of the transistor n-ch.

Here, when + 5V is applied to the input voltage Vin, the transistor n-ch is turned on, but the transistor p-ch is turned off, and the output voltage Vout is 0V. On the other hand, when the input voltage Vin is 0 V, the transistor n-ch is turned off, and since the power supply V _DD is +5 V, the potential difference between the gate and source of the transistor p-ch is 5 V, and the output voltage Vout is +5 V. Is output. Thus, since the potential relationship between the input voltage Vin and the output voltage Vout is inverted, the circuit shown in FIG. 11 can be applied as an inverter circuit.

  Since the arithmetic device 41 includes the transistors p-ch and n-ch, which are electronic elements manufactured by the above-described manufacturing method, a high-integration and low-cost arithmetic device is provided.

  Hereinafter, several examples of the present invention will be described together with comparative examples.

[Example 1]
Using the process of FIG. 1, printing was performed under the following conditions, and the surface shape of the coating film after coating was evaluated.

(1) Stencil 3: Nickel stencil with a plurality of 100 μm square film-forming portions opened at 100 μm intervals as shown in FIG. 12 (2) Ultraviolet light: wavelength 250 nm, output: 9 J / cm ²
(3) Wettability changing layer 2: After firing, a precursor of a material having a structural formula of Chemical Formula 1 or Chemical Formula 2 is applied, heated after film formation.

  After coating on the glass substrate 1 by a spin coat method and baking at 210 ° C., the stencil plate (1) was adhered, and ultraviolet rays were irradiated under the condition (2).

(4) Material of coating liquid 4: Polyaniline manufactured by Olmecon (5) Coating liquid 4 solvent, concentration: water, 4 wt%
(6) Application means of coating solution 4: Kiss coater The stencil 3 and the substrate 1 were scanned in the Y direction, and immediately after the application, the stencil 3 was peeled off from the substrate 1 and dried by heating.

(7) Printing plate fixing means: permanent magnet 6 (see FIG. 5) (substrate 1: 0.5 mm thick non-alkali glass)
(8) Evaluation method: ULVAC, stylus type surface shape measuring instrument DEKTAK3
The surface roughness, the X direction, and the Y direction of the obtained thin film were measured at 8 locations, and the average was calculated.
The results are shown in Table 1.

[Example 2]
Two stencils 3 of (1) of Example 1 are laminated, and the material of the coating liquid 4 of (4) is converted to 3

The experiment was conducted in the same manner as in Example 1 except that the organic semiconductor material shown in (5), the solvent of the coating liquid 4 of (5), and the concentration were toluene and 0.5 wt%. The results are shown in Table 1. At this time, the static contact angle between the stencil 3 and the coating solution 4 and the static contact angle between the energy applying portion on the surface of the substrate 1 and the coating solution 4 were both 10 degrees or less.

[Example 3]
An experiment was performed in the same manner as in Example 2 except that a spherical gap material having a diameter of 20 μm was sprayed between the two stencil plates 3 of Example 2 (1) and the pattern was aligned. The results are shown in Table 1.

[Example 4]
In the printing process of Example 3, an experiment was performed in the same manner as in Example 3 except that the stencil 3 was peeled off from the substrate 1 after being allowed to stand at room temperature for 30 seconds after application of the coating liquid 4, and then dried by heating. The results are shown in Table 1.

[Example 5]
An experiment was performed in the same manner as in Example 4 except that the cross-sectional shape of the stencil 3 of Example 4 was changed to a taper shape having a dimensional relationship shown in FIG. The results are shown in Table 1.

[Example 6]
The experiment was performed in the same manner as in Example 4 except that the surface of the stencil plate 3 of Example 4 was coated with a fluorine-based material (Asahi Guard AG7000, manufactured by Asahi Glass Co., Ltd.). The results are shown in Table 1. At this time, the static contact angle between the surface of the stencil plate 3 and the coating liquid 4 was 43 degrees.

[Example 7]
An experiment was conducted in the same manner as in Example 5 except that the coating liquid applying means of Example 6 was a spray coater. The results are shown in Table 1.

[Comparative Example 1]
An experiment was conducted in the same manner as in Example 2 except that printing was performed using only one sheet of Example 2 (1). The results are shown in Table 1. In Table 1, an asterisk (*) indicates that measurement is not possible because the coating film is connected between adjacent film forming parts.

It is a schematic sectional drawing which shows the manufacturing method of one embodiment of this invention in process order. It is explanatory drawing regarding the wettability of a liquid. It is a schematic sectional drawing which shows the lamination | stacking relationship of two stencil plates. It is a schematic sectional drawing which shows the measurement location of surface roughness. It is a schematic sectional drawing which shows the example which used the permanent magnet for the board | substrate contact | adherence means. It is a schematic plan view which shows the example of a pattern of the stencil containing the pattern which floats easily. It is explanatory drawing regarding the presence or absence of the rising of the coating liquid by the presence or absence of surface treatment. It is a schematic sectional drawing which shows the example of the stencil whose cross-sectional shape is a taper shape. It is a fundamental sectional view showing a structural example of an FET transistor as an electronic element. It is a schematic circuit diagram which shows the structural example of a liquid crystal display device. It is a schematic circuit diagram which shows the structural example of an arithmetic unit. It is a top view which shows the dimensional relationship of the stencil used for an Example. It is a schematic sectional drawing which shows the dimensional relationship of the stencil whose cross-sectional shape used for an Example is a taper shape. It is sectional drawing which shows the intaglio offset printing method of patent document 2 in order of a process. It is sectional drawing which shows the example of a TFT structure of a nonpatent literature 2. It is sectional drawing which shows the electrically conductive film pattern formation method of patent document 3 in order of a process. It is sectional drawing which shows a general stencil printing process in order of a process.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Board | substrate 2 Surface property change layer 3,3A, 3B Stencil 4 Coating liquid 6 Permanent magnet, board | substrate contact | adherence means 21 Electronic element 31 Display apparatus 41 Arithmetic unit

Claims (22)

Critical surface tension by applying energy onto the substrate, or the production of electronic elements to form a surface-variable layer made of an insulating material whose critical surface tension and the surface shape changes, finely patterned electronic devices on the surface-variable layer A method,
Prior to the formation of the electronic element constituent material, a step of closely adhering a stencil having a desired pattern shape on the surface property change layer formed on the substrate;
Changing the wettability of the surface property change layer by applying energy to the surface property change layer to which the stencil is adhered; and
Applying the patterning by applying at least one coating liquid of the electronic element constituent material on the substrate while keeping the stencil in close contact with the surface property changing layer having changed wettability; and
A method for manufacturing an electronic device comprising:   The method for manufacturing an electronic device according to claim 1, wherein the surface property changing layer is made of a polymer material having a hydrophobic group in a side chain.   The method for manufacturing an electronic device according to claim 1, wherein a plurality of stencils having substantially the same pattern are adhered and stacked as the stencil on the surface property change layer formed on the substrate.   The method for manufacturing an electronic device according to claim 3, wherein an interface distance between the stencil plates is made larger than an interface distance between the surface property changing layer and the stencil plate.   The method of manufacturing an electronic device according to claim 4, wherein the surface roughness of the surface where the stencil contacts each other is made larger than the surface roughness of the surface of the stencil contacting the surface property changing layer.   The manufacturing method of the electronic element of Claim 4 which interposed the gap material in the interface which the said stencil contacts. The stencil is made of a material adsorbed by magnetic force,
The method for manufacturing an electronic device according to claim 1, wherein the stencil is brought into close contact with the substrate using a magnet or an electromagnet as the substrate contact means.   On the stencil after energy is applied to change the wettability of the surface property changing layer, the mesh plate has a continuous pattern finer than the fine pattern of the electronic element to be formed and is adsorbed by magnetic force. The manufacturing method of the electronic element of Claim 7 including the process of laminating | stacking and arrange | positioning on the said board | substrate.   9. The method of manufacturing an electronic element according to claim 8, wherein the magnetic attractive force of the substrate contact means on the mesh plate is larger than the magnetic attractive force of the substrate contact means on the stencil. The stencil is made of a material that is adsorbed by static electricity,
The method for manufacturing an electronic device according to claim 1, wherein the stencil is brought into close contact with the substrate using static electricity as a substrate contact means.   On the stencil after energy is applied to change the wettability of the surface property change layer, a mesh plate that has a continuous pattern finer than the fine pattern of the electronic element to be formed and is electrostatically adsorbed The method for manufacturing an electronic device according to claim 10, comprising a step of stacking and disposing on the substrate.   12. The method of manufacturing an electronic device according to claim 11, wherein the electrostatic chucking force of the substrate contact means on the mesh plate is larger than the electrostatic chucking force of the substrate contact means on the stencil.   Including a step of performing a surface treatment on the surface of the stencil so that a static contact angle between the coating liquid and the stencil is larger than a contact angle between the energy applying portion on the substrate surface and the coating liquid. Item 13. The method for manufacturing an electronic device according to any one of Items 1 to 12.   The method for manufacturing an electronic device according to claim 13, wherein fluorine or a silicone compound is used for the surface treatment.   The method for manufacturing an electronic device according to claim 1, wherein the application liquid is applied by a spray coating method.   The method for producing an electronic device according to claim 1, wherein the application liquid is applied by an ink jet coating method.   The method for producing an electronic device according to claim 1, wherein the application liquid is applied by a dubbing coating method.   The electron according to any one of claims 1 to 14, wherein the coating liquid is applied using at least one of a blade coater, a bar coater, a kiss coater, a gravure coater, a flexo coater, a knife coater, a curtain coater, and a spin coater. Device manufacturing method.   The method for manufacturing an electronic device according to claim 1, further comprising a step of removing the stencil from the substrate after increasing the viscosity of the coating solution by a predetermined method after applying the coating solution. .   The method of manufacturing an electronic device according to claim 19, wherein a cross-sectional shape of the hole of the stencil in direct contact with the substrate is a tapered shape in which the substrate side is expanded.   21. The method of manufacturing an electronic device according to claim 1, wherein energy application for changing the wettability of the surface property changing layer is performed by ultraviolet irradiation. 21. The method of manufacturing an electronic device according to claim 1, wherein energy application for changing wettability of the surface property changing layer is performed by plasma irradiation.

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