JP2006167696A - Pattern forming method, pattern forming apparatus, and method for manufacturing electronic application equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method capable of forming various kinds of patterns with high fineness and high accuracy by a simple process. <P>SOLUTION: After a material 3 having flowability is applied on a substrate 1 having a hydrophilic portion 1a and a liquid-repellent portion 1b on the surface, the substrate 1 coated with the material 3 and a member 4 having a hydrophilic surface are relatively moved in such a manner that the member 4 and the material 3 come into contact with each other. The surface free energy of the hydrophilic portion 1a is made to ≥50 mJ/m<SP>2</SP>. The surface free energy of the liquid-repellent portion 1b is made to ≤30 mJ/m<SP>2</SP>. The surface free energy of the member 4 having the hydrophilic surface is made to ≥50 mJ/m<SP>2</SP>. The spacing between the substrate 1 and the member 4 is made to 0.1 μm to 10 mm. The material 3 having the flowability is a liquid, solution mixture, dispersion liquid, etc. The moving speed is made to 0./01 to 1,000 m/s. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a pattern forming method, a pattern forming apparatus, and an electronic application apparatus manufacturing method, and is suitable for application to, for example, forming various patterns used in an electronic application apparatus.

Conventionally, as a pattern forming method, for example, a method using an offset printing method, an ink jet method, a slit coating method or the like is known.
In the offset printing method, ink is filled using a roll onto a lithographic plate whose hydrophilicity and oil repellency are controlled (see, for example, Non-Patent Document 1). In a normal offset printing method, water is supported in advance on the hydrophilic portion of the plate, and after the oil-based ink is coated on the roll, the plate and the roll are brought into contact with each other. In the waterless offset printing method, the oil repellent part is formed of a silicone resin.
Kazuhito Izumi, “Introduction to New Printing Machinery” (Publishing Department, Japan Society for Printing Technology, published on October 31, 2001)

The ink jet method is an excellent method capable of directly forming a designed pattern on a substrate without using a photolithography technique. In this inkjet method, lyophilicity and liquid repellency are controlled on a substrate for pattern formation due to problems such as the accuracy of driving position of the inkjet head, the size of ejected droplets, and the landing accuracy of ejected droplets. Ingenuity such as providing layers has been incorporated. For example, Patent Document 1 discloses a method for appropriately landing ink jet droplets on a lyophobic / liquid repellent pattern.
JP 2003-317945 A

The slit coat method is a method that can possibly improve the definition limit of the ink jet method. For example, Patent Document 2 discloses details thereof, but this method is used only for applying a liquid onto a substrate having controlled lyophilicity and liquid repellency, and remains in the liquid repellent part. It is assumed that the liquid is removed in a separate process.
JP 2003-260406 A

However, the offset printing method has a problem that since the ink repels water, the pattern outline tends to be unclear and it is difficult to apply to electronic products that require a high-definition pattern. Further, in the waterless offset printing method in which the oil-repellent portion is formed of a silicone resin, the fineness is 30 μm or more in terms of the production method, and it is difficult to achieve higher definition.
In the ink jet method, even if the technique disclosed in Patent Document 1 is used, it is considered that there is a limit of definition depending on the size (20 μm to) of the ink jet droplet and the landing accuracy (± 30 μm).
In the slit coating method, as disclosed in Patent Document 2, it is assumed that the liquid remaining in the liquid repellent part is removed by rotating the substrate, tilting, gas blowing, etc. in a separate process. There is a problem that becomes complicated.
In addition to the above methods, methods such as immersing a substrate with controlled lyophilicity and liquid repellency in a liquid have been proposed, but as the pattern becomes more precise, the liquid will spread over a plurality of lyophilic parts. Problems such as filling (FIG. 13) and the need to perform liquid repellent treatment on the back surface of the substrate that does not require a pattern are pointed out. In FIG. 13, reference numeral 101 denotes a substrate, 101a denotes a lyophilic part, 101b denotes a liquid repellent part, and 102 denotes a liquid.

  Accordingly, the problem to be solved by the present invention is that a pattern forming method and a pattern forming apparatus capable of forming various patterns with high definition, high accuracy and simple steps, and an electronic application apparatus using the pattern forming method. It is in providing the manufacturing method of.

In order to solve the above problem, the first invention is:
Applying a fluid material on a substrate having a lyophilic part and a liquid repellent part on the surface;
A pattern forming method comprising: a step of relatively moving the substrate on which the material is applied and a member whose surface is lyophilic so that the member and the material are in contact with each other. .

In a substrate having a lyophilic portion and a lyophobic portion on the surface, the surface free energy of the lyophilic portion is generally 50 mJ / m ² or more, and the surface free energy of the lyophobic portion is 30 mJ / m ² or less. The material having fluidity is a liquid, a mixed solution, a dispersion, or the like, and its composition, solvent, etc. are selected according to the pattern to be formed. The surface free energy of a member having a lyophilic surface is generally 50 mJ / m ² or more. The shape of this member can be selected as required, but is typically a rod shape (bar shape). The moving speed when the member and the fluid material are relatively moved so as to come into contact with each other can be selected as necessary, but is generally 0.01 mm / s or more and 1000 mm / s. Hereinafter, it is typically 0.5 mm / s or more and 100 mm / s or less. In this case, the gap between the substrate and the member can be selected within a range where the fluid material applied onto the substrate and the member are in contact with each other. It is 1 to 10 mm, preferably 1 to 1 mm, typically 5 to 300 μm. With respect to the relative movement between the substrate coated with a fluid material and the member, the substrate may be fixed and the member may be moved relative to the substrate, or the member may be fixed. The substrate may be moved with respect to this member. Typically, the substrate on which the fluid material is applied and the above member are moved relatively in parallel with each other. This pattern forming method further includes a step of drying or firing the material after relatively moving the substrate on which the material is applied and the lyophilic member, as necessary.
This pattern forming method can be applied to the formation of various patterns. Specific examples include printed circuit board electrode patterns, light scattering sheet scattering layer patterns, various electronic device electrode patterns, transistor insulating layer patterns, coating semiconductor patterns, and organic electroluminescence (EL) material patterns. It can be applied to the formation of a protective film pattern, a nanoparticle pattern, and the like.

The second invention is
While applying a fluid material on a substrate having a lyophilic part and a liquid repellent part on the surface, the substrate on which the material is applied and the surface lyophilic member And a pattern forming method characterized by having a step of relatively moving the material and the material in contact with each other.
In the second invention, what has been described in relation to the first invention is valid as long as it is not against the nature thereof.

The third invention is
A substrate holding means having a lyophilic part and a liquid repellent part on the surface;
Means for applying a fluid material to the substrate;
A member whose surface is lyophilic,
A pattern forming apparatus comprising: means for relatively moving the substrate and the member coated with the material so that the member and the material are in contact with each other.
In the third invention, what has been described in relation to the first invention is valid as long as it is not contrary to the nature thereof.

The fourth invention is:
A step of immersing a substrate having a lyophilic part and a liquid repellent part on a surface in a fluid material accommodated in a predetermined container;
The substrate is lifted from the material, and when the substrate passes through the interface between the material and the external space, the material is filled by capillary action between the lyophilic member and the substrate. A pattern forming method comprising the steps of:

In the fourth invention, for example, a plurality of types of materials are accommodated in the container in a state where they are separated from each other in the depth direction, the substrate is immersed in the bottom layer material from the bottom of the container, and the plurality of types of materials are sequentially added. The substrate is pulled up so as to pass, and at this time, when the substrate passes through the interface between the materials, the material on the lower layer side is filled between the lyophilic member and the substrate by a capillary phenomenon. Alternatively, a plurality of types of materials are stored in the container in a state where they are separated from each other in the depth direction and / or the horizontal direction, the substrate is immersed in one material, and the substrate is moved so as to sequentially pass through the plurality of types of materials. The substrate is pulled up from another material, and when the substrate passes through the interface between the materials, the material on the rear side in the traveling direction is filled between the lyophilic member and the substrate by the capillary phenomenon. To.
In the fourth invention, what has been described in relation to the first invention is valid as long as it is not contrary to the nature thereof.

The fifth invention is:
A container for storing a material having fluidity;
Means for immersing a substrate having a lyophilic part and a liquid repellent part on the surface of the material contained in the container, and pulling up the substrate from the material;
When the substrate is pulled up from the material, the surface is lyophilic, provided that the material is filled by capillary action between the substrate and the substrate when passing through the interface between the material and the external space. It is a pattern formation apparatus characterized by having this member.
In the fifth invention, for example, when a plurality of types of materials are accommodated in the container in a state where they are separated from each other in the depth direction, the lower layer side between the substrates when the substrate passes through the interface between the materials. The surface further has a lyophilic member provided so as to be filled with the material. Alternatively, when a plurality of types of materials are stored in the container in a state where they are separated from each other in the depth direction and / or the horizontal direction, the traveling direction due to capillary action between the substrates when the substrates pass through the interface between the materials. The surface further has a lyophilic member provided to fill the material on the back side.
In the fifth invention, what has been described in relation to the first invention is valid as long as it is not contrary to the nature thereof.

The sixth invention is:
Applying a fluid material on a substrate having a lyophilic part and a liquid repellent part on the surface;
And a step of moving the substrate on which the material is applied and a member whose surface is lyophilic so that the member and the material are in contact with each other. Is the method.

The seventh invention
While applying a fluid material on a substrate having a lyophilic part and a liquid repellent part on the surface, the substrate on which the material is applied and the surface lyophilic member And a method of manufacturing the electronic application device, characterized by having a step of relatively moving the material and the material in contact with each other.

The eighth invention
A step of immersing a substrate having a lyophilic part and a liquid repellent part on a surface in a fluid material accommodated in a predetermined container;
The substrate is lifted from the material, and when the substrate passes through the interface between the material and the external space, the material is filled by capillary action between the lyophilic member and the substrate. A method for manufacturing an electronic application device.
In the sixth to eighth inventions, the electronic application device includes various devices using various patterns such as an electrode pattern, for example, a liquid crystal display and other image display devices.

In the present invention configured as described above, a material having fluidity attached to a substrate having a lyophilic portion and a lyophobic portion on the surface and a member having a lyophilic surface are relatively disposed. By moving, the material can remain only in the lyophilic portion of the substrate after the movement.
In addition, when the substrate having a lyophilic portion and a lyophobic portion on the surface passes through the interface between the material having fluidity and the external space, the capillary is interposed between the lyophilic member and the substrate. By allowing the material to be filled by the phenomenon, the material can remain only in the lyophilic portion of the substrate after the movement.

  According to the present invention, various patterns can be formed with high definition, high accuracy, and simple steps. And by using this pattern formation method, electronic application apparatuses, such as a liquid crystal display, can be manufactured at low cost.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
1 and 2 show a pattern forming method according to a first embodiment of the present invention.
In the first embodiment, as shown in FIG. 1A, first, a substrate 1 having a lyophilic part 1a and a liquid repellent part 1b on the surface is prepared. Here, the surface free energy of the lyophilic portion 1a is 50 mJ / m ² or more, the surface free energy of the liquid repellent portion 1b is less than 30 mJ / m ^2. The substrate 1 can be formed as follows, for example. In the first method, a photosensitive polyimide or photoresist is applied onto a substrate such as a lyophilic glass substrate, and a mask pattern is formed by patterning this using a photolithography method. The surface of the uncovered glass substrate is modified with a plasma gas containing a fluorine material to make it liquid repellent. Thereafter, the mask pattern is removed. In this case, the surface of the glass substrate covered with the mask pattern is lyophilic. In the second method, after applying a fluororesin solution as a liquid repellent material to the entire surface of a substrate such as a lyophilic glass substrate, a pattern is formed by an imprint method. In this case, the pattern portion is lyophobic and the original substrate portion on which this pattern is not formed is lyophilic. A silicone resin such as PDMS (polydimethylsiloxane) may be used instead of the fluororesin. In the third method, as a liquid repellent material, a silane coupling agent having a fluorine group or a methyl group and having a methoxy group or an ethoxy group chemically bonded to an inorganic material is diluted with water or an organic solvent, Is applied to the entire surface of a substrate such as a lyophilic glass substrate, and the film obtained by drying is patterned by performing ultraviolet (UV) ozone treatment or oxygen plasma treatment using a metal mask. Do. In this case, the pattern portion is lyophobic and the original substrate portion on which this pattern is not formed is lyophilic. This pattern may be formed by irradiating ultraviolet rays through a photomask.

  Next, as shown in FIG. 1B, the substrate 1 is placed on the stage 2 of the pattern forming apparatus, and a predetermined dropping device (not shown) provided above the stage 2 is used to place one on the substrate 1. A liquid 3 having fluidity as a pattern material is dropped onto a part or the whole. The amount of the liquid 3 needs to be sufficient with respect to the amount finally left in the lyophilic part 1a, and the liquid level is at a height that allows contact with the lyophilic bar used in the next step. It is desirable. In addition, when the liquid 3 is dropped on a part of the substrate 1, the liquid 3 is dropped at a leading position with respect to the traveling direction of the substrate 1. In FIG. 1B, the case where the liquid 3 is dripped in the position used as the head with respect to the advancing direction of the board | substrate 1 is shown.

Next, as shown in FIG. 1C, with respect to the bar 4 having a lyophilic surface with a rectangular cross section, for example, disposed parallel to the surface of the substrate 1 by a support member not shown, The stage 2 is moved in the horizontal plane. In this case, the gap between the substrate 1 and the bar 4 is preferably 1 μm or more and 1 mm or less. The surface free energy of the bar 4 is 50 mJ / m ² or more. Specifically, the material of the bar 4 is, for example, a metal or alloy such as aluminum (Al) or stainless steel, glass, silicon (Si), or the like.

When the stage 2 is moved with respect to the lyophilic bar 4 as described above, the upper part of the liquid 3 on the substrate 1 comes into contact with the bar 4 as shown in FIG. 2A. At this time, since the surface of the bar 4 is lyophilic, the liquid 3 is regulated by the bar 4 and is held (or fixed) around it. In this way, the stage 2 is moved until the substrate 1 comes out of the bar 4 while the liquid 3 is held on the bar 4. This state is shown in FIG. 2B. As shown in FIG. 2B, in the liquid repellent part 1b of the moving substrate 1, the liquid 3 moves so as to slide, but the liquid 3 does not remain, whereas in the lyophilic part 1a, the surface tension and the liquid 3 itself. The amount of the liquid 3 determined by the surface tension of the liquid remains. The excess liquid 3 that did not remain in the lyophilic portion 1 a out of the liquid 3 dropped first is held on the bar 4, or left on the stage 2 at a position behind the substrate 1 in the traveling direction. These excess liquids 3 can be recovered and reused.
If necessary, the substrate 1 with the liquid 3 remaining in the lyophilic portion 1a is dried or fired according to the properties of the liquid 3 to be used.
In this way, the target pattern 5 is obtained as shown in FIG. 1F.

  According to the first embodiment, on the surface of the substrate 1 having the lyophilic portion 1a and the liquid repellent portion 1b on the surface, the fluidity that becomes the material of the pattern is provided at the leading position with respect to the traveling direction of the substrate 1. After the liquid 3 is dropped, the substrate 1 is moved parallel to the lyophilic bar 4 so that the upper part of the liquid 3 on the substrate 1 is brought into contact with the bar 4 and the liquid 3 is applied to the bar 4. In this state, the substrate 1 is moved until it comes to a position off the bar 4, so that the liquid 3 can be left only on the surface of the lyophilic portion 1a of the substrate 1, and dried as necessary. Or the target pattern 5 can be finally formed by baking. According to this method, the lyophilic portion 1a and the lyophobic portion 1b can be formed with high definition and high accuracy by a photolithography method. Therefore, the target pattern 5 can be compared with the conventional offset printing method or inkjet method. High definition and high precision. Further, according to this method, the substrate 1 having the lyophilic portion 1 a and the liquid repellent portion 1 b on the surface is prepared, the liquid 3 is dropped on the substrate 1, and the substrate 1 is moved in parallel with the bar 4. It is not necessary to provide a process for removing unnecessary ink as in the conventional slit coating method, so that the target pattern 5 can be formed at a low cost by a simple process.

Next explained is a pattern forming method according to the second embodiment of the invention.
In the second embodiment, as shown in FIG. 3, a slit coater 6 is used for applying the liquid 3 onto the substrate 1. In the slit coater 6, the liquid 3 is discharged from the tip of the slit 6a. Then, the slit coater 6 is approached from above the substrate 1, and the liquid 3 is discharged onto the substrate 1 from the tip of the slit 6 a while moving the substrate 1 parallel to the bar 4 as indicated by the arrow in FIG. 3. Apply.
Since other than the above is the same as in the first embodiment, the description thereof is omitted.
According to the second embodiment, in addition to the same advantages as those of the first embodiment, the application of the liquid 3 onto the substrate 1 and the filling of the liquid 3 into the lyophilic part 1a are performed in the same process. Therefore, the advantage that the pattern can be formed by a simpler process can be obtained.

Next explained is a pattern forming method according to the third embodiment of the invention.
In the third embodiment, as shown in FIG. 4, the vertical relationship between the stage 2 and the substrate 1 is reversed from that of the first and second embodiments, and a capillary coater is used for applying the liquid 3 onto the substrate 1. 7 is used. In this capillary coater 7, the liquid 3 is discharged from the tip of the capillary 7a by capillary action. Then, the capillary coater 7 is approached from below the substrate 1, and the substrate 3 is moved in parallel to the bar 4 as shown by the arrow in FIG. 4, while the liquid 3 is transferred from the tip of the capillary 7a to the substrate 1 by capillary action. Discharge and apply.
Since other than the above is the same as in the first embodiment, the description thereof is omitted.
According to the third embodiment, the same advantages as those of the second embodiment can be obtained.

Next explained is a pattern forming method according to the fourth embodiment of the invention.
In the fourth embodiment, as shown in FIG. 5, the cross-sectional shape of the bar 4 whose surface is lyophilic is a semicircular shape convex toward the substrate 1 side.
Since other than the above is the same as in the first embodiment, the description thereof is omitted.
According to the fourth embodiment, the same advantages as those of the first embodiment can be obtained.

Next explained is a pattern forming method according to the fifth embodiment of the invention.
In the fifth embodiment, as shown in FIG. 6, the cross-sectional shape of the bar 4 having a lyophilic surface is circular. The bar 4 can be rotated around its central axis, and can be rotated as necessary.
Since other than the above is the same as in the first embodiment, the description thereof is omitted.
According to the fifth embodiment, advantages similar to those of the first embodiment can be obtained.

In Example 1, a case where the pattern formation method according to the fifth embodiment is applied to formation of a plating electrode pattern will be described.
First, the board | substrate 1 which has the lyophilic part 1a and the liquid repellent part 1b on the surface was formed as follows using a glass substrate.
Corning 1737 glass was used as the glass substrate. On top of that, a positive photosensitive polyimide (Photo Nice PW-1530) manufactured by Toray Industries, Inc. was applied as a pattern forming material by spin coating (2000 rpm / 30 seconds), followed by drying (120 ° C./3 minutes). After that, pattern exposure (broadband UV light source, i-line 250 mJ / cm ² ) is performed with a manual exposure machine (MA-1200 type) manufactured by Dainippon Screen Mfg. Co., Ltd., and development (2. 90% paddle development with 38% tetramethylammonium hydroxide (TMAH) solution) and baking (140 ° C./30 seconds + 300 ° C./60 minutes). The polyimide pattern thus obtained had a thickness of 2.5 μm, the highest definition of the pattern, and the line / space was 10/10 (μm).

Next, the surface of the polyimide pattern formed as described above was subjected to fluorine plasma radical treatment using a CDE (Chemical Dry Etching) apparatus (CDE-N80) manufactured by Shibaura Mechatronics. The process conditions at this time are as follows.
O ₂ : 40 sccm
CF ₄ : 270 sccm
N ₂ : 80 sccm
Pressure: 80Pa
Power: 700W
Substrate temperature: 70 ° C
Time: 30 seconds By this fluorine plasma radical treatment, the free energy of the polyimide pattern surface became 18.0 mJ / m ² , and a highly liquid repellent pattern was obtained. At the same time, the free energy on the glass substrate surface at this time is 70 mJ / m ² , and lyophilicity is obtained. Thus, as shown in FIG. 7A, a substrate 1 having a lyophilic portion 1a made of a glass substrate 8 and a liquid repellent portion 1b made of polyimide subjected to fluorine plasma radical treatment was formed.

  Next, the substrate 1 is filled with a liquid 3 as a fluid material for forming a plating electrode. For the filling of the liquid 3, a pattern forming apparatus manufactured by the present inventors was used. A schematic configuration of the pattern forming apparatus is shown in FIG. As shown in FIG. 8, in this pattern forming apparatus, a stage 2 is provided on a base 9 so as to be horizontally movable, and a substrate 1 is placed on the stage 2. The lyophilic bar 4 is obtained by winding a lyophilic film 11 around the outer periphery of the roll 10. The stage 2 and the bar 4 are each driven by a stepping motor and can be controlled either synchronously or asynchronously. The stage 2 has a height adjusting mechanism and a vacuum suction function for the substrate 1.

  Liquid 3 was filled under the following process conditions. As the liquid 3, a silane coupling agent KBM-603 / ethyl lactate diluted solution (concentration: 2.0 wt%) manufactured by Shin-Etsu Chemical Co., Ltd. was used. The gap g between the substrate 1 and the bar 4 was 100 μm, and the feeding speed of the substrate 1 was 2 mm / s. As the lyophilic film 10, a 2.0 mm thick APR (registered trademark) film manufactured by Asahi Kasei Corporation was used. By the above process, as shown in FIG. 7A, the pattern 5 of KBM-603, which is an amino silane coupling agent, was formed only on the lyophilic part 1a. The thickness of this pattern 5 was 1 nm. Next, in order to chemically bond the silane coupling agent and the glass substrate 8, drying at 120 ° C./5 minutes was performed. Thereafter, ultrasonic cleaning was performed for 20 minutes while the substrate 1 was immersed in an ethanol solution, the excess silane coupling agent was removed, and the substrate 1 was dried at 100 ° C. for 5 minutes.

Next, the substrate 1 was immersed in a palladium catalyst solution for electroless plating, and a catalyst treatment was performed. Since palladium forms a coordinate bond with the amine in the silane coupling agent, it gives good adhesion to the plating film formed in the next step. Further, since palladium does not bond to glass, it can be attached only to a region where a silane coupling agent is present. Thus, the granular palladium catalyst 12 is formed only on the pattern 5 as shown in FIG. 7B. The particle diameter of the palladium catalyst 12 was 10 nm.
Next, a Ni film was formed by an electroless Ni plating process. As the plating solution, Ni-B plating solution BEL-801 manufactured by Uemura Kogyo Co., Ltd. was used.
Through the above series of processes, as shown in FIG. 7C, a plating electrode pattern 13 made of a Ni film having a line / space definition of 10/10 (μm) was obtained.

Next explained is a pattern forming method according to the sixth embodiment of the invention.
In the sixth embodiment, a pattern forming apparatus as shown in FIG. 9 is used. As shown in FIG. 9, in this pattern forming apparatus, a pattern forming liquid 3 is placed in a container 21. A lyophilic bar 4 is provided at the interface between the liquid 3 and the external space. The lower part of the bar 4 is preferably immersed in the liquid 3. This is to ensure that the liquid 3 is finally left only on the lyophilic part 1a of the substrate 1. The substrate 1 is configured to be movable up and down by a drive mechanism (not shown), and can be dipped in the liquid 3 and pulled up.

Using this pattern forming apparatus, a pattern is formed as follows.
First, the substrate 1 is lowered vertically from above the container 21 and completely immersed in the liquid 3, and then the substrate 1 is gradually pulled up. When the substrate 1 passes through the interface between the liquid 3 and the external space, the liquid 3 is filled between the substrate 1 and the bar 4 by capillary action, and as the substrate 1 is pulled up, the liquid 3 only on the lyophilic portion 1a. Is left behind. Thus, the target pattern is formed only on the lyophilic portion 1a.
Since other than the above is the same as in the first embodiment, the description thereof is omitted.
According to the sixth embodiment, the same advantages as those of the first embodiment can be obtained.

In Example 2, a case where the pattern forming method according to the sixth embodiment is applied to formation of an indium-tin oxide (ITO) electrode pattern will be described.
First, a substrate 1 having a lyophilic part 1a and a liquid repellent part 1b was produced in the same manner as in Example 1.
As the liquid 3 for pattern formation, a needle-like ITO fine particle dispersion (SC-100, manufactured by Sumitomo Metal Mining Co., Ltd.) was used. The pulling speed of the substrate 1 was 1 mm / s, and the gap between the substrate 1 and the bar 4 was 50 μm.
After leaving the needle-like ITO fine particle dispersion only on the lyophilic part 1a under the above conditions, firing was performed at 120 ° C. for 1 hour in a nitrogen substitution furnace. As a result, an ITO electrode pattern having a thickness of 1 μm and a sheet resistance of 10 ³ Ω / □ was obtained. This ITO electrode pattern had a definition of 10/10 (μm) in line / space.

Next explained is a pattern forming method according to the seventh embodiment of the invention.
In the seventh embodiment, a pattern forming apparatus as shown in FIG. 10 is used. As shown in FIG. 10, in this pattern forming apparatus, two different types of liquids 3a and 3b for pattern formation are placed in a container 21 in a state where they are separated from each other in the depth direction. The liquids 3a and 3b have different specific gravities (in this case, the specific gravity of the liquid 3a is greater than the specific gravity of the liquid 3b) and are not compatible. Further, lyophilic bars 4 are provided at the interface between the lower liquid 3a and the upper liquid 3b and at the interface between the upper liquid 3b and the external space, respectively. The lower part of the bar 4 at the interface between the lower liquid 3a and the upper liquid 3b is preferably immersed in the lower liquid 3a, and the lower part of the bar 4 at the interface between the upper liquid 3b and the external space is in the liquid 3b. It is desirable to be immersed in In this case, the substrate 1 can be introduced into the liquid 3a from the substrate inlet 22 provided on the bottom surface of the container 21 by a drive mechanism (not shown), and can be pulled out of the container 21. ing. For example, a pair of rollers 23a and 23b is installed in the substrate insertion port 22, and the substrate 3 is sandwiched from both sides by the rollers 23a and 23b in synchronization with the introduction of the substrate 1 into the liquid 3a. This prevents leakage outside the container 21.

Using this pattern forming apparatus, a pattern is formed as follows.
First, the substrate 1 is introduced into the lower liquid 3a from the substrate inlet 22 on the bottom surface of the container 21 and gradually lifted. When the substrate 1 passes through the interface between the liquid 3a and the liquid 3b, the liquid 3a is filled between the substrate 1 and the bar 4 by capillary action, and as the substrate 1 is pulled up, the liquid 3a is only on the lyophilic portion 1a. Is left behind. When the substrate 1 is further lifted and passes through the interface between the liquid 3b and the external space, the liquid 3b is filled between the substrate 1 and the bar 4 by capillary action, and the liquid 3a left on the lyophilic portion 1a Liquid 3b is left on top. In this way, two different types of liquids 3a and 3b are filled on the lyophilic part 1a. Finally, a two-layer structure pattern made of different materials is formed only on the lyophilic portion 1a.
Since other than the above is the same as in the first embodiment, the description thereof is omitted.
According to the seventh embodiment, in addition to the same advantages as those of the first embodiment, it is possible to obtain an advantage that a pattern having a two-layer structure can be easily formed.

In Example 3, a case where the pattern forming method according to the seventh embodiment is applied to formation of a polytetrafluoroethylene / ITO electrode pattern will be described.
First, a substrate 1 having a lyophilic part 1a and a liquid repellent part 1b was produced in the same manner as in Example 1.
As the liquid 3a for pattern formation, a polytetrafluoroethylene resin solution having a specific gravity of 1.78 (polytetrafluoroethylene AF1600 manufactured by Mitsui Fluorochemical Co., Ltd.) was used. As the liquid 3b for pattern formation, a needle-like ITO fine particle dispersion (SC-100, manufactured by Sumitomo Metal Mining Co., Ltd.) having a specific gravity of 1.5 was used. The pulling speed of the substrate 1 was 1 mm / s, and the gap between the substrate 1 and the bar 4 was 50 μm.
Under the above conditions, the polytetrafluoroethylene resin and the needle-like ITO fine particle dispersion were sequentially left only on the lyophilic portion 1a of the substrate 1, and then baked at 120 ° C. for 1 hour in a nitrogen substitution furnace. As a result, an ITO electrode pattern having a thickness of 1 μm and a sheet resistance of 10 ³ Ω / □ was obtained on a polytetrafluoroethylene resin having a thickness of 500 nm. This ITO electrode pattern had a line / space definition of 20/20 (μm). In this case, since the polytetrafluoroethylene resin has a sufficiently large thickness of 500 nm, a sufficient antioxidant effect can be obtained.

Next explained is a pattern forming method according to the eighth embodiment of the invention.
In the eighth embodiment, a pattern forming apparatus as shown in FIG. 11 is used. As shown in FIG. 11, in this pattern forming apparatus, two different types of liquids 3a and 3b for pattern formation are placed in a container 21 in a state where they are separated from each other in the depth direction and in the horizontal direction. The liquids 3a and 3b have different specific gravities (in this case, the specific gravity of the liquid 3a is greater than the specific gravity of the liquid 3b) and are not compatible. In this case, the liquids 3a and 3b are separated from each other by the difference in specific gravity in the depth direction, and separated from each other by the partition plate 24 in the horizontal direction. Further, lyophilic bars 4 are provided at the interface between the lower liquid 3a and the upper liquid 3b and at the interface between the upper liquid 3b and the external space, respectively. The lower part of the bar 4 at the interface between the lower liquid 3a and the upper liquid 3b is preferably immersed in the lower liquid 3a, and the lower part of the bar 4 at the interface between the upper liquid 3b and the external space is in the liquid 3b. It is desirable to be immersed in In this case, the substrate 1 is lowered vertically from above the one side portion of the partition plate 24 by a driving mechanism (not shown) and completely immersed in the liquid 3a, and then in the liquid 3a as indicated by an arrow in FIG. And can be pulled out of the container 21 through the liquid 3b.

Using this pattern forming apparatus, a pattern is formed as follows.
First, the substrate 1 is immersed vertically in the liquid 3a on one side of the partition plate 24 of the container 21, and further moved in the liquid 3a as indicated by an arrow, and pulled up vertically in a state where the substrate 1 is vertical. When the substrate 1 passes through the interface between the liquid 3a and the liquid 3b, the liquid 3a is filled between the substrate 1 and the bar 4 by capillary action, and as the substrate 1 is pulled up, the liquid 3a is only on the lyophilic portion 1a. Is left behind. When the substrate 1 is further lifted and passes through the interface between the liquid 3b and the external space, the liquid 3b is filled between the substrate 1 and the bar 4 by capillary action, and the liquid 3a left on the lyophilic portion 1a Liquid 3b is left on top. In this way, two different types of liquids 3a and 3b are filled on the lyophilic part 1a. Finally, a two-layer structure pattern made of different materials is formed only on the lyophilic portion 1a.
Since other than the above is the same as in the first embodiment, the description thereof is omitted.
According to the eighth embodiment, the same advantages as those of the seventh embodiment can be obtained.

Next explained is a pattern forming method according to the ninth embodiment of the invention.
In the ninth embodiment, a pattern forming apparatus as shown in FIG. 12 is used. As shown in FIG. 12, in this pattern forming apparatus, similar to the eighth embodiment, two different types of liquids 3a and 3b for pattern formation are separated from each other in the depth direction and the horizontal direction in the container 21. It is put in the state. The liquids 3a and 3b have different specific gravities (in this case, the specific gravity of the liquid 3a is greater than the specific gravity of the liquid 3b) and are not compatible. In this case, the liquids 3a and 3b are separated from each other by the difference in specific gravity in the depth direction and separated from each other by the partition plate 24 in the horizontal direction. Further, a lyophilic bar 4 is provided at the interface between the lower layer liquid 3a and the upper layer liquid 3b on one side of the partition plate 24 and the interface between the liquid 3a on the other side of the partition plate 24 and the external space. . The lower part of the bar 4 at the interface between the lower layer liquid 3a and the upper layer liquid 3b on one side of the partition plate 24 is preferably immersed in the lower layer liquid 3a, and the liquid 3a on the other side of the partition plate 24 and the external space It is desirable that the lower part of the bar 4 at the interface is immersed in the liquid 3a. In this case, the substrate 1 is vertically lowered from above the one side portion of the partition plate 24 by a drive mechanism (not shown), immersed in the liquid 3b, and then moved in the liquid 3a as indicated by an arrow in FIG. The partition plate 24 can be pulled out of the container 21 through the liquid 3a on the other one side.

Using this pattern forming apparatus, a pattern is formed as follows.
First, the substrate 1 is immersed vertically in the liquid 3b on one side of the partition plate 24 of the container 21, and after passing through the interface between the liquid 3b and the liquid 3a vertically, the liquid 3a is partitioned as indicated by arrows. The plate 24 is moved to the other one side, and the substrate 1 is pulled out of the container 21 in a vertical state. Thus, when the substrate 1 passes through the interface between the liquid 3a and the liquid 3b, the liquid 3b is filled between the substrate 1 and the bar 4 by capillary action, and as the substrate 1 is pulled up, the liquid 3b only on the lyophilic portion 1a. Is left behind. When the substrate 1 is pulled up from the liquid 3a, the liquid 3a is filled between the substrate 1 and the bar 4 by capillary action, and the liquid 3a remains on the liquid 3b left on the lyophilic portion 1a. In this way, two different types of liquids 3b and 3a are sequentially filled on the lyophilic part 1a. Finally, a two-layer structure pattern made of different materials is formed only on the lyophilic portion 1a.
Since other than the above is the same as in the first embodiment, the description thereof is omitted.
According to the ninth embodiment, the same advantages as those of the seventh embodiment can be obtained.

Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments and examples, and various modifications based on the technical idea of the present invention are possible. It is.
For example, the numerical values, structures, shapes, materials, raw materials, processes, and the like given in the above-described embodiments and examples are merely examples, and numerical values, structures, shapes, materials, raw materials, processes, and the like that are different from these as necessary. May be used.

It is sectional drawing for demonstrating the pattern formation method by 1st Embodiment of this invention. It is sectional drawing for demonstrating the pattern formation method by 1st Embodiment of this invention. It is sectional drawing for demonstrating the pattern formation method by 2nd Embodiment of this invention. It is sectional drawing for demonstrating the pattern formation method by 3rd Embodiment of this invention. It is sectional drawing for demonstrating the pattern formation method by 4th Embodiment of this invention. It is sectional drawing for demonstrating the pattern formation method by 5th Embodiment of this invention. It is sectional drawing for demonstrating the pattern formation method by Example 1 of this invention. It is a basic diagram which shows the pattern formation apparatus used in the pattern formation method by Example 1 of this invention. It is sectional drawing for demonstrating the pattern formation method by 6th Embodiment of this invention. It is sectional drawing for demonstrating the pattern formation method by 7th Embodiment of this invention. It is sectional drawing for demonstrating the pattern formation method by 8th Embodiment of this invention. It is sectional drawing for demonstrating the pattern formation method by 9th Embodiment of this invention. It is sectional drawing for demonstrating the problem of the conventional pattern formation method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Stage 3, 3a, 3b ... Liquid, 4 ... Bar, 5 ... Pattern, 6 ... Slit coater, 7 ... Capillary coater, 8 ... Glass substrate, 10 ... Roll, 11 ... Lipophilic film , 12 ... Palladium catalyst, 13 ... Plating electrode pattern, 21 ... Container, 22 ... Substrate inlet, 24 ... Partition plate

Claims (21)

Applying a fluid material on a substrate having a lyophilic part and a liquid repellent part on the surface;
And a step of relatively moving the substrate on which the material is applied and a member whose surface is lyophilic so that the member and the material are in contact with each other.   The pattern forming method according to claim 1, further comprising a step of drying or baking the material after relatively moving the substrate to which the material is applied and the member. Surface free energy of the lyophilic portion of said substrate is at 50 mJ / m ² or more, the claims surface free energy of the liquid repellency of the portion of the substrate is equal to or less than 30 mJ / m ² 2. The pattern forming method according to 1. The pattern forming method according to claim 1, wherein the surface free energy of the member is 50 mJ / m ² or more.   2. The pattern forming method according to claim 1, wherein the moving speed is 0.01 mm / s or more and 1000 mm / s or less.   2. The pattern forming method according to claim 1, wherein the substrate coated with the material and the member are relatively moved in parallel with each other.   The pattern forming method according to claim 1, wherein a gap between the substrate and the member is 0.1 μm or more and 10 mm or less.   The pattern forming method according to claim 1, wherein a gap between the substrate and the member is 1 μm or more and 1 mm or less.   2. The pattern forming method according to claim 1, wherein the substrate coated with the material is fixed, and the member is moved with respect to the substrate coated with the material.   The pattern forming method according to claim 1, wherein the member is fixed, and the substrate on which the material is applied is moved with respect to the member.   While applying a fluid material on a substrate having a lyophilic part and a liquid repellent part on the surface, the substrate on which the material is applied and the surface lyophilic member And a pattern forming method comprising a step of relatively moving the material and the material in contact with each other. A substrate holding means having a lyophilic part and a liquid repellent part on the surface;
Means for applying a fluid material to the substrate;
A member whose surface is lyophilic,
A pattern forming apparatus comprising: means for relatively moving the substrate and the member coated with the material so that the member and the material are in contact with each other. A step of immersing a substrate having a lyophilic part and a liquid repellent part on a surface in a fluid material accommodated in a predetermined container;
The substrate is lifted from the material, and when the substrate passes through the interface between the material and the external space, the material is filled by capillary action between the lyophilic member and the substrate. A pattern forming method comprising the steps of:   A plurality of types of materials are accommodated in the container in a state of being separated from each other in the depth direction, and the substrate is immersed in the bottom layer material from the bottom of the container, so that the plurality of types of materials pass sequentially. The substrate is pulled up, and at this time, when the substrate passes through the interface between the materials, the material on the lower layer side is filled by a capillary phenomenon between a member having a lyophilic surface and the substrate. The pattern forming method according to claim 13.   A plurality of types of materials are accommodated in the container in a state where they are separated from each other in the depth direction and / or the horizontal direction, the substrate is immersed in one of the materials, and the plurality of types of materials are sequentially passed through the container. The substrate is moved, and the substrate is pulled up from the other one of the materials. At this time, when the substrate passes through the interface between the materials, the surface is lyophilic between the member and the substrate by capillary action. The pattern forming method according to claim 13, wherein the material on the rear side in the traveling direction is filled. A container for storing a material having fluidity;
Means for immersing a substrate having a lyophilic part and a liquid repellent part on the surface of the material contained in the container, and pulling up the substrate from the material;
When the substrate is pulled up from the material, the surface is lyophilic, provided that the material is filled by capillary action between the substrate and the substrate when passing through the interface between the material and the external space. And a pattern forming apparatus.   When a plurality of types of materials are accommodated in the container in a state where they are separated from each other in the depth direction, the material on the lower layer side due to capillary action between the substrates when the substrates pass through the interface between the materials. The pattern forming apparatus according to claim 16, further comprising a member having a lyophilic surface provided so as to be satisfied.   When a plurality of types of materials are stored in the container in a state where they are separated from each other in the depth direction and / or the horizontal direction, when the substrate passes through the interface between the materials, capillary action occurs between the substrate and the substrate. 17. The pattern forming apparatus according to claim 16, further comprising a member having a lyophilic surface provided so as to be filled with the material on the rear side in the traveling direction. Applying a fluid material on a substrate having a lyophilic part and a liquid repellent part on the surface;
And a step of moving the substrate on which the material is applied and a member whose surface is lyophilic so that the member and the material are in contact with each other. Method.   While applying a fluid material on a substrate having a lyophilic part and a liquid repellent part on the surface, the substrate on which the material is applied and the surface lyophilic member And a method of manufacturing the electronic application apparatus, comprising: a step of relatively moving the material and the material so as to contact each other. A step of immersing a substrate having a lyophilic part and a liquid repellent part on a surface in a fluid material accommodated in a predetermined container;
The substrate is lifted from the material, and when the substrate passes through the interface between the material and the external space, the material is filled by capillary action between the lyophilic member and the substrate. A method of manufacturing an electronic application device.

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