JP2008307448A - Pattern forming method, electro-optic device manufacturing method, and electronic equipment manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a high grade pattern without increasing a cost. <P>SOLUTION: The pattern is formed by applying a functional liquid on a substrate P having a lyophilic part Pa or a liquid repellent part H with respect to the functional liquid. The pattern forming method has a first step for forming the liquid repellent part H by applying a droplet containing a liquid repellent material on the substrate having lyophilic part and a second step for applying the functional liquid on the lyophilic part Pa surrounded by the water repellent part H. In the first step, the width HA of the liquid repellent part H is adjusted by controlling the discharge quantity and the discharge pitch of the droplet of the liquid repellent material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a pattern forming method, an electro-optical device manufacturing method, and an electronic device manufacturing method.

  When a pattern is formed using a droplet discharge method (inkjet method), a pattern is formed by discharging a liquid droplet (ink) and landing on a predetermined position on a substrate. As described above, when droplets are ejected and landed on the substrate, depending on the characteristics of the substrate surface, the landed droplets may become too wet or spread. In this case, there arises a problem that a desired wiring pattern cannot be obtained.

Thus, Patent Document 1 discloses a technique for forming a lyophilic pattern by lyophobic processing the surface to be a pattern forming surface of a substrate and irradiating the lyophobic surface with an ultraviolet laser beam that has passed through a photocatalyst. ing.
Patent Document 2 discloses a technique in which only a light-exposed portion is hydrophilized by applying a water-repellent substrate containing a photocatalyst on a substrate on which a pattern is to be formed, and then exposing through a mask. .
Japanese Patent Laid-Open No. 2004-200244 JP-A-11-344804

However, the following problems exist in the conventional technology as described above.
Since the technique described in the above-mentioned patent document uses an expensive exposure machine, photomask, or laser light source, it causes a problem of increasing costs. In addition, since a liquid repellent material that is originally necessary only for the non-patterned surface is applied to the entire surface of the substrate, it is not desirable from the viewpoint of material saving.

  The present invention has been made in consideration of the above points, and provides a pattern forming method, an electro-optical device manufacturing method, and an electronic device manufacturing method capable of forming a high-quality pattern without causing an increase in cost. Objective.

In order to achieve the above object, the present invention employs the following configuration.
The pattern forming method of the present invention is a pattern forming method for forming a pattern by applying the functional liquid to a substrate having a lyophilic part and a liquid repellent part with respect to the functional liquid. A first step of applying droplets containing a liquid repellent material to form the liquid repellent portion, and a second step of applying the functional liquid to the lyophilic portion between the liquid repellent portions, In the first step, the width of the liquid repellent part is adjusted by adjusting the discharge amount and the discharge pitch of the liquid repellent material droplets.
Therefore, in the pattern formation method of the present invention, the functional liquid is applied to the lyophilic part, and the pattern according to the arrangement of the lyophilic part is raised to a predetermined position on the substrate by the functional liquid repelled by the liquid repellent part. It can be formed with high accuracy. Here, in the present invention, the width of the lyophilic portion, that is, the width of the pattern can be easily adjusted by adjusting the discharge amount and the discharge pitch of the liquid repellent material to adjust the width of the liquid repellent portion. Can do. Further, in the present invention, since the liquid repellent portion is formed by patterning by applying droplets containing a liquid repellent material in the first step, there is no need to use an expensive exposure machine, photomask, laser light source, etc. Can be prevented.

In the present invention, a table showing a correlation between a discharge amount and a discharge pitch of droplets including the liquid repellent material and a width of the liquid repellent portion is held. In the first step, the table is used. A procedure for applying droplets containing the liquid repellent material can be suitably employed.
Thereby, in the present invention, the desired liquid repellent part width, that is, the discharge amount and the discharge pitch of the liquid droplets containing the liquid repellent material used when forming the desired lyophilic part (pattern) width, and It can be selected quickly and can contribute to the improvement of productivity.

In the present invention, a procedure in which droplets containing the liquid-repellent material landed on the substrate are applied so that the adjacent droplets overlap each other can be suitably employed.
As a result, in the present invention, it is possible to apply liquid droplets containing a liquid repellent material in a single scan to form a liquid repellent portion, which can contribute to an improvement in productivity.

As said liquid repellent material, the structure containing at least one of a silane compound and a compound which has a fluoroalkyl group is employable. In this case, as the silane compound, a structure that is a self-assembled film can be employed.
In addition, the liquid repellent portion may be formed by a self-assembled film made of a compound having the fluoroalkyl group on the surface of the substrate.

On the other hand, as the liquid repellent portion, a structure formed by a self-assembled film having an alkyl group and hydrogen on the surface of the substrate can be employed.
Furthermore, as the liquid repellent material, a configuration including a fluororesin can be employed.

In the present invention, a procedure of applying the functional liquid droplets to the lyophilic portion in the second step can also be suitably employed.
Thereby, in this invention, it becomes possible to perform both a 1st process and a 2nd process with a droplet discharge system, and can aim at common use of equipment in both processes, and can reduce production cost. .

In the present invention, a configuration in which the functional liquid includes a conductive material can also be suitably employed.
Thereby, in this invention, a good conductive pattern can be formed, without causing a cost increase.

In the present invention, the functional liquid can suitably adopt a configuration including a plating catalyst material.
Thereby, in this invention, it becomes possible to form a precise | minute and high quality pattern by performing a plating process with respect to the plating catalyst formed, without causing the cost increase.

In addition, the electro-optical device manufacturing method of the present invention includes a step of forming a pattern by the pattern forming method described above.
Moreover, the electronic device manufacturing method of the present invention is characterized by including a step of forming a pattern by the pattern forming method described above.
Therefore, according to the electro-optical device manufacturing method and the electronic device manufacturing method of the present invention, it is possible to manufacture an electro-optical device and an electronic device having a high-quality pattern without causing an increase in cost.

Further, the electro-optical device is an electromagnetic wave shield having a mesh portion formed in a mesh shape with a conductive wire and a frame portion formed around the mesh portion with the conductive wire, and the mesh portion and the A configuration in which the frame portion is formed by the pattern forming method can also be suitably employed.
Thereby, in this invention, it becomes possible to manufacture the electromagnetic wave shield which has a good quality pattern, without causing a cost increase. In the present invention, the shield characteristic and the aperture ratio are easily adjusted by adjusting the discharge amount and discharge pitch of the liquid-repellent droplets and adjusting the width of the liquid-repellent part, that is, the line width of the mesh part. It becomes possible.

Embodiments of a pattern forming method, an electro-optical device manufacturing method, and an electronic device manufacturing method according to the present invention will be described below with reference to FIGS.
In each drawing used for the following description, the scale of each member is appropriately changed to make each member a recognizable size.

(Droplet discharge device)
First, a droplet discharge device used in the pattern forming method according to the present embodiment will be described.
FIG. 1 is a schematic configuration diagram of a droplet discharge device.
The droplet discharge device (inkjet device) IJ discharges (drops) droplets from the droplet discharge head onto the substrate P. The droplet discharge head 301, the X-direction drive shaft 304, and the Y-direction A guide shaft 305, a control device CONT, a stage 307, a cleaning mechanism 308, a base 309, and a heater 315 are provided. The stage 307 supports the substrate P on which ink (liquid material) is provided 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 301 is a multi-nozzle type droplet discharge head having a plurality of discharge nozzles, and the longitudinal direction and the X-axis direction are matched. The plurality of ejection nozzles are provided on the lower surface of the droplet ejection head 301 in the X-axis direction at regular intervals. From the discharge nozzle of the droplet discharge head 301, the ink containing the conductive fine particles described above is discharged onto the substrate P supported by the stage 307.

An X direction drive motor 302 is connected to the X direction drive shaft 304. The X-direction drive motor 302 is a stepping motor or the like, and rotates the X-direction drive shaft 304 when an X-direction drive signal is supplied from the control device CONT. When the X-direction drive shaft 304 rotates, the droplet discharge head 301 moves in the X-axis direction.
The Y-direction guide shaft 305 is fixed so as not to move with respect to the base 309. The stage 307 includes a Y direction drive motor 303. The Y direction drive motor 303 is a stepping motor or the like, and moves a stage 307 in the Y direction when a drive signal in the Y direction is supplied from the control device CONT.

The control device CONT supplies a droplet discharge control voltage to the droplet discharge head 301. Further, a drive pulse signal for controlling movement of the droplet discharge head 301 in the X direction is supplied to the X direction drive motor 302, and a drive pulse signal for controlling movement of the stage 307 in the Y direction is supplied to the Y direction drive motor 303.
The cleaning mechanism 308 is for cleaning the droplet discharge head 301. The cleaning mechanism 308 includes a Y-direction drive motor (not shown). The cleaning mechanism moves along the Y-direction guide shaft 305 by driving the Y-direction drive motor. The movement of the cleaning mechanism 308 is also controlled by the control device CONT.
Here, the heater 315 is means for heat-treating the substrate P by lamp annealing, and performs evaporation and drying of the solvent contained in the liquid material applied on the substrate P. The heater 315 is also turned on and off by the control device CONT.

The droplet discharge device IJ discharges droplets onto the substrate P while relatively scanning the droplet discharge head 301 and the stage 307 that supports the substrate P. Here, in the following description, the X direction is a non-scanning direction, and the Y direction orthogonal to the X direction is a scanning direction.
Accordingly, the discharge nozzles of the droplet discharge head 301 are provided side by side at regular intervals in the Y direction, which is the non-scanning direction. In FIG. 1, the droplet discharge head 301 is disposed at a right angle to the traveling direction of the substrate P, but the angle of the droplet discharging head 301 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 301. Further, the distance between the substrate P and the nozzle surface may be arbitrarily adjusted.

FIG. 2 is a cross-sectional view of the droplet discharge head 301.
The droplet discharge head 301 is provided with a piezo element 322 adjacent to a liquid chamber 321 that stores a liquid material (such as wiring ink). The liquid material is supplied to the liquid chamber 321 via a liquid material supply system 323 including a material tank that stores the liquid material.
The piezo element 322 is connected to a drive circuit 324, and a voltage is applied to the piezo element 322 via the drive circuit 324 to deform the piezo element 322, whereby the liquid chamber 321 is deformed and the liquid material is discharged from the nozzle 325. Is discharged.
In this case, the amount of distortion of the piezo element 322 is controlled by changing the value of the applied voltage. Further, the strain rate of the piezo element 322 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.

In addition to the electromechanical conversion method, the droplet discharge method includes a charge control method, a pressure vibration method, an electrothermal conversion method, an electrostatic suction method, and the like. In the charge control method, a charge is applied to a material by a charging electrode, and the flight direction of the material is controlled by a deflection electrode and discharged from a nozzle. In addition, the pressure vibration method is a method in which an ultra-high pressure of, for example, about 30 kg / cm ² is applied to the material and the material is discharged to the nozzle tip side. When no control voltage is applied, the material moves straight from the 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 nozzle.

  In the electrothermal conversion method, a material is rapidly vaporized by a heater provided in a space in which 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 in a space in which the material is stored, a meniscus of the material is formed on the 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. The amount of one drop of the liquid material (fluid) discharged by the droplet discharge method is, for example, 1 to 300 nanograms.

Next, a method for forming a pattern using the droplet discharge apparatus IJ will be described with reference to FIGS.
Here, as shown in FIGS. 3A and 3B, a plurality of (three in this case) liquid repellent portions H are formed in a streaky pattern on a substrate P having at least a surface Pa as a lyophilic portion. A case will be described in which a conductive wiring pattern (pattern) W is formed between the liquid repellent portions H provided with a gap therebetween. The liquid repellent portion described here indicates a region where the contact angle with respect to a droplet containing a conductive material (hereinafter referred to as a pattern droplet) is a predetermined value or more, and the lyophilic portion is a conductive material. The area | region where the contact angle with respect to the droplet containing is below a predetermined value is shown.

  As the substrate P, various materials such as glass, quartz glass, Si wafer, plastic film, and metal plate 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.

The pattern forming method according to the present embodiment forms the wiring pattern W by applying the wiring pattern ink described above onto the substrate P, and includes a surface treatment step, a liquid repellent portion forming step, and a material arrangement. It is roughly composed of a process and a heat treatment / light treatment process.
Hereinafter, each process will be described in detail.

(Surface treatment process)
In the surface treatment process, the surface Pa of the substrate P is subjected to a cleaning process to improve the lyophilicity.
For example, when the substrate P is a glass substrate, the surface thereof is lyophilic with respect to the wiring pattern forming material (ink), but the lyophilicity is further enhanced by this surface treatment.

Specifically, in the surface treatment process, UV excimer cleaning, low pressure mercury lamp cleaning, O ₂ plasma cleaning, acid cleaning using HF, sulfuric acid, etc., alkali cleaning, ultrasonic cleaning, megasonic cleaning, corona processing Glow cleaning, scrub cleaning, ozone cleaning, hydrogen water cleaning, microbubble cleaning, fluorine cleaning, etc. are performed.

Here, when the contact angle of the surface (lyophilic part) Pa to the pattern droplet exceeds 25 degrees, bulge (droplet accumulation) is likely to occur, and when it is 20 degrees or less, no bulge occurs. Therefore, in this embodiment, the contact angle with respect to the pattern droplets on the substrate surface Pa is set to 20 degrees or less by adjusting the cleaning process conditions.
Specifically, for example, in the case of UV excimer cleaning, the cleaning process can be adjusted by a combination of irradiation time, intensity, wavelength, heat treatment (heating) of UV light (ultraviolet light), etc. For example, in the case of O ₂ plasma cleaning, the lyophilicity (contact angle) can be adjusted by adjusting the plasma treatment time. By this cleaning treatment, even when a foreign matter such as an organic substance adheres to the surface Pa, it can be removed from the surface Pa, and the cleanliness and lyophilicity can be maintained.

(Liquid repellent part forming step)
Subsequently, the lyophobic portion H is formed in a predetermined region (around the region where the pattern W is formed) on the surface Pa of the substrate P on which the cleaning process (lyophilic process) has been performed.
Specifically, using the above-described droplet discharge device IJ, a liquid droplet containing a material having liquid repellency from the droplet discharge head 301 to the pattern droplet (hereinafter referred to as a liquid repellent droplet). ) Is applied to a predetermined region on the substrate P.

As a material having liquid repellency, a silane compound, a compound having a fluoroalkyl group, a fluororesin (a resin containing fluorine), and a mixture thereof can be used.
As a silane compound, (A) General formula (1)
R ¹ Si X ¹ _m X ² _(3-m) (1)
(Where R1 Represents an organic group, X ¹ And X ² is —OR ² , ^-R 2, represents -Cl, ^{R 2} Represents an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3. 1 type, or 2 or more types of silane compounds (component A) can be used.

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, a chlorine group, a 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 desorbed is relatively small, can be easily removed, and the deterioration of the denseness of the formed film can be suppressed.

Examples of the silane compound represented by the general formula (I) include dimethyldimethoxysilane, diethyldiethoxysilane, 1-propenylmethyldichlorosilane, propyldimethylchlorosilane, propylmethyldichlorosilane, propyltrichlorosilane, propyltriethoxysilane, propyltriethoxysilane. Methoxysilane, styrylethyltrimethoxysilane, tetradecyltrichlorosilane, 3-thiocyanatepropyltriethoxysilane, p-tolyldimethylchlorosilane, p-tolylmethyldichlorosilane, p-tolyltrichlorosilane, p-tolyltrimethoxysilane, p- Tolyltriethoxysilane, di-n-propyldi-n-propoxysilane, diisopropyldiisopropoxysilane, di-n-butyldi-n-butoxysilane, di-sec Butyldi-sec-butyroxysilane, di-t-butyldi-t-butyloxysilane, octadecyltrichlorosilane, octadecylmethyldiethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane (ODS), octadecyldimethylchlorosilane, octadecylmethyldichlorosilane, octadecylmethoxy Dichlorosilane, 7-octenyldimethylchlorosilane, 7-octenyltrichlorosilane, 7-octenyltrimethoxysilane, octylmethyldichlorosilane, octyldimethylchlorosilane, octyltrichlorosilane, 10-undecenyldimethylchlorosilane, undecyltrichlorosilane , Vinyldimethylchlorosilane, methyloctadecyldimethoxysilane, methyldodecyldiethoxy Run, methyloctadecyldimethoxysilane, methyloctadecyldiethoxysilane, n-octylmethyldimethoxysilane, n-octylmethyldiethoxysilane, triacontyldimethylchlorosilane, triaconyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri -N-propoxysilane, methylisopropoxysilane, methyl-n-butyroxysilane, methyltri-sec-butyroxysilane, methyltri-t-butoxyxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethylisopropoxysilane , Ethyl-n-butyroxysilane, ethyltri-sec-butyloxysilane, ethyltri-t-butyloxysilane, n-propyltri Methoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, hexadecyltrimethoxysilane, n-octyltrimethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-propyltriethoxysilane, isobutyl Triethoxysilane, n-hexyltriethoxysilane, hexadecyltriethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltriethoxysilane, 2- [2- (trichlorosilyl) ethyl] pyridine 4- [2- (trichlorosilyl) ethyl] pyridine, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,3- (trichlorosilylmethyl) heptacosane, dibenzyldimethoxysilane, di Benzyldiethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane, phenylmethyldiethoxysilane, phenyldimethylethoxysilane, benzyltriethoxysilane, benzyltrimethoxysilane, Benzylmethyldimethoxysilane, benzyldimethylmethoxysilane, benzyldimethoxysilane, benzyldiethoxysilane, benzylmethyldiethoxysilane, benzyldimethylethoxysilane, benzyltriethoxysilane, dibenzyldimethoxysilane, dibenzyldiethoxysilane, 3-acetoxypropyl Trimethoxysilane, 3-acryloxypropyltrimethoxysilane, allyltrimethoxysilane, Ryltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, 6- (aminohexylaminopropyl) trimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenylethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, ω-aminoundecyltrimethoxysilane, amyltriethoxysilane, benzoxacilepin dimethyl ester, 5- (bicycloheptenyl) trieth Sisilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 8-bromooctyltrimethoxysilane, bromophenyltrimethoxysilane, 3-bromopropyltrimethoxysilane, n-butyltrimethoxysilane, 2-chloro Methyltriethoxysilane, chloromethylmethyldiethoxysilane, chloromethylmethyldiisopropoxysilane, p- (chloromethyl) phenyltrimethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 2 Cyanoethyltrimethoxysilane, cyanomethylphenethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 2- (3-cyclohexenyl) ethyltrimethoxysilane, 2- (3-cyclohexenyl) ethyltriethoxysilane, 3-cyclohexenyl Trichlorosilane, 2- (3-cyclohexenyl) ethyltrichlorosilane, 2- (3-cyclohexenyl) ethyldimethylchlorosilane, 2- (3-cyclohexenyl) ethylmethyldichlorosilane, cyclohexyldimethylchlorosilane, cyclohexylethyldimethoxy Silane, cyclohexylmethyldichlorosilane, cyclohexylmethyldimethoxysilane, (cyclohexylmethyl) trichlorosilane, cyclohexyltrichlorosilane, cyclohexyltri Methoxysilane, cyclooctyltrichlorosilane, (4-cyclooctenyl) trichlorosilane, cyclopentyltrichlorosilane, cyclopentyltrimethoxysilane, 1,1-diethoxy-1-silacyclopent-3-ene, 3- (2,4-dinitrophenyl) Amino) propyltriethoxysilane, (dimethylchlorosilyl) methyl-7,7-dimethylnorpinane, (cyclohexylaminomethyl) methyldiethoxysilane, (3-cyclopentadienylpropyl) triethoxysilane, N, N-diethyl -3-aminopropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (furfuryloxymethyl) triethoxy Lan, 2-hydroxy-4- (3-triethoxypropoxy) diphenyl ketone, 3- (p-methoxyphenyl) propylmethyldichlorosilane, 3- (p-methoxyphenyl) propyltrichlorosilane, p- (methylphenethyl) methyl Dichlorosilane, p- (methylphenethyl) trichlorosilane, p- (methylphenethyl) dimethylchlorosilane, 3-morpholinopropyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltri Methoxysilane, 1,2,3,4,7,7, -hexachloro-6-methyldiethoxysilyl-2-norbornene, 1,2,3,4,7,7, -hexachloro-6-triethoxysilyl- 2-norbornene, 3-iodopropyltrimethoxylane, 3 -Isocyanatopropyltriethoxysilane, (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, methyl {2- (3-trimethoxysilylpropylamino) ethylamino} -3-propionate, 7-octenyltrimethoxysilane, RN-α-phenethyl-N'-triethoxy Silylpropylurea, S-N-α-phenethyl-N′-triethoxysilylpropylurea, phenethyltrimethoxysilane, phenethylmethyldimethoxysilane, phenethyldimethylmethoxysilane, phenethyl Methoxysilane, phenethyldiethoxysilane, phenethylmethyldiethoxysilane, phenethyldimethylethoxysilane, phenethyltriethoxysilane, (3-phenylpropyl) dimethylchlorosilane, (3-phenylpropyl) methyldichlorosilane, N-phenylaminopropyltrimethoxy Silane, N- (triethoxysilylpropyl) dansilamide, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, 2- (triethoxysilylethyl) -5- (chloroacetoxy) bicycloheptane, ( S) -N-triethoxysilylpropyl-O-menth carbamate, 3- (triethoxysilylpropyl) -p-nitrobenzamide, 3- (triethoxysilyl) propylsuccinic anhydride, N- [5- Trimethoxysilyl) -2-aza-1-oxo-pentyl] caprolactam, 2- (trimethoxysilylethyl) pyridine, N- (trimethoxysilylethyl) benzyl-N, N, N-trimethylammonium chloride, phenylvinyldi Ethoxysilane, 3-thiocyanatopropyltriethoxysilane, (tridecafluoro-1,1,2,2, -tetrahydrooctyl) triethoxysilane, N- {3- (triethoxysilyl) propyl} phthalamic acid, (3, 3,3-trifluoropropyl) methyldimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 1-trimethoxysilyl-2- (chloromethyl) phenylethane, 2- (trimethoxysilyl) ) Ethylphenylsulfonyl azide, β-trimeth Sisilylethyl-2-pyridine, trimethoxysilylpropyldiethylenetriamine, N- (3-trimethoxysilylpropyl) pyrrole, N-trimethoxysilylpropyl-N, N, N-tributylammonium bromide, N-trimethoxysilylpropyl-N, N, N-tributylammonium chloride, N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, vinylmethyldiethoxylane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane , Vinyldimethylethoxysilane, vinylmethyldichlorosilane, vinylphenyldichlorosilane, vinylphenyldiethoxysilane, vinylphenyldimethylsilane, vinylphenyl Tylchlorosilane, vinyltriphenoxysilane, vinyltris-t-butoxysilane, adamantylethyltrichlorosilane, allylphenyltrichlorosilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, phenyltrichlorosilane, phenyldimethylchlorosilane , Phenylmethyldichlorosilane, benzyltrichlorosilane, benzyldimethylchlorosilane, benzylmethyldichlorosilane, phenethyldiisopropylchlorosilane, phenethyltrichlorosilane, phenethyldimethylchlorosilane, phenethylmethyldichlorosilane, 5- (bicycloheptenyl) trichlorosilane, 5- (bicyclo Heptenyl) triethoxysilane, 2- (bicycloheptyl) di Methylchlorosilane, 2- (bicycloheptyl) trichlorosilane, 1,4-bis (trimethoxysilylethyl) benzene, bromophenyltrichlorosilane, 3-phenoxypropyldimethylchlorosilane, 3-phenoxypropyltrichlorosilane,
t-butylphenylchlorosilane, t-butylphenylmethoxysilane, t-butylphenyldichlorosilane, p- (t-butyl) phenethyldimethylchlorosilane, p- (t-butyl) phenethyltrichlorosilane, 1,3- (chlorodimethylsilyl) Methyl) heptacosane, ((chloromethyl) phenylethyl) dimethylchlorosilane, ((chloromethyl) phenylethyl) methyldichlorosilane, ((chloromethyl) phenylethyl) trichlorosilane, ((chloromethyl) phenylethyl) trimethoxysilane, Chlorophenyltrichlorosilane, 2-cyanoethyltrichlorosilane, 2-cyanoethylmethyldichlorosilane, 3-cyanopropylmethyldiethoxysilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropyl Methyldichlorosilane, 3-cyanopropyl dimethyl ethoxy silane, 3-cyanopropyl methyl dichlorosilane, 3-cyanopropyl trichloro silane, and the like.

Examples of fluorine-containing silane compounds (liquid repellent silane compounds) include fluorine-containing alkylsilane compounds. That is, it has a structure represented by a perfluoroalkyl structure C _n F _{2n + 1} bonded to Si, and examples thereof include a compound represented by the following general formula (2). In formula (2), n represents an integer from 1 to 18, and m represents an integer from 2 to 6. X ¹ and ^{X 2 -OR 2,} -R 2, shows a -Cl, ^{R 2} contained in ^{X 1} and ^{X 2} represents an alkyl group having 1 to 4 carbon atoms, a is an integer from 1 to 3 is there.

_{C n F 2n + 1 (CH} 2) m SiX 1 a X 2 (3-a) ... (2)
X ¹ is a functional group for forming an alkoxy group, a chlorine group, a 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 desorbed is relatively small, can be easily removed, and the deterioration of the denseness of the formed film can be suppressed.
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.

When a fluororesin is used for forming the liquid repellent portion H, a solution obtained by dissolving a predetermined amount of fluororesin in a predetermined solvent is used. Specifically, “EGC1720” manufactured by Sumitomo 3M Limited (0.1% by weight of fluororesin dissolved in HFE (hydrofluoroether) solvent) can be used. In this case, it is possible to adjust the droplet discharge head 301 so that it can be stably discharged by mixing HFE with an alcohol, hydrocarbon, ketone, ether, or ester solvent as appropriate. In addition, as a fluororesin, “Lumiflon” manufactured by Asahi Glass Co., Ltd. (dissolvable in various solvents), “OPTOOL” manufactured by Daikin Industries, Ltd. (solvent: PFC, HFE, etc.), “manufactured by Dainippon Ink & Chemicals, Inc.” “Dick guard” (solvent: toluene, water / ethylene glycol) or the like can be used.
Further, as the resin containing fluorine, F group in the side _{chain, -CF 3, -CF 2 -,} - CF 2 CF 3, - (CF 2) nCF 3, be those containing the -CF 2 CFCl- Is possible.

Then, as shown in FIGS. 4A and 4B, the liquid repellent liquid droplets L containing the above liquid repellent material are continuously discharged from the liquid droplet discharge head 301 to each liquid repellent portion H. (First step).
At this time, in each liquid repellent portion H, the liquid repellent liquid droplet L that has landed on the surface Pa of the substrate P is ejected and applied to a position where adjacent liquid droplets overlap each other. Thereby, each liquid repellent portion H is applied and formed by one scan of the droplet discharge head 301 and the substrate.

Here, as shown in FIG. 3A, the width WA of the wiring pattern W is set by the difference between the arrangement pitch HP of the liquid repellent portions H and the width HA of the liquid repellent portions H. Since the arrangement pitch HP is determined as a specification of the wiring pattern W, the width WA of the wiring pattern W depends on the width HA of the liquid repellent portion H. In this embodiment, the width HA of the liquid repellent portion H is managed by the discharge amount of the liquid repellent droplets L discharged from the droplet discharge head 301 and the discharge pitch LP shown in FIG.
Specifically, for example, the discharge amount of the droplet L is set to two (La, Lb, for example, La = 2.5 pl, Lb = 4.5 pl), and the discharge pitch LP is set to 10 for each discharge amount La, Lb. , 20 and 30 μm, the width HA of the liquid repellent portion H formed on the substrate P is held as a table corresponding to the discharge amount and the discharge pitch LP, and the desired width HA is obtained. When the liquid repellent portion H is formed, a discharge amount and a discharge pitch LP corresponding to the width HA are called from the table, and in the liquid repellent droplet discharge step, the liquid discharge is performed at the called discharge amount and discharge pitch LP. The droplet L is discharged.

Then, by pre-drying the liquid repellent droplets L discharged on the substrate P, the linear liquid repellent portions H are spaced from each other on the substrate P as shown in FIGS. 5 (a) and 5 (b). It is formed with a thickness of several nanometers to several tens of nanometers.
The liquid repellent portion H uses the liquid repellent material described above to make the contact angle with respect to the pattern droplets 50 degrees or more. Accordingly, the contrast (contact angle difference) between the lyophilic part (surface) Pa and the liquid repellent part H is 30 degrees or more.

(Material placement process)
Next, a pattern droplet is discharged between the liquid repellent portions H of the surface Pa of the substrate P to form a wiring pattern W.
The wiring pattern forming material is generally composed of a dispersion liquid in which conductive fine particles are dispersed in a dispersion medium. In the present embodiment, as the conductive fine particles, for example, metal fine particles containing any one of gold, silver, copper, palladium, nickel, and ITO, these oxides, and conductive polymers and superconductors. Fine particles are used.
These conductive fine particles can be used by coating the surface with an organic substance or the like in order to improve dispersibility.
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 possibility that clogging may occur in the nozzle of the liquid discharge head described later. On the other hand, if it is smaller than 1 nm, the volume ratio of the coating agent to the conductive fine particles becomes large, and the ratio of the organic matter in the obtained film becomes excessive.

  The dispersion medium 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. Of these, water, alcohols, hydrocarbon compounds, and ether compounds are preferred from the viewpoints of fine particle dispersibility and dispersion stability, and ease of application to the droplet discharge method (inkjet method). More preferred dispersion media include water and hydrocarbon compounds.

  The surface tension of the conductive fine particle dispersion is preferably in the range of 0.02 N / m to 0.07 N / m. When the liquid is ejected by the ink jet method, if the surface tension is less than 0.02 N / m, the wettability of the ink composition to the nozzle surface increases, and thus flight bending tends to occur, exceeding 0.07 N / m. Since the meniscus shape at the nozzle tip is not stable, it becomes difficult to control the discharge amount and the 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 dispersion within a range that does not significantly reduce the contact angle with the substrate. The nonionic surface tension modifier improves the wettability of the liquid to the substrate, improves the leveling property of the film, and helps prevent the occurrence of fine irregularities in the film. The surface tension modifier may contain an organic compound such as alcohol, ether, ester, or ketone, if necessary.

  The viscosity of the dispersion is preferably 1 mPa · s to 50 mPa · s. When a liquid material is ejected as droplets using the inkjet 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 hole The clogging frequency of the liquid becomes high, and it becomes difficult to smoothly discharge the droplets.

  Then, as shown in FIGS. 6A and 6B, the pattern droplets WL including the wiring pattern forming material are continuously discharged from the droplet discharge head 301 into the gap between the liquid repellent portions H. And apply (second step). Specifically, the pattern is formed at a predetermined pitch while relatively moving the droplet discharge head 301 and the substrate P along the length direction (wiring pattern forming direction) of the liquid repellent portion H (lyophilic portion Pa). A plurality of liquid droplets WL are discharged.

  Here, since the surface Pa of the substrate P has a contact angle of 20 degrees or less with respect to the pattern droplet WL, the applied pattern droplet WL repels without being divided or causing a bulge. It spreads between the liquid parts H. Further, since the difference (contrast) in contact angle between the liquid repellent part H and the surface Pa with respect to the pattern liquid droplet WL is 30 degrees or more, the pattern liquid droplet WL is formed on the basis of the difference in wettability. Is repelled from the surface and introduced into the surface Pa between the liquid repellent portions H and collected. As this contrast, 30 degrees or more is sufficient, but it is more preferable that it is 35 degrees or more in consideration of an embodiment described later.

  The liquid repellent part H has a thickness as small as several nanometers to several tens of nanometers, and thus does not have a function as a partition that defines the position of the applied pattern droplet WL. The pattern droplet WL is disposed in the lyophilic portion Pa due to the above-described difference in contact angle (wetting property).

(Heat treatment / light treatment process)
Next, in the heat treatment / light treatment step, the dispersion medium or the coating agent contained in the droplets disposed on the substrate is removed. That is, the liquid material for forming a conductive film disposed on the substrate needs to completely remove the dispersion medium in order to improve electrical contact between the fine particles. Further, when a coating agent such as an organic substance is coated on the surface of the conductive fine particles in order to improve dispersibility, it is also necessary to remove this coating agent.

  The heat treatment and / or light treatment is usually performed in the air, but may be performed in an inert gas atmosphere such as nitrogen, argon, or helium as necessary. The treatment temperature of the heat treatment and / or the light treatment depends on the boiling point (vapor pressure) of the dispersion medium, the type and pressure of the atmospheric gas, the thermal behavior such as the dispersibility and oxidation of the fine particles, the presence and amount of the coating agent, It is determined appropriately in consideration of the heat resistant temperature.

For example, in order to remove the coating agent made of organic matter, it is necessary to bake at about 300 ° C. Moreover, when using a board | substrate, such as a plastic, it is preferable to carry out at room temperature or more and 100 degrees C or less. Here, baking was performed at 250 ° C. for 60 minutes.
The heat treatment and / or light treatment may be performed using lamp annealing in addition to general heat treatment using a heating means such as a hot plate or an electric furnace. The light source used for lamp annealing is not particularly limited, but excimer laser such as infrared lamp, xenon lamp, YAG laser, argon laser, carbon dioxide laser, XeF, XeCl, XeBr, KrF, KrCl, ArF, ArCl, etc. Can be used. These light sources generally have a power 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.
By the heat treatment and / or light treatment, electrical contact between the fine particles is ensured and converted into a conductive film.
The linear wiring pattern W shown in FIG. 3A is formed on the substrate P through the series of steps described above.

(Example)
Solvent-metal was glycol-ITO, ether-ITO, glycol-Ni, water-Ag, hydrocarbon-Ag, liquid-repellent part H width HA = 100 μm, wiring pattern W width WA = 40 μm. FIG. 7 shows the relationship among the contact angle, contrast, and drawing result of the liquid repellent part H and the lyophilic part Pa.
As shown in this figure, if the contact angle of the lyophilic part is 20 ° or less, no bulge is generated, and the contact angle of the lyophobic part is 50 ° or more and the contrast is 30 ° or more (preferably 35 ° or more). Then, it was possible to form a uniform wiring pattern satisfactorily.

  As described above, in the present embodiment, since the liquid repellent portion H is formed by applying the liquid repellent droplet L to the substrate P having the surface Pa of the lyophilic portion, an expensive exposure machine or There is no need to use a photomask, a laser light source, etc., and it is possible to prevent an increase in cost. In the present embodiment, the width HA of the liquid repellent portion H, that is, the width of the wiring pattern W can be easily adjusted by adjusting the discharge amount and discharge pitch of the liquid repellent droplets L. In particular, in the present embodiment, since a table showing the correlation between the discharge amount and the discharge pitch and the width HA of the liquid repellent portion H is used, the liquid repellent set according to the width WA of the wiring pattern W to be formed. The discharge amount and discharge pitch of the conductive droplet L can be selected easily and quickly, which can contribute to the improvement of productivity.

  In the present embodiment, the liquid-repellent liquid droplets L that have landed on the substrate P are applied so that the adjacent liquid droplets L overlap each other. Each liquid repellent portion H can be formed by one scan, which can contribute to further improvement in productivity.

(Electro-optical device)
Next, a plasma display device which is an example of an electro-optical device manufactured using the pattern forming method will be described with reference to FIGS.
FIG. 8 is an exploded perspective view of a plasma display device (electro-optical device) 500 according to this embodiment.
The plasma display device 500 includes glass substrates 501 and 502 arranged to face each other, and a discharge display unit 510 formed therebetween.

  Address electrodes 511 are formed in stripes at predetermined intervals on the upper surface of the glass substrate 501, and a dielectric layer 519 is formed so as to cover the address electrodes 511 and the upper surface of the glass substrate 501. A partition wall 515 is formed on the dielectric layer 519 so as to be positioned between the address electrodes 511 and 511 and along the address electrodes 511. In addition, a phosphor 517 is disposed inside a stripe-shaped region partitioned by the partition 515. The phosphor 517 emits red, green, or blue fluorescence. The red phosphor 517 (R) is disposed on the bottom and side surfaces of the red discharge chamber 516 (R), and the green discharge chamber 516 (G). A green phosphor 517 (G) is disposed on the bottom and side surfaces of the blue discharge chamber, and a blue phosphor 517 (B) is disposed on the bottom and side surfaces of the blue discharge chamber 516 (B).

On the other hand, on the glass substrate 502 side, display electrodes 512 made of a plurality of transparent conductive films are formed in stripes at predetermined intervals in a direction orthogonal to the previous address electrodes 511 and supplement the display electrodes 512 with high resistance. Therefore, a bus electrode 512 a is formed on the display electrode 512. Further, a dielectric layer 513 is formed so as to cover them, and a protective film 514 made of MgO or the like is further formed.
The glass substrate 501 and the glass substrate 502 are bonded to each other with the address electrodes 511... And the display electrodes 512.
The discharge display unit 510 is a collection of a plurality of discharge chambers 516. Of the plurality of discharge chambers 516, a red discharge chamber 516 (R), a green discharge chamber 516 (G), a blue discharge chamber 516 (B), a pair of three discharge chambers 516 and a pair of display electrodes The enclosed area is arranged to constitute one pixel.
The address electrodes 511 and the display electrodes 512 are connected to an AC power supply (not shown). By energizing each electrode, the phosphor 517 emits light in the discharge display portion 510, and color display is possible.

In the present embodiment, the display electrode 512, the bus electrode 512a, and the address electrode 511 are formed using the pattern forming method described above.
The address electrodes 511 are formed in the surface treatment process, the liquid repellent part formation process, the material arrangement process, and the heat treatment / light treatment process on the glass substrate 501 in the same manner as the wiring pattern W described above. Is omitted.

Hereinafter, a procedure for forming the display electrode 512 and the bus electrode 512a will be described with reference to FIGS.
First, similarly to the wiring pattern W described above, after performing the surface treatment process on the lyophilic portion of the glass substrate 502 and the surface 502a which is the first pattern formation surface, as shown in FIGS. Then, the liquid repellent part 500H surrounding the periphery of the region where the display electrode 512 is formed is formed. The liquid repellent portion 500H was also formed by discharging and applying liquid repellent droplets obtained by mixing the above-described ODS with a mixture of aromatic hydrocarbons with a droplet discharge amount of 2.5 pl and a discharge pitch of 50 μm, for example. Then, display droplets 512 are formed by discharging and applying pattern droplets containing ITO fine particles in the gaps between the liquid repellent portions 500H and firing them at 300 ° C. for 1 hour. Further, by heating the liquid repellent part 500H, the liquid repellency of the liquid repellent part 500H is removed.

  Subsequently, with respect to the glass substrate 502 on which the display electrode 512 is formed in this manner, as shown in FIGS. 10A and 10B, the region where the bus electrode 512a is formed is surrounded (sandwiched). Similarly to the formation of the liquid repellent part 500H, the liquid repellent part 512H is formed by ejecting and applying liquid repellent droplets in which the above-described ODS is mixed with an aromatic hydrocarbon mixture. At this time, a part of the display electrode 512 is exposed in a region where the bus electrode 512a is formed.

Then, a pattern droplet containing Ag fine particles is ejected and applied to a part of the exposed display electrode 512 in a gap between the liquid repellent portions 512H, and baked at 300 ° C. for 1 hour. Thus, as shown in FIGS. 11A and 11B, a bus electrode 512a that is electrically connected to the display electrode 512 is formed.
Even when the display electrode 512, the bus electrode 512a, and the address electrode 511 are formed, the width of the display electrode 512, the bus electrode 512a, and the address electrode 511 is adjusted by adjusting the width of the liquid repellent portion and the discharge amount and discharge pitch based on a previously held table.

  As described above, even in this embodiment, patterns such as the display electrodes 512, the bus electrodes 512a, and the address electrodes 511 can be formed without using an expensive exposure machine, photomask, laser light source, etc. This makes it possible to easily and quickly select the discharge amount and discharge pitch of the liquid repellent droplets set according to the width of the pattern to be formed, thereby improving productivity. Can contribute.

  As the transparent conductive film forming material for forming the display electrode 512, in addition to the above-described ITO, at least one component metal (indium, tin, antimony, aluminum, and zinc) of the metal oxide for forming the transparent conductive film is used. Fine particles of these metals, fine particles of at least one alloy composed of two or more metals selected from these component metals, and mixed fine particles of these metal fine particles and alloy fine particles can be used.

(Electromagnetic wave shield)
Next, an electromagnetic wave shield which is an example of an electro-optical device manufactured using the pattern forming method will be described with reference to FIG.
Fig.12 (a) is a top view of an electromagnetic wave shield, FIG.12 (b) is a side view.
The electromagnetic wave shield (electro-optical device) SL shown in this figure has a configuration in which a pattern PT is formed by a conductive wire on a transparent substrate P such as a transparent resin or a glass substrate.

  The pattern PT includes a mesh portion MS formed in a mesh shape in which a plurality of straight wirings intersect with each other with a space therebetween, and a frame portion GB formed around the mesh portion MS. The mesh part MS and the frame part GB are all formed of the above-described metals (Au, Ag, Cu, palladium, nickel, ITO, etc.). The wiring constituting the mesh portion MS improves the shielding performance as the width increases. However, since the aperture ratio decreases, the wiring is appropriately set according to the specifications required for the electromagnetic wave shield SL. In this embodiment, the wiring width is 30 μm or less and the wiring pitch is 250 to 400 μm.

When the electromagnetic shield SL is formed, similarly to the wiring pattern W described above, it is formed by a surface treatment process, a liquid repellent part formation process, a material arrangement process, and a heat treatment / light treatment process for the glass substrate P. In this liquid repellent part forming step, the liquid repellent droplets obtained by mixing the above-described ODS with a mixture of aromatic hydrocarbons are formed according to the line width of the mesh part MS to be formed (that is, the width of the lyophilic part to be formed). The liquid-repellent part 513H is formed by discharging and applying to the region to be the opening of the mesh part MS, for example, with a discharge amount of 2.5 pl and a discharge pitch of 50 μm. Then, liquid droplets containing the metal fine particles are applied to the lyophilic part (surface of the glass substrate P) exposed in the gap between the liquid repellent parts 513H and the edge of the substrate, for example, at a discharge amount of 2.2 pl and a discharge pitch of 30 μm. The electromagnetic wave shield SL having the mesh part MS and the frame part GB can be formed by discharging and applying and baking under conditions of 300 ° C. for 1 hour.
By using such an electromagnetic wave shield SL, not only the influence of the health hazard on the human body but also the influence of the high frequency electromagnetic wave noise generated from the electronic device can be reduced, and the disturbance of the screen and the noise of the speaker can be reduced.

  As described above, also in the present embodiment, the pattern PT including the mesh part MS and the frame part GB can be formed without using an expensive exposure machine, photomask, laser light source, and the like, thereby preventing an increase in cost. It becomes possible, and it becomes possible to easily and quickly select the discharge amount and discharge pitch of the liquid repellent droplets set according to the width of the pattern to be formed, which contributes to the improvement of productivity. it can.

(Liquid crystal display device)
Next, a liquid crystal display device which is an example of an electro-optical device manufactured using the pattern forming method will be described with reference to FIGS.
FIG. 13 is a plan view of the liquid crystal display device according to the present invention as viewed from the counter substrate side shown together with each component, and FIG. 14 is a cross-sectional view taken along the line HH ′ of FIG. FIG. 15 is an equivalent circuit diagram of various elements and wirings in a plurality of pixels formed in a matrix in the image display region of the liquid crystal display device, and FIG. 16 is a partial enlarged cross-sectional view of the liquid crystal display device. In each drawing used in the following description, the scale is different for each layer and each member so that each layer and each member can be recognized on the drawing.

  13 and 14, in the liquid crystal display device (electro-optical device) 100 according to the present embodiment, a pair of TFT array substrate 10 and counter substrate 20 are attached by a sealing material 52 that is a photo-curable sealing material. The liquid crystal 50 is sealed and held in the region partitioned by the sealing material 52. The sealing material 52 is formed in a frame shape that is closed in a region within the substrate surface, does not include a liquid crystal injection port, and does not have a trace sealed with the sealing material.

  A peripheral parting 53 made of a light shielding material is formed in a region inside the region where the sealing material 52 is formed. A data line driving circuit 201 and a mounting terminal 202 are formed along one side of the TFT array substrate 10 in a region outside the sealing material 52, and the scanning line driving circuit 204 is formed along two sides adjacent to the one side. Is formed. On the remaining side of the TFT array substrate 10, a plurality of wirings 205 are provided for connecting between the scanning line driving circuits 204 provided on both sides of the image display area. Further, at least one corner of the counter substrate 20 is provided with an inter-substrate conductive material 206 for establishing electrical continuity between the TFT array substrate 10 and the counter substrate 20.

Instead of forming the data line driving circuit 201 and the scanning line driving circuit 204 on the TFT array substrate 10, for example, a TAB (Tape Automated Bonding) substrate on which a driving LSI is mounted and a peripheral portion of the TFT array substrate 10 The terminal group formed in the above may be electrically and mechanically connected via an anisotropic conductive film. In the liquid crystal display device 100, depending on the type of the liquid crystal 50 to be used, that is, depending on the operation mode such as TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, or normally white mode / normally black mode. A retardation plate, a polarizing plate, and the like are arranged in a predetermined direction, but the illustration is omitted here.
Further, when the liquid crystal display device 100 is configured for color display, in the counter substrate 20, for example, red (R), green (G), A blue (B) color filter is formed together with the protective film.

  In the image display region of the liquid crystal display device 100 having such a structure, as shown in FIG. 15, a plurality of pixels 100a are configured in a matrix, and each of these pixels 100a has a pixel switching region. TFT (switching element) 30 is formed, and a data line 6 a for supplying pixel signals S 1, S 2,..., Sn is electrically connected to the source of the TFT 30. The pixel signals S1, S2,..., Sn to be written to the data line 6a may be supplied line-sequentially in this order, or may be supplied for each of a plurality of adjacent data lines 6a. . Further, the scanning line 3a is electrically connected to the gate of the TFT 30, and the scanning signals G1, G2,..., Gm are applied to the scanning line 3a in a pulse-sequential manner in this order at a predetermined timing. It is configured.

  The pixel electrode 19 is electrically connected to the drain of the TFT 30, and the pixel signal S1, S2,..., Sn supplied from the data line 6a is obtained by turning on the TFT 30 as a switching element for a certain period. Write to each pixel at a predetermined timing. The pixel signals S1, S2,..., Sn written in the liquid crystal via the pixel electrode 19 in this way are held for a certain period with the counter electrode 121 of the counter substrate 20 shown in FIG. In order to prevent the held pixel signals S1, S2,..., Sn from leaking, a storage capacitor 60 is added in parallel with the liquid crystal capacitor formed between the pixel electrode 19 and the counter electrode 121. For example, the voltage of the pixel electrode 19 is held by the storage capacitor 60 for a time that is three orders of magnitude longer than the time when the source voltage is applied. Thereby, the charge retention characteristics are improved, and the liquid crystal display device 100 with a high contrast ratio can be realized.

FIG. 16 is a partial enlarged cross-sectional view of the liquid crystal display device 100 having the bottom gate type TFT 30, and the gate wiring 61 is formed on the glass substrate P constituting the TFT array substrate 10 by the pattern forming method of the above embodiment. Has been.
A semiconductor layer 63 made of an amorphous silicon (a-Si) layer is stacked on the gate wiring 61 with a gate insulating film 62 made of SiNx interposed therebetween. A portion of the semiconductor layer 63 facing the gate wiring portion is a channel region. On the semiconductor layer 63, junction layers 64a and 64b made of, for example, an n + -type a-Si layer for obtaining an ohmic junction are stacked, and the channel is protected on the semiconductor layer 63 in the central portion of the channel region. An insulating etch stop film 65 made of SiNx is formed. The gate insulating film 62, the semiconductor layer 63, and the etch stop film 65 are patterned as shown in the figure by performing resist coating, photosensitive / developing, and photoetching after vapor deposition (CVD).

  Further, the bonding electrodes 64a and 64b and the pixel electrode 19 made of ITO are formed in the same manner, and are patterned as shown in the figure by performing photoetching. Banks 66 are provided on the pixel electrode 19, the gate insulating film 62, and the etch stop film 65, and silver droplets are discharged between the banks 66 using the above-described droplet discharge device IJ. Thus, a source line and a drain line can be formed.

As shown in FIG. 17, a recess is provided in the gate insulating film 62, a semiconductor layer 63 is formed in the recess substantially flush with the surface of the gate insulating film 62, and bonding layers 64a, 64b, The pixel electrode 19 and the etch stop film 65 can also be formed. In this case, by making the groove bottom between the banks 66 substantially flat as compared with FIG. 16, the bent portions of these layers and the source lines and drain lines are reduced, and a high characteristic TFT with improved flatness can be obtained. it can.
As described above, in the present embodiment, it is possible to obtain the liquid crystal display device 100 that is high quality, thin, and highly integrated.

  In the TFT configured as described above, after applying the liquid repellent droplets and patterning the liquid repellent portion and the lyophilic portion using the above-described droplet discharge device IJ, for example, a silver compound droplet is discharged to the lyophilic portion. As a result, gate lines, source lines, drain lines, etc. can be formed without using an expensive exposure machine, photomask, laser light source, etc. The discharge amount and discharge pitch of the liquid repellent droplets set according to the width of the pattern to be set can be selected easily and quickly, which can contribute to the improvement of productivity.

In the above embodiment, the TFT 30 is used as a switching element for driving the liquid crystal display device 100. However, the present invention can be applied to, for example, an organic EL (electroluminescence) display device in addition to the liquid crystal display device. An organic EL display device has a structure in which a thin film containing a fluorescent inorganic and organic compound is sandwiched between a cathode and an anode, and is excited by injecting electrons and holes into the thin film and recombining them. It is an element that emits light by using light emission (fluorescence / phosphorescence) when a child (exciton) is generated and the exciton is deactivated. Then, on the substrate having the TFT 30 described above, among the fluorescent materials used for the organic EL display element, a material exhibiting each emission color of red, green and blue, that is, a light emitting layer forming material and a hole injection / electron transport layer are provided. A self-luminous full-color EL device can be manufactured by using ink as a material to be formed and patterning each.
The range of the electro-optical device in the present invention includes such an organic EL device, and it is possible to obtain a high-quality organic EL device that realizes desired characteristics and does not cause defects such as a short circuit.

(Non-contact card media)
Subsequently, an embodiment of a non-contact card medium will be described. As shown in FIG. 18, a non-contact type card medium (electronic device) 400 according to the present embodiment includes a semiconductor integrated circuit chip 408 and an antenna circuit 412 in a housing formed of a card base 402 and a card cover 418. At least one of power supply and data transmission / reception is performed by at least one of electromagnetic waves and capacitive coupling with an external transceiver (not shown).

In the present embodiment, the antenna circuit 412 is formed by the pattern forming method according to the embodiment.
According to the contactless card medium manufacturing method of the present embodiment, it is possible to prevent an increase in cost and contribute to an improvement in productivity.
In addition to the above, the electro-optical device according to the present invention is a surface conduction type that utilizes a phenomenon in which electron emission is caused by flowing a current through a small-area thin film formed on a substrate in parallel to the film surface. It can also be applied to an electron-emitting device or the like.

(Electronics)
Next, specific examples of the electronic device according to the present invention will be described.
FIG. 19A is a perspective view showing an example of a mobile phone. In FIG. 19A, reference numeral 600 denotes a mobile phone body, and reference numeral 601 denotes a liquid crystal display unit including the liquid crystal display device of the above embodiment.
FIG. 19B is a perspective view showing an example of a portable information processing apparatus such as a word processor or a personal computer. In FIG. 19B, reference numeral 700 denotes an information processing device, 701 denotes an input unit such as a keyboard, 703 denotes an information processing body, and 702 denotes a liquid crystal display unit including the liquid crystal display device of the above embodiment.
FIG. 19C is a perspective view showing an example of a wristwatch type electronic device. In FIG. 19C, reference numeral 800 denotes a watch body, and reference numeral 801 denotes a liquid crystal display unit including the liquid crystal display device of the above embodiment.
Since the electronic devices shown in FIGS. 19A to 19C are provided with the liquid crystal display device of the above-described embodiment, it is possible to prevent an increase in cost and improve productivity. .
In addition, although the electronic device of this embodiment shall be provided with a liquid crystal device, it can also be set as the electronic device provided with other electro-optical apparatuses, such as an organic electroluminescent display apparatus and a plasma type display apparatus.

  As described above, the preferred embodiments according to the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the examples. Various shapes, combinations, and the like of the constituent members shown in the above-described examples are examples, and various modifications can be made based on design requirements and the like without departing from the gist of the present invention.

  For example, in the above-described embodiment, a liquid material containing a conductive material as the functional liquid has been described. However, the functional liquid is a metal, semiconductor, ceramic, organic material, pigment, or optical material that is used as a functional liquid and desired on the substrate. It is a material which obtains a thin film through a firing step by placing it at the position. Examples of the function include conductivity, insulating properties, semiconductor properties, light collecting properties, light selective absorption properties, luminescence properties such as fluorescence or phosphorescence, and orientation control of liquid crystal molecules.

  In the above-described embodiment, the wiring main body is formed with the functional liquid. However, the present invention is not limited to this, and a plating catalyst film is formed by applying droplets containing a plating catalyst material such as palladium. May be. In this case, when performing the plating process in a subsequent process, a highly dense wiring (such as Cu) can be easily and inexpensively formed by performing the plating process.

  Moreover, in the said embodiment, in order to improve lyophilicity with respect to the board | substrate P, although demonstrated as what implements a washing process as a surface treatment process, it is not limited to this, For example, it is a functional liquid (for pattern A configuration in which a silane coupling agent or a titanium coupling agent exhibiting lyophilicity with respect to (liquid droplets) is applied to the surface Pa, or a configuration in which titanium oxide fine particles are applied may be employed.

It is a schematic block diagram of a droplet discharge apparatus. 2 is a cross-sectional view of a droplet discharge head 301. It is a figure which shows the liquid-repellent part and wiring pattern which were formed on the board | substrate. It is a figure which shows a pattern formation process. It is a figure which shows a pattern formation process. It is a figure which shows a pattern formation process. It is a figure which shows the relationship between the contact angle of a liquid repellent part and a lyophilic part, contrast, and a drawing result. It is an exploded perspective view of a plasma display device. It is a figure which shows the procedure which forms a display electrode and a bus electrode. It is a figure which shows the procedure which forms a display electrode and a bus electrode. It is a figure which shows the procedure which forms a display electrode and a bus electrode. It is a figure which shows an electromagnetic wave shield. It is the top view which looked at the liquid crystal display device from the counter substrate side. It is sectional drawing which follows the H-H 'line | wire of FIG. It is an equivalent circuit diagram of a liquid crystal display device. It is a partial expanded sectional view of a liquid crystal display device same as the above. It is a partial expanded sectional view of the liquid crystal display device of another form. It is a disassembled perspective view of a non-contact type card medium. It is a figure which shows the specific example of an electronic device.

Explanation of symbols

  GB: Frame portion, H: Liquid repellent portion, L: Droplet, MS: Mesh portion, P: Substrate, Pa: Surface (lyophilic portion), SL: Electromagnetic wave shield (electro-optical device), W: Wiring pattern (pattern) ), 100 ... Liquid crystal display device (electro-optical device), 400 ... Non-contact card medium (electronic device), 500 ... Plasma display device (electro-optical device), 600 ... Mobile phone body (electronic device), 700 ... Information Processing device (electronic equipment), 800 ... Watch body (electronic equipment)

Claims (14)

A pattern forming method for forming a pattern by applying the functional liquid to a substrate having a lyophilic part and a liquid repellent part with respect to the functional liquid,
A first step of forming droplets containing a liquid repellent material on the substrate having the lyophilic portion to form the liquid repellent portion;
A second step of applying the functional liquid to the lyophilic part between the liquid repellent parts,
In the first step, the width of the liquid repellent part is adjusted by adjusting the discharge amount and discharge pitch of the liquid repellent material droplets. In the pattern formation method of Claim 1,
Holds a table showing the correlation between the discharge amount and discharge pitch of droplets containing the liquid repellent material and the width of the liquid repellent part,
In the first step, a liquid droplet containing the liquid repellent material is applied using the table. In the pattern formation method of Claim 1 or 2,
A pattern forming method, wherein droplets containing the liquid repellent material landed on the substrate are applied so that adjacent droplets overlap each other. In the pattern formation method as described in any one of Claim 1 to 3,
The liquid repellent material contains at least one of a silane compound and a compound having a fluoroalkyl group. In the pattern formation method of Claim 4,
The pattern forming method, wherein the silane compound is a self-assembled film. In the pattern formation method of Claim 4 or 5,
The pattern forming method, wherein the liquid repellent portion is formed on the surface of the substrate by a self-assembled film made of a compound having the fluoroalkyl group. In the pattern formation method of Claim 4 or 5,
The liquid-repellent part is formed by a self-assembled film having an alkyl group and hydrogen on the surface of the substrate. In the pattern formation method as described in any one of Claim 1 to 3,
The pattern forming method, wherein the liquid repellent material contains a fluororesin. In the pattern formation method as described in any one of Claim 1 to 8,
In the second step, the functional liquid droplets are applied to the lyophilic portion. In the pattern formation method as described in any one of Claim 1 to 9,
The pattern forming method, wherein the functional liquid includes a conductive material. In the pattern formation method as described in any one of Claim 1 to 10,
The pattern forming method, wherein the functional liquid contains a plating catalyst material.   An electro-optical device manufacturing method comprising a step of forming a pattern by the pattern forming method according to claim 1. The electro-optical device manufacturing method according to claim 12,
The electro-optical device is an electromagnetic wave shield having a mesh portion formed in a mesh shape with a conductive wire and a frame portion formed around the mesh portion with the conductive wire,
The electro-optical device manufacturing method, wherein the mesh portion and the frame portion are formed by the pattern forming method.   An electronic device manufacturing method comprising a step of forming a pattern by the pattern forming method according to claim 1.

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