WO2016047362A1 - Materiau de revetement, procede de formation de motif, dispositif electronique et procede de fabrication associe - Google Patents

Materiau de revetement, procede de formation de motif, dispositif electronique et procede de fabrication associe Download PDF

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Publication number
WO2016047362A1
WO2016047362A1 PCT/JP2015/074271 JP2015074271W WO2016047362A1 WO 2016047362 A1 WO2016047362 A1 WO 2016047362A1 JP 2015074271 W JP2015074271 W JP 2015074271W WO 2016047362 A1 WO2016047362 A1 WO 2016047362A1
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solvent
pattern
coating material
droplet ejection
electronic device
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PCT/JP2015/074271
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English (en)
Japanese (ja)
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梅田　賢一
文彦 望月
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富士フイルム株式会社
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Priority to JP2016550061A priority Critical patent/JP6385449B2/ja
Priority to KR1020177007932A priority patent/KR101981408B1/ko
Publication of WO2016047362A1 publication Critical patent/WO2016047362A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
    • H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
    • H01L21/461—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/469—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After-treatment of these layers
    • H01L21/471—Inorganic layers
    • H01L21/473—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film

Definitions

  • the present invention relates to a coating material, a pattern forming method, and a method for manufacturing an electronic device, and more particularly, a coating material capable of obtaining a good cross-sectional pattern in which a coffee stain shape does not occur in an inkjet process related to the printed electronics field, and the coating material
  • the present invention relates to a pattern forming method using the ink as an inkjet ink and a method for manufacturing an electronic device having a functional layer formed by a pattern formed using the pattern forming method.
  • the cause of the coffee stain shape is generally the occurrence of Marangoni convection due to the concentration dependence of the surface tension.
  • the surface tension at the end of the droplet which tends to increase in concentration due to drying, increases.
  • a gradient of surface tension is generated in the droplet, and the entire liquid is wet and spread so as to be drawn toward the end. For this reason, the solute concentrates at the end portion, resulting in a pattern shape in which the edge rises (see Patent Document 1).
  • the wiring pattern disclosed in Patent Document 1 is formed of a conductive liquid on a high surface energy portion that has been changed from the low surface energy portion by applying energy to the wettability changing layer and has improved wettability with respect to the liquid.
  • the planar view shape of the conductive pattern layer is a rectangular wiring shape having rounded end portions with chamfered corners.
  • the edge of the wiring pattern having a rectangular shape in plan view of the conductive pattern layer is rounded so that the edge rises at the sharp corner of the end of the wiring shape having a rectangular shape in plan view.
  • the edge of the rectangular wiring shape in the plan view has an edge even if it is round, the edge swells even if it is low, preventing the edge swell itself. There is a problem that it cannot be done.
  • solutions used in general coating processes such as spin coating and slit coating often use a solution configuration in which the relationship between the surface tension and the concentration is proportional. In particular, when a solution configuration of “wetting” is used, the rise of the edge portion is an unavoidable problem.
  • the present invention is used in the field of printed electronics in view of the above-described problems and problems of the prior art, and a coating material capable of obtaining a good cross-sectional pattern by suppressing the rising of the edge of the pattern. It is an object of the present invention to provide a pattern forming method used, and a method for manufacturing an electronic device manufactured using a pattern formed using the pattern forming method.
  • the coating material according to the first aspect of the present invention is a coating material for forming a pattern having the highest point of droplet ejection within a region within 20% from the center of droplet ejection, and includes a raw material and a solubility parameter.
  • Two types of solvents A and B which are good solvents having an SP value of 20.3 MPa 1/2 or less, are configured, and the solvent A has a higher surface tension and a higher vapor pressure than the solvent B.
  • the volume content is 20% or more and 50% or less.
  • the solvent A has a surface tension of 1.17 times or higher and a vapor pressure of 1.57 times or higher than the solvent B. Further, the surface tension of solvent A at 20 ° C. is 27 mN / m or more and the vapor pressure is 1.1 kPa or more, and the surface tension of solvent B at 20 ° C. is 23 mN / m or less and 0.7 kPa or less. preferable. Moreover, it is preferable that the solvent A is contained 35% or more and 50% or less as a solvent volume content. Moreover, it is preferable that the raw material is comprised with the silazane compound. Moreover, it is preferable that it is an inkjet coating material.
  • the pattern forming method according to the second aspect of the present invention uses the coating material according to the first aspect to form a pattern having the highest point of droplet ejection within an area within 20% from the center of droplet ejection. It is characterized by forming.
  • a pattern having the highest point of droplet ejection within a region within 20% of the center of droplet ejection passes through the center of the droplet ejection within 20% from the center of droplet ejection, and has edges on both sides of this center.
  • a pattern having the maximum value of the cross-sectional profile of droplet ejection is preferable.
  • it is preferable that the edge part of the both sides of the cross-sectional profile of a droplet is rounded.
  • the electronic device manufacturing method according to the third aspect of the present invention is characterized in that at least one layer of the electronic device is manufactured by the pattern forming method according to the second aspect of the present invention.
  • at least one layer of the electronic device is at least one of an insulating layer, a protective layer, and an interlayer insulating layer.
  • the electronic device is preferably a thin film transistor.
  • the edge of a pattern is used in the field of printed electronics, and a solvent of a solution is composed of two or more components, and the relationship between the surface tension and the concentration dependency at the time of droplet drying is made inversely proportional.
  • Coating material capable of obtaining a good cross-sectional pattern by suppressing the swell of the substrate, a pattern forming method using the coating material, and a method for manufacturing an electronic device manufactured using the pattern formed using the pattern forming method Can be provided.
  • FIG. 1 It is sectional drawing which shows typically an example of the pattern of the droplet formation formed in the pan formation method using the coating material which concerns on this invention. It is a cross-sectional schematic diagram of one Example of the transistor which is one Embodiment of the electronic device manufactured by this invention method.
  • (A), (B) and (C) are schematic diagrams showing an ink jet droplet pattern image formed using the coating material of Example 1, a graph showing a cross-sectional profile of this droplet pattern image, and
  • Example 1 4 is a drawing-substituting photograph of a spin coat film formed by using the coating material.
  • (A), (B), and (C) are schematic diagrams showing an ink jet droplet pattern image formed using the coating material of Comparative Example 1, a graph showing a cross-sectional profile of this droplet pattern image, and Comparative Example 1 4 is a drawing-substituting photograph of a spin coat film formed by using the coating material.
  • the coating material according to the present invention is for forming a pattern having the highest point of droplet ejection within a region within 20% from the center of droplet ejection.
  • the raw material and the solubility parameter SP value are 20.3 MPa 1/2.
  • 2 types of solvents A and B which are the following good solvents, the solvent A has a higher surface tension and a higher vapor pressure than the solvent B, and the solvent volume content is 20% or more and 50 % Or less.
  • the coating material according to the present invention is a liquid coating material used to form a predetermined pattern constituting the functional layer when a functional layer such as an electronic device such as a thin film transistor is laminated.
  • An inkjet coating material is preferable.
  • the electronic device is not particularly limited as long as it is an electronic device to which the printed electronics technology is applied.
  • a thin film transistor, a solar cell, an RFID, a temperature monitor, a gas sensor, a biological sensor, a pressure sensor, an infrared ray A sensor, organic EL illumination, a display device, etc. can be mentioned.
  • the functional film is not particularly limited as long as it is a functional film constituting at least one layer of an electronic device or the like, and examples thereof include an insulating layer, a protective layer, an interlayer insulating layer, a gas barrier layer, and an optical thin film. .
  • FIG. 1 is a cross-sectional view schematically showing an example of the pattern shape of droplet ejection formed by the pattern forming method of the present invention using the coating material of the present invention.
  • the droplets 10 formed in the present invention are formed by convex patterns formed on the substrate 12, preferably ink droplets that are deposited on the substrate 12 by inkjet. Has a convex pattern.
  • the upper surface of the pattern of the droplet ejection 10 is within a region 20 within 20% of the center of the droplet ejection 10 when the center 14 of the droplet ejection 10 is taken in the direction perpendicular to the bottom surface of the droplet ejection 10, that is, the surface of the substrate 12.
  • the pattern of the droplet ejection 10 is as follows: a cross-sectional profile 18 obtained by cutting the droplet ejection 10 through a plane perpendicular to the bottom surface, that is, the surface of the substrate 12.
  • the convex pattern shape having the highest point in the region 20 within 20% from the center of the droplet ejection 10 is preferable.
  • the shape of the pattern may be any profile, and the edge 16 may be square, but is rounded, for example, existing on both sides of the center 14 of the droplet 10. It is preferable to have a curved surface shape that is convex upward from both edges 16 of the droplet 10 toward its center 14, and the upper surface of the convex pattern of the droplet ejection 10 and the cross-sectional profile 18 are as shown in the example shown in FIG. In the center 14, which has a curved surface shape convex upward from the edge 16 of the droplet 10 existing on both sides of the center 14 toward the center 14, and within the region 20 within 20% of the center 14 of the droplet 10. Having the highest score The most preferred.
  • the pattern of the droplet ejection 10 is not particularly limited, but is preferably a pattern formed by an ink jet method. However, any pattern may be used as long as it is a pattern by an ink jet method. It may be a circular pattern of a single ink droplet ejected from an inkjet nozzle, or may be a linear pattern, or a plurality of inks ejected from a plurality of inkjet nozzles It may be a closed curve pattern such as a circle or an ellipse formed by droplets, or may be a linear pattern.
  • the method of cutting the cross section of the droplet ejection in the present invention can be applied to any pattern of droplet ejection, for example, in a closed curve pattern or a linear pattern, that is, through the center of the droplet ejection.
  • Any cross section may be used as long as it is cut by a plane perpendicular to the bottom surface. That is, the droplet ejection profile may be a profile in any cross section.
  • the cross-sectional profile in this invention can be measured using the optical interference type surface roughness meter Veeco Wyko apparatus. It can detect by measuring the cross section obtained by the light interference method of a white LED and a green LED (535 nm) light source.
  • the coating material for forming the droplet ejection pattern as described above needs to be composed of two solvents A and B having different surface tension and vapor pressure as the solvent of the solution.
  • the two types of solvent A and solvent B are good solvents that easily dissolve the raw material of the coating material, and have a solubility parameter (SP value) of 20.3 MPa 1/2 or less, preferably 14.1 to 20 .3 or less solvent.
  • SP value solubility parameter
  • the reason why the SP values of the two types of solvent A and solvent B are limited to 20.3 MPa 1/2 or less is that if the SP value is more than 20.3 MPa 1/2 , the solubility decreases. Because.
  • solvents examples include aliphatic hydrocarbons such as pentane (14.3), hexane (14.9), heptane (15.1), octane (15.6), and dodecane (16.2), Cycloaliphatic hydrocarbons such as methylcyclohexane (16.0), cyclohexane (16.8), and cyclopentane (17.8), cumene (16.8), propylbenzene (17.6), ethylbenzene (18.
  • aliphatic hydrocarbons such as pentane (14.3), hexane (14.9), heptane (15.1), octane (15.6), and dodecane (16.2)
  • Cycloaliphatic hydrocarbons such as methylcyclohexane (16.0), cyclohexane (16.8), and cyclopentane (17.8), cumene (16.8), propylbenzene (17.6), ethylbenzene (18.
  • the SP value of such an organic solvent is determined, for example, by the method described in “Polymer Handbook”, 4th edition, pages VII-675 to VII-711 [in particular, the formula (B3) on page 676 and (B8) ) Formula].
  • the values shown in Table 1 (page VII-683) and Table 7 to Table 8 (pages VII-688 to VII-711) of the document can be adopted.
  • the SP value when the organic solvent is a mixed solvent of a plurality of solvents can be determined by a known method.
  • the SP value of the mixed solvent can be obtained as the sum of products of the SP value of each solvent and the volume fraction, assuming that additivity is established.
  • the good solvent is a solvent that easily dissolves the raw material to be a solute, preferably a solvent that is mixed infinitely with the raw material over the entire range of common temperature, for example, the SP value of the liquid of the raw material A solvent having a difference from the SP value of 10 MPa 1/2 or less is preferred.
  • solvent A and solvent B having different surface tension and vapor pressure from among the good solvents having the SP value as described above.
  • one solvent for example, solvent A
  • the solvent A preferably has a surface tension of 1.17 times or higher and a vapor pressure of 1.57 times or higher than the solvent B, more preferably a surface tension of 1.25 times or higher.
  • the vapor pressure is preferably 1.8 times higher.
  • the surface tension of the solvent A at 20 ° C.
  • the vapor pressure is 1.1 kPa or more
  • the surface tension of the solvent B at 20 ° C. is 23 mN / m or less and 0.7 kPa or less. It is more preferable.
  • the upper limit values of the ratio of the surface tension and the vapor pressure of the solvent A to the solvent B are not particularly limited, but are preferably 6 times or less and 10 times or less, respectively.
  • the upper limits of the surface tension and vapor pressure at 20 ° C. of the solvent A are not particularly limited, but are more preferably, for example, 90 mN / m or less and 100 kPa or less, respectively.
  • the lower limit values of the surface tension and vapor pressure at 20 ° C. of the solvent B are not particularly limited, but are more preferably, for example, 15 mN / m or more and 0.1 kPa or more, respectively.
  • the surface tension of the solution is a weighted average that takes into account the component composition ratio.
  • the edge portion dries faster than the central portion of the droplet ejection, and as a result, the density rises at the edge portion and the surface tension increases. Therefore, the relationship between the surface tension and the concentration dependency is proportional. As a result, it seems that the edge portion of the droplet ejection rises and the coffee stain phenomenon cannot be suppressed.
  • the volatilization rate of each solvent varies depending on the vapor pressure. For this reason, in the drying process, when the influence of the effect of the solvent A having a high surface tension and a high volatility increases, the concentration dependence relationship of the surface tension is in an inversely proportional form. That is, since the drying of the droplet is faster at the edge portion than at the central portion of the droplet, the concentration of the solution is high in the edge portion solution, but the solvent A having a high surface tension and high volatility Since the solvent evaporates faster than the solvent B having low tension and low volatility, the ratio of the solvent A decreases in the solvent at the edge portion, and the ratio of the solvent B having low surface tension and low volatility increases.
  • the surface tension of the solvent is lower in the edge portion than in the central portion. Therefore, the surface tension is reduced at the edge of the droplet where the concentration is high, and the surface tension is increased at the center of the droplet. As a result, the rise of the edge portion can be suppressed, and the coffee stain phenomenon can be suppressed.
  • the highest point of droplet ejection is within an area within 20% from the center of droplet ejection, and the coffee stain phenomenon can be suppressed.
  • the ratios of the surface tension and vapor pressure of the solvent A to the solvent B, the values of the surface tension and vapor pressure of the solvent A, and the values of the surface tension and vapor pressure of the solvent B are limited to the predetermined ranges described above. This is because the relationship of the concentration dependence of the surface tension of the solution in the droplet ejection is preferable to make it an inversely proportional relationship appropriate for suppressing the bulge of the edge portion.
  • the solvent A having a high surface tension and a high vapor pressure is 20% or more as a solvent volume content in the solution. It is necessary to contain 50% or less. The reason is that if the solvent volume content of the solvent A having a high surface tension and a high vapor pressure is within the range of 20% to 50%, as shown in FIG.
  • the pattern of the droplet ejection 10 having the highest point in the region within% and having the pattern shape defined by the present invention can be formed, and the coffee stain phenomenon can be suppressed.
  • the solvent volume content of the solvent A having a high surface tension and a high vapor pressure is preferably 35% or more and 50% or less. In this case, not only has the highest point within an area within 20% of the center 14 of the droplet ejection 10, but also the edge 16 portion can form a rounded convex droplet ejection pattern.
  • the raw material of the coating material according to the present invention is not particularly limited as long as the droplet ejection pan can be formed, but for forming a predetermined droplet ejection pattern constituting a functional layer of an electronic device such as a thin film transistor. More preferably, for example, a silazane compound, polystyrene, polycarbonate, polyethylene and the like can be mentioned.
  • a silazane compound is a compound having a silicon-nitrogen bond (—SiN—) in its structure, and is a silicon oxide film (hereinafter also referred to as an SiO 2 film) serving as a functional film such as an insulating layer, a protective layer, or an interlayer insulating layer.
  • a silicon oxynitride film hereinafter also referred to as SiON film
  • SiN film silicon nitride film
  • Such SiO 2 film, SiON film, and SiN film can be suitably used for various applications. Examples thereof include a gate insulating film, an interlayer insulating film, a gas barrier film, and an optical thin film of a transistor.
  • the silazane compound may be a low molecular compound or a high molecular compound (a polymer having a predetermined repeating unit).
  • low molecular weight silazane compounds include hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, and the like. It is done.
  • the type of the high molecular weight silazane compound (polysilazane compound) is not particularly limited. For example, it is a compound having a main skeleton composed of units represented by the following general formula (1) described in JP-A-8-112879. Preferably there is.
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group. .
  • the polysilazane is preferably perhydropolysilazane (hereinafter, also referred to as “PHPS”) in which all of R 1 , R 2 , and R 3 are hydrogen atoms from the viewpoint of better insulating properties.
  • PHPS perhydropolysilazane
  • Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and can be a liquid or solid substance (depending on the molecular weight). As the perhydropolysilazane, a commercially available product may be used.
  • Examples of the commercially available product include AQUAMICA NN120, NN120-20, NN110, NAX120, NAX120-20, NAX110, NL120A, NL120-20, NL110A, NL150A, NP110, NP140 (made by AZ Electronic Materials Co., Ltd.) etc. are mentioned.
  • polysilazane examples include silicon alkoxide addition polysilazane obtained by reacting polysilazane represented by the above general formula with silicon alkoxide (for example, JP-A-5-238827), and glycidol addition obtained by reacting glycidol.
  • Polysilazane for example, JP-A-6-122852
  • alcohol-added polysilazane for example, JP-A-6-240208
  • metal carboxylate obtained by reacting a metal carboxylate
  • Polysilazane for example, JP-A-6-299118
  • acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex
  • metal fine particles are added.
  • Obtained metal fine particle Polysilazane e.g., JP-A-7-196986 JP
  • the molecular weight of the polysilazane compound is not particularly limited, but for example, those having a polystyrene-reduced average molecular weight in the range of 1,000 to 20,000 are preferred, and those having a molecular weight in the range of 1,000 to 10,000 are more preferred. These polysilazane compounds can be used in combination of two or more.
  • the mass ratio of the silazane compound and the solvent (solvent A and solvent B) (mass of silazane compound / mass of solvent (solvent A and solvent B)) in the coating material of the present invention is not particularly limited, and the functional film to be formed
  • the optimum mass ratio is appropriately selected according to the thickness of the (coating film), but is preferably 0.01 to 0.50, more preferably 0.05 to 0.20, from the viewpoint of excellent droplet ejection properties.
  • the coating material of this invention can also contain another additive component as needed. Examples of such components include viscosity modifiers and crosslinking accelerators.
  • the coating material of the present invention is basically configured as described above.
  • the pattern forming method of the present invention uses the above-described coating material of the present invention to form a pattern having the highest point of droplet ejection within a region 20 within 20% from the center of the droplet ejection 10 as shown in FIG. Is the method.
  • a solvent A which is a good solvent for the raw material and has a high surface tension and a high vapor pressure
  • a solvent B which is both low are used as the solvent.
  • the formed droplet ejection pattern can form a pattern having the highest point of droplet ejection within a region 20 within 20% from the center of the droplet ejection 10 as shown in FIG.
  • the method for ejecting the coating material of the present invention is not particularly limited, but by using an inkjet method, for example, droplets of the coating material of the present invention are ejected from the inkjet nozzle onto the substrate 12 to form droplets 10. As long as it can be formed, any method may be used.
  • the pattern of the droplet ejection 10 formed in the present invention is a pattern having the highest point of droplet ejection within the region 20 within 20% from the center of the droplet ejection 10, one or more inkjet nozzles are used.
  • the pattern may be a closed-curve pattern such as a circle or an ellipse formed by one or more ink droplets ejected from or a linear pattern.
  • a droplet of the coating material of the present invention is ejected from an inkjet nozzle to form a pattern of droplets 10 on the substrate 12
  • a plurality of inkjet nozzles are provided on the fixed substrate 12.
  • the attached carriage may be moved, the substrate 12 may be intermittently conveyed and the carriage may be moved, or the carriage 12 may be fixed and the substrate 12 may be conveyed.
  • the substrate on which the coating material of the present invention is ejected to form a droplet ejection pattern, its shape, structure, and size are not particularly limited and can be appropriately selected depending on the purpose.
  • the structure of the substrate may be a single layer structure or a laminated structure.
  • the material of the substrate is not particularly limited, and for example, an inorganic material such as glass, alumina, YSZ (yttrium stabilized zirconium), a resin material, a composite material thereof, or the like can be used. Among these, a resin substrate or a composite material thereof is preferable from the viewpoint of light weight and flexibility.
  • the thickness of the pattern 10 of the droplets 10 after pattern formation is efficient in, for example, ultraviolet irradiation and / or heat treatment so as to be suitable for post-processing applied to the pattern of droplets 10 formed on the substrate 12. It is preferable to be thin so that it can be cured (converted). For this reason, the thickness of the droplet ejection pattern is preferably 1.0 ⁇ m or less, and more preferably 0.5 ⁇ m or less. On the other hand, although there is no lower limit to the thickness of the droplet ejection pattern, it is preferably 0.05 ⁇ m or more, and more preferably 0.1 ⁇ m or more from the viewpoint of film formability.
  • a flexible substrate is used as the substrate and a coating material containing a silazane compound is used as the coating material of the present invention, it is converted into a SiO 2 film, a SiON film, or a SiN film after the droplet ejection pattern is formed by the coating material of the present invention.
  • a droplet ejection pattern of the coating material of the present invention may be formed on both surfaces of the substrate.
  • the pattern forming method of the present invention is basically configured as described above.
  • the method for producing an electronic device of the present invention is a method for producing at least one layer constituting an electronic device as a functional film by a droplet ejection pattern formed by using the above-described pattern forming method of the present invention.
  • a thin film transistor is a typical example as an electronic device
  • a gate insulating film of a thin film transistor is a typical example as a functional film
  • a SiON film formed from the coating material of the present invention using a silazane compound as a raw material is formed as a gate oxide film.
  • An example will be described as a representative example, but the present invention is of course not limited thereto.
  • FIG. 2 is a schematic cross-sectional view of one example of a thin film transistor which is one embodiment of the electronic device of the present invention.
  • the thin film transistor 50 includes a substrate 52, a gate electrode 54 disposed on the substrate 52, a gate insulating film 56 disposed on the gate electrode 54, and an oxide semiconductor disposed on the gate insulating film 56.
  • the layer 58 includes at least a source electrode 60 and a drain electrode 62 disposed on the oxide semiconductor layer 58.
  • the gate insulating film 56 is formed by using the coating material of the present invention containing two types of solvents that use a silazane compound as a raw material, are good solvents for the raw material, and have different surface tension and vapor pressure. It is formed of a SiON film having a droplet ejection pattern formed by the method.
  • the thin film transistor 50 is a bottom-gate thin film transistor.
  • the SiON film according to the present invention may be applied to the gate insulating film of the top gate type thin film transistor.
  • the gate insulating film 56 is disposed adjacent to the oxide semiconductor layer 58 and the SiON film is used, the interface characteristics with the oxide semiconductor layer 58 are further improved, and the performance as a thin film transistor is further improved.
  • the surface that has been subjected to the oxidation step is preferably disposed on the oxide semiconductor layer 58 side.
  • FIG. 2 an embodiment of an oxide thin film transistor using an oxide semiconductor layer is described in detail.
  • the SiON film according to the present invention is used as a gate insulating film of an organic thin film transistor using an organic semiconductor layer containing an organic semiconductor material. Can also be suitably used.
  • the gate electrode 54 is formed on the substrate 52 by a known method, for example, by vacuum deposition or sputtering of an electrode material. Form.
  • a conversion process is performed, and the SiON film is gate-insulated.
  • the film 56 is formed.
  • an oxide semiconductor layer 58 is formed over the gate insulating film 56 by a known method, and the patterned source electrode separated in the same manner as the gate electrode 54 over the formed oxide semiconductor layer 58. 60 and the drain electrode 62 are formed.
  • the thin film transistor 50 can be manufactured by the method of the present invention.
  • the substrate, gate electrode, gate insulating film, oxide semiconductor layer, source electrode, and drain electrode will be described in detail.
  • the substrate plays a role of supporting a gate electrode, a source electrode, a drain electrode, and the like, which will be described later.
  • substrate is not restrict
  • the material of the gate electrode examples include gold (Au), silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, sodium, and other metals; In 2 O 3 , SnO 2 , ITO Conductive oxides such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polydiacetylene; semiconductors such as silicon, germanium, and gallium arsenide; and carbon materials such as fullerene, carbon nanotube, and graphite. Especially, it is preferable that it is a metal, and it is more preferable that they are silver and aluminum.
  • the thickness of the gate electrode is not particularly limited, but is preferably 10 nm to 1000 nm, and more preferably 50 nm to 500 nm.
  • a method for forming the gate electrode is not particularly limited, and examples thereof include a method of vacuum depositing or sputtering an electrode material on a substrate, a method of applying or printing an electrode forming composition, and the like.
  • examples of the patterning method include a photolithography method; a printing method such as ink jet printing, screen printing, offset printing, letterpress printing; and a mask vapor deposition method.
  • the gate insulating film is formed from the above-described SiO 2 film, SiON film, or SiN film.
  • the coating material of the present invention containing two types of solvents that use a silazane compound as a raw material is a good solvent for the raw material, and has different surface tension and vapor pressure.
  • the droplet ejection pattern is subjected to a conversion process after drying or without drying.
  • a conversion treatment is performed by irradiating ultraviolet rays and / or heating the droplet ejection pattern (applying a heat treatment). By performing such treatment, conversion from the silazane compound to a desired SiON film or SiN film proceeds. In this way, a SiON film or a SiN film having a pattern shape with no rising edge can be formed as a gate insulating film.
  • a conversion treatment is performed by irradiating ultraviolet rays and / or heating the droplet ejection pattern (applying a heat treatment). By carrying out such a treatment, conversion from the silazane compound to a desired SiO 2 film proceeds. In this way, a SiO 2 film having a pattern shape with no edge rise can be formed as a gate insulating film.
  • the thickness of the gate insulating film is not particularly limited, but is preferably 70 to 1000 nm.
  • FIG. 2 shows a mode in which the gate insulating film is a SiON film, but the mode is not limited to this mode.
  • the mode is not limited to this mode.
  • a laminated insulating film in which a SiON film and another gate insulating film are laminated may be used as long as it has a droplet ejection pattern shape.
  • the portion in contact with the oxide semiconductor layer is preferably the SiON film of the present invention.
  • the other gate insulating film include a polymer insulating film containing a polymer as an insulating material.
  • polyethylene polyethylene
  • PP polypropylene
  • PTFE polytetrafluoroethylene
  • PVC polyvinyl chloride
  • PVA polyvinyl alcohol
  • PVP polyvinyl phenol
  • PVP polyvinyl pyrrolidone
  • PS polystyrene
  • PMMA polymethyl methacrylate
  • PAN polyacrylonitrile
  • PC polycarbonate
  • PET poly (ethylene terephthalate)
  • PPS polyphenylene sulfide
  • PI polyimide
  • BCB benzocyclobutene
  • CyPe polycyclopentene
  • PI polysilsesquioxane
  • the oxide semiconductor layer functions as an active layer (channel).
  • one or more of indium (In), gallium (Ga), tin (Sn), and zinc (Zn) are used. It consists of an oxide of a mixture. Examples of such an oxide include indium gallium zinc oxide (IGZO, InGaZnO).
  • indium gallium zinc oxide In—Al—Zn—O, In—Sn—Zn—O, In—Zn—O, In—Sn—O, Zn—O, Sn—O, etc. May be used.
  • the thickness of the oxide semiconductor layer is not particularly limited, but is preferably 5 to 300 nm.
  • a method for forming the oxide semiconductor layer is not particularly limited, and a known method can be employed. For example, spin coating, ink jet, dispenser, screen printing, letterpress printing or intaglio printing can be used. Further, a vapor phase method such as a sputtering method or a vapor deposition method may be employed.
  • ⁇ Source electrode, drain electrode> Specific examples of the material of the source electrode and the drain electrode are the same as those of the gate electrode described above.
  • a method for forming the source electrode and the drain electrode is not particularly limited. For example, a method of vacuum-depositing or sputtering an electrode material on a substrate on which a gate electrode, a gate insulating film, and an oxide semiconductor layer are formed; The method of apply
  • a specific example of the patterning method is the same as that of the gate electrode described above.
  • the channel length of the source electrode and the drain electrode is not particularly limited, but is preferably 0.01 to 1000 ⁇ m.
  • the channel width of the source electrode and the drain electrode is not particularly limited, but is preferably 0.01 to 5000 ⁇ m.
  • the electronic device manufacturing method of the present invention is basically configured as described above.
  • Example I First, a polysilazane solution (120 series: dibutyl ether solvent and 110 series: xylene solvent) manufactured by AZ-EM was used as a raw material, and various solvents were mixed as solvent A and solvent B at a volume ratio of 1: 1. A mixed solution of ⁇ 2 and Comparative Examples 1-8 was obtained. These mixed solutions of Examples 1 and 2 and Comparative Examples 1 to 8 are shown in Table 1. The values of vapor pressure and surface tension shown in Table 1 are values at 20 ° C.
  • Examples 1 and 2 and Comparative Examples 1 to 8 were ejected using an inkjet apparatus DMP2830 manufactured by FUJIFILM DIMATIX, and the pattern shape of the ejected droplets, that is, the cross-sectional profile was confirmed.
  • the cross-sectional profile was confirmed by measuring the optical interference image with Wyko manufactured by Veeco. The case where the maximum value was obtained in an area within 20% from the central portion of the droplet ejection pattern was evaluated as A, and the case where the maximum value was taken in an area other than 20% from the central portion was evaluated as B.
  • the results are shown in Table 1.
  • Example II Next, in the combination of the raw material of Example 1, the solvent A and the solvent B, the wettability of the spin coat film and the ink jet pattern are obtained by changing the volume content of toluene as the solvent A and dibutyl ether as the solvent B. Changes in the pattern shape of the image, especially its edge shape, were confirmed. The wettability of the spin coat film was evaluated in the same manner as in Example I.
  • the pattern shape of the ink jet pattern image is AA when the maximum value in the cross-sectional profile is in the central portion (within 20% of the center) of the droplet ejection pattern and the edge portion is rounded, and the center of the droplet ejection pattern.
  • the mixed solutions of Examples 21 to 22 and Comparative Examples 21 to 22 are shown in Table 3.
  • the values of vapor pressure and surface tension shown in Table 3 are values at 20 ° C.
  • Example 21 to 22 The obtained mixed solutions of Examples 21 to 22 and Comparative Examples 21 to 22 were spin-coated on a silicon substrate, thereby confirming wettability. Evaluation of the wettability of the spin coat film was performed in the same manner as in Example I. The results are shown in Table 3. As is apparent from the results shown in Table 3, when the solvent B is dibutyl ether, the solvent A is toluene and chlorobenzene, the surface tension ratio between the solvent A and the solvent B is 1.17 or more, and the vapor pressure ratio is 1. In Examples 21 and 22, which were 57 or more, it was confirmed that the spin coat film had an unfavorable B evaluation.
  • Example I the mixed solution of Examples 21 to 22 and Comparative Examples 21 to 22 was ejected using an inkjet apparatus DMP2830 manufactured by FUJIFILM DIMATIX, and the pattern shape of the ejected droplets, that is, the cross-sectional profile was obtained. confirmed.
  • the cross-sectional profile was confirmed by measuring the optical interference image with Wyko manufactured by Veeco. Evaluation of the pattern shape (cross-sectional profile) of droplet ejection was performed in the same manner as in Example I.
  • the results are shown in Table 3.
  • Table 3 As is apparent from the results shown in Table 3, in Examples 21 to 22, which are solution structures in which a film was not formed well by spin coating, the highest value was obtained in the region of 20% from the center in the formed ink jet pattern image. It was confirmed that a good A evaluation cross-sectional profile having a smooth convex shape from the edge toward the center was obtained.

Abstract

　La présente invention concerne un matériau de revêtement servant à former un motif dans lequel le point le plus haut d'une gouttelette se situe dans une région comprise dans la plage de 20 % à partir du centre de la gouttelette, le matériau de revêtement contenant deux types de solvants A et B qui constituent de bons solvants dont la valeur de paramètre de solubilité SP est inférieure ou égale à 20,3 MPa1/2 par rapport à un matériau brut. Le solvant A présente une tension superficielle et une pression de vapeur supérieures à celles du solvant B, et la teneur en volume du solvant est comprise entre 20 % et 50 %. Le procédé de formation de motif selon la présente invention consiste à former le motif mentionné précédemment à l'aide du matériau de revêtement. Le procédé de fabrication d'un dispositif électronique selon la présente invention consiste à fabriquer au moins une couche d'un dispositif électronique à partir d'un motif déposé au moyen du procédé de formation de motif.
PCT/JP2015/074271 2014-09-26 2015-08-27 Materiau de revetement, procede de formation de motif, dispositif electronique et procede de fabrication associe WO2016047362A1 (fr)

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KR1020177007932A KR101981408B1 (ko) 2014-09-26 2015-08-27 도포 재료, 패턴 형성 방법 및 전자 디바이스의 그 제조 방법

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JP2020111651A (ja) * 2019-01-09 2020-07-27 凸版印刷株式会社 塗布剤、印刷物及び印刷物の製造方法
WO2021124802A1 (fr) * 2019-12-17 2021-06-24 コニカミノルタ株式会社 Composition d'encre servant à former une couche d'étanchéité de dispositif électronique, procédé de formation de couche d'étanchéité de dispositif électronique et couche d'étanchéité de dispositif électronique

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WO2021124802A1 (fr) * 2019-12-17 2021-06-24 コニカミノルタ株式会社 Composition d'encre servant à former une couche d'étanchéité de dispositif électronique, procédé de formation de couche d'étanchéité de dispositif électronique et couche d'étanchéité de dispositif électronique
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JP6385449B2 (ja) 2018-09-05
TW201612975A (en) 2016-04-01

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