TW201324597A - Method for pattern formation - Google Patents

Abstract

A method for pattern formation to form a tiny pattern, including steps below: on a first film having transformation functions of hydrophilicity and hydrophobicity, the hydrophilicity or the hydrophobicity of a pattern formation area that forms a pattern is changed, wherein the first film is formed on a substrate; and a second film, formed on the pattern formation area, is dried to form the pattern. When a thickness of the second film is 0.1 μ m, viscosity is equal to or under 3 mPa.s.

Description

Pattern forming method

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a pattern forming method for controlling a liquid repellency to form a fine pattern, for example, a pattern having a line width of less than 50 μm, and more particularly to an electrode for forming an electric wiring or a semiconductor, or a precursor (precursor) The pattern forming method.

In recent years, a technique of forming wiring of an electronic circuit and forming a fine pattern such as an electric wiring pattern on a substrate has been attracting attention. The fine pattern is formed, for example, by using a liquid ejecting head (inkjet head) of an inkjet method. At this time, a pattern is drawn by dripping a liquid of metal particles or resin particles from the inkjet head, and the pattern is cured by heating or the like to form an electric wiring pattern.

In addition, the following methods are also employed: forming on a flexible substrate (support) such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN). The liquid-repellent film forms wiring of the electronic circuit on the liquid-repellent film and forms a fine pattern such as an electric wiring pattern on the substrate.

Patent Document 1 discloses a method for producing a conductive substrate, which comprises the steps of: a substrate having an average surface roughness of 1.2 nm or more and 5 nm or less and a maximum height of surface irregularities of 0.1 μm or more and 1.0 μm or less. After coating the organic resin solution, heating is performed to form an organic resin layer having an average surface roughness of 1 nm or less and a maximum convex height of surface irregularities of 30 nm or less; ultraviolet irradiation and electron beam irradiation of the organic resin layer; Corona discharge or ozone treatment forms a lyophilic region on at least a portion of the surface of the organic resin layer; and a conductive layer is formed in the lyophilic region.

Patent Document 1 discloses that a conductive layer can be formed by a dipping method, a dropping method, a spray coating method, a doctor blade method, a die coating method, and a plate coating method. A printing method such as (offset) or screen, or an inkjet method or the like ([0096]).

Further, Patent Document 1 discloses a method for producing an organic field effect transistor including a resin substrate, a gate electrode, a gate insulating layer, a source electrode, a gate electrode, and an organic half layer. In the method for producing an airport effect transistor, a hydrophobic organic layer is formed, and the hydrophobic organic layer is subjected to a surface modification treatment to lyophilize the hydrophobic organic layer, and the lyophilized portion is formed by an inkjet method or the like. A conductive polymer, a metal colloid, an organic metal, or the like is applied, and then heat treatment is performed to form a source electrode and a drain electrode.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-289054

As disclosed in Patent Document 1, the organic resin layer is subjected to ultraviolet ray irradiation, electron beam irradiation, corona discharge, or ozone treatment to form a lyophilic region on the surface of the organic resin layer, and the ink repellency is equal to the lyophilic property. The region forms a conductive layer.

Further, Patent Document 1 discloses a method of manufacturing an airport effect transistor. The distance between the source electrode and the drain electrode of an airport effect transistor is 10 μm. Left and right, the positional accuracy of the source electrode and the drain electrode is required to be micron order precision. As such, the pattern is required to have a positional accuracy of micrometer order to exhibit a prescribed function.

Here, according to "2007 Inkjet Technology Encyclopedia (publisher: Electronic Journal, publication date: 2007.6)", in the inkjet method, the usual ink droplets have a diameter of 16 μm to 30 μm, and the volume It is 2 x 10 ^-12 liters (picoliter). The ink droplets can be drawn with a line width of 30 μm. Further, even with the printing method, it is difficult to achieve the accuracy of the distance between the source electrode and the drain electrode. As described above, it is extremely difficult to achieve the above-described micron-level precision by using the inkjet method or the printing method alone, and even if the above-described micron-order precision can be achieved, the efficiency is extremely poor.

An object of the present invention is to solve the problems of the prior art described above, and to provide a pattern forming method capable of forming a pattern with high precision even in a fine pattern such as a pattern having a line width of less than 50 μm.

In order to achieve the above object, the present invention provides a pattern forming method which is a pattern forming method of a fine pattern, comprising the steps of forming on a first film having a hydrophilic/hydrophobic conversion function formed on a substrate. The hydrophilicity change of the pattern forming region of the pattern; the formation of the second film in the pattern forming region, the drying of the second film to form a pattern, and the viscosity of the second film at a thickness of 0.1 μm of 3 mPa. s below.

In addition, the fine pattern means a pattern having a line width of less than 50 μm.

Preferably, the first film is a film which changes in hydrophilicity and hydrophobicity by ultraviolet rays, and the pattern forming region is formed by ultraviolet light exposure, and the second film is formed by non-image The first inter-surface force acting between the first film and the first film is -50 Pa to -10 Pa, and the second inter-surface force acting between the first film and the first film in the pattern formation region is the first surface. Below 90% of the inter-force, and is negative.

It is preferable to form a concave portion of 10 nm or more in the pattern formation region by ultraviolet light exposure. For example, the second film is formed by an inkjet method or a printing method. For example, the pattern is an electric wiring or a semiconductor electrode, or a precursor of an electric wiring or an electrode for a semiconductor.

Further, it is preferable that the second inter-surface force is 0 to 90% of the first inter-surface force and is a negative value.

According to the present invention, even in a fine pattern, for example, a pattern having a line width of less than 50 μm, a pattern can be formed with high precision.

Therefore, according to the present invention, for example, the accuracy of the distance between the source electrode and the drain electrode can be improved, and a thin film transistor can be formed with high precision. Thereby, when the thin film transistor is applied to the display, the unevenness of the drain current value of each pixel can be alleviated, and as a result, unevenness in brightness can be reduced.

Hereinafter, the pattern forming method of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

FIG. 1 is a schematic view showing an example of a pattern forming apparatus used in a pattern forming method according to an embodiment of the present invention. 2(a) is a schematic plan view of a substrate on which a first film is formed used in a pattern forming method, and FIG. 2(b) is a schematic cross-sectional view showing a substrate on which a first film is formed used in a pattern forming method.

The pattern forming apparatus 10 (hereinafter simply referred to as the forming apparatus 10) shown in FIG. 1 is, for example, a roll-to-roll type apparatus, and performs various processes while transporting the substrate G in the longitudinal direction. The forming device 10 is a forming device that forms a fine pattern, for example, a pattern having a line width of less than 50 μm.

The forming apparatus 10 includes a mark forming portion 12, a detecting portion 14, an exposure portion 16, and a pattern forming portion 18. Further, the forming apparatus 10 includes an input unit 30, a drawing data creating unit 32, a storage unit 34, an image processing unit 36, and a control unit 38. The operation of each component in the forming apparatus 10 is controlled by the control unit 38.

In the forming apparatus 10, the substrate G is wound around the rotating shaft 40 and mounted in a roll shape. The rotating shaft 40 continuously feeds the substrate G, and a motor (not shown) is connected to the rotating shaft 40, for example. The rotating shaft 40 continuously feeds the substrate G in the conveying direction D by the motor.

Further, a winding shaft 42 that winds up the substrate G that has passed through the mark forming portion 12, the detecting portion 14, the exposure portion 16, and the pattern forming portion 18 is provided. A motor (not shown) is connected to the winding shaft 42, for example. The winding shaft 42 is rotated by the motor to wind the substrate G in a roll shape on the take-up shaft 42. Thereby, the substrate G is transported in the transport direction D.

In the present embodiment, as shown in FIG. 2(b), the first film 50 is formed on the substrate G. The first film 50 contains a liquid repellent. The liquid repellent has a function of changing the degree of lyophilicity by light of a predetermined wavelength, for example, ultraviolet light (UV light). The function of the degree of lyophilicity is, for example, a hydrophilic-hydrophobic conversion function. The degree of lyophilicity of the first film 50 varies. Function (hydrophobic conversion function).

As shown in FIG. 2(a), on the surface 50a of the first film 50, an alignment mark M (mark pattern) is formed at four corners of the outer edge of the rectangular formation region S to form a pattern.

Hereinafter, the substrate G will be specifically described.

Since the forming apparatus 10 of the present embodiment is a roll-to-roll type, a resin film is used as the substrate G from the viewpoints of productivity, flexibility, and the like. The resin film is not particularly limited, and the material, shape, structure, thickness and the like of the resin film can be appropriately selected from known conditions.

Examples of the resin film include polyester resin films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) modified polyester, polyethylene (PE) resin film, and poly a polyolefin resin film such as a polypropylene (PP) resin film, a polystyrene resin film or a cyclic olefin resin, or a vinyl resin film such as polyvinyl chloride or polyvinylidene chloride. Polyetheretherketone (PEEK) resin film, polysulfone (PSF) resin film, polyethersulphone (PES) resin film, polycarbonate (PC) resin film, polyamine resin film, A polyimide film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, or the like.

In the case where a thin film transistor (TFT) is formed by the forming device 10 and the thin film transistor is used for a display or the like, the substrate G is preferably a transparent resin film as long as the light transmittance of the wavelength in the visible light region is 80. More than or equal to the resin film. Among them, transparency, heat resistance, ease of handling, In terms of strength and cost, a biaxially oriented polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyether ruthenium film, a polycarbonate film, and more preferably a biaxial ring are preferred. The polyethylene terephthalate film and the biaxially stretched polyethylene naphthalate film are extended.

In addition, the forming device 10 may be monolithic as described later. In this case, the substrate G may be a substrate such as a Si wafer, a quartz glass, a glass, a plastic, or a metal plate, as long as it can be formed on the surface layer of the substrate. The semiconductor film, the metal film, the dielectric film, the organic film, and the like are not particularly limited.

A film made of a semiconductor film, a metal film, a dielectric film, an organic film, a film containing a functional material, or a functional element can be used as a substrate on the surface of the substrate.

Next, a specific example of the liquid-repellent constituting the first film 50 will be described. The first film 50 functions as a hydrophilic-hydrophobic conversion functional material as described above, and includes a liquid repellency agent. The thickness (film thickness) of the first film 50 is preferably 0.001 μm to 1 μm, and more preferably 0.01 μm to 0.1 μm.

As will be described later in detail, the first film 50 differs in the inter-surface force acting between the portion not irradiated with energy (non-pattern forming region) and the portion irradiated with energy (pattern forming region) and the second film.

Therefore, the liquid-repellent agent constituting the first film must have an inter-surface force acting between the second film and the conditions described in detail below.

Among the liquid repellency agents, examples of the inorganic material include titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), barium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), and cerium oxide ( An oxide such as Bi ₂ O ₃ ) or iron oxide (Fe ₂ O ₃ ). One or two or more of these oxides may be optionally used. For example, in the case of titanium dioxide, there are an anatase type and a rutile type, and any one may be used, but it is preferably Anatase type titanium dioxide.

In the liquid repellency agent, the binder is preferably a binder having a high binding energy which does not decompose by photoexcitation of the oxide, and the binder has a function of an oxide. In the case where the wettability has a function of changing, it is preferred that the main skeleton of the binder has the above-mentioned high binding energy which does not decompose by photoexcitation of the oxide, and contains an organic substitution which can be decomposed by the action of the oxide. Examples of the binder of the base include, for example, a sol-gel reaction, such as hydrolysis or polycondensation of chlorine or alkoxysilane, and the like, and a large-strength organic polyoxane, and The reactive anthrone having excellent water-based and oil-repellent properties produces an organic polyoxane obtained by crosslinking.

Further, a stable organic ruthenium compound which does not undergo a crosslinking reaction such as dimethylpolysiloxane or a above-mentioned organopolyoxane may be mixed together in the binder.

Further, the oxide-containing layer may be decomposed by the action of the oxide under irradiation of energy, thereby decomposing the wettability on the oxide-containing layer. As such a decomposing substance, a surfactant having a function of decomposing by an action of an oxide and changing the wettability of the surface of the photocatalyst-containing layer by decomposition can be mentioned.

Specifically, a fluorine-based or anthrone-based nonionic surfactant can be used, and a cationic surfactant, an anionic surfactant, or an amphoteric surfactant can also be used. In addition to the surfactant, it can also be listed: Polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane , melamine resin, polycarbonate, polyvinyl chloride, polyamide, polyimine, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, Oligomers such as nylon, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, polymers, and the like.

Further, examples of the lyophilic compound include a guanidine salt such as a diazonium salt, a phosphonium salt or a phosphonium salt, an o-nitrobenzylsulfonate compound, and a p-nitrobenzylsulfonate used together with a sensitizer. Acid ester/salt compound, 1,2,3-triphenyl, N-indenyl sulfonate/salt compound, oxime sulfonate compound, α-keto sulfonate compound, diazide naphthoquinone 4-sulfonate/salt compound, diazo disulfone compound, diterpene compound, ketosulfone compound, o-nitrobenzyl ester compound, metaalkoxybenzyl ester compound, ortho-nitrite Base benzylamine compound, benzoisoester compound, benzamidine compound, 2,4-dinitrobenzenesulfonate, 2-diazo-1,3 diketone compound, phenol ester A compound, an o-nitrobenzylphenol compound, a 2,5-cyclohexadienone compound, a sulfonated polyolefin, an aryldiazonium sulfonate or the like.

The mark forming portion 12 is formed on the first film 50 having the hydrophilic-hydrophobic conversion function, for example, as shown in Fig. 2(a), on the surface 50a of the first film 50 on the substrate G, in the rectangular formation region S. The four corners of the outer edge form an alignment mark M (marking pattern).

The mark forming portion 12 includes, for example, a mark exposure portion and a mark printing portion, and the mark exposure portion is provided on the upstream side in the conveyance direction D.

The mark exposure unit includes a light source (not shown) that can irradiate the first film 50 with light having a wavelength that changes the liquid repellency of the first film 50 to a lyophilic property, a mask (not shown), and a mask (not shown). And a mark printing unit (not shown). As the light source, for example, a light source that can irradiate light of an ultraviolet region having a wavelength of 300 (nm), 365 (nm), or 405 (nm) or the like is used.

The mask is, for example, a mask that forms the circular alignment mark M shown in Fig. 2(a). In addition, the shape of the alignment mark M is not limited to a circular shape.

The mark printing portion prints the visible ink on the exposed region where the mark pattern of the alignment mark M is exposed, and forms the alignment mark M.

Further, the mark printing portion is not particularly limited as long as it can supply the visible ink to the exposed region where the mark pattern is exposed, and the entire printing method can be performed. Further, for example, inkjet, screen printing, letterpress printing, or gravure printing can be used.

The visual ink used to form the alignment mark M uses an ink that absorbs or reflects light of a wavelength that does not change the hydrophilicity of the first film 50, so that the first film 50 is unnecessary when the alignment mark M is detected. The pro-hydrophobic conversion. Therefore, the visible ink can be appropriately selected depending on the wavelength at which the first film 50 generates the hydrophilic-hydrophobic transition, and for example, an ink that reflects or absorbs light having a wavelength of 500 nm or more is used. Further, as the visual ink, for example, a water-soluble ink or a metal ink can be used.

The detecting unit 14 detects the position mark information of the alignment mark M by detecting the alignment mark M, and the detecting unit 14 is connected to the image processing unit 36. Detection unit 14 package A strain sensor (not shown) and an alignment detecting unit (not shown) are included.

The strain sensor detects the alignment mark M using light of a wavelength that does not cause the hydrophilicity change of the first film 50, for example, using a light source including a light emitting diode (LED), and a complementary metal oxide semiconductor (Complementary) Optical strain sensor of imaging elements such as Metal Oxide Semiconductor (CMOS), Charge Coupled Device (CCD). Further, in the case where the visible ink can reflect or absorb light having a wavelength of 500 nm or more, the light source uses a light source that irradiates light having a wavelength of 500 nm or more. Specifically, the wavelength of the light source is, for example, a wavelength of 633 nm, 660 nm, 590 nm, or infrared (IR).

The strain sensor irradiates the alignment mark M with light having a wavelength of 500 nm or more, and photographs the alignment marks M of the four corners of the outer edge portion of the formation region S previously provided in FIG. 2(a) to obtain, for example, Image data of four alignment marks M. The image data of the four alignment marks M is output as a group to the alignment detecting portion.

The alignment detecting unit sets, for example, the position of each alignment mark M, the size and orientation of the alignment mark M, and the distance between the alignment marks M, etc., based on the image data of each alignment mark M obtained by the strain sensor. The calculation is performed in comparison with the design value of the size, arrangement position, and the like of the alignment mark M, thereby generating strain information of the substrate G (position information of the alignment mark M). The strain information of the substrate G is, for example, the expansion and contraction direction of the substrate G and the amount of expansion and contraction of the substrate G. Specifically, the strain information of the substrate G is the expansion and contraction direction of the formation region S surrounded by the four alignment marks M, the amount of expansion and contraction, the rotation direction of the formation region S, the amount of rotation, and the enlargement of the formation region S from a predetermined size. Quantity or The amount of the reduction, the trapezoidal shape, and the like. The strain information of the substrate G is output to the image processing unit 36. Further, as described below, the image processing unit 36 creates correction data (correction exposure data) for exposure and correction data for correction (correction of the drip pattern data) based on the strain information of the substrate G.

In addition, the imaging method of the alignment mark M of the strain sensor is not particularly limited. For example, the strain sensor is moved two-dimensionally, and the alignment mark M of the fixed substrate G is imaged. The substrate G is moved, and the alignment mark M facing the substrate G is photographed.

The exposure portion 16 is for forming a fine pattern, for example, a pattern having a line width of less than 50 μm, and the exposure portion 16 can form the pattern forming region of the pattern to be less than the above line width.

Depending on the pattern forming method, the pattern to be formed is, for example, a wiring portion of an electronic circuit, a constituent portion of an electronic component such as a thin film transistor (hereinafter referred to as TFT), or a wiring of an electronic circuit, or a precursor of a constituent portion of an electronic component such as a TFT. .

The exposure unit 16 performs a process of converting the pattern formation region in which the pattern is formed by the pattern forming portion 18 into a lyophilic property in the first film 50 formed on the substrate G (hereinafter referred to simply as lyophilic treatment). ). An exposure unit (not shown) and a gas supply unit (not shown) are provided in the exposure unit 16. The exposure unit 16 is connected to the image processing unit 36.

In addition, "transformation into lyophilic property" means a state in which the contact angle of the droplet with respect to the first film 50 is relatively small. That is, it means a state in which the liquid repellency is different.

Specifically, the first inter-surface force is -50 Pa to -10 Pa, and the second inter-surface force is a negative value and is 90% or less of the first inter-surface force.

The exposure unit converts the first film 50 into lyophilic light by irradiating (exposing) the surface of the first film 50 of the substrate G, for example, on the pattern forming region where the pattern is formed. The light source in the exposure unit uses a light source having the same wavelength as the light source of the mark exposure portion, and for example, a light source that can irradiate light of an ultraviolet region having a wavelength of 300 (nm), 365 (nm), or 405 (nm) or the like can be used. Laser source.

The output of the ultraviolet light in the exposure unit is, for example, 1 to several tens (mJ/cm ² ). Further, depending on the composition of the substrate, there is a fear that the output of the ultraviolet light is high and deterioration occurs. Therefore, as long as it can be converted into lyophilicity, the output of ultraviolet light is preferably low.

Further, a recess of 10 nm or more may be formed on the first film 50 by the exposure unit. Thereby, the adhesion of the pattern to the first film is improved.

The exposure unit may use an exposure unit using a digital exposure type of laser light and an exposure unit of a mask exposure method.

In the digital exposure method, the pattern forming region of the pattern is irradiated with laser light by the pattern forming material output from the image processing unit 36, and the lyophilic treatment is performed to make the pattern forming region lyophilic.

In the case where the exposure unit uses the exposure unit of the digital exposure method, a serial method may be employed in which, for example, the exposure unit is scanned in a direction orthogonal to the conveyance direction D of the substrate G, for example, in the pattern formation region. The area where the exposure process can be realized by one scan in this direction performs the lyophilization process. One lyophilization treatment in the scanning direction After the completion, the substrate G is moved by a predetermined amount in the transport direction D, and the next region of the same pattern forming region is subjected to lyophilic treatment, and this operation is repeated to perform lyophilic treatment on the entire pattern forming region.

Further, a scanning optical portion (not shown) that scans the laser light may be provided in the exposure unit, and the laser beam may be scanned without scanning the exposure unit during the lyophilization process.

Further, the exposure unit may be an array type exposure unit that can irradiate a plurality of laser beams in a width direction orthogonal to the transport direction D of the substrate G.

The gas supply unit supplies a reaction gas for forming the pattern formation region of the substrate G to be lyophilic when necessary to irradiate light. The concentration (filling amount) of the reaction gas on the substrate G, the supply timing, and the like can be adjusted by the gas supply unit. As the reaction gas, for example, a gas containing oxygen or a gas containing nitrogen is used.

Further, if the first film 50 is lyophilized by merely irradiating ultraviolet light, it is not always necessary to provide a gas supply unit.

The pattern forming portion 18 forms a second film which is dried and becomes a pattern in the lyophilic pattern forming region.

The second film to be patterned is, for example, a wiring of an electronic circuit, a component of an electronic component such as a thin film transistor, or a wiring of an electronic circuit, or a precursor of a component of an electronic component such as a TFT. The second film will be described in detail below.

The pattern forming portion 18 is not particularly limited as long as the second film can be formed in the pattern forming region. For example, a printing method can be used. Inkjet method. When the printing method is used, the second film can be formed over the entire surface depending on the pattern formation region.

As the inkjet method, a piezoelectric type, a thermal method, or the like can be suitably used. Further, the ink jet head used in the ink jet method may use a serial type or a full line type.

When an inkjet method using an inkjet head is used, a pattern is formed by dropping ink droplets on the lyophilic pattern formation region based on the drip pattern data indicating the position of the lyophilic pattern formation region. . The size of the ink droplets dripped from the inkjet head is about 16 μm to 30 μm.

Further, in the case of using the ink jet method, since the ink droplets are dripped according to the drip pattern data, the drip position of the ink droplets can be easily changed by changing the drip pattern data.

The input unit 30 includes an input device (not shown) for the operator (user) to perform various inputs, and a display unit (not shown). The input device can use various forms of input devices such as a keyboard, a mouse, a touch panel, and a button.

The operator can input and memorize various processing conditions and operating conditions in the mark forming portion 12, the detecting portion 14, the exposure portion 16, and the pattern forming portion 18 in the memory portion 34 via the input portion 30, and can include the formation to be formed. The pattern information (design data) of the TFT including the position information (arrangement information) of each component of the TFT and the shape information of each component of the TFT, the position information of the alignment mark M of the substrate G, and the alignment mark Shape information such as the size of M is input and memorized in the memory unit 34.

In addition, the operator can know the target via the display portion of the input unit 30. The state of the forming portion 12, the detecting portion 14, the exposure portion 16, and the pattern forming portion 18 is recorded. The display unit can also function as a mechanism for displaying a warning such as an error message. Further, the display unit can also function as a notification unit that notifies the abnormality.

The drawing data creating unit 32 computer-aided design (Computer Aided Design) including shape information input from the input unit 30, for example, position information (arrangement information) including the respective components of the TFT, and the size of each component of the TFT. The CAD data is converted into data, and is converted into a data format usable when the exposure unit 16 irradiates the pattern forming region with UV light, and the pattern data, for example, the constituent portions of the TFT, is made available in the exposure unit 16. Exposure data. The exposure unit 16 irradiates the pattern formation region with UV light based on the exposure data.

The drawing data creating unit 32 converts, for example, the pattern data of the TFT described in the vector form (vector data) into a raster form (raster data). Further, if the input data format can be utilized by the exposure unit 16, it is not necessary to perform data conversion. At this time, the pattern data creation unit 32 does not perform data conversion, or the pattern data such as TFT is input to the image processing unit 36 without passing through the drawing data creation unit 32.

The memory unit 34 stores various information necessary for the pattern material, for example, the pattern of the TFT, in the forming device 10. For example, the information input to the forming device 10 via the input unit 30 includes pattern information of the TFT or the like. Further, the memory unit 34 can store the information on which the strain information including the substrate formed by the detecting unit 14 corresponds, or the information on which component of the TFT is formed, for example. Further, the memory unit 34 can form the structures of the device 10. The set conditions, processing conditions, etc. of the part are memorized.

The image processing unit 36 is connected to the detection unit 14, the exposure unit 16, the pattern forming unit 18, the drawing data creating unit 32, and the storage unit 34, and inputs the strain information of the substrate G created by the detecting unit 14.

The image processing unit 36 changes the formation position of the pattern to be formed on the first film 50 based on the strain information of the substrate G output from the detecting unit 14, and functions as an adjustment unit for pattern formation.

The image processing unit 36 compares the strain information of the substrate G with the allowable range, and when the strain of the substrate G exceeds the allowable range, the corrected exposure data for correcting the exposure data is created based on the strain information of the substrate G to change the UV light. Irradiation position.

When the exposure unit 16 is a digital exposure machine, the image processing unit 36 creates corrected exposure pattern data for correcting the pattern data indicating the position of the pattern formation region based on the strain information of the substrate G. The corrected exposure pattern data is output to the exposure unit 16, and the exposure unit 16 irradiates the pattern formation region with UV light based on the corrected exposure pattern data to make the pattern formation region lyophilic. Thereby, the appropriate position can be lyophilized.

Further, when the pattern forming unit 18 is an inkjet method, the image processing unit 36 creates a corrected drip pattern material for correcting the drip pattern data based on the strain information of the substrate G, and changes the change in the exposure position. The drop position of the ink drop. The corrected drip pattern data is output to the pattern forming portion 18, and the pattern forming portion 18 forms a second film in the lyophilic pattern forming region based on the corrected drip pattern data. Thereby, the second film can be formed at an appropriate position.

Further, the image processing unit 36 compares the strain information of the substrate G with the allowable range, and does not create the corrected exposure data when the strain of the substrate G is within the allowable range. Therefore, the exposure data input to the image processing unit 36 is directly output to the exposure unit 16 without being corrected. The exposure unit 16 irradiates the pattern formation region with UV light based on the exposure data.

Further, the forming apparatus 10 of the present embodiment is a roll-to-roll method, but is not limited to this embodiment. The forming apparatus 10 may be, for example, a one-piece type in which the substrate G is processed piece by piece.

In the present embodiment, for example, a pattern can be formed as shown in FIGS. 3(a) to 3(d) and 4(a) to 4(d).

As shown in FIGS. 3(a) and 4(a), a substrate on which the first film 50 is formed on the surface of the substrate G is prepared.

Then, according to the exposure data, the exposure portion 16 irradiates the pattern formation region 52 in which the fine pattern is formed on the surface 50a of the first film 50 as shown in FIGS. 3(b) and 4(b). The pattern forming region 52 has a width of less than 50 μm.

Next, as shown in FIGS. 3(c) and 4(c), the second film 54 is formed in the pattern forming region 52 by, for example, an inkjet method.

When the second film 54 is naturally dried, for example, the film thickness of the second film 54 is continuously reduced, and finally dried, and the pattern 56 can be formed as shown in FIGS. 3(d) and 4(d).

In the forming apparatus 10 of the present embodiment, for example, as shown in FIG. 5(a), a plurality of TFTs 60 are formed in one formation region S (see FIG. 2(a)).

The TFT 60 shown in FIG. 5(a) and FIG. 5(b) includes a gate electrode 62, The semiconductor layer 64, the source electrode 66a, and the drain electrode 66b are formed of the second film.

A film 80 is formed on the substrate G, and a TFT 60 is formed on the film 80. The film 80 is provided, for example, in order to obtain a predetermined flatness for forming the gate electrode 62, and to improve electrical insulation. This film 80 corresponds to the first film 50.

In the TFT 60, a gate electrode 62 is formed on the surface 80a of the film 80, and a gate insulating layer 82 is formed to cover the gate electrode 62 and the film 80. A semiconductor layer 64 that functions as an active layer is formed on the surface 82a of the gate insulating layer 82. On the semiconductor layer 64, a predetermined gap is formed as the channel region 68 to form a source electrode 66a and a drain electrode 66b. Further, a protective layer 84 is formed to cover the source electrode 66a and the drain electrode 66b.

Further, the gate insulating layer 82 and the protective layer 84 are formed by the same liquid-repellent agent as the film 80. The thickness of the gate insulating layer 82 and the protective layer 84 is, for example, the thickness (film thickness) of the film 80. It is preferably 0.001 μm to 1 μm, and more preferably 0.01 μm to 0.1 μm.

The TFT 60 is lyophilic to form a region where the gate electrode 62 is formed on the surface 80a of the film 80 by the exposure portion 16 of the forming device 10, and the gate is formed in the lyophilic formation region by the pattern forming portion 18. Electrode electrode 62.

Since the forming device 10 does not have the function of forming an insulating layer, the gate insulating layer 82 is formed using other devices. Similarly to the film 80, the gate insulating layer 82 is formed, for example, by a liquid-repellent agent having a hydrophilic-hydrophobic conversion function which changes in hydrophilicity and hydrophobicity by ultraviolet light.

Thereafter, on the surface 82a of the gate insulating layer 82, the formation region of the semiconductor layer 64 is lyophilized by the exposure portion 16 of the forming device 10, and the pattern forming portion 18 is lyophilized. The region forms a semiconductor layer 64.

Next, the formation region of the source electrode 66a and the drain electrode 66b is lyophilized by the exposure portion 16 of the forming device 10, and the source electrode 66a is formed in the lyophilic region by the pattern forming portion 18. With the drain electrode 66b.

Then, a protective layer 84 made of, for example, a resin is formed using another device. Since no member is formed on the protective layer 84, the protective layer 84 does not need to be constituted by a liquid-repellent such as the film 80 having a hydrophilic-hydrophobic conversion function which changes in hydrophilicity by ultraviolet light.

According to the pattern forming method of the present embodiment, since the length of the channel region does not change, unevenness in characteristics of the TFT can be suppressed.

In the present embodiment, the second film 54 which is a pattern has a viscosity of 3 mPa when the thickness is 0.1 μm. s below.

The inventors have found that by setting the viscosity of the second film 54 to a thickness of 0.1 μm, the repulsion time can be about 2 seconds as shown in Fig. 6 .

Thereby, after the second film 54 is formed, and before the second film 54 is dried, the second film 54 is repelled in the liquid-repellent region. Therefore, even if the second film 54 is formed in the non-pattern forming region (liquid-repellent region), it can be formed in the pattern forming region before being dried to form a pattern. In addition, FIG. 6 was obtained under the condition that the inter-surface force was -20 Pa and the thickness was 0.1 μm.

In the present embodiment, the second film 54 which is a pattern is made thick. The viscosity is 3 mPa at a degree of 0.1 μm. s or less, even a fine pattern, for example, a pattern having a line width of less than 50 μm, may be formed in a pattern forming region having a line width of less than 50 μm before the second film 54 is dried to form a pattern.

Further, it is preferable that the first inter-surface force acting between the non-pattern formation region and the first film 50 in the non-pattern formation region is -50 Pa to -10 Pa, and the second film 54 is in the pattern formation region and The first inter-surface force acting between the membranes 50 is 90% or less of the first inter-surface force, and the first inter-surface force and the second inter-surface force are both negative values.

More preferably, the second inter-surface force is 0 to 90% of the first inter-surface force and is a negative value.

The present inventors have found that the difference between the surface-to-surface force of the non-pattern forming region and the pattern forming region in the present invention is 10% or more of the inter-surface force of the non-pattern forming region, so that the non-pattern forming region can be formed. The second film is repelled from the pattern forming region. That is, it was found that the second film of the non-pattern forming region can be moved toward the pattern forming region side.

Since the difference in the inter-surface force may be about 10% of the inter-surface force in the non-pattern forming region, the pattern forming region does not have to be lyophilized, and the non-pattern forming region and the pattern forming region may be in a liquid-repellent state. The pattern can be formed by changing the degree of liquid repellency of the non-pattern forming region and the pattern forming region. Therefore, when the pattern formation region is formed, the energy applied to the first film 50 can be reduced, and adverse effects such as deterioration of the first film 50 other than lyophilization can be suppressed.

In the present invention, regarding the non-pattern forming region and the pattern forming region The difference in the surface force of the domains, etc., was analyzed and verified as follows.

Specifically, as shown in FIG. 7( a ), the state of the initial surface Sc of the second film is analyzed after a predetermined period of time has elapsed. Here, the initial surface refers to the surface at the time of forming the second film.

The analysis model 100 shown in Fig. 7(b) is used in the analysis of Fig. 7(a). In the analysis model 100, the surface of the support 102 corresponding to the first film 50 is divided into the lyophilic portion 104 and the liquid-repellent portion 106, and a liquid having a uniform thickness corresponding to the second film 54 is formed on the support 102. Membrane 108. Further, the symbol B indicates the boundary between the lyophilic portion 104 and the liquid-repellent portion 106.

For example, when the liquid film 108 is repelled in the liquid-repellent portion 106, the liquid film 108 flows, and the state of the liquid film 109 changes as shown in Fig. 7(c). In this manner, the flow of the liquid film 108 generated by the lyophilic portion 104 and the liquid-repellent portion 106 is analyzed by simulation.

Further, in the analysis model 100 shown in FIG. 7(b), the width direction L is set to 1 pitch from the end of the lyophilic portion 104 to the end of the liquid-repellent portion 106. 1 pitch is 50 μm.

When the flow of the liquid film 108 is analyzed, the following formulas 1 to 3 are combined to form a fourth-order partial differential equation of the surface position h of the liquid film 108. The partial differential equation is numerically solved under, for example, a periodic boundary condition, whereby thin film formation and repulsion due to the inter-surface force in the initial state of the flat liquid film can be obtained. In addition, the following formula 1 represents the temporal change of the liquid surface of the liquid film 108, and the following formula 2 shows the relationship between the film thickness change and the flow rate shown in FIG.

[Number 1]

Here, the inter-surface force 求出 can be obtained by the following formula 4. Further, a _H of the above formula 2 and the following formula 4 is a Hamaker constant. According to A. Sharma, G. Reiter (1996), the Hamak constant is represented by the following formula 5.

The d ₀ of the above formula 5 is a cutoff distance, and is assigned 0.158 nm. S ^{d is} represented by the following formula 6, and γ _L ^d and γ _S ^{d of the} following formula 6 can be obtained by measuring the contact angle.

Here, as shown in FIG. 9, there are droplets 122 on the surface of the solid 120, and in the case where the droplets 122 are in equilibrium, the surface tension (γ _S ) of the solid, the interfacial tension between the solid and the liquid (γ _SL ), The surface tension (γ _L ) of the liquid has a relationship of Young's formula shown by the following formula 7. In addition, θ is a contact angle.

[Number 7] γ _L . Cos θ = γ _S - γ _SL

According to DKOwens and RC Wendt, J. Appl. Polym. Sci., 13, 1741 (1969), the following formula 8 can be obtained. By obtaining the γ _L ^d and γ _S ^d according to the following Equation 8, and measuring the contact angle θ, the Hammer constant a _H represented by the above Equation 5 can be obtained.

γ _L ^d : liquid side dispersion component

γ _S ^d : solid side dispersion component

γ _L ^h : liquid side non-dispersive component

γ _S ^h : solid side non-dispersive component

In the numerical analysis, the calculation area was set to 1/2 pitch, and the end portion was provided at the center of the liquid-repellent portion 106. In other words, the analysis range is defined as a range from the center of the lyophilic portion 104 in the width direction L to the center of the liquid-repellent portion 106 centering on the boundary B in the analysis model 100.

The computational algorithm uses the difference method (Time Euler Method). The third derivative is set to 7 points difference, and the first order differential coefficient is set to 5 points difference. Set the area division to 40 divisions.

In addition, the basic calculation condition is to set the viscosity to 1 mPa. s~10 mPa. s, the density was set to 1000 kg/m ³ , the surface tension was set to 20 mN/m, the film thickness was set to 0.1 μm, and the calculation area was set to 25 μm. Further, regarding the flow of the liquid film 108, the change from the initial state to 2 seconds was calculated.

In the present embodiment, when solving the above partial differential equation, for example, the above conditions are used. Further, the conditions for solving the above partial differential equation are not limited to the above conditions.

An example of numerical analysis results is shown in Figs. 10(a) to 10(c). The symbol Sc shown in Fig. 10(a) indicates the initial surface. In Figs. 10(a) and 10(b), the right side of the boundary B with respect to the lyophilic portion 104 and the liquid-repellent portion 106 is the liquid-repellent portion 106. The left side is the lyophilic portion 104. In addition, the symbol w represents the calculated temporal direction. Further, Fig. 10(a) shows changes in the liquid surface position from the state of the initial surface Sc to 2 seconds, and Fig. 10(b) shows changes in the inter-surface force from the initial state to 2 seconds. The line in the graph of Fig. 10(a) indicates the amount of displacement at equal intervals from time 0.

As shown in Fig. 10 (a), the position of the liquid surface changes continuously with time from the initial surface, and the film thickness on the right side (the liquid-repellent portion 106) decreases, and the film thickness on the left side (the lyophilic portion 104) increases. The analysis model 100a shown in Fig. 10(c) shows the state of the final liquid film 109. Further, as shown in FIG. 10(b), the inter-surface force increases as the surface-to-surface force on the liquid-repellent portion 106 side increases with time. Although the change in the inter-surface force is generated symmetrically with respect to the boundary B between the lyophilic portion 104 and the liquid-repellent portion 106, the inter-surface force on the liquid-repellent portion 106 side is increased to be generated from the liquid-repellent portion 106 to the lyophilic portion 104. The flow.

Further, an example of the result of the numerical analysis when the Hammer constant a _{H is} changed is shown in FIGS. 11(a) to 11(c).

In addition, in Fig. 11 (a) to Fig. 11 (c), relative to the lyophilic portion The right side of the boundary B between the 104 and the liquid-repellent portion 106 is the liquid-repellent portion 106, and the left side is the lyophilic portion 104. Symbol B indicates the boundary between the lyophilic portion 104 and the liquid-repellent portion 106, the symbol Sc indicates the initial surface, and the symbol w indicates the calculated temporal direction. Further, the position from the initial surface Sc to the position of the liquid surface after 2 seconds was calculated.

The results of the numerical analysis are shown in Figs. 11(a) to 11(c). Further, in Fig. 11(a), the Hammer constant a _H is -1.6 × 10 ^-19 (Nm), and in Fig. 11 (b), the Hammer constant a _H is -1.9 × 10 ^-19 (Nm), Fig. 11 (c) The medium-hamak constant a _H is -2.2 × 10 ^-19 (Nm).

The lines in the graphs of Figs. 11(a) to 11(c) indicate the amounts of displacement at equal intervals from time 0.

As shown in Fig. 11 (a) to Fig. 11 (c), according to numerical analysis, when the absolute value of the Hammer constant a _H is increased, changes such as non-rejection, neutral stability, and repulsion occur.

Further, even in the non-repellent state of Fig. 11(a), the liquid level changes, the film thickness on the side of the lyophilic portion 104 increases, the film thickness of the liquid-repellent portion 106 decreases, and the liquid surface is stabilized in a curved state.

Further, as shown in Fig. 11(a), as the time passes, the liquid surface is uneven, but the change gradually becomes slow and closes to a fixed shape. When the displacement amount of the rightmost end (corresponding to the center of the liquid-repellent portion 106) of FIG. 11(a) is plotted against the time, the value is asymptotically fixed, so that a downwardly convex curve or a displacement amount is formed. The time differential is close to zero. This condition is called non-rejection.

Further, as described above, when the displacement amount of the rightmost end (the portion corresponding to the center of the liquid-repellent portion 106) of FIG. 11(b) is plotted with respect to the time, Then, the amount of displacement at the right end is monotonously decreasing as time passes. There is always a slight deviation between the surface tension and the surface force, and although the liquid film is thinned, no cracking occurs. This condition is called neutral stability.

Further, as described above, when the displacement amount of the rightmost end (corresponding to the center of the liquid-repellent portion 106) of FIG. 11(c) is plotted against the time, the thinning progresses rapidly, so that the time differential of the acceleration displacement amount is changed. Large and the film thickness reaches zero. This condition is referred to as exclusion.

In this way, non-rejection, neutral stability, and repulsion can be performed by plotting the displacement amount of the rightmost end (the portion corresponding to the center of the liquid-repellent portion 106) with respect to the time, and determining the temporal change of the displacement amount at the rightmost end.

Next, the analysis model 100 shown in FIG. 7(b) and another analysis model in which the arrangement positions of the liquid-repellent portion 106 and the lyophilic portion 104 in the analysis model 100 shown in FIG. 7(b) are exchanged are not shown (not shown). The analysis is performed by changing the inter-surface force to determine which of the non-repellent state, the neutral stable state, and the repulsion state as shown in FIGS. 11(a) to 11(c) above. The analysis results are shown in Fig. 12. At this time, the analysis is also performed under the condition of solving the above partial differential equation, and the viscosity is also set to 1 mPa. s~10 mPa. s.

As shown in Fig. 12, the region α _{1 which} is higher than the oblique line α is a case where the right side is lyophilic and the right side is repelled. For example, it corresponds to the analysis model 100 shown in FIG. 7(a). On the other hand, the region α _{2 which} is lower than the oblique line α is a case where the left side is lyophilic and the left side is repelled. For example, it is equivalent to the other analysis models described above.

Even if it is non-repulsive, it is somewhat thinned, so it is balanced with the surface tension, so even if it is stable, the surface of the liquid film is not completely flat. In the non-rejection of the region α ₁ , for example, as in the analysis model 110 shown in FIG. 13( a ), the liquid film 109 on the side of the lyophilic portion 104 is thickened, and the thickness of the liquid film 109 on the side of the liquid-repellent portion 106 is reduced. The liquid dispensing portion 106 is not exposed.

Further, when using an analytical model to represent the α ₁ rejection region, like the example in FIG. 13 112, a portion of the liquid-repellent portion 106 (b), the model is exposed, the thickness of the film 109 lyophilic portion 104 is thickened .

In the analysis model 110 and the analysis model 112, the same components as those of the analysis model 100 are denoted by the same reference numerals, and detailed description thereof will be omitted.

As shown in Fig. 12, in the region α ₁ and the region α ₂ , the inter-surface force is in the range of -50 Pa to -10 Pa, and the inter-surface force of the portion where the inter-surface force is high is defined by the difference in the inter-surface force. More than 10% of them become exclusion. In other words, the second film in the non-pattern forming region can be moved toward the pattern forming region side by defining the inter-surface force.

Further, by changing the viscosity of the liquid film 108 and using the analysis model shown in FIG. 7(b) above, the partial differential equation is solved under the above conditions, and the film thickness of the liquid film 108 and the surface inter-force force which becomes the repulsion state are investigated. Relationship. Therefore, a detailed explanation about the analysis is omitted. Fig. 14 shows the relationship between the film thickness of the liquid film 108 and the surface-to-surface force which becomes a repulsion state.

In Fig. 14, the straight line F ₁ to the straight line F ₃ indicate the repulsion and non-repulsive boundaries at the respective viscosities, and the case where the neutral state is obtained in Fig. 12 is plotted.

In addition, the inter-surface force which will become a neutral state, that is, the inter-surface force of the repulsion and the non-repulsive boundary is referred to as a defined inter-surface force.

In FIG. 14, the region β ₁ on the upper side of the straight line F ₁ to the straight line F ₃ is a repulsive region, and the region β ₂ on the lower side of the straight line F ₁ to the straight line F _{3 is} a non-repulsive region.

As shown in Fig. 14, as long as the film has a low viscosity (1 mPa.s, 3 mPa.s) in the range of 0.1 μm to 0.3 μm, the actual interfacial force (-50 Pa to -10 Pa) is obtained. Reproduction occurs.

According to the above, it can also be seen that the surface interfacial force (-50 Pa~-10 Pa) specified in the present invention has a viscosity of 3 mPa. The low viscosity of s produces rejection. Further, as shown in FIG. 6, since the film is repelled in about 2 seconds, the second film in the non-pattern forming region can be moved to the pattern forming region side before the liquid film is dried.

In the following, the constituents of the electronic component such as the wiring for forming the electronic circuit, the thin film transistor, or the wiring of the electronic circuit, and the material of the second film used for the precursor of the electronic component such as the TFT are specifically described.

The conductive material of the second film contains conductive fine particles, and the particle diameter of the conductive fine particles is preferably 1 nm or more and 100 nm or less. This is because if the particle diameter of the conductive fine particles is larger than 100 nm, the nozzle is likely to be clogged, and the ejection by the inkjet method becomes difficult. Further, when the particle diameter of the conductive fine particles is less than 1 nm, the volume ratio of the coating agent to the conductive fine particles becomes large, and the ratio of the organic substances in the obtained film becomes excessive.

The dispersoid concentration is 1% by mass or more and 80% by mass or less, and can be adjusted according to the desired film thickness of the conductive film. When the dispersoid concentration exceeds 80% by mass, aggregation tends to occur, and it is difficult to obtain a uniform film.

The surface tension of the dispersion of the conductive fine particles is preferably in the range of 20 mN/m or more and 70 mN/m or less. The reason is that when the liquid is ejected by the inkjet method, if the surface tension is less than 20 mN/m, the ink set The wettability of the object on the nozzle surface is increased, so that flight bending is likely to occur. When the thickness exceeds 70 mN/m, the shape of the meniscus at the tip of the nozzle is unstable, so that the control of the discharge amount and the discharge timing becomes difficult.

The conductive material contains, for example, silver fine particles. As the metal fine particles other than silver, for example, any of gold, platinum, copper, palladium, rhodium, iridium, ruthenium, iridium, iron, tin, zinc, cobalt, nickel, chromium, titanium, rhenium, tungsten, or indium may be used. One, or an alloy of any two or more combinations may be used. In addition, silver halide can also be used. Among them, silver nanoparticles are preferred. In addition to the metal fine particles, a conductive polymer, fine particles of a superconductor, or the like can be used.

Examples of the coating material applied to the surface of the conductive fine particles include an organic solvent such as xylene or toluene, and citric acid.

The dispersion medium to be used is not particularly limited as long as it is a dispersion medium in which the conductive fine particles are dispersed and does not cause aggregation. Examples of the dispersion medium include alcohols such as methanol, ethanol, propanol and butanol. Alkane, n-octane, decane, toluene, xylene, cymene, durene, hydrazine, dipentene, tetrahydronaphthalene, decahydronaphthalene a hydrocarbon compound such as cyclohexylbenzene, or ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol An ether compound such as alcohol methyl ether, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether or p-dioxane, and propylene carbonate Or a polar compound such as γ-butyrolactone, N-methyl-2-pyrrolidone, dimethylformamide, dimethyl hydrazine or cyclohexanone. In these dispersion media, the dispersion of fine particles Water, an alcohol, a hydrocarbon compound, and an ether compound are preferable in terms of the stability of the liquid and the dispersion in the inkjet method, and a more preferable dispersion medium is water or a hydrocarbon compound. . These dispersion media may be used singly or in the form of a mixture of two or more.

Further, as the binder (additive), one or a combination of two or more of them may be used: an alkyd resin, a modified alkyd resin, a modified epoxy resin, a urethane oil, an amine group. Formate resin, rosin resin, rosin oil, maleic acid resin, maleic anhydride resin, polybutene resin, diallyl phthalate resin, polyester resin, polyester oligomer , mineral oil, vegetable oil, urethane oligomer, copolymer of (meth)allyl ether and maleic anhydride (other monomers (such as styrene, etc.) may also be added to the copolymer as a total Polymerization component) and the like. Further, in the metal paste of the present invention, a dispersing agent, a wetting agent, a tackifier, a leveling agent, a scum preventing agent, and a gelatinizing agent may be appropriately selected and added. ), silicon oil, silicon resin, antifoaming agent, plasticizer, etc. as additives.

Further, a normal paraffin wax, a paraffin wax, a cycloalkane or an alkylbenzene may also be used as the solvent.

Further, as the conductive material, a conductive organic material may be used. For example, a polymer-based soluble material such as polyaniline, polythiophene or polyphenylenevinylene may be contained.

It is also possible to contain an organic metal compound instead of metal fine particles. The organometallic compound referred to herein is a compound which precipitates as a metal by decomposition by heating. Such organometallic compounds are: chlorine (triethylphosphine) gold, chlorine (trimethyl) Phosphine) gold, chlorine (triphenylphosphine) gold, silver 2,4-glutarate complex, trimethylphosphine (hexafluoroacetamidine) silver complex, copper cyclooctane hexafluoroglutarate A diene complex or the like.

Other examples of the conductive fine particles include a resist, an acrylic resin as a linear insulating material, and a decane compound which becomes ruthenium after heating (for example, trioxane, pentadecane, cyclotrimethane, 1,1). '-bicyclotetraoxane, etc.), metal complexes, and the like. These can be dispersed in the liquid in the form of fine particles, and can also be dissolved and present in the liquid.

Further, as the liquid containing the conductive organic material, an aqueous solution of polyethylene dioxythiophene (PEDOT)/polystyrene sulfonic acid (PPS), which is a conductive polymer, may be used. Polyaniline (PANI), an aqueous solution of a conductive polymer in which PESOT (polystyrenesulfonic acid) is doped with PEDOT (polyethylenedioxythiophene).

As a material for constituting the semiconductor layer 64, an inorganic semiconductor such as CdSe, CdTe, GaAs, InP, Si, Ge, carbon nanotube, fluorenone or ZnO; pentacene, hydrazine, Organic low molecular weight such as tetracene, phthalocyanine, polyacetylene conductive polymer, poly-para-phenylene and its derivatives, polyphenylene acetylene and its derivatives (polyphenylene) is a conductive polymer, polypyrrole and its derivatives, polythiophene and its derivatives, heterocyclic conductive polymers such as polyfuran and its derivatives, and ionic conductive polymers such as polyaniline and its derivatives. And other organic semiconductors.

In addition, the gate insulating layer 82 is not made to have the same composition as the film 80. In the case of the material having a large electrical insulation which constitutes the interlayer insulating film such as the protective layer 84, the following materials can be used. Specifically, examples of the organic material include polyimine, polyamidimide, epoxy resin, silsesquioxane, polyvinylphenol, polycarbonate, fluorine resin, and polypair. Toluene (poly paraxylylene), polyvinyl butyral, etc., polyvinyl phenol and polyvinyl alcohol can also be used after crosslinking by a suitable crosslinking agent. For example, polyfluorinated xylene, fluorinated polyimine, fluorinated polyarylene ether, polytetrafluoroethylene, polychlorotrifluoroethylene, poly(α,α,α',α'-tetrafluoro-p-pair Fluorinated polymers such as toluene), poly(ethylene/tetrafluoroethylene), poly(ethylene/chlorotrifluoroethylene), fluorinated ethylene/propylene copolymer, polyolefin-based polymers, and polystyrene, poly(α) -methylstyrene), poly(α-vinylnaphthalene), polyvinyltoluene, polybutadiene, polyisoprene, poly(4-methyl-1-pentene), poly(2-methyl) -1,3-butadiene), parylene, poly[1,1-(2-methylpropane) bis(4-phenyl)carbonate], polycyclohexyl methacrylate, polychlorinated Styrene, poly(2,6-dimethyl-1,4-phenylene ether), polyvinylcyclohexane, polyarylene ether, polyphenylene, polystyrene-co-alpha-a Poly(styrene-co-α-methylstyrene), ethylene/ethyl acrylate copolymer, poly(styrene/butadiene), poly(styrene/2,4-dimethylstyrene), etc. .

Examples of the porous insulating film include a phosphonium phosphate glass in which phosphorus is added to cerium oxide, a borophosphonite glass in which phosphorus and boron are added to cerium oxide, a polyimine, and a polyacrylic acid. A porous insulating film such as a system. Further, a porous insulating film having a siloxane chain such as a porous methyl sesquiterpene oxide, a porous hydrogen sesquioxane or a porous methyl hydrogen sesquioxane can be formed.

Next, the material used for the first film 50 will be described.

For example, a material containing a photocatalyst can be used for the first film 50. At this time, fluorine is contained in the photocatalyst-containing material, and when the first film (including the photocatalyst layer) including the photocatalyst-containing material is irradiated with energy, the fluorine content on the surface of the photocatalyst-containing material is caused by the action of the photocatalyst. Lower than before energy irradiation. Further, the photocatalyst-containing layer may contain a decomposing substance which can be decomposed by the action of a photocatalyst caused by energy irradiation, thereby changing the wettability on the photocatalyst-containing layer.

Hereinafter, photocatalysts, binders, and other components of the photocatalyst-containing material will be described.

First, the photocatalyst will be described. Examples of the photocatalyst used in the present embodiment include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), barium titanate (SrTiO ₃ ), and tungsten oxide (WO). ₃ ), bismuth oxide (Bi ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ) may be used alone or in combination of two or more kinds from the photocatalysts.

In particular, titanium dioxide has a high band gap energy, is chemically stable, is non-toxic, and is easy to obtain, and thus can be preferably used. The titanium dioxide has an anatase type and a rutile type, and any of the present embodiment may be used, and preferably an anatase type titanium oxide. The anatase type titanium dioxide has an excitation wavelength of 380 nm or less.

As such an anatase type titanium dioxide, for example, an anatase type titanium dioxide sol which is desulfated with hydrochloric acid (STS-02 (average particle diameter: 7 nm) manufactured by Ishihara Sangyo Co., Ltd., and ST-made by Ishihara Sangyo Co., Ltd.) K01), nitric acid decondensed anatase type titanium dioxide sol (Nissan The company produces TA-15 (average particle size 12 nm) and so on.

The smaller the particle diameter of the photocatalyst, the more effective the photocatalytic reaction can be produced. Therefore, it is preferable that the average particle diameter is 50 nm or less, and it is preferable to use a photocatalyst of 20 nm or less.

The photocatalyst in the photocatalyst-containing layer is contained in an amount of 5 wt% to 60 wt%, preferably in the range of 20 wt% to 40 wt%. Further, the thickness of the photocatalyst-containing layer is preferably in the range of 0.05 μm to 10 μm.

Next, the adhesive will be described. The change in wettability on the photocatalyst-containing layer can be classified into three types: the first form is caused by the photocatalyst acting on the binder itself, and the second form is produced by including the photocatalyst layer containing the decomposed substance. The decomposition substance is decomposed by the action of the photocatalyst caused by the energy irradiation, thereby changing the wettability on the photocatalyst-containing layer; and the third aspect is changed by combining the forms. The adhesive used in the first embodiment and the third embodiment must have a function of changing the wettability on the photocatalyst-containing layer by the action of the photocatalyst, and in the second embodiment, such a function is not particularly required.

As the binder used in the second embodiment, the binder having a function of changing the wettability on the photocatalyst layer by the action of the photocatalyst is not particularly required, as long as the main skeleton has no light excitation by the photocatalyst. The high binding energy of decomposition is not particularly limited. Specifically, a polyoxyalkylene which does not contain an organic substituent or contains a small amount of an organic substituent which can be hydrolyzed or polycondensed by tetramethoxynonane, tetraethoxydecane or the like can be mentioned. And get.

In the case of using such a binder, it is necessary to contain a decomposing substance described later as an additive in the photocatalyst-containing layer, and the decomposed substance can be decomposed by the action of a photocatalyst caused by energy irradiation, thereby allowing the photocatalyst-containing layer to be decomposed. The wettability changes.

Next, a binder which is required to change the wettability on the photocatalyst layer by the action of the photocatalyst, which is used in the first embodiment and the third embodiment, will be described. As such a binder, a binder having a high binding energy which does not decompose by photoexcitation of the photocatalyst and which contains an organic substituent which can be decomposed by the action of a photocatalyst is preferable as the binder. An organopolysiloxane which exhibits high strength by hydrolysis or polycondensation of chlorine or alkoxysilane or the like by a sol-gel reaction, and organically obtained by crosslinking a reactive anthrone having excellent water repellency and oil repellency. Polyoxane and the like.

The organopolysiloxane having a large strength obtained by hydrolyzing or polycondensing chlorine or an alkoxysilane or the like by a sol-gel reaction or the like is preferably a compound of the formula: Y _n SiX _(4-n) ( Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amine group, a phenyl group or an epoxy group, and X represents an alkoxy group, an ethyl group or a halogen. n is an integer of 0 to 3) One or two or more kinds of hydrolyzed condensates or organohydrogenated alkane of a cohydrolyzed condensate. Further, the carbon number of the group represented by Y herein is preferably in the range of 1 to 20, and the alkoxy group represented by X is preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group. .

In addition, as the binder, a polyfluorooxane containing a fluoroalkyl group is particularly preferably used, and specific examples thereof include one or two or more kinds of hydrolyzed condensates and cohydrolyzed condensates of the following fluoroalkyl decanes. A binder which is well known as a fluorine-based decane coupling agent can be usually used.

CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ; (CF ₃ ) ₂ CF(CF ₂ ) ₄ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ; (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ; (CF ₃ ) ₂ CF(CF ₂ ) ₈ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ; CF ₃ (C ₆ H ₄ )C ₂ H ₄ Si(OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₃ (C ₆ H ₄ )C ₂ H ₄ Si(OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₅ (C ₆ H ₄ )C ₂ H ₄ Si( OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₇ (C ₆ H ₄ ) C ₂ H ₄ Si(OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiCH ₃ ( OCH ₃ ) ₂ ; (CF ₃ ) ₂ CF(CF ₂ ) ₄ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ; (CF ₃ ) ₂ CF(CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ (CF ₃ ) ₂ CF(CF ₂ ) ₈ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (C ₆ H ₄ )C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₃ (C ₆ H ₄ )C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₅ (C ₆ H ₄ )C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF _{2 7} (C ₆ H ₄ )C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₇ SO ₂ N(C ₂ H ₅ )C ₂ H ₄ CH ₂ Si(OCH ₃ ) ₃

By using the fluoroalkyl group-containing polyoxyalkylene as the binder, the liquid repellency of the non-irradiated portion containing the photocatalyst layer is greatly improved, and the function of inhibiting the adhesion of the metal paste is exhibited.

In addition, examples of the reactive anthrone having excellent water repellency and oil repellency include a compound having a skeleton represented by the following formula.

Wherein n is an integer of 2 or more, and R ¹ and R ² are each a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, which is a molar ratio as a whole. Less than 40% of the groups are a vinyl group, a phenyl group, or a halogenated phenyl group. Further, a compound in which R ¹ and R ² are a methyl group has the smallest surface energy, and is preferably a methyl group of 60% or more in terms of a molar ratio. Further, in the molecular chain, at least one or more reactive groups such as a hydroxyl group are present at the chain end or the side chain.

Further, a stable organic ruthenium compound such as dimethyl polysiloxane or a non-crosslinking reaction may be mixed with the above-mentioned organopolyoxane in a binder.

Next, the decomposition of the substance will be described.

In the second aspect and the third aspect, it is necessary to further change the wettability on the photocatalyst-containing layer by further including a photocatalyst layer containing a decomposing substance which can be photocatalyst caused by energy irradiation. Decomposed by action. That is, in the case where the binder itself does not have a function of changing the wettability on the photocatalyst-containing layer, and when such a function is insufficient, it is necessary to add the decomposed substance as described above to produce the photocatalyst-containing layer. Changes in wettability or assist in such changes.

Examples of such a decomposing substance include a surfactant which has a function of being decomposed by the action of a photocatalyst and which has a function of changing the wettability of the surface of the photocatalyst-containing layer by decomposition. Specifically, a hydrocarbon system such as NIKKOL BL, NIKKOL BC, NIKKOL BO, and NIKKOL BB manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, ZONYL FSO, and Asahi Glass manufactured by DuPont Co., Ltd. SURFLON S-141, SURFLON 145 manufactured by the company, MEGAFAC F-141, MEGAFAC 144 manufactured by Dainippon Ink and Chemicals Co., Ltd., FTERGENT F manufactured by NEOS -200, FTERGENT F251, UNIDYNE DS-401 manufactured by Daikin Industries Co., Ltd., UNIDYNE 402, FLUORAD FC-170, FLUORAD 176, etc. manufactured by 3M Co., Ltd. As the active agent, a cationic surfactant, an anionic surfactant, or an amphoteric surfactant may also be used.

In addition, in addition to the surfactant, polyvinyl alcohol, Unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, polychlorinated Ethylene, polyamide, polyimine, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, nylon, polyester, polybutadiene, Oligomers such as polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, polymers, and the like.

Further, it is preferable that the photocatalyst-containing layer is formed such that the photocatalyst-containing layer contains fluorine, and when the photocatalyst-containing layer is irradiated with energy, the fluorine content on the surface of the photocatalyst-containing layer is compared with energy by the action of the photocatalyst. Reduce before irradiation.

The content of fluorine contained in the fluorine-containing photocatalyst-containing layer as described above is preferably a lyophilic property having a low fluorine content formed by irradiation with energy when the fluorine content of the portion not irradiated with energy is 100. The fluorine content in the region is 10 or less, preferably 5 or less, and particularly preferably 1 or less.

Further, as the first film 50, a self-assembled film containing an organic molecular film or the like can also be used. The organic molecular film for treating the surface of the substrate has a functional group capable of bonding to the substrate on one end side, and a functional group for modifying the surface property of the substrate to liquid repellency or the like (control surface energy) on the other end side, and A carbon chain having a linear or partially branched carbon chain connecting the functional groups, and the organic molecular film is bonded to the substrate to form a molecular film, for example, a monomolecular film.

The self-assembled film is a film formed by aligning a compound, and the compound contains a bonding functional group capable of reacting with a constituent atom such as a substrate or a base layer, and a linear molecule other than the functional group, and the straight chain molecule Phase of chain molecules Interaction has a very high degree of alignment. Since the self-assembled film is a film formed by aligning a single molecule, the film thickness can be made extremely thin, and a film having a uniform molecular level can be formed. That is, since the same molecule is located on the surface of the film, it is possible to impart uniform and excellent liquid repellency to the surface of the film.

For example, when a fluoroalkyl decane is used as the compound having high alignment property, each compound is formed so as to align the fluoroalkyl group on the surface of the film to form a self-assembled film, so that uniform liquid repellency can be imparted to the surface of the film.

Examples of the compound which forms the self-assembled film include heptadecafluoro-1,1,2,2-tetrahydroindenyltriethoxydecane, heptafluoro-1,1,2,2-tetrahydroindenyl group. Trimethoxydecane, heptadecafluoro-1,1,2,2-tetrahydroindenyl trichlorodecane, tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxydecane, tridecafluoro a fluoroalkyl group such as -1,1,2,2-tetrahydrooctyltrimethoxydecane, tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorodecane or trifluoropropyltrimethoxydecane Decane (hereinafter referred to as "FAS"). When these compounds are used, it is also preferred to use one compound alone, but it is not limited if the two or more compounds are used in combination without impairing the intended object of the present invention. Further, in the present invention, when the above-described FAS is used as the compound for forming a self-assembled film, it is preferable to provide adhesion to the substrate and good liquid repellency.

FAS can usually be represented by the structural formula R _n SiX _(4-n) . Here, n represents an integer of 1 or more and 3 or less, and X is a hydrolyzable group such as a methoxy group, an ethoxy group or a halogen atom. Further, R is a fluoroalkyl group and has (CF ₃ )(CF ₂ )x(CH ₂ )y (where x represents an integer of 0 or more and 10 or less, and y represents an integer of 0 or more and 4 or less). When a plurality of R or X bonds are bonded to Si, R or X may be all the same or different. The hydrolyzable group represented by X can form a stanol by hydrolysis, reacts with a hydroxyl group of the substrate substrate, and bonds to the substrate with a decane bond. On the other hand, since R has a fluorine group such as (CF ₃ ) on the surface, the surface of the substrate such as a substrate can be modified to a surface which is not wetted (low surface energy).

The self-assembled film containing an organic molecular film or the like can be placed in the same sealed container as the substrate and placed on the substrate at room temperature for about 2 days to 3 days. Further, by maintaining the entire sealed container at 100 ° C, the above-mentioned self-assembled film can be formed on the substrate for about 3 hours. The above method is a method of forming a self-assembled film from a gas phase, but it is also possible to form a self-assembled film from a liquid phase. For example, the substrate is immersed in a solution containing a raw material compound, washed, and dried to obtain a self-assembled film on the substrate.

Further, it is preferred that the surface of the substrate is irradiated with ultraviolet light or washed with a solvent to perform pretreatment before forming the self-assembled film.

The first film 50 may include a material whose critical surface tension is largely changed by imparting energy. Such a material may be exemplified by a polymer material having a hydrophobic group in a side chain, and the polymer material may be exemplified by a main chain having a skeleton such as polythenimine or (meth) acrylate, or via a bonding group. A material having a side chain having a hydrophobic group bonded thereto.

Examples of the hydrophobic group include a group having a terminal structure of -CF ₂ CH ₃ , -CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , -CF ₂ H, -CFH ₂ or the like. In order to make the molecular chains easy to align with each other, a group having a long carbon chain length is preferable, and a group having a carbon number of 4 or more is more preferable. Further, a polyfluoroalkyl group in which two or more hydrogen atoms of an alkyl group are substituted by a fluorine atom (hereinafter referred to as "Rf group") is preferable, and an Rf group having a carbon number of 4 to 20 is particularly preferable, and a carbon number is particularly preferable. Rf base of ~12. The Rf group has a linear structure or a branched structure, and is preferably a linear structure. Further, the hydrophobic group is preferably a perfluoroalkyl group in which all of the hydrogen atoms of the alkyl group are substantially substituted by a fluorine atom. The perfluoroalkyl group is preferably a group represented by C _n F _2n+1 - (where n is an integer of 4 to 16), and particularly preferably a group in which n is an integer of 6 to 12. The perfluoroalkyl group may be a linear structure or a branched structure, and is preferably a linear structure.

The above material has a property of becoming lyophilic when it is in contact with a liquid or a solid in a heated state, and becomes lyophobic when heated in air. This property is known in detail in Japanese Patent No. 2796575 and the like. That is, the above materials can change the critical surface tension by imparting thermal energy (selection of the contact medium).

Further, examples of the hydrophobic group include a group having a terminal structure such as -CH ₂ CH ₃ , -CH(CH ₃ ) ₂ or -C(CH ₃ ) ₃ which does not contain a fluorine atom. At this time, in order to make the molecular chains easy to align with each other, a group having a long carbon chain length is preferable, and a group having a carbon number of 4 or more is more preferable. The hydrophobic group may be a linear structure or a branched structure, and is preferably a linear structure. The above alkyl group may further 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 or alkoxy group having 1 to 12 carbon atoms. It is considered that the more the bonding sites of R, the lower the surface energy (the smaller the critical surface tension), and the lyophobic property. It is estimated that a part of the bonds are cut by ultraviolet irradiation or the like, or the alignment state changes, and the critical surface tension increases to become lyophilic.

Other than this, the hydrophobic group may also be an organic fluorenyl group which can be represented by -SiR ₃ . Here, R is an organic group containing a decane bond.

Among the above hydrophobic groups, particularly the hydrophobic group having a methylene group, the bonding energy of C-H (338 kJ/mol) and fluorine The C-F bond (552 kJ/mol) of the material and the Si-C bond (451 kJ/mol) of the anthrone-based material are small. Therefore, a part of the bonds can be easily cut by energy imparting such as ultraviolet irradiation.

The polymer material having a hydrophobic group in the side chain may, for example, be a polymer material containing polyimine. Since the polyimide has excellent electrical insulating properties, chemical resistance, and heat resistance, there is no problem in that when an electrode layer or the like is formed on the insulating wet-changing layer, temperature changes due to solvent or firing are caused. Produces swelling or cracking. Therefore, in the laminated structure, an insulating wet-changing layer which is excellent in electrical insulating properties and which is not damaged during the manufacturing process and has high reliability can be formed. In addition, when the insulating wettability variable layer 2 is composed of two or more kinds of materials, it is preferable that materials other than the polymer material having a hydrophobic group in the side chain are also contained in consideration of heat resistance, solvent resistance, and affinity. Polyimine.

Further, in general, a polyimide material has a relative dielectric constant lower than that of SiO ₂ which is generally used as an insulating material, and is suitable as an interlayer insulating film. The hydrophobic group of the polyimine having a hydrophobic group in the side chain is, for example, any one of the chemical formulas shown below.

Here, X is -CH ₂ - or -CH ₂ CH ₂ -, and A ¹ is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene substituted by 1 to 4 fluorines. A, A ² , A ³ and A ⁴ are each independently a single bond, 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene substituted with 1 to 4 fluorines, B ¹ , B ² and B ³ are each independently a single bond or -CH ₂ CH ₂ -, B ₄ is an alkylene group having 1 to 10 carbon atoms, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently carbon. The number is an alkyl group of 1 to 10, and p is an integer of 1 or more.

In the above chemical formula, T, U and V are each independently a benzene ring or a cyclohexane ring, and any H on the rings may be substituted with an alkyl group having 1 to 3 carbon atoms and a fluorine having 1 to 3 carbon atoms. Substituting F, Cl or CN, m and n are each independently an integer of 0~2, h is an integer of 0~5, R is H, F, Cl, CN or a monovalent organic group, and two when m is 2. When V or n is 2, the two Vs may be the same or different.

In the above formula, the linking group Z is CH ₂ , CFH, CF ₂ , CH ₂ CH ₂ or CF ₂ O, the ring Y is 1,4-cyclohexylene or 1 to 4 H may be substituted by F or CH ₃ . 1,4-phenylene, A ¹ ~A ³ are each independently a single bond, 1,4-cyclohexylene or 1~4 H can be substituted by F or CH ₃ 1,4-phenylene, B ¹ ~B ^{3 is} independently a single bond, an alkylene group having 1 to 4 carbon atoms, an oxygen atom, an alkyloxy group having 1 to 3 carbon atoms or a stretching alkyl group having 1 to 3 carbon atoms, and R is H, optionally CH ₂ may be a C ₂ -substituted alkyl group having 1 to 10 carbon atoms, or 1 CH ₂ may be substituted by CF ₂ with a C 1-9 alkoxy or alkoxyalkyl group, and the amine group is relative to benzene. The bonding position of the ring is any position. Wherein, in the case where Z is CH ₂ , B ¹ to B ^{3 are} not simultaneously an alkylene group having 1 to 4 carbon atoms, Z is CH ₂ CH ₂ , and ring Y is 1,4-phenylene group. In the case, A ¹ and A ^{2 are} not all single bonds, and when Z is CF ₂ O, ring Y is not 1,4-cyclohexylene.

In the above chemical formula, R 2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, Z ₁ is a CH ₂ group, m is 0 to 2, ring A is a benzene ring or a cyclohexane ring, and 1 is 0 or 1, each Y _{1 is} independently an oxygen atom or a CH ₂ group, and each n _{1 is} independently 0 or 1.

In the above chemical formula, each Y _{2 is} independently an oxygen atom or a CH ₂ group, and R 3 and R 4 are independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a perfluoroalkyl group, and at least one of them is an alkyl group having 3 or more carbon atoms. Or a perfluoroalkyl group, each n _{2 being} independently 0 or 1.

The details of these materials are described in detail in Japanese Patent Laid-Open No. 2002-162630, Japanese Patent Laid-Open No. 2003-96034, and Japanese Patent Laid-Open No. 2003-267982. Moreover, various materials, such as an aliphatic type, an alicyclic type, and an aromatic type, can be used for the tetracarboxylic dianhydride which comprises the main chain skeleton of these hydrophobic groups. Specifically, there are pyromellitic dianhydride and cyclobutane IV. Formic acid dianhydride, butane tetracarboxylic dianhydride, and the like. Further, a material described in detail in Japanese Laid-Open Patent Publication No. Hei 11-193345, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei 11-193346, and Japanese Patent Application Laid-Open No. Hei No. Hei 11-193347.

The polyimine containing a hydrophobic group of the above chemical formula may be used singly or in combination with other materials. Among them, when used in combination, in view of heat resistance, solvent resistance, and affinity, it is preferred that the material to be mixed is also a polyimide. Further, a polyimine containing a hydrophobic group not represented by the above chemical formula may also be used.

Further, the first film 50 may contain a photopolymerization initiator, a monomer and/or an oligomer of acrylic acid.

The first film 50 may be a blending material which has a side chain which does not have wettability and which is composed only of a main chain, and which contains a main chain and controls wettability to impart energy. a blend of polyimines that previously produces a low surface energy side chain; or a precursor of a polyimine that does not have a side chain that controls wettability but consists of only a backbone, and a host A blend of polyamines, a precursor of a polyimine that controls the wettability and produces a low surface energy side chain prior to imparting energy. As long as it is a material composed of only a main chain without a side chain for controlling wettability, and a material containing a main chain and a material for controlling a wettability and a side chain which generates a low surface energy before energy is imparted, Even a resin such as an epoxy resin, a fluororesin, an acrylic resin, a polyvinyl phenol, or a polyvinyl butyral can form fine depressions (concavities and convexities) by imparting energy such as ultraviolet rays.

In this case, as the insulating material, the first film 50 may be made of polyimide, polyamidimide, epoxy resin, sesquiterpene oxide, polyvinylphenol, polycarbonate or fluorine. Resin, parylene, polyvinyl butyral, etc., polyvinyl phenol and polyvinyl alcohol may also be used after crosslinking by a suitable crosslinking agent. As the inorganic material, TiO ₂ , SiO ₂ or the like can be used.

Further, as the first film 50, a self-assembled monomolecular film or the like containing an organic molecular film or the like can be used. The organic molecular film has a functional group capable of bonding to the substrate on one end side, and has a functional group which changes the surface property of the substrate to liquid repellency or the like (control surface energy) on the other end side. The organic molecular film includes a carbon chain in which the functional groups are bonded, or a part of a carbon chain which is branched, and is bonded to a substrate to form a molecular film, for example, a monomolecular film. The self-assembled film is a functional group containing a bond capable of reacting with a constituent atom such as a substrate or the like, and a linear molecule other than the functional group, and has a pole by interaction of the linear molecule. A film formed by the alignment of a highly aligning compound.

Since the self-assembled monomolecular film is formed by aligning a single molecule, the film thickness can be made extremely thin, and a film having a uniform molecular level can be formed. That is, since the same molecule is located on the surface of the film, it is possible to impart uniform and excellent liquid repellency to the surface of the film. The self-assembled monomolecular film containing an organic molecular film or the like can be placed in the same sealed container as the substrate, and the substrate can be placed on the substrate at room temperature for about 2 to 3 days.

Further, by maintaining the entire sealed container at 100 ° C, the above-described self-assembled monomolecular film can be formed on the substrate for about 3 hours. The above method is a method of forming a self-assembled film from a gas phase, but it is also possible to form a self-assembled monomolecular film from a liquid phase. For example, the substrate is immersed in a solution containing a raw material compound, washed, and dried to obtain a self-assembled monomolecular film on the substrate. In addition, it is desirable to irradiate the surface of the substrate with ultraviolet light before forming the self-assembled monomolecular film. Pretreatment is carried out by light or by washing with a solvent. By performing the above treatment, the surface of the substrate can be made uniform in liquid repellency.

The present invention basically consists of the above. In the above, the present invention is not limited to the above-described embodiments, and various modifications and changes can be made without departing from the spirit and scope of the invention.

10‧‧‧ pattern forming device (forming device)

12‧‧‧Marking Department

14‧‧‧Detection Department

16‧‧‧Exposure Department

18‧‧‧ Pattern Formation Department

30‧‧‧ Input Department

32‧‧‧Description of the Department of Information

34‧‧‧Memory Department

36‧‧‧Image Processing Department

38‧‧‧Control Department

40‧‧‧Rotary axis

42‧‧‧Winding shaft

50‧‧‧1st film

50a‧‧‧ Surface of the first film

52‧‧‧ pattern forming area

54‧‧‧2nd film

56‧‧‧ patterns

60‧‧‧TFT

62‧‧‧gate electrode

64‧‧‧Semiconductor layer

66a‧‧‧Source electrode

66b‧‧‧汲electrode

68‧‧‧Channel area

80‧‧‧ film

80a‧‧‧ Surface of the membrane

82‧‧‧ gate insulation

82a‧‧‧ Surface of the gate insulation

84‧‧‧Protective layer

100, 100a, 110, 112‧‧‧ analytical models

102‧‧‧Support

104‧‧‧ lyophilic department

106‧‧‧Draining Department

108, 109‧‧‧ liquid film

120‧‧‧ solid

122‧‧‧ droplets

B‧‧‧ border

D‧‧‧Transfer direction

F ₁ , F ₂ , F3‧‧‧ straight line

L‧‧‧Width direction

M‧‧‧ alignment mark

S‧‧‧ formation area

Z, G‧‧‧ substrate

Sc‧‧‧ initial surface

W‧‧‧ Calculated time direction

‧‧‧‧Slash

α ₁ , α ₂ ‧‧‧ areas

_{1 1} ‧‧‧ exclusion zone

β ₂ ‧‧‧non-rejected areas

γ _L ‧‧‧ surface tension of liquid

γ _S ‧‧‧ surface tension of solids

γ _SL ‧‧‧Interfacial tension between solid and liquid

Θ‧‧‧contact angle

FIG. 1 is a schematic view showing an example of a pattern forming apparatus used in a pattern forming method according to an embodiment of the present invention.

2(a) is a schematic plan view showing a substrate on which a first film is formed used in a pattern forming method, and FIG. 2(b) is a schematic cross-sectional view showing a substrate on which a first film is formed used in a pattern forming method. .

3(a) to 3(d) are schematic cross-sectional views showing a pattern forming method in order of steps.

4(a) to 4(d) are schematic plan views showing the pattern forming method in order of steps, and correspond to the respective steps of Figs. 3(a) to 3(d).

Fig. 5 (a) is a schematic view showing a thin film transistor formed by using the pattern forming method of the embodiment of the present invention, and Fig. 5 (b) is a cross-sectional view corresponding to the line H-H of Fig. 5 (a).

Fig. 6 is a graph showing the relationship between the liquid viscosity and the repulsion time.

Fig. 7(a) is a schematic view for explaining repulsion, Fig. 7(b) is a schematic perspective view showing an analysis model of repulsion, and Fig. 7(c) is a schematic view showing a change in film thickness due to repulsion of the analysis model. Stereo picture.

Fig. 8 is a schematic view showing the relationship between the change in film thickness used for analysis rejection and the flow rate.

Fig. 9 is a schematic view for explaining the Young's formula.

Fig. 10(a) is a view showing a film thickness distribution obtained by analysis, Fig. 10(b) is a view showing an inter-surface force obtained by analysis, and Fig. 10(c) is a schematic perspective view showing a film thickness distribution.

Fig. 11 (a) to Fig. 11 (c) are diagrams showing the distribution of the film thickness obtained by the analysis, Fig. 11 (a) shows a non-repellent state, Fig. 11 (b) shows a neutral state, and Fig. 11 (c) shows a repulsive state. status.

Fig. 12 is a view showing the relationship between the force between the surfaces and the repulsion.

Fig. 13 (a) is a schematic perspective view showing an analysis model of a non-repulsive state, and Fig. 13 (b) is a schematic perspective view showing an analysis model of a repulsion state.

Fig. 14 is a view showing the relationship between the film thickness and the force between the limit surfaces.

50‧‧‧1st film

50a‧‧‧ Surface of the first film

56‧‧‧ patterns

G‧‧‧Substrate

Claims (10)

A pattern forming method which is a pattern forming method of a fine pattern, comprising the steps of: forming a pattern forming region of the pattern on a first film having a hydrophilic/hydrophobic conversion function formed on a substrate a second film is formed in the pattern forming region, and the second film is dried to form the pattern, and the second film has a viscosity of 3 mPa when the thickness is 0.1 μm. s below. The pattern forming method according to claim 1, wherein the first film is a film having a change in hydrophilicity and hydrophobicity by ultraviolet rays; the pattern forming region is formed by ultraviolet light exposure; and the second film is in a non-pattern The first inter-surface force acting between the first film and the first film in the formation region is -50 Pa to -10 Pa, and the second inter-surface force acting between the first film and the first film in the pattern formation region is The first inter-surface force is 90% or less and is a negative value. The pattern forming method according to claim 2, wherein the concave portion having a thickness of 10 nm or more is formed by exposing the ultraviolet ray to the pattern forming region. The pattern forming method according to any one of claims 1 to 3, wherein the second film is formed by an inkjet method or a printing method. The pattern forming method according to any one of the items 1 to 3, wherein the pattern is an electric wiring or a semiconductor electrode or a precursor of an electric wiring or an electrode for a semiconductor. The pattern forming method according to claim 4, wherein the pattern is an electric wiring or a semiconductor electrode or a precursor of an electric wiring or a semiconductor electrode. The pattern forming method according to Item 2 or 3, wherein the second inter-surface force is 0 to 90% of the first inter-surface force and is a negative value. The pattern forming method according to claim 4, wherein the second inter-surface force is 0 to 90% of the first inter-surface force and is a negative value. The pattern forming method according to claim 5, wherein the second inter-surface force is 0 to 90% of the first inter-surface force and is a negative value. The pattern forming method according to claim 6, wherein the second inter-surface force is 0 to 90% of the first inter-surface force and is a negative value.