JP2006108506A - Film pattern forming method and substrate manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film pattern forming method with which a fine film pattern can be accurately and stably formed. <P>SOLUTION: The film pattern forming method for forming a film pattern on a substrate includes the steps of disposing a liquid-repellent material on the substrate to form a liquid-repellent film; disposing a photocatalyst containing material on the liquid-repellent film to form a photocatalyst containing material film; decomposing a liquid-repellent area on the liquid-repellent film in contact with the photocatalyst containing material film, and modifying the area into a lyophilic area by irradiating the photocatalyst containing material film with energy beams, to form a pattern comprised of wet different portions; and removing the photocatalyst containing material film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a film pattern forming method for forming a film pattern on a substrate and a method for manufacturing a substrate provided with the film pattern.

  Conventionally, a photolithography method has been widely used as a method for manufacturing a device having a fine wiring pattern (film pattern) such as a semiconductor integrated circuit. Recently, Japanese Patent Application Laid-Open No. 11-274671 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2000/2000. As disclosed in JP-A-216330 and the like, a device manufacturing method using a droplet discharge method has attracted attention.

  The technology disclosed in the above publication arranges a material on a substrate by discharging droplets made of a functional liquid material containing a pattern forming material in a pattern forming region on the substrate from a droplet discharge head, It forms a wiring pattern, and is very effective in that it can be used for various types of small-volume production.

  Since the resolution of this ink jet recording head is as fine as several hundred dpi (for example, 400 dpi), if a functional liquid material can be discharged from each nozzle hole, a facility such as a semiconductor factory is not required, and the order of μm order. It is considered that an arbitrary pattern can be formed with a width.

  However, when the droplets ejected by the ink jet method land on the substrate surface, there are problems that the droplets spread widely on the substrate surface, and that the shape of the droplets remains in the contour of the film pattern as it is, or there are irregularities .

  Therefore, in order to solve the above problems, a low-cost functional liquid material application method is used, and a film pattern manufacturing method and a manufacturing method capable of forming fine wiring without causing droplets to wet and spread unnecessarily Devices have been studied.

  As one of them, a method of forming a film pattern by forming a liquid-repellent region and a lyophilic region on a substrate and disposing a functional liquid material in the lyophilic region has been studied. . In such a method, a self-organized monomolecular film formed by a fluorine-based silane coupling agent is used for a substrate such as glass in order to impart liquid repellency to the substrate. In order to pattern this liquid-repellent self-assembled monolayer, decomposition processing of the self-assembled monolayer by ultrashort wavelength UV (for example, excimer UV light of 172 nm) is generally used. There are problems such as long time, thermal expansion of the substrate due to light irradiation, and damage to the substrate due to the very short UV wavelength.

  Therefore, as disclosed in Japanese Patent Application Laid-Open No. 2001-272774, a lyophilic liquid repellent pattern forming method utilizing formation of a photocatalyst on a substrate surface has been considered (Patent Document 3). However, in such a method, since it is necessary to form a layer having photocatalytic properties on the substrate surface, there is a problem that a layer containing a photocatalyst remains in the lower layer of the film pattern on the finally obtained substrate. .

As a method for improving this, Japanese Patent Application Laid-Open No. 2000-249821 discloses that a photocatalyst containing layer side substrate having a photocatalyst containing layer and a pattern forming body substrate having a characteristic change layer are separated from each other when performing exposure. Has been disclosed (Patent Document 4). In this method, since the decomposition of the self-assembled monolayer does not proceed unless the photocatalyst containing layer side substrate having the photocatalyst containing layer is in contact with the pattern forming substrate having the characteristic change layer, the pattern forming substrate is flat. In some cases, the self-assembled monolayer can be decomposed, but if the surface of the substrate for pattern formation is uneven, there will be areas where the self-assembled monolayer will not be decomposed. There was a problem that unevenness occurred.
Japanese Patent Laid-Open No. 11-274671 JP 2000-216330 A JP 2001-272774 A JP 2000-249821 A

  By the way, in recent years, the density of circuits constituting a device has been increased, and for example, further miniaturization and thinning of wiring patterns (film patterns) are required. However, when such a fine wiring pattern (film pattern) is to be formed by the method using the droplet discharge method, it is difficult to form a fine wiring pattern accurately and stably due to the above-described problems. Met.

  The present invention has been made in view of the above problems of the prior art, and an object of the present invention is to provide a film pattern forming method capable of forming a fine film pattern with high accuracy and stability.

  The present invention has been made to solve the above problems, and is a film pattern forming method for forming a film pattern on a substrate, wherein a liquid repellent material is disposed on the substrate, and the liquid repellent film is formed. Forming a photocatalyst-containing material film by discharging and arranging a photocatalyst-containing material on the liquid-repellent film using a droplet discharge method, and irradiating the photocatalyst-containing material film with energy rays The present invention provides a method for forming a film pattern comprising the steps of making a liquid-repellent region in contact with the photocatalyst-containing material film a lyophilic region and removing the photocatalyst-containing material film.

  By taking such a configuration, it is possible to form a state in which the photocatalyst-containing material is in direct contact with the liquid-repellent film not only when the surface of the substrate is flat but also when the surface is uneven. A lyophilic / liquid repellent pattern can be formed by short-time energy irradiation without causing unevenness. In addition, since the photocatalyst-containing material film is present on the outermost layer of the multilayer film, the photocatalyst-containing material can be easily removed after energy irradiation, and there is no problem that the photocatalyst-containing layer remains in the lower layer of the film pattern.

  Preferred embodiments of the invention are as follows. The photocatalyst-containing material is preferably arranged using a droplet discharge method. By using the droplet discharge method, a fine and complicated film pattern can be formed on the substrate. Further, the use efficiency of the material can be improved as compared with the case where the metal thin film formed on the substrate is patterned using the photolithography technique, which contributes to the reduction of the production cost of the film pattern.

  The energy beam irradiation is preferably performed from the substrate side. Here, the “substrate side” means the side opposite to the side on which the liquid repellent film and the photocatalyst containing material film are formed, and the side on which the liquid repellent film and the photocatalyst containing material film are formed is the substrate. This is the so-called back side. The photocatalyst used in the present invention absorbs an energy ray of 250 to 500 nm and exhibits a photocatalytic effect. However, since a decomposition reaction occurs on the side where the energy ray strikes, the decomposition efficiency is better when irradiated from the back side of the substrate. Therefore, it is preferable that the liquid repellent film can be made lyophilic in a short time.

  The step of forming the liquid repellent film is preferably a step of forming a liquid repellent organic thin film on the substrate. The liquid repellent organic thin film is preferably an organic thin film composed of organic molecules containing fluorine.

  The photocatalyst-containing material is preferably a fine particle dispersion containing one or more substances selected from titanium oxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide.

  The average particle diameter of the fine particles in the fine particle dispersion is preferably 1 μm or less. By setting the average particle size to 1 μm or less, the coating property when a film pattern is formed using a droplet discharge method is improved. That is, nozzle clogging and the like are less likely to occur.

  The energy beam may have a wavelength of 250 to 500 nm. That is, by using the fine particle dispersion as a photocatalyst-containing material, photocatalytic properties can be obtained even with light in the long wavelength UV or visible light region.

Prior to the step of forming the liquid repellent film, it is preferable to include a step of subjecting the substrate to ultraviolet (UV) irradiation treatment, O ₂ plasma treatment using oxygen as a treatment gas in the atmosphere, or ozone cleaning treatment.

  In addition, after the step of removing the photocatalyst-containing material film, a step of forming a conductive film by disposing a liquid material containing conductive fine particles in the lyophilic region can be further provided.

  Further, the present invention is a method for manufacturing a substrate on which a film pattern is formed, wherein the film pattern is formed on the substrate by the method for forming a film pattern of the present invention described above. The manufacturing method of this is provided. According to this manufacturing method, a substrate having a fine film pattern can be manufactured at low cost.

  ADVANTAGE OF THE INVENTION According to this invention, the formation method of the film pattern which can form a fine film pattern accurately and stably can be provided.

  Hereinafter, an embodiment of a film pattern forming method and a substrate manufacturing method of the present invention will be described with reference to the drawings.

  First, a device manufacturing apparatus applicable to film pattern formation and device manufacturing according to an embodiment of the present invention will be described. As this device manufacturing apparatus, a droplet discharge apparatus (inkjet apparatus) that manufactures a device by discharging (dropping) droplets from a droplet discharge head onto a substrate is used.

  FIG. 1 is a perspective view showing a schematic configuration of the droplet discharge device IJ. In FIG. 1, a droplet discharge device IJ includes a droplet discharge head 1, an X-axis direction drive shaft 4, a Y-axis direction guide shaft 5, a control device CONT, a stage 7, a cleaning mechanism 8, and a base. 9 and a heater 15.

  The stage 7 supports the substrate P on which ink is placed by the droplet discharge device IJ, and includes a fixing mechanism (not shown) that fixes the substrate P at a reference position.

  The droplet discharge head 1 is a multi-nozzle type droplet discharge head having a plurality of discharge nozzles, and the longitudinal direction and the X-axis direction coincide with each other. The plurality of ejection nozzles are provided on the lower surface of the droplet ejection head 1 at regular intervals along the X-axis direction. From the ejection nozzle of the droplet ejection head 1, the ink containing the conductive fine particles described above is ejected onto the substrate P supported by the stage 7.

  An X-axis direction drive motor 2 is connected to the X-axis direction drive shaft 4. The X-axis direction drive motor 2 is a stepping motor or the like, and rotates the X-axis direction drive shaft 4 when a drive signal in the X-axis direction is supplied from the control device CONT. When the X-axis direction drive shaft 4 rotates, the droplet discharge head 1 moves in the X-axis direction.

  The Y-axis direction guide shaft 5 is fixed so as not to move with respect to the base 9. The stage 7 includes a Y-axis direction drive motor 3. The Y-axis direction drive motor 3 is a stepping motor or the like, and moves the stage 7 in the Y-axis direction when a drive signal in the Y-axis direction is supplied from the control device CONT.

  The control device CONT supplies the droplet discharge head 1 with a voltage for controlling droplet discharge. Further, the control device CONT supplies a drive pulse signal for controlling the movement of the droplet discharge head 1 in the X-axis direction to the X-axis direction drive motor 2, and the stage 7 to the Y-axis direction drive motor 3. A drive pulse signal for controlling the movement in the Y-axis direction is supplied.

  The cleaning mechanism 8 is for cleaning the droplet discharge head 1 and includes a Y-axis direction drive motor (not shown). By driving the Y-axis direction drive motor, the cleaning mechanism 8 moves along the Y-axis direction guide shaft 5. The movement of the cleaning mechanism 8 is also controlled by the control device CONT.

  Here, the heater 15 is means for heat-treating the substrate P by lamp annealing, and evaporates and dries the solvent contained in the ink applied on the substrate P. The heater 15 is also turned on and off by the control device CONT.

  The droplet discharge device IJ scans the substrate P while relatively moving the droplet discharge head 1 and the stage 7 supporting the substrate P, and discharges droplets onto the substrate P. Here, in the following description, the Y-axis direction is a scanning direction, and the X-axis direction orthogonal to the Y-axis direction is a non-scanning direction. Therefore, the discharge nozzles of the droplet discharge head 1 are provided at regular intervals in the X-axis direction, which is the non-scanning direction.

  In FIG. 1, the droplet discharge head 1 is arranged at a right angle to the traveling direction of the substrate P, but the angle of the droplet discharging head 1 is adjusted so as to intersect the traveling direction of the substrate P. It may be. In this way, the pitch between the nozzles can be adjusted by adjusting the angle of the droplet discharge head 1. Further, the distance between the substrate P and the nozzle surface may be arbitrarily adjustable.

  FIG. 2 is a diagram for explaining the principle of discharging a liquid material by the piezo method. In FIG. 2, a piezo element 22 is installed adjacent to a liquid chamber 21 that stores a liquid material (ink for forming a wiring pattern, functional liquid). The liquid material is supplied to the liquid chamber 21 via a liquid material supply system 23 including a material tank that stores the liquid material. The piezo element 22 is connected to a drive circuit 24, and a voltage is applied to the piezo element 22 through the drive circuit 24 to deform the piezo element 22, whereby the liquid chamber 21 is deformed and liquid is discharged from the discharge nozzle 25. Material is dispensed. In this case, the amount of distortion of the piezo element 22 is controlled by changing the value of the applied voltage. Further, the strain rate of the piezo element 22 is controlled by changing the frequency of the applied voltage. Since the droplet discharge by the piezo method does not apply heat to the material, it has an advantage of hardly affecting the composition of the material.

  Next, as an example of an embodiment of the thin film pattern forming method of the present invention, a method for forming a conductive film wiring on a substrate will be described in detail with reference to FIGS.

  As described above, the film pattern forming method according to the present embodiment is a film pattern forming method for forming a film pattern on a substrate. A liquid repellent material is disposed on the substrate, and the liquid repellent film is formed on the substrate. Forming the photocatalyst-containing material film on the liquid-repellent film by using a droplet discharge method, and irradiating the photocatalyst-containing material film with energy rays. A step of making the liquid-repellent region in contact with the photocatalyst-containing material film a lyophilic region, and a step of removing the photocatalyst-containing material film.

  Hereinafter, each step will be described in detail.

(Process for forming a liquid repellent film)
First, as the substrate P to be used, as shown in FIG. 3C to be described later, when the substrate P is exposed from the side where the liquid repellent film 31 and the photocatalyst-containing material film 32 are formed, glass, quartz, Various semiconductor wafers such as silicon, plastic films, metal plates, etc. can be used. Also included are those in which a semiconductor film, a metal film, a dielectric film, an organic film or the like is formed as a base layer on the surface of these various material substrates.

  However, as shown in FIG. 4C, which will be described later, when exposure is performed from the substrate P side (the side on which the liquid repellent film 31 and the photocatalyst-containing material film 32 are not formed), for example, UV light or the like is used. A substrate made of a material that transmits light is used. Preferred materials include transparent flexible materials such as quartz glass, Pyrex (registered trademark) glass, synthetic quartz plate, and the like, or transparent flexible flexible materials such as transparent resin films and optical resin plates. Materials etc. can be mentioned.

  Once the substrate P is prepared, next, as shown in FIG. 3A, the surface of the substrate P is subjected to a liquid repellent treatment to form a liquid repellent film 31. As the liquid repellent treatment, for example, a method of forming a self-assembled film on the substrate surface, a method of performing plasma treatment, or a method of applying a polymer compound having liquid repellency to the surface of the substrate P can be used. Any liquid repellent treatment can form a highly liquid repellent organic thin film on the surface of the substrate P.

  In the self-assembled film forming method, a self-assembled film made of an organic molecular film or the like is formed on the surface of a substrate on which a conductive film wiring is to be formed. The organic molecular film for treating the substrate surface has a functional group that can bind to the substrate and a functional group that modifies the surface properties of the substrate such as a lyophilic group or a liquid-repellent group (controlling the surface energy) on the opposite side. And a carbon straight chain or a partially branched carbon chain connecting these functional groups, and is bonded to a substrate and self-assembles to form a molecular film, for example, a monomolecular film.

  Here, the “self-assembled film” is composed of a binding functional group capable of reacting with constituent atoms such as an underlayer of a substrate and other linear molecules, and has extremely high orientation due to the interaction of the linear molecules. It is a film formed by orienting a compound having Since this self-assembled film is formed by orienting single molecules, the film thickness can be extremely reduced, and the film is uniform at the molecular level. That is, since the same molecule is located on the surface of the film, uniform and excellent liquid repellency and lyophilicity can be imparted to the surface of the film.

  As the compound having high orientation, for example, a silane compound represented by the following general formula (1) can be used.

(1) R ¹ SiX ¹ _a X ² _(3-a)
In Formula (1), R ¹ represents an organic group, X ¹ and X ² represent —OR ² , —R ² , and —Cl, and R ² contained in X ¹ and X ² has 1 to 4 carbon atoms. And a is an integer of 1 to 3.

In the silane compound represented by the general formula (1), an organic group is substituted on the silane atom, and an alkoxy group, an alkyl group, or a chlorine group is substituted on the remaining bonds. Examples of the organic group R ¹ include, for example, phenyl group, benzyl group, phenethyl group, hydroxyphenyl group, chlorophenyl group, aminophenyl group, naphthyl group, anthrenyl group, pyrenyl group, thienyl group, pyrrolyl group, cyclohexyl group, cyclohexane Hexenyl, cyclopentyl, cyclopentenyl, pyridinyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, octadecyl, n- Octyl group, chloromethyl group, methoxyethyl group, hydroxyethyl group, aminoethyl group, cyano group, mercaptopropyl group, vinyl group, allyl group, acryloxyethyl group, methacryloxyethyl group, glycidoxypropyl group, acetoxy group Etc. can be illustrated.

X ¹ is a functional group for forming an alkoxy group, chlorine group, Si—O—Si bond, or the like, and is hydrolyzed by water to be removed as an alcohol or an acid. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

The number of carbon atoms of R ² is preferably in the range of 1 to 4 from the viewpoint that the molecular weight of the alcohol to be eliminated is relatively small, can be easily removed, and can suppress a decrease in the denseness of the formed film.

A typical silane compound represented by the general formula (1) includes a fluorine-containing alkylsilane compound exhibiting liquid repellency. Particularly, R ¹ has a structure represented by a perfluoroalkyl structure (C _n F _{2n + 1} ), and a compound represented by the general formula (2) can be exemplified.

(2) C _n F _{2n + 1} (CH ₂ ) _m SiX ¹ _a X ² _(3-a)
In the formula (2), n represents an integer of 1 to 18, m represents an integer of 2 to 6, and X ^1, X ² and a represent the same meaning as in the formula (1).

  By using a fluorine-containing alkylsilane compound, each compound is oriented so that a fluoroalkyl group is located on the surface of the film, and a self-assembled film is formed. Thus, uniform liquid repellency is imparted to the surface of the film. be able to.

More specifically, CF ₃ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , 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 ) ₅ —CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₇ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₁₁ —CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₃ —CH ₂ CH ₂ —Si (CH ₃ ) (OCH ₃ ) ₂ , CF _{3 (CF 2) 7 -CH 2} CH 2 -Si (CH 3) (OCH 3) 2, CF 3 (CF 2) 8 -CH 2 CH 2 -Si (CH 3) (OC 2 H 5) 2, CF ₃ (CF ₂ ) ₈ —CH ₂ CH ₂ —Si (C ₂ H ₅ ) (OC ₂ H ₅ ) _{2 and the} like.

In addition, R ¹ may include those having a perfluoroalkyl ether structure (C _n F _{2n + 1} O (C _p F _2p O) _r ). The compound represented by Formula (3) can be illustrated.

_{(3) C p F 2p +} 1 O (C p F 2p O) r (CH 2) m SiX 1 a X 2 (3-a)
In the formula, m represents an integer of 2 to 6, p represents an integer of 1 to 4, r represents an integer of 1 to 10, and X ^1, X ² and a represent the same meaning as described above.

Specific examples of the compound include CF ₃ O (CF ₂ O) ₆ —CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ , CF ₃ O (C ₃ F ₆ O) ₄ —CH ₂ CH ₂ — Si (OCH ₃ ) ₃ , CF ₃ O (C ₃ F ₆ O) ₂ (CF ₂ O) ₃ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ O (C ₃ F ₆ O) ₈ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ O (C ₄ F ₉ O) ₅ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ O (C ₄ F ₉ O) ₅ —CH ₂ CH _{2 -Si (CH 3) (OC} 2 H 5) 2, CF 3 O (C 3 F 6 O) 4 -CH 2 CH 2 -Si (C 2 H 5) (OCH 3) 2 , and the like.

  The compound illustrated above as a compound which forms a self-assembled film may be used independently, and may be used in combination of 2 or more type. By combining the fluorine-containing alkylsilane compound, adhesion with the substrate and good liquid repellency can be obtained.

  A self-assembled film composed of an organic molecular film or the like is formed on the substrate P by placing the above raw material compound and the substrate P in the same sealed container and leaving them at room temperature for about 2 to 3 days. The Further, by holding the entire sealed container at 80 to 140 ° C., it is formed on the substrate P in about 1 to 3 hours. These are formation methods from the gas phase, but a self-assembled film can also be formed from the liquid phase. For example, the self-assembled film is formed on the substrate P by immersing the substrate P in a solution containing the raw material compound for 30 minutes to 6 hours, washing and drying. Moreover, a self-assembled film can be formed by immersion for 5 minutes to 2 hours by heating a solution containing a raw material compound to 40 to 80 ° C. Prior to the formation of the self-assembled film, it is desirable that the surface of the substrate P be subjected to pretreatment such as irradiation with ultraviolet light, ozone treatment, plasma treatment, or cleaning with an acid or alkali solution.

Moreover, the liquid repellent treatment by the plasma treatment method is an effective method when the substrate P is made of an organic material such as a resin substrate or when an existing organic film is provided on the substrate P. Specifically, for example, a plasma processing method (CF ₄ plasma processing method) using tetrafluoromethane (CF ₄ ) as a processing gas in an air atmosphere can be employed. The conditions for the CF ₄ plasma treatment are, for example, a plasma power of 50 to 1000 W, a tetrafluoromethane (CF ₄ ) gas flow rate of 50 to 100 ml / min, a substrate transport speed of 0.5 to 1020 mm / sec with respect to the plasma discharge electrode, and a substrate temperature. Is 70-90 degreeC. The processing gas is not limited to tetrafluoromethane (CF ₄ ), and other fluorocarbon-based gases can also be used.

  In the case of applying a liquid repellent polymer compound to the surface of the substrate P, for example, the liquid repellent layer 31 may be formed by applying a fluorine-containing polyimide resin or the like on the substrate P using a spin coat method or the like. it can. The liquid repellent polymer compound is not limited to the above polyimide resin, and a monomer, oligomer or polymer containing a fluorine atom in the molecule can be used. For example, polytetrafluoroethylene (PTFE) , Ethylene-4-fluoroethylene copolymer, hexafluoropropylene-4-fluoroethylene copolymer, polyvinylidene fluoride (PVdF), poly (pentadecafluoroheptylethyl methacrylate) (PPFMA), poly (perfluorooctylethyl) Acrylate) and other long-chain perfluoroalkyl structures such as ethylene, acrylate, methacrylate, vinyl, urethane, and silicone polymers.

(Step of forming photocatalyst-containing material film)
After forming the liquid repellent film 31, a photocatalyst containing material film 32 is formed on the liquid repellent film 31 by discharging a photocatalyst containing material film 32 as shown in FIG. Here, examples of the discharge technique of the droplet discharge method include a charge control method, a pressure vibration method, an electromechanical conversion method, an electrothermal conversion method, and an electrostatic suction method. In the charge control method, a charge is applied to a material with a charging electrode, and the flight direction of the material is controlled with a deflection electrode to be discharged from a discharge nozzle. In addition, the pressure vibration method is a method in which an ultra-high pressure of about 30 kg / cm ² is applied to the material to discharge the material to the nozzle tip side, and when the control voltage is not applied, the material moves straight from the discharge nozzle. When discharged and a control voltage is applied, electrostatic repulsion occurs between the materials, and the materials are scattered and are not discharged from the discharge nozzle. The electromechanical conversion method utilizes the property that a piezoelectric element (piezoelectric element) is deformed by receiving a pulse-like electric signal. The piezoelectric element is deformed through a flexible substance in a space where material is stored. Pressure is applied, and the material is extruded from this space and discharged from the discharge nozzle.

  In the electrothermal conversion method, a material is rapidly vaporized by a heater provided in a space where the material is stored to generate bubbles, and the material in the space is discharged by the pressure of the bubbles. In the electrostatic attraction method, a minute pressure is applied to a space in which a material is stored, a meniscus of material is formed on the discharge nozzle, and an electrostatic attractive force is applied in this state before the material is drawn out. In addition to this, techniques such as a system that uses a change in the viscosity of a fluid due to an electric field and a system that uses a discharge spark are also applicable. The droplet discharge method has an advantage that the use of the material is less wasteful and a desired amount of the material can be accurately disposed at a desired position. In addition, the amount of one drop of the liquid material (photocatalyst-containing material or the like) discharged by the droplet discharge method is, for example, 1 to 300 nanograms.

  As the photocatalyst-containing material used in this step, a material that exhibits better lyophilicity by ultraviolet exposure can be used. The photocatalyst-containing material is not particularly limited as long as the photocatalyst-containing material has a configuration that changes the characteristics of the property-changing layer in contact with the photocatalyst in the photocatalyst-containing material film 32. The photocatalyst-containing material film may be washed and removed after irradiation with energy rays so that the remaining photocatalyst-containing material does not cause decomposition action. From the viewpoint of requiring a step, a fine particle dispersion is preferable.

  In this photocatalyst-containing material film 32, the action mechanism of a photocatalyst represented by titanium dioxide as described later is not necessarily clear, but carriers generated by light irradiation react directly with nearby compounds, Alternatively, it is considered that the active oxygen species generated in the presence of oxygen and water change the chemical structure of the organic matter. In this embodiment, it is considered that this carrier acts on the compound in the liquid repellent film 31 that contacts the photocatalyst-containing material film 32.

Examples of the photocatalyst used in the present embodiment include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), and tungsten oxide (WO ₃ ), which are known as optical semiconductors. , Bismuth oxide (Bi ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ), and one or a mixture of two or more selected from these can be used.

  In the present embodiment, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes an anatase type and a rutile type, and both can be used in the present invention, but anatase type titanium dioxide is preferred. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.

  Examples of materials dispersed in such anatase titanium dioxide dispersant include, for example, hydrochloric acid peptized anatase titania sol (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size 7 nm), Ishihara Sangyo Co., Ltd.) ST-K01), nitric acid peptized anatase titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)), and the like.

  The smaller the particle size of the photocatalyst, the more effective the photocatalytic reaction occurs. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst having a particle size of 20 nm or less.

  The photocatalyst-containing material film 32 in the present embodiment may be formed by a photocatalyst alone as described above, but a fine particle dispersion in which fine particles containing one or more photocatalysts are dispersed in a dispersant. preferable.

  In the case of a fine particle dispersion, as a dispersant, alcohols such as ethanol, methanol, N-propanol, N-propanol, isopropanol and sec-butanol, hydrocarbons such as N-hexane, xylene and toluene, methylene chloride, Carbon tetrachloride, 1,1,1-trichloroethane, Freon 141b, halogenated hydrocarbons such as fluorobenzene, polyhydric alcohols such as ethylene glycol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, One or more types selected from silicone oils such as dimethyl silicone oil and water are used.

  The content of the photocatalyst in the fine particle dispersion can be set in the range of 5 to 60% by weight, preferably 20 to 40% by weight. The thickness of the photocatalyst-containing material film 32 is preferably in the range of 0.05 to 10 μm.

  The photocatalyst-containing material can contain a surfactant in addition to the photocatalyst and the dispersant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176 can be used, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.

  In addition to the above surfactants, the photocatalyst-containing layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. It can be included.

(Decomposing the liquid-repellent region to change it into a lyophilic region)
After the photocatalyst containing material film 32 is formed, as shown in FIG. 3C, energy rays (arrows) are irradiated toward the surface on which the liquid repellent film 31 and the photocatalyst containing material film 32 are formed.

  Examples of the light source that can be used for the energy ray irradiation include a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, an excimer laser, a YAG laser, and various other light sources.

  The light irradiation amount at the time of exposure is set to an irradiation amount necessary for the photocatalyst-containing material film 32 to change the lyophobic film 31 to be lyophilic by the action of the photocatalyst. At this time, the sensitivity can be increased by exposing the substrate P while heating.

  In FIG. 3C, energy rays (indicated by arrows in the figure) are irradiated toward the surface on which the liquid repellent film 31 and the photocatalyst-containing material film 32 are formed. In the form, the irradiation direction of the energy rays is not limited to this, and as shown in FIG. 4C, if the substrate P and the liquid repellent film 31 transmit light, the substrate side, that is, You may irradiate toward the surface in which the liquid repellent film 31 and the photocatalyst containing material film 32 are not formed.

  By irradiating the energy beam, the liquid repellent region in contact with the exposed photocatalyst containing material film 32 is decomposed by the photocatalytic properties of the photocatalyst containing material film 32, and the wettability is changed. A lyophilic region 33 is formed.

  The wavelength of the energy ray is generally 400 nm or less, preferably 380 nm or less. However, by adding a small amount of iron oxide or the like to the photocatalyst-containing material, the photocatalytic property is exhibited by long wavelength UV or visible light. In such a case, the wavelength of the energy beam can be set to 250 to 500 nm.

(Step of removing photocatalyst-containing material film)
After the lyophilic region 33 is formed, the photocatalyst-containing material film 32 is removed and the lyophobic region 31a and the lyophilic region 33 are formed on the substrate P as shown in FIG. Is done. Removal of the photocatalyst-containing material film 32 can dissolve the photocatalyst-containing material film 32 and does not affect the film composition of the liquid repellent region 31a and the lyophilic region 33 formed on the substrate P. If there is no particular limitation, for example, alcohols such as ethanol, methanol, N-propanol, N-propanol, isopropanol and sec-butanol, hydrocarbons such as N-hexane, xylene and toluene, methylene chloride, tetrachloride Carbon, 1,1,1-trichloroethane, Freon 141b, halogenated hydrocarbons such as fluorobenzene, polyhydric alcohols such as ethylene glycol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, dimethyl silicone It can carry out using organic solvents, such as silicone oils, such as oil.

(Conductive film formation process)
After the lyophobic region 31a and the lyophilic region 33 are formed on the substrate P, as shown in FIG. 3E, a liquid material containing conductive fine particles in the lyophilic region 33 is used as the conductive film ink. The conductive film 34 is formed by discharging.

  The conductive film ink used for forming the conductive film 34 is made of a dispersion liquid in which conductive fine particles are dispersed in a dispersant. In the present embodiment, as the conductive fine particles, for example, metal fine particles containing at least one of gold, silver, copper, aluminum, palladium, ITO, and nickel, these oxides, and conductivity Polymer or superconductor fine particles are used.

  In order to improve the dispersibility, these conductive fine particles can be used by coating the surface with an organic solvent such as xylene or toluene, citric acid or the like. The particle diameter of the conductive fine particles is preferably 1 nm or more and 0.1 μm or less. If it is larger than 0.1 μm, there is a risk of clogging in the discharge nozzle of the droplet discharge head described later. On the other hand, if the thickness is smaller than 1 nm, the volume ratio of the coating material to the conductive fine particles becomes large, and the ratio of organic substances in the obtained film becomes excessive. In the case of using a coating material coated with conductive fine particles, it is also possible to use an ink that does not exhibit conductivity in the form of a liquid, but exhibits conductivity when dried or sintered.

  Examples of the organometallic compound include compounds and complexes containing, for example, gold, silver, copper, palladium, etc., which deposit metal by thermal decomposition. Specifically, chlorotriethylphosphine gold (I), chlorotrimethylphosphine gold (I), chlorotriphenylphosphine gold (I), silver (I) 2,4-pentanedionate complex, trimethylphosphine (hexafluoroacetylacetonate ) Silver (I) complex, copper (I) hexafluoropentanediotocyclooctadiene complex, and the like.

  As the liquid dispersant or solvent containing at least one of the conductive fine particles and the organometallic compound, those having a vapor pressure at room temperature of 0.001 mmHg to 200 mmHg (about 0.133 Pa to 26600 Pa) are preferable. . This is because if the vapor pressure is higher than 200 mmHg, the dispersant or the solvent rapidly evaporates after ejection, making it difficult to form a good film.

  The vapor pressure of the dispersant or solvent is more preferably 0.001 mmHg to 50 mmHg (about 0.133 Pa to 6650 Pa). This is because if the vapor pressure is higher than 50 mmHg, nozzle clogging due to drying tends to occur when droplets are ejected by the droplet ejection method, and stable ejection becomes difficult. On the other hand, in the case of a dispersant or solvent having a vapor pressure lower than 0.001 mmHg at room temperature, drying becomes slow and the dispersant or solvent tends to remain in the film, and after heat and / or light treatment in the subsequent step. It becomes difficult to obtain a good conductive film.

  The dispersant is not particularly limited as long as it can disperse the conductive fine particles and does not cause aggregation. For example, in addition to water, alcohols such as methanol, ethanol, propanol, butanol, n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, cymene, durene, indene, dipentene, tetrahydronaphthalene, decahydro Hydrocarbon compounds such as naphthalene and cyclohexylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 1,2-dimethoxyethane, bis (2- Methoxyethyl) ether, ether compounds such as p-dioxane, propylene carbonate, γ- Butyrolactone, N- methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, can be exemplified polar compounds such as cyclohexanone. Among these, water, alcohols, hydrocarbon compounds, and ether compounds are preferable and more preferable dispersants in terms of the fine particle dispersibility, the stability of the dispersion, and the ease of application to the droplet discharge method. Examples thereof include water and hydrocarbon compounds.

  The dispersoid concentration in the case where the conductive fine particles are dispersed in the dispersant is preferably 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. If it exceeds 80% by mass, aggregation tends to occur and it becomes difficult to obtain a uniform film. For the same reason, the solute concentration in the organometallic compound solution is preferably in the same range as the dispersoid concentration.

  The surface tension of the conductive film ink is preferably in the range of 0.02 N / m to 0.07 N / m. When the conductive film ink is ejected by the droplet ejection method, if the surface tension is less than 0.02 N / m, the wettability of the ink to the nozzle surface increases, and thus flight bending easily occurs, resulting in 0.07 N / m. If it exceeds the upper limit, the shape of the meniscus at the tip of the nozzle is not stable, and it becomes difficult to control the discharge amount and discharge timing. In order to adjust the surface tension, a small amount of a surface tension regulator such as a fluorine-based, silicone-based, or nonionic-based material may be added to the conductive film ink as long as the contact angle with the substrate is not significantly reduced. The nonionic surface tension modifier improves the wettability of the ink to the substrate, improves the leveling property of the film, and helps prevent the occurrence of fine irregularities on the film. The surface tension modifier may contain an organic compound such as alcohol, ether, ester, or ketone, if necessary.

  The viscosity of the conductive film ink is preferably 1 mPa · s to 50 mPa · s. When ejecting ink as droplets using the droplet ejection method, if the viscosity is less than 1 mPa · s, the nozzle periphery is easily contaminated by the outflow of the ink, and if the viscosity is greater than 50 mPa · s, the nozzle The frequency of clogging in the holes increases, and it becomes difficult to smoothly discharge droplets.

  As such a conductive film ink, specifically, an organic solvent of a silver fine particle dispersion (trade name “Perfect Silver” manufactured by Vacuum Metallurgical Co., Ltd.) in which silver fine particles having a diameter of about 10 nm are dispersed in an organic solvent is tetradecane. An example is one prepared by substituting and diluting to prepare a solution having a concentration of 60 wt%, a viscosity of 8 mPa · s, and a surface tension of 0.022 N / m.

  When the conductive film ink having the above-described configuration is ejected from the droplet ejection head 1 onto the existing liquid-repellent film 31 on the substrate P, the applied ink component, that is, the dispersant, etc. The liquid-repellent region 31 a formed on the conductive film 31 collects in the lyophilic region 33 due to the liquid-repellent action, and conductive fine particles (for example, silver fine particles) in the ink are aggregated in the lyophilic region 33. Remains. At this time, since the conductive film ink is arranged along the lyophilic region 33, the aggregate of the fine particles also has substantially the same planar shape as the lyophilic region 33.

  If the conductive film ink is thus disposed on the lyophilic region 33, the conductive film ink is dried under heating conditions of, for example, 80 ° C. for 30 seconds. The heating temperature in this drying step is set to a temperature at which the conductive fine particles or the organometallic compound in the ink are not bonded to each other, that is, a temperature equal to or lower than the sintering temperature. When such heat treatment is performed, the liquid content in the conductive film ink evaporates, and the aggregate of conductive fine particles or organometallic compound remaining on the lyophilic region 33 has been substantially removed. It becomes.

  As a heating means used in the drying step, a heating lamp can be used in addition to a normal hot plate, an electric furnace or the like. The light source used for lamp annealing is not particularly limited, but an infrared lamp, a xenon lamp, a YAG laser, an argon laser, a carbon dioxide laser, an excimer laser such as XeF, XeCl, XeBr, KrF, KrCl, ArF, ArCl, etc. is used as a light source. Can be used. In general, these light sources have an output in the range of 10 W to 5000 W, but in the present embodiment, a range of 100 W to 1000 W is sufficient.

  When the drying step is completed, the conductive film 34 is heated to sinter the aggregate of conductive particles on the lyophilic region 33. When the conductive film ink containing the metal organic compound is used, the metal organic compound is decomposed by this heat treatment to form a conductive layer pattern of the metal thin film. When the conductive film ink containing both the conductive fine particles and the organometallic compound is used, the conductive film pattern is formed by a mixture of the conductive fine particles and the metal generated by the decomposition of the organometallic compound.

  In the drying step and the sintering step, the substrate P is subjected to a heat treatment or a light irradiation treatment. The conditions for the heat treatment or the light irradiation treatment are the boiling point (vapor pressure) of the dispersant, the type of the atmospheric gas, The pressure is appropriately determined in consideration of thermal behavior such as fine particle dispersibility and oxidation, presence / absence and amount of coating material, heat resistant temperature of the substrate, and the like.

  For example, when the conductive fine particles are covered with a coating material, it is necessary to remove the coating material before the above-described sintering step, and thus the heating is performed to about 300 ° C. in the sintering step.

  Through the above steps, a conductive film pattern (film pattern) composed of a laminated film of the liquid repellent film 31 and the conductive film 34 can be formed on the substrate P.

  According to the film pattern forming method of the present embodiment, the conductive film 34 is formed on the substrate P via the liquid repellent film 31 by using the droplet discharge method. Can be directly formed on the substrate P, and a high-contrast liquid repellent / lyophilic region can be formed on the substrate P with high efficiency. And since the electrically conductive film 34 which comprises the principal part among film | membrane patterns is formed via the lyophilic area | region 33, it becomes the thing excellent in the reliability which does not produce malfunctions, such as a short circuit, although it is a fine shape. Therefore, according to the forming method of the present embodiment, a fine and highly reliable film pattern can be efficiently formed on the substrate. In addition, since both the photocatalyst-containing material film 32 and the conductive film 34 are formed using a droplet discharge method, the material usage efficiency is higher than when a metal thin film formed on a substrate is patterned using a photolithography technique. As a result, the manufacturing cost of the film pattern can be reduced.

  In the present embodiment, as a preferred example, an example in which a liquid material including a photocatalyst-containing material or conductive fine particles is discharged and arranged using an ink jet method has been described. However, spin coating, spray coating, dip coating, roll coating, and beading are described. It can also be applied by a known application method such as coating.

  In the present embodiment, the case where a film pattern mainly composed of the conductive film 34 is formed on the substrate P has been described. However, as the film pattern, an insulating film formed in place of the conductive film 34 or a semiconductor film may be used. May be formed. In the case of forming an insulating film, for example, silicon is used as a skeleton of polysilazane, polysiloxane, siloxane-based resist, polysilane-based resist, etc. Inorganic polymer materials and photosensitive inorganic materials, including silica glass, alkyl siloxane polymers, alkyl silsesquioxane polymers, hydrogenated alkyl silsesquioxane polymers, spin-on glass films containing any of polyaryl ethers, diamond films, And a fluorinated amorphous carbon film.

  On the other hand, when forming a semiconductor film, an amorphous silicon semiconductor film can be formed by using liquid silicon hydride as an ink. Alternatively, the semiconductor film can be formed using a copolymer of fluorene and bithiophene. This is a conjugated polymer and exhibits semiconductor properties. And it can melt | dissolve using toluene, organic solvents, such as xylene and trimethylbenzene. Examples of the semiconductor film material include naphthalene, anthracene, tetracene, pentacene, hexacene, phthalocyanine, perylene, hydrazone, triphenylmethane, diphenylmethane, stilbene, arylvinyl, pyrazoline, triphenylamine, triarylamine, oligothiophene. , Low molecular organic semiconductor materials such as phthalocyanine or derivatives thereof, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polythiophene, polyhexylthiophene, poly (p-phenylenevinylene), polytinylenevinylene, poly Arylamine, pyrene formaldehyde resin, ethylcarbazole formaldehyde resin, fluorene-bithiophene copolymer, fluorene-arylamine copolymer The mentioned organic semiconductor material of a polymer such as derivatives thereof, may be used singly or in combination of two or more of them, is particularly preferable to use an organic semiconductor material of a polymer. A polymer organic semiconductor material can be formed by a simple method and can be oriented relatively easily. Of these, a fluorene-bithiophene copolymer or polyarylamine is particularly preferred because it is difficult to oxidize in air and is stable.

  The film pattern forming method of the present invention can be used for forming a wiring pattern such as a conductive wiring of a substrate or a mounting wiring of a semiconductor. Further, the present invention can be applied to formation of material layers and wiring patterns of various devices such as organic electroluminescence devices, liquid crystal display devices, electro-optical devices such as plasma display devices.

  A glass substrate was used as the substrate, and this glass substrate was subjected to ozone cleaning at UV254 nm. Next, a FAS solution and an ozone-cleaned glass substrate were placed in a sealed container, and a glass substrate having a liquid-repellent self-assembled monolayer formed on the substrate surface was manufactured by heating at 120 ° C. for 2 hours. .

Separately, a fine particle dispersion solution having the following composition was prepared.
Anatase type titania (average particle size 5nm) 25% by weight
0.5% by weight of silicon dioxide
2% by weight of methanol
Isopropyl alcohol 72% by weight
N-butanol 0.5% by weight

  The titania fine particle dispersion prepared as described above is used as a photocatalyst-containing material, and is ejected and arranged on a glass substrate on which a liquid-repellent self-assembled monolayer is formed by an inkjet method. ) Was formed.

The substrate on which the titania fine particle film was formed was irradiated with 308 nm excimer UV (1.5 mW / cm ² ) as an energy ray for 5 minutes. FIG. 5 shows the results of measuring the change in liquid repellency (change in wettability) of the liquid repellent self-assembled monolayer surface (liquid repellent region) over time at this time. FIG. 6 shows the results of measuring the change in liquid repellency (change in wettability) of the self-assembled monolayer surface (lyophilic region) in contact with the photocatalyst film over time.

  Next, in order to remove the titania fine particle film, the substrate was washed with acetone. As a result, a lyophilic region was formed on the substrate.

  Separately, an organic solvent in a silver fine particle dispersion (trade name “Perfect Silver”, manufactured by Vacuum Metallurgy Co., Ltd.) in which silver fine particles having a diameter of about 10 nm are dispersed in an organic solvent is diluted with tetradecane, and the concentration is 60 wt. %, The viscosity was 8 mPa · s, and the surface tension was 0.022 N / m.

Then, the silver fine particle dispersion prepared as described above was discharged and arranged with respect to the lyophilic region by an ink jet method to form a film pattern of silver fine particles only in the target region.
Finally, this film pattern was baked by a conventional method to form a silver wiring pattern.

  Excimer UV is irradiated for 15 minutes from the back side of the glass substrate (the surface on which the line pattern of the self-assembled monolayer film and titania fine particle film is not formed) in order to decompose the self-assembled monolayer film to form a lyophilic region. A silver wiring pattern was formed in the same manner as in Example 1 except that.

  As in Example 1, the change in liquid repellency (change in wettability) on the surface of the liquid-repellent self-assembled monolayer (liquid-repellent region) and the surface of the self-assembled monolayer in contact with the photocatalyst film (lyophilic) As a result of measuring the change in liquid repellency (change in wettability) over time, a better result than that of Example 1 was obtained.

It is a perspective view which shows schematic structure of the droplet discharge apparatus IJ. It is a figure for demonstrating the discharge principle of the liquid material by a piezo system. It is a figure which shows an example of embodiment of the thin film pattern formation method which concerns on this invention. It is a figure which shows the other example of embodiment of the thin film pattern formation method which concerns on this invention. Changes in liquid repellency (change in wettability) of the liquid repellent self-assembled monolayer surface (liquid repellent region) when irradiated with 308 nm excimer UV (1.5 mW / cm ² ) for 5 minutes over time Shows the measurement results. FIG. 2 shows the results of measurement over time of a change in liquid repellency (change in wettability) on the surface of a self-assembled monolayer film (lyophilic region) in contact with a photocatalyst film when irradiated with excimer UV under the same conditions as FIG. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Droplet discharge head, 2 ... X-axis direction drive motor, 3 ... Y-axis direction drive motor, 4 ... X-axis direction drive shaft, 5 ... Y-axis direction drive shaft, 7 ... Stage, 8 ... Cleaning mechanism, 9 ... 15: heater, 21 ... liquid chamber, 22 ... piezo element, 23 ... liquid material supply system, 24 ... drive circuit, 25 ... discharge nozzle, 31 ... liquid repellent film, 31a ... liquid repellent area, 32 ... Photocatalyst-containing material film, 33 ... lyophilic region, 34 ... conductive film

Claims (11)

A film pattern forming method for forming a film pattern on a substrate,
Placing a liquid repellent material on the substrate and forming a liquid repellent film;
A step of disposing a photocatalyst-containing material on the liquid repellent film to form a photocatalyst-containing material film;
By irradiating the photocatalyst-containing material film with energy rays, the liquid-repellent region of the liquid-repellent film in contact with the photocatalyst-containing material film is decomposed and changed into a lyophilic region, and the wettability is different. Forming a pattern of parts;
Removing the photocatalyst-containing material film;
A method of forming a film pattern comprising:   2. The film pattern forming method according to claim 1, wherein the material containing the photocatalyst is disposed by a droplet discharge method.   3. The method of forming a film pattern according to claim 1, wherein the energy beam is irradiated from the substrate side.   4. The film pattern forming method according to claim 1, wherein the step of forming the liquid repellent film is a step of forming a liquid repellent organic thin film on the substrate.   5. The method for forming a film pattern according to claim 1, wherein the liquid repellent organic thin film is an organic thin film made of an organic molecule containing fluorine.   The photocatalyst-containing material is a fine particle dispersion containing one or more substances selected from titanium oxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide. Item 6. The method for forming a film pattern according to any one of Items 1 to 5.   The film pattern forming method according to claim 6, wherein an average particle size of the fine particles in the fine particle dispersion is 1 μm or less.   The film pattern forming method according to claim 1, wherein the energy ray has a wavelength of 250 to 500 nm of ultraviolet light, visible light, or laser.   9. The film pattern forming method according to claim 1, further comprising a step of cleaning the substrate with ozone prior to the step of forming the liquid repellent film.   10. The method according to claim 1, further comprising a step of disposing a liquid material containing conductive fine particles in the lyophilic region and forming a conductive film after the step of removing the photocatalyst-containing material film. The method for forming a film pattern according to any one of the preceding claims. A method of manufacturing a substrate on which a film pattern is formed,
A method for manufacturing a substrate, comprising forming a film pattern on the substrate by the method for forming a film pattern according to claim 1.

Images