JP2009283547A - Forming method and forming apparatus for conductive pattern, and conductive substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem that when a resin film having low thermal resistance is used as a base for a conductive pattern forming method of using and printing a dispersion solution of metal particulates on the base and heating the printed body to sinter the metal particulates, the base may be fused when the metal particulates are sintered to deform or discolor, and further it is difficult to shorten the sintering time of the metal particulates. <P>SOLUTION: Prepared is the printed body 100 formed by using and pattern-printing the dispersion solution wherein particulates of metal or a metal compound are dispersed on the nonconductive base. The printed body 100 is exposed to microwave surface wave plasma in a treatment chamber 11 of a pattern forming apparatus which generates the microwave surface wave plasma and the metal particulates of the pattern printed body are sintered to form the conductive pattern. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention draws a pattern on a non-conductive substrate using a fine particle dispersion in which fine particles of a metal or metal compound are dispersed, exposes the pattern to microwave surface wave plasma, and removes fine particles present in the drawn pattern. The present invention relates to a pattern forming method for performing a sintering process to form a conductive pattern, a pattern forming apparatus thereof, and a conductive substrate patterned by the above pattern forming method or pattern forming apparatus.

  There is already known a circuit board that forms a circuit pattern by drawing a pattern on a non-conductive substrate surface using a fine particle dispersion in which metal fine particles are dispersed, and sintering the metal fine particles present in the pattern. .

  For example, a paste composition in which metal fine particles made of a metal such as gold, silver, copper, or an alloy thereof are stably dispersed in an organic solvent is used for drawing on the substrate surface, and then on the drawn substrate. A circuit temperature is formed by applying a heating temperature and sintering the fine metal particles.

  The paste composition used in such a circuit pattern forming method is a compound (for example, amine, alcohol, phenol, thiol) that can coordinate the surface of metal fine particles having an average primary particle diameter of 1 to 100 nm with the metal element. In the paste composition, the fine metal particles are dispersed and exist in a stable form in an organic solvent.

In addition, drawing using the paste composition is performed using various methods such as ink jet and screen printing.
Then, a heating temperature (for example, 180 ° C. × 30 minutes) is applied to the drawing pattern to remove the coating layer of the metal fine particles, and the metal fine particles are sintered together to form a circuit pattern.
Note that epoxy, polyimide, thermosetting resin, or the like is used for the substrate.

According to the circuit pattern forming method described above, it is possible to produce a build-up wiring board, a plastic wiring board, a printed wiring board, etc. For example, the line / space is 25 μm / 25 μm and the specific resistance is 4 × 10 ⁻⁵ Ω. A fine circuit pattern can be formed.

JP 2002-299833 A

  In the conventional circuit pattern forming method described above, when a resin film having low heat resistance is used as a base material, the base material may be melted and deformed when the metal fine particles are sintered, and the fine particles are coated. It is necessary to lengthen the heating time in order to remove the compound to be performed, and it is difficult to shorten the formation time of the conductive pattern.

In particular, for base metal fine particles such as copper and nickel, and metal compound fine particles such as copper oxide, it is necessary to sinter in a reducing gas atmosphere in order to suppress and reduce oxidation during sintering. However, since a temperature of 300 ° C. or higher is necessary for the reduction reaction, for example, sintering on a resin film having a low heat resistance having a melting point of 280 ° C. or lower is, for example, 120 ° C. to 150 ° C. There is a problem that it is more difficult because it is thermally deformed at a temperature of ° C.
Moreover, since it takes a long time to control the atmosphere of the reducing gas and to sinter, it is very difficult to sinter the pattern produced on the roll film.

Furthermore, for those with a large area, there is a difficulty in forming a uniform conductive pattern, and since the base material may be discolored, it is necessary to form a conductive pattern for conductive parts that require high transmittance. Not suitable.
The present invention aims to solve such problems as much as possible.

In order to achieve the above-mentioned object, the conductive pattern forming method of the present invention draws a pattern on a non-conductive substrate using a fine particle dispersion in which fine particles are dispersed, and sinters the fine particles of the pattern. And a method of forming a conductive pattern.
And for drawing the pattern, a fine particle dispersion in which fine particles made of metal or a metal compound are dispersed is used, and for the sintering process, microwave energy is supplied from an irradiation window of a processing chamber consisting of a decompression chamber, An electrodeless plasma generating means for generating surface wave plasma along the irradiation window is used in the processing chamber.
In this way, the drawing pattern is exposed to microwave surface wave plasma having a low electron temperature and a high electron density to sinter the fine particles of the pattern.

The above-mentioned fine particles made of a metal or a metal compound are fine particles made of a metal compound such as a noble metal such as gold or silver, a base metal such as copper or nickel, or an alloy made of two or more metals.
As the base metal fine particles such as copper fine particles, metal fine particles whose surface is oxidized and metal fine particles which are oxidized to the inside can also be used.

The fine particles preferably have an average primary particle diameter of 1 to 100 nm.
About this average primary particle diameter, it can measure from the observation image by a transmission electron microscope.
Fine particle synthesis methods include physical methods obtained by pulverizing metal powders, chemical dry methods such as CVD, vapor deposition, sputtering, and thermal plasma, chemical reduction, and electrolysis. It can be realized by adopting a method such as a wet method.

The surface of the fine particles is preferably covered with a dispersion protective agent in order to be stabilized in the dispersion.
Water, methanol, or the like can be used as a solvent for the above dispersion for dispersing the fine particles.

Furthermore, an inorganic material substrate or a synthetic resin substrate is used as the base material depending on the application.
The synthetic resin substrate may be in the form of a film.
In order to improve the adhesion between the substrate and the conductive layer, it is preferable to form an easy-adhesive component on the substrate surface or to modify the substrate surface.
The fine particle dispersion is drawn by a normal printing method, and then the fine particle dispersion on the substrate is dried.

The drawn metal fine particle layer is exposed to microwave surface wave plasma and sintered.
For this sintering, electrodeless plasma generating means for supplying microwave energy from the irradiation window into the processing chamber and generating surface wave plasma in the processing chamber can be used.
As the plasma generating means, microwave energy having a frequency of 2450 MHz is supplied from the irradiation window of the processing chamber, and the electron temperature is about 1 eV or less and the electron density is about 1 × 10 ¹¹ to 1 × 10 ¹³ in the processing chamber. A cm ⁻³ microwave surface wave plasma can be generated.

On the other hand, the following first invention, second invention, and third invention are proposed as inventions of a pattern forming apparatus for forming a conductive pattern.
The pattern forming apparatus of the first invention draws a pattern on a non-conductive substrate using a fine particle dispersion in which fine particles made of metal or a metal compound are dispersed, and sinters the fine particles present in the pattern. A pattern forming apparatus for forming a conductive pattern, wherein microwave energy is supplied from an irradiation window of a processing chamber configured as a decompression chamber, and electrodeless plasma generating means for generating surface wave plasma along the irradiation window in the processing chamber And a processing table for arranging the substrate on which the pattern is drawn in the processing chamber, the substrate on which the drawing pattern is drawn is arranged on the processing table, and the drawing temperature is set in the processing chamber, and the electronic temperature is The conductive pattern is formed by sintering fine particles of the drawing pattern by being exposed to a microwave surface wave plasma having a low and high electron density.

  The pattern forming apparatus according to the second invention draws a pattern on a non-conductive substrate using a fine particle dispersion in which fine particles made of metal or a metal compound are dispersed, and sinters the fine particles present in the pattern. A pattern forming apparatus for forming a conductive pattern, wherein microwave energy is supplied from an irradiation window of a processing chamber configured as a decompression chamber, and electrodeless plasma generating means for generating surface wave plasma along the irradiation window in the processing chamber And a processing stand for arranging the substrate on which the pattern is drawn in the processing chamber, a first preliminary chamber associated with the carry-in port of the processing chamber, and a second preliminary chamber associated with the carry-out port The chamber, the first preliminary chamber are decompressed and the inlet is opened, and a loading mechanism for feeding the substrate on which the pattern is drawn from the first preliminary chamber onto the treatment table in the treatment chamber, and the second preliminary chamber are decompressed. Both are equipped with a carry-out mechanism that opens the carry-out port and feeds the substrate on which the pattern is drawn from the treatment table in the treatment chamber to the second preliminary chamber. A series of unloading, exposing the fine particles present in the drawing pattern to a microwave surface wave plasma having a low electron temperature and a high electron density in a processing chamber, and sintering the fine particles of the drawing pattern to form a conductive pattern It is the structure which forms.

In the first and second inventions described above, a base material in which a pattern is drawn on the base material such as glass or resin material having a predetermined size using the fine particle dispersion is prepared in advance.
In the pattern forming apparatus according to the first aspect of the present invention, the drawn base material is placed in the processing chamber of the electrodeless plasma generating means, placed on the processing table, and then supplied with microwave energy (microwave power). To do.
As a result, plasma is generated in the processing chamber, but this plasma becomes surface wave plasma generated in a large amount in the processing chamber near the irradiation window.
In the present application, this surface wave plasma is referred to as microwave surface wave plasma for convenience.
Therefore, the drawing pattern of the substrate is exposed to microwave surface wave plasma having a low electron temperature and a high electron density, and the fine particles of the drawing pattern are sintered to form a conductive pattern.

In the pattern forming apparatus of the second invention, when a substrate on which a pattern is drawn is placed in the first preliminary chamber, the substrate is fed onto a processing table in the processing chamber by the carrying-in means.
The processing chamber is configured to generate microwave surface wave plasma regardless of whether the substrate is loaded or unloaded. The drawn substrate is exposed to the microwave surface wave plasma on the processing table, and the fine particles of the drawing pattern are burned. As a result, a conductive pattern is formed.
Subsequently, since the drawn base material is sent out to the second preliminary chamber by the carry-out means, the substrate having the conductive pattern can be taken out from the second preliminary chamber.

  In the pattern forming apparatuses according to the first and second inventions described above, the drawn base material is exposed to the microwave surface wave plasma on the processing table, so that deformation or melting caused by temperature rise may occur. In order to prevent adverse effects, the processing table can be provided with a cooling means for cooling the back surface of the substrate.

  When the pattern forming apparatus according to the first and second inventions described above is drawn on a film-like substrate, a portion separated from the portion joined to the processing table surface may be generated due to the curved portion of the substrate. In order to solve this problem, a suction holding unit that sucks the drawn base material into the processing table by air suction may be provided.

  In the pattern forming apparatus of the first and second inventions described above, it is preferable to form the processing surface on a gently bulging surface in order to increase the degree of joining of the drawn base materials.

The pattern forming apparatus according to the first and second inventions described above can include a driving unit that rotates the processing table so that the microwave surface wave plasma uniformly strikes the drawn substrate.

Note that the substrate drawn with the dispersion of the base metal fine particles is exposed to the microwave surface wave plasma, and after the fine particles of the drawn pattern are sintered and become conductive patterns, the substrate is taken out from the processing chamber in a high temperature state. Since the conductive pattern may oxidize when exposed to the atmosphere, in the case of the pattern forming apparatus according to the first aspect of the invention, the conductive substrate should be removed from the processing chamber after the temperature of the conductive substrate has dropped to the normal temperature (room temperature). To do.
In order to solve this problem, the pattern forming apparatus according to the second aspect of the invention preferably includes a gas supply means for supplying an oxidation-suppressing gas that suppresses oxidation of the conductive pattern to the second preliminary chamber.

  Further, the pattern forming apparatus of the third invention draws a pattern on a non-conductive substrate using a fine particle dispersion in which fine particles made of metal or a metal compound are dispersed, and sinters the fine particles present in the pattern. A pattern forming apparatus for processing and forming a conductive pattern, which supplies microwave energy from an irradiation window of a processing chamber configured as a decompression chamber and generates surface wave plasma along the irradiation window in the processing chamber And a winding reel that winds up a flexible substrate having a long diameter on which a pattern is drawn, a winding reel that winds up the flexible substrate, and a drawing reel provided between the two reels. A plasma processing roller for irradiating the surface with microwave surface wave plasma, and the flexible base material supplied from a winding reel While moving to the take-up reel through the processing roller, the fine particles present in the drawing pattern are exposed to microwave surface wave plasma with a low electron temperature and a high electron density, and then subjected to a sintering process to make it conductive. The pattern is formed.

  The pattern forming apparatus according to the third aspect of the invention is provided with a cooling means for cooling the plasma processing roller because the drawn flexible substrate is heated by being exposed to the microwave surface wave plasma in the process of passing through the plasma processing roller. It is preferable to cool the back surface of the flexible substrate.

  Furthermore, it is preferable to provide a cooling roller between the plasma processing roller and the take-up reel, cool the flexible substrate with drawing that has been heated by plasma heating with the cooling roller, and take up the take-up reel with the temperature lowered. .

  In the pattern forming apparatus of the third aspect of the invention, in order to uniformly apply the microwave surface wave plasma to the flexible base material with drawing, the plasma processing roller is rotated forward and backward to reciprocate the flexible base material at a small distance. It is possible to provide forward / reverse drive means.

On the other hand, even if the substrate is drawn using a dispersion of base metal fine particles, base metal fine particles whose surface is oxidized, or base metal oxide fine particles which are oxidized to the inside, the first, second and third inventions A conductive pattern can be formed in substantially the same manner as described above. However, a reducing gas such as hydrogen gas is supplied to the processing chamber together with microwave energy, and microwave surface wave plasma is generated in the reducing gas atmosphere. By adopting such a configuration, reduction treatment and sintering treatment of fine particles existing in the drawing pattern are performed.
Further, as the plasma generating means of the first, second and third inventions described above, microwave energy having a frequency of 2450 MHz is supplied from the irradiation window of the processing chamber, and the electron temperature is about 1 eV or less in the processing chamber. A microwave surface wave plasma having a density of about 1 × 10 ¹¹ to 1 × 10 ¹³ cm ⁻³ can be generated.

As described above, the present invention sinters a substrate drawn using a dispersion of metal fine particles or metal compound fine particles using plasma generating means to form a conductive pattern.
The plasma generating means supplies microwave energy (microwave power) from the irradiation window of the processing chamber including the decompression chamber, and generates surface wave plasma generated by microwave excitation near the irradiation window in the processing chamber.
Therefore, since the microwave surface wave plasma can be generated without an electrode, the electron temperature is low, and the electron density is high, the following effects can be obtained.

Even when using a resin film with low heat resistance, for example, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) as the base material, the base material melts when the metal fine particles are sintered because the electron temperature is low, There is no such thing as deformation.
In addition, since the electron density is higher than the conventional method for forming a conductive pattern, the sintering time can be shortened as much as possible.
As a result, the range of use of this type of conductive substrate is widened, and it is advantageous for reducing the production cost.

Furthermore, since the micro surface wave plasma is generated by an electrodeless plasma generating means, it is possible to form a conductive pattern on a large area substrate, and substrate damage (deformation, discoloration, etc.) due to plasma concentrated by the electrode. Absent.
In addition, sintering by microwave surface wave plasma is optimal for forming a conductive pattern on a conductive substrate that requires high transmittance in the base material because the base material does not discolor.
In addition, the microwave surface wave plasma can be generated in a decompression chamber for supplying microwave energy and becomes a plasma generating means having a simple configuration, so that it can be easily put into practical use.

  In particular, substrate fine particles drawn with a dispersion of base metal fine particles and copper fine particles whose surfaces are at least oxidized are exposed to microwave surface wave plasma generated in a reducing gas atmosphere. Thus, reduction treatment can be performed simultaneously with sintering even at a low temperature.

Furthermore, since the microwave surface wave plasma has an effect of decomposing and removing organic substances, it also has an effect of promoting the sintering of the fine particles of the base material drawn using a dispersion of noble metal fine particles.
In particular, since organic substances are decomposed, a very high-density and high-purity metal thin film can be obtained.

  On the other hand, according to the pattern forming apparatus of the present invention, the reduction treatment and the sintering treatment can be performed simultaneously and continuously, so that it is suitable for continuous production of conductive substrates, and a drawn long-diameter flexible base material is entrained. Since plasma processing is performed with the plasma processing roller while supplying from the reel, it becomes possible to reduce and sinter the substrate with a long-diameter drawing, and further, if it is configured to be exposed to plasma while cooling the drawn substrate, There is an effect that the thermal damage of the substrate can be reduced as much as possible.

First, an embodiment of a method for forming a conductive pattern will be described.
In the practice of the present invention, a substrate on which a pattern is drawn using a fine particle dispersion is prepared in advance.
The fine particle dispersion is prepared by dispersing fine particles made of a metal or a metal compound in a solvent.

As the fine metal particles, base metals such as copper, nickel, tin, iron, and chromium are used in addition to noble metals such as gold, silver, platinum, palladium, rhodium, iridium, ruthenium, and osmium.
The fine particles of the metal compound are preferably fine particles such as oxides, nitrides and sulfides of these metals, and fine particles made of a metal compound such as an alloy composed of two or more kinds of metals.
In addition, in the case of fine particles of base metal such as copper, the surface may be oxidized by oxygen in the atmosphere, but such base metal fine particles whose surface is oxidized or base metal fine particles which are oxidized to the inside are also used can do.

Metals or metal compounds are easy to produce fine particles. In particular, silver, copper and oxides and alloys thereof are suitable fine particles in terms of conductivity and cost.
The fine particles of the metal or metal compound preferably have an average primary particle diameter of 1 to 100 nm.
About this average primary particle diameter, it can measure from the observation image by a transmission electron microscope.

  Examples of the solvent include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin, aromatic hydrocarbons such as toluene and xylene, acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate and propyl acetate, and hydrocarbons such as cyclohexane and tetradecane can be employed.

Furthermore, when the metal or metal compound is dispersed in a solvent, the surface is preferably covered with a dispersion protective agent in order to stabilize the dispersion in the dispersion.
As a dispersion protective agent, for example, as a polymer material, a water-soluble polymer such as polyvinylpyrrolidone, a graft copolymer polymer, as a low-molecular material, a surfactant, a thiol group that interacts with a metal, an amino group, A compound having a hydroxyl group or a carboxyl group can be used.

In addition, for the purpose of enhancing adhesion to the substrate, improving film formability, and imparting printability to the dispersion, for example, resins such as polyester resin, acrylic resin, urethane resin, and ethyl silicate An inorganic paint such as a silicate oligomer may be added as a binder component.
Moreover, you may add a viscosity modifier, a surface tension modifier, a stabilizer, etc. as needed.

A pattern is drawn on a non-conductive substrate using the fine particle dispersion prepared in this manner.
As the substrate, an inorganic material substrate or a synthetic resin substrate is used depending on the application.
The synthetic resin substrate may be in the form of a film.
As the inorganic material substrate, for example, glass (for example, soda lime glass, alkali-free glass, borosilicate glass, quartz glass, etc.), alumina, or the like can be employed.
Examples of the plastic substrate or film include polyethylene, polypropylene, acrylic resin, polystyrene, polycarbonate, polyimide, polyamideimide, polyethersulfone, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetherimide, Epoxy resin, glass-epoxy resin, polyphenylene ether, paper material, etc. can be employed.
In particular, it may be a substrate having a melting point of 280 ° C. or lower, such as polypropylene, acrylic resin, polyethylene, PET, PEN and the like.

In order to improve the adhesion between the base material and the conductive layer, an easy-adhesive component can be formed on the base material surface, or the base material surface can be modified.
Examples of the film formation of the easy-adhesive component include a method of forming a metal thin film such as nickel, chromium, titanium, a method of applying a thermoplastic adhesive, a thermosetting adhesive, a photocurable adhesive, etc. A method of applying an organic-inorganic coupling agent can be employed.
Examples of the method for modifying the surface of the substrate include corona treatment, ultraviolet treatment, excimer lamp treatment, and atmospheric pressure plasma treatment.

A pattern is drawn on the substrate using the fine particle dispersion.
Specifically, a pattern corresponding to the conductive pattern to be formed is determined and drawn using a fine particle dispersion.
This drawing can be realized by, for example, gravure printing, screen printing, offset printing, flexographic printing, ink jet printing, dispenser printing, spin coating, bar coating, and the like.

After drawing as described above, the fine particle dispersion on the substrate is dried.
This drying may be performed by a normal method. For example, the solvent can be dried using an oven or an infrared heating furnace.

The substrate prepared by drawing a pattern in advance as described above is exposed to microwave surface wave plasma, and the conductive fine particles of the drawing pattern are fused to realize conductivity.
Note that the fusion means that a part or the whole of the fine particles forms a continuous film by sintering, melting or the like. In the present application, this fusion is called “sintering” for convenience.

As the microwave surface wave plasma, a plasma generator for generating surface wave plasma by supplying microwave energy into a decompressed processing chamber can be used.
As described above, the microwave surface wave plasma has characteristics of high electron density and low electron temperature, and is an electrodeless plasma, and therefore does not damage the substrate.
Specifically, the microwave surface wave plasma has a high electron density of 1 × 10 ¹¹ to 1 × 10 ¹³ cm ⁻³ and has a strong action of removing organic substances. Forming a sex pattern.

  Therefore, by exposing the drawn substrate to the microwave surface wave plasma, the conductive fine particles made of noble metal such as gold and silver are removed from the dispersion protective material covering the surface by the microwave surface wave plasma. They are sintered together to form a conductive layer.

In addition, when using a dispersion of fine particles of base metal such as copper or nickel, the surface is covered with an oxide film and a dispersion protective film, so a reducing gas such as hydrogen gas that reduces the oxide film is treated. Supply to the room.
That is, the drawn substrate is exposed to microwave surface wave plasma generated in the presence of a reducing gas, and the oxide film is reduced along with the removal of the dispersion protective film.
As a result, the conductive fine particles are sintered to form a conductive layer.
The dispersion of base metal fine particles such as copper oxide fine particles that have been oxidized to the inside is subjected to the same sintering treatment as when the above-described dispersion of base metal fine particles is used.

The reducing gas includes hydrogen, carbon monoxide, ammonia, nitrogen, or a mixed gas thereof. Hydrogen gas is particularly preferable for removing organic substances adhering to the surface of the fine particles.
Further, the reducing gas has an effect that plasma is easily generated when an inert gas such as helium, argon, neon, krypton, or xenon is mixed and used.

Next, an embodiment of a pattern forming apparatus for conductive patterns will be described with reference to FIG.
FIG. 1 is a schematic configuration diagram showing a pattern forming apparatus, and a substrate (drawn substrate) 100 to be plasma-treated is placed on a processing table 12 provided in a processing chamber 11.
The drawn base material 100 is a base material prepared in advance by drawing a pattern using the fine particle dispersion as described above, and is placed on the processing table 12 by opening the door 13 of the processing chamber 11. In this case, the processing chamber 11 is taken out.

A microwave irradiation window 14 sealed with quartz glass is provided on the ceiling wall of the processing chamber 11, and surface wave plasma is generated by the microwave power (microwave energy) irradiated from the microwave irradiation window 14.
Microwave power is sent to the microwave irradiation window 14 from a coupling hole 16 provided in the waveguide 15.
That is, the waveguide 15 forms a waveguide system circuit together with the isolator 17, the power monitor 18, the tuner 19, and the like, and the microwave power of the frequency 2450 MHz output from the magnetron 20 is passed through the waveguide system circuit. And propagates into the processing chamber 11 through the coupling hole 16 and the microwave irradiation window 14.
The microwave power is a high frequency power of 2450 mHz, but a frequency range of 2450 MHz / ± 50 MHz is allowed due to an accuracy error of the magnetron 20 and the like.

The processing chamber 11 is provided with a hydrogen supply path (pipe) 21 for supplying hydrogen gas. The hydrogen supply path 21 is provided with a flow meter 22 and a valve 23.
Further, the processing chamber 11 is provided with a vacuum pump path (pipe) 24 for decompressing the inside of the processing chamber 11. The vacuum pump path 24 is provided with a vacuum pump 25 and a valve 26.
In addition, the processing chamber 11 is provided with a pressure gauge 27 for measuring the reduced pressure state in the processing chamber 11.

According to the pattern forming apparatus described above, the microwave power supplied into the processing chamber 11 is turned into plasma, and surface wave plasma along the microwave irradiation window 14 is generated in the processing chamber 11.
This surface wave plasma is generated as a microwave surface wave plasma having an electron temperature as low as about 1 eV or less and an electron density as high as about 1 × 10 ¹¹ to 1 × 10 ¹³ cm ^−3. The drawn substrate 100 to be exposed fuses the conductive fine particles present in the pattern in a short time to form a conductive pattern.

Next, embodiments of the pattern forming apparatus will be described as apparatus embodiments 1 and 2 with reference to the drawings.
In the description of the following examples, glass, resin film, and the like are referred to as “substrate”, and a substrate on which a pattern is drawn using a fine particle dispersion is referred to as “printed matter”.

Apparatus Example 1
2 is a simplified perspective view of the pattern forming apparatus shown as the apparatus embodiment 1, and FIG. 3 is a simplified cross-sectional view of the pattern forming apparatus.
In this embodiment, a quadrilateral printed material 100 drawn on a base material using a metal or metal compound fine particle dispersion is prepared in advance, and the printed material 100 is heated to form a conductive pattern.

As shown in the figure, this pattern forming apparatus is provided with a processing table 32 in a processing chamber 31 for generating surface wave plasma 30, and a printed material 100 is placed on the processing table 32 and exposed to plasma.
In the present embodiment, the microwave power output from the three magnetrons 33a, 33b, and 33c is sent into the processing chamber 31 via the respective waveguide circuits 34a, 34b, and 34c, and a wide range of surface waves are transmitted. Generate plasma.
As already described, the waveguide system circuit is a circuit system such as an isolator, a power monitor, and a tuner provided in the waveguides 35a, 35b, and 35c.

In addition, microwave power irradiation windows 36a, 36b, and 36c are provided on the ceiling wall of the processing chamber 31 so as to face the coupling holes of the waveguides 35a, 35b, and 35c arranged in parallel.
The irradiation windows 36a, 36b, and 36c are made of quartz glass so as to seal the processing chamber 31.
The processing chamber 31 is provided with a hydrogen supply path (pipe) 37 for supplying hydrogen gas and a vacuum pump path 38. Reference numeral 39 is a valve provided in the hydrogen supply path (pipe) 37, and reference numerals 40 and 41 are valves provided in the vacuum pump path 38 and a vacuum pump.

On the other hand, the processing chamber 31 is provided with a first spare chamber 42 that can communicate with the carry-in port 31a and a second spare chamber 43 that can communicate with the carry-out port 31b.
That is, the first preliminary chamber 42 opens the normally closed shutter 44 provided in the carry-in port 31a to communicate with the processing chamber 31, and the second pre-chamber 43 has a normally closed structure provided in the carry-out port 31b. The shutter 45 is opened to communicate with the processing chamber 31.

The first preliminary chamber 42 is a part chamber that should be called a standby chamber for carrying the printed material 100 into the processing chamber 31, and is provided with a lid plate 42 a that can be sealed, and the printed material 100 is opened by opening the lid plate 42 a. Is delivered into the first spare chamber 42.
The first preliminary chamber 42 is provided with a carry-in moving plate 46 for loading the printed material 100 and carrying it into the processing chamber 31.
The carry-in moving plate 46 is provided with a drive mechanism for moving back and forth between the first preliminary chamber 42 and the processing table 32 in the processing chamber 31. However, the carry-in moving plate 46 is manually advanced and retracted. It is good also as a structure.

  In addition, a vacuum pump path (pipe) 47 is disposed in the first preliminary chamber 42 described above, and the first preliminary chamber 42 is decompressed and the shutter 44 is opened with the cover plate 42a closed, and the printed matter 100 is printed. Is carried into the processing chamber 31.

The carry-in moving plate 46 and the processing table 32 are configured as shown in FIG.
That is, through holes 32a are provided at four positions of the processing table 32, and a push-up bar 48 that pushes up the printed material 100 once through the through holes 32a is provided.
The push-up bar 48 is provided on the lower side of the processing table 32 so as to advance in the vertical direction and to move backward.

FIG. 5 shows an operation for carrying in the printed material 100.
As shown in FIG. 5A, when the carry-in moving plate 46 on which the printed material 100 is placed advances onto the processing table 32, as shown in FIG. 5B, the pusher bar 48 rises to push up the printed material 100. .
With this push-up operation, the carry-in moving plate 46 moves backward, and thereafter, as shown in FIG. 5C, the push-up collar 48 is lowered and the printed matter 100 is placed on the processing table 32.

The second preliminary chamber 43 is for carrying out the printed material 100 sintered in the processing chamber 31 and is configured in substantially the same manner as the first preliminary chamber 42.
That is, the pressure is reduced by the vacuum pump path (pipe) 49, the shutter 45 is opened in the reduced pressure state, the carry-out moving plate 50 is reciprocated, and the printed matter 100 is carried out into the second preliminary chamber 43.

Further, at the time of carry-out, the reverse operation is performed as compared with the carry-in operation shown in FIG.
That is, the printed material 100 is pushed up from the state of FIG. 5C as shown in (B), and the carry-out moving plate 50 enters between the processing table 32 and the printed material 100.
Subsequently, the push-up bar 48 descends and the printed material 100 is placed on the carry-out movement plate 50 and carried out by the backward movement of the carry-out movement plate 50.
The carry-out moving plate 50 is provided with a drive mechanism for moving back and forth between the second preliminary chamber 43 and the processing table 32 in the processing chamber 31, but the carry-in moving plate 50 is manually advanced and retracted. It is good also as a structure.

After the printed material 100 is carried out into the second preliminary chamber 43, the shutter 45 is closed, and further, a cooling gas is supplied from the gas supply path 51 into the second preliminary chamber 43 to lower the temperature of the printed material 100. Then, the lid 43a is opened and the printed matter 100 is taken out.
This is because the temperature of the printed material 100 immediately after sintering is high, and if the printed material 100 is immediately taken out from the second preliminary chamber 43, the sintered pattern of base metal fine particles such as copper may be oxidized.
As the cooling gas, hydrogen gas, argon gas, nitrogen gas, helium gas, carbon dioxide gas and the like are effective.
Therefore, in the case of sintering a substrate drawn with a dispersion of non-oxidized metal fine particles, the cooling gas supplied to the second preliminary chamber 43 is not necessarily required.

  In addition, reference numerals 52 and 53 shown in FIG. 3 are air paths (pipes) for sending air to the first and second auxiliary chambers 42 and 43 to be atmospheric pressure, 54 is a vacuum pump, and 55 to 59 are valves. .

As described above, the pattern forming apparatus according to the apparatus embodiment 1 delivers the printed material 100 prepared in advance to the first preliminary chamber 42, places it on the carry-in moving plate 46, and closes the lid 42 a, thereby forming the first preliminary chamber 42. While reducing the pressure, the shutter 44 is opened, and the printed material 100 is carried in by the carry-in moving plate 46.
Note that when the carry-in moving plate 46 on which the printed material 100 is placed on the processing table 32 is retracted, the shutter 44 is closed, and then the first preliminary chamber 42 is returned to normal pressure (atmospheric pressure).

The printed material 100 placed on the processing table 32 is exposed to the microwave surface wave plasma 30, and the printed material 100 is heated to sinter the conductive fine particles.
Thereafter, the shutter 45 is opened, the carry-out moving plate 50 advances from the decompressed second preliminary chamber 43, and the printed material 100 is carried into the second preliminary chamber 43.
Subsequently, the shutter 45 is closed, and the printed material 100 that becomes the conductive substrate is cooled by the cooling gas.

From the above, the sintered printed material 100, that is, the conductive substrate on which the conductive pattern is formed can be taken out from the second preliminary chamber 43.
As a result, according to the first embodiment, the conductive pattern can be formed by semi-automatically sintering the drawing pattern.

In the apparatus embodiment 1 described above, the processing table 32 can be rotated to uniformly irradiate the entire printed matter 100 with the surface wave plasma 30.
In addition, as shown in FIG. 6, a cooling pipe 60 that circulates cold water is provided in the processing table 32, and cooling can be performed from the back surface of the printed material 100 heated by the microwave surface wave plasma 30.

On the other hand, since the printed material 100 is only placed on the processing table 32, a stable position may not be maintained.
Therefore, as the next step of FIG. 5B in which the push-up collar 48 is configured as a suction pipe and the printed material 100 is placed on the processing table 32, the operation state of FIG. Can be stabilized on the processing table 32.

Further, as shown in FIG. 8, it is preferable that the processing table 32 has a gently bulging surface as shown in FIG. 8 in order to surface-bond the printed material 100, and the printed material 100 is attached by a suction pipe using the lifting rod 48. It can be sucked and held.
Further, as means for sucking air, a plurality of suction holes 61 may be provided in the processing table 32 as shown in FIGS. The processing table 32 includes an air suction pipe 62 and the like.

Apparatus Example 2
FIG. 11 is a simplified perspective view showing another embodiment of the pattern forming apparatus, and FIG. 12 is a simplified sectional view of the pattern forming apparatus.
In this example, a long printed material 200 drawn on a long flexible substrate having a predetermined width using a fine particle dispersion of a metal or metal compound is prepared in advance, and the printed material 200 is exposed to microwave surface wave plasma to conduct electricity. Forming a sex pattern.

As shown in the figure, in the apparatus embodiment 2, a winding reel 72 around which a long printed material 200 is wound, a winding reel 73 around which the printed material 200 is wound, and a plasma treatment between the reels 72 and 73. The roller 74 is arranged in the processing chamber 71.
In the second embodiment, cooling rollers 77, 78, 79, and 80 for circulating cold water are provided between the plasma processing roller 74 and the take-up reel 73 along with the guide rollers 75 and 76.
The reels 72 and 73 and the rollers 74 are provided with a drive mechanism for controlling the rotation of the reels 72 and 73 and the rollers 74, and the reels 72, 73 and the rollers 74 can be taken out from the processing chamber 71.

Further, similarly to the apparatus embodiment 1, three waveguides 81a, 81b, 81c transmitting microwave power are arranged in parallel, and the processing chamber 71 is passed through the irradiation windows 82a, 82b, 82c from the coupling holes of these waveguides. It is configured to generate surface wave plasma by propagating microwave power therein.
In addition, in the apparatus embodiment 2, the gas supply path 83 for supplying hydrogen gas is arranged as the shunt pipes 83a to 83d corresponding to the waveguides 81a, 81b and 81c, and similarly the vacuum pump path. 84 is also arranged as shunt pipes 84a to 84d.

  As described above, by arranging the gas supply path 83 and the vacuum pump path 84 by the shunt pipe, the hydrogen gas is equalized in the processing chamber 71, and as can be seen from FIG. 12, the shunt pipe By directing the tip toward the upper direction of the processing roller 74, the hydrogen gas as the reducing gas can be used more effectively.

In the pattern forming apparatus according to the second embodiment, the printed matter 200 fed from the take-up reel 72 is exposed to the microwave surface wave plasma while moving along the plasma processing roller 74, and the conductive fine particles of the printed matter 200 are exposed. Sintered.
Thereafter, the temperature of the printed material 200 is lowered in the process of being moved by the guide of the cooling roller, and the printed material 200 having a low temperature is taken up by the take-up reel 73.

Thus, according to the second embodiment of the present apparatus, the printed material 200 fed out from the take-up reel 72 can be continuously heated to sinter the conductive fine particles of the drawing pattern.
Further, the printed matter 200 whose temperature has been increased by heating the microwave surface wave plasma is sent through the cooling rollers 77 to 80, and the printed matter 200 whose temperature has been lowered is taken up by the take-up reel 73. If this is the case, the take-up reel 73 can be removed from the processing chamber 71.
Note that the sintered printed matter 200 wound around the take-up reel 73 is appropriately processed thereafter to obtain an electric component having a conductive pattern.

FIG. 13 is a simplified cross-sectional view of a pattern forming apparatus showing an improved example of the apparatus embodiment 2.
In this improved example, three plasma processing rollers 74a, 74b, 74c are provided, and each of the waveguides 81a, 81b, 81c has irradiation windows 85a, 85b corresponding to the plasma processing rollers 74a, 74b, 74c. , 85c.
According to this improved example, since the printed material 200 is exposed to the microwave surface wave plasma at each of the three plasma processing rollers 74a, 74b, and 74c during the movement, the sintering time of the conductive fine particles of the printed material 200 is increased. Can be further shortened.

In the pattern forming apparatus of the apparatus embodiment 2 and the improved example described above, the reel and the processing roller are rotated forward and backward so that the microwave surface wave plasma is evenly exposed to the printed matter 200, and the printed matter 200 is reciprocated at a small distance. A forward / reverse drive mechanism can be provided.
Further, the apparatus embodiment 2 and the improved example include a cooling means for cooling the plasma processing roller, and the printed material 200 can be exposed to the microwave surface wave plasma while the back surface of the printed material 200 is cooled.

Subsequently, Examples of the pattern forming method will be described as Method Examples 1 to 5.
This method embodiment was carried out by conducting an experiment using the pattern forming apparatus shown in FIGS.
In this experiment, the processing chamber 31 was depressurized to 1 × 10 ⁻³ Pa or less by the vacuum pump path 38, and then hydrogen gas was supplied as a reducing gas from the hydrogen supply path 37 into the processing chamber 11 at a flow rate of 100 sccm. .

Moreover, about each method Example, it evaluated with the following method about the electroconductive component.
(1) Substrate damage The presence or absence of deformation or discoloration of the substrate after firing was visually observed.
(2) Total light transmittance change The total light transmittance of an Example and a comparative example is based on JISK-7361-1 using a turbidimeter (brand name: NDH2000, Nippon Denshoku Industries Co., Ltd. product). Using the measured value, a decrease amount (%) of the transmittance after irradiation with respect to the transmittance of the film before plasma irradiation was calculated.

(3) Conductivity Volume resistivity was measured by a four-probe method according to JIS K7194 using a resistivity meter (trade name: Loresta GP, manufactured by Dia Instruments).

(4) Surface observation The structure of the surface and the cross section was observed using the scanning electron microscope (Brand name: S-4500, product made from Hitachi High Technology).
As for the cross section, the surface obtained by cutting the sample with a microtome was observed.

Method Example 1
A toluene dispersion of copper fine particles (trade name: Cu metal ink, manufactured by ULVAC Material Co., Ltd., average primary particle size of 5 nm) was adjusted to a solid content of 30% by mass.
Excimer lamp irradiation treatment was performed on a polyimide substrate (trade name: Kapton 300H, manufactured by Toray DuPont Co., Ltd.) having a film thickness of 75 μm, and then the substrate was fixed to a glass substrate with an adhesive tape, and a spin coating method was used. Copper fine particles were applied (drawn).
Thereafter, it was naturally dried at room temperature to produce a printed material 100.

Subsequently, the printed material 100 is put into the processing chamber 31, and microwave surface wave hydrogen plasma (surface wave plasma in a hydrogen gas atmosphere) is irradiated for 100 seconds at a hydrogen introduction pressure of 20 Pa and a microwave power of 600 W. Was removed from the processing chamber 31.
There was no damage such as deformation and discoloration on the printed material 100.

Metallic luster was observed on the surface of the printed material 100, and the volume resistivity as a conductive substrate was measured to be 4.28 × 10 ⁻⁶ Ω · cm.
There was no peeling of the fine particle sintered layer from the substrate, and adhesion was good.
When the surface of the printed material 100 was observed with a scanning electron microscope, a structure in which the fine particles were melted, sintered, and fused was observed.
Similarly, when the cross section was observed, the thickness of the fine particle sintered layer was 0.4 μm, and it was a uniform and high-density film without voids.

Method Example 2
An alcohol dispersion of copper oxide fine particles (manufactured by C-I Kasei Co., Ltd., average primary particle size 40 nm) was adjusted to a solid content of 15% by mass.
Excimer lamp irradiation treatment was performed on a 125 μm thick polyethylene naphthalate substrate (trade name: Teonex Q81, manufactured by Teijin DuPont Films Ltd.), and then the substrate was fixed to a glass substrate with an adhesive tape, and a spin coating method was used. Then, copper oxide fine particles were applied.
Thereafter, it was naturally dried at room temperature to produce a printed material 100.

Subsequently, the printed material 100 was put into the processing chamber 31, and microwave surface wave hydrogen plasma was irradiated for 100 seconds at a hydrogen introduction pressure of 20 Pa and a microwave power of 600 W, and then the printed material 100 was taken out from the processing chamber 31.
There was no damage such as deformation and discoloration on the printed material 100. The film thickness of the fine particle layer was 0.3 μm.
On the surface of the printed matter 100 is seen metallic luster, was measured for volume resistivity as a conductive component, 7.39 × 10 ^{over 6} Omega · cm, and the had low resistance.
There was no peeling of the fine particle sintered layer from the substrate, and adhesion was good.
When the surface of the printed material 100 was observed with a scanning electron microscope, a structure in which the fine particles were melted, sintered, and fused was observed.
When the cross section was observed, it was a high-density film that was uniform and free of voids.

Comparative Example 1
In the same manner as in Method Example 2, copper oxide fine particles were applied and dried to produce a printed material 100.
Subsequently, the printed material 100 was baked for 60 minutes at 230 ° C. at a heating rate of 10 ° C./min in an oven (argon gas atmosphere containing 4% hydrogen gas) instead of microwave surface wave hydrogen plasma. Thereafter, the print 100 was taken out of the oven after being naturally cooled to room temperature.

The printed material 100 was curled and deformed, and the fine particle layer on the surface of the printed material 100 had many scratches.
Metallic luster was not seen on the surface of the printed matter 100, and the volume resistivity was measured and found to be as high as 1 × 10 ⁷ Ω · cm or higher.

  By using microwave surface wave hydrogen plasma, fusion of fine particles was able to proceed in a short time even on a low heat resistant substrate that could not be fired in an oven.

Method Example 3
The same dispersion of fine copper oxide particles as in Method Example 2 was used. Excimer lamp irradiation treatment was performed on a polyethylene terephthalate base material (trade name: Toyobo Ester Film E5000, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm, and then the base material was fixed to a glass substrate with an adhesive tape, and a spin coating method was used. Then, copper oxide fine particles were applied.
Thereafter, it was naturally dried at room temperature to produce a printed material 100.

Subsequently, the printed material 100 was put into the processing chamber 31, and microwave surface wave hydrogen plasma was irradiated for 100 seconds at a hydrogen introduction pressure of 20 Pa and a microwave power of 600 W, and then the printed material 100 was taken out from the processing chamber 31.
There was no damage such as deformation and discoloration on the printed material 100.
The film thickness of the fine particle layer was 0.3 μm.
Metallic luster was observed on the surface of the printed material 100, and the volume resistivity as a conductive substrate was measured to be 7.63 × 10 ⁻⁶ Ω · cm.
There was no peeling of the fine particle sintered layer from the substrate, and adhesion was good.
When the surface of the printed material 100 was observed with a scanning electron microscope, a structure in which the fine particles were melted, sintered and fused was observed.
When the cross section was observed, it was a high-density film that was uniform and free of voids.
See Table 1 below.

Comparative Example 2
In the same manner as in Method Example 3, a dispersion of copper oxide fine particles was applied and dried to prepare a printed matter 100.
Subsequently, the printed material 100 is baked at 200 ° C. for 60 minutes in an oven (argon gas atmosphere containing 4% hydrogen gas) in an oven instead of microwave surface wave hydrogen plasma. After natural cooling to room temperature, the printed material 100 was taken out of the oven.

The printed material 100 was deformed by heat shrinkage, and damage such as clouding of the back surface was observed.
The film thickness of the fine particle layer was 0.3 μm.
Metallic luster was not seen on the surface of the printed matter 100, and the volume resistivity of the conductive pattern of the printed matter 100 was measured.
See Table 1 below.

Comparative Example 3
In the same manner as in Example 3, copper oxide fine particles were applied and dried to produce a printed product 100.
Subsequently, the printed material 100 was put in an oven, and instead of microwave surface wave hydrogen plasma, high-frequency hydrogen plasma was irradiated at a hydrogen introduction pressure of 20 Pa and 600 W for 100 seconds, and then the printed material 100 was taken out of the oven.
The high frequency plasma was generated by installing a 13.56 MHz high frequency power source in the same apparatus as the microwave surface wave hydrogen plasma amateur.
There was no damage such as deformation and discoloration on the printed material 100. The film thickness of the fine particle layer was 0.3 μm.
Metallic luster was observed on the surface of the printed matter 100, and the volume resistivity of the conductive pattern of the printed matter 100 was measured to be 4.14 × 10 ⁻⁴ Ω · cm, which is higher than that of Example 3. Met.
See Table 1 below.

Comparative Example 4
When a printed material 100 similar to Comparative Example 3 was irradiated with high-frequency hydrogen plasma at a hydrogen introduction pressure of 20 Pa and 600 W for 400 seconds, a part of the printed material 100 was severely deformed and caused thermal contraction.
A part of the volume resistivity that did not shrink was measured and found to be 2.62 × 10 ⁻⁵ Ω · cm, which is higher than that of Example 3.
See Table 1 below.

  From the above results, microwave surface wave hydrogen plasma can be sintered in a short time even when reduction sintering is not sufficient with high-frequency plasma against low heat resistance substrate such as PET substrate. I understand that there is.

Method Example 4
Using the same dispersion of copper oxide fine particles as in Example 3 and a polyethylene terephthalate base material, a printed material 100 in which a 3 mm wide line pattern was formed by a bar coating method using a mask tape was produced.
Subsequently, the printed material 100 was put into the processing chamber 31, and microwave surface wave hydrogen plasma was irradiated for 100 seconds at a hydrogen introduction pressure of 20 Pa and a microwave power of 600 W, and then the printed material 100 was taken out from the processing chamber 31.

There was no damage such as deformation and discoloration on the printed material 100.
Further, when the total light transmittance of the pattern-unformed portion was compared before and after the plasma treatment, the change was 0.0%. The fine particle layer of the pattern forming part was 0.3 μm.
Furthermore, metallic luster was seen in the pattern forming portion, and when the volume resistivity of the pattern forming portion was measured, it was 8.55 × 10 ⁻⁶ Ω · cm, and the resistance was reduced.
There was no peeling from the substrate of the fine particle sintered layer of the pattern forming part, and the adhesion was good.

Comparative Example 5
In the same manner as in Example 4, a patterned printed material 100 was produced.
Subsequently, the printed material 100 was put in an oven, and high-frequency hydrogen plasma was irradiated for 100 seconds at a pressure of 20 Pa and 600 W when hydrogen was introduced instead of the microwave surface wave hydrogen plasma, and then the printed material 100 was taken out of the oven.
The high frequency plasma was generated by installing a 13.56 MHz high frequency power source in the same apparatus as the microwave surface wave hydrogen plasma.
The pattern formation part showed metallic luster, but the pattern non-formation part was discolored brown.
When the total light transmittance of the pattern-unformed part was compared before and after the plasma treatment, the transmittance was reduced by 2.3%.

Method Example 5
An alcoholic dispersion of silver fine particles (trade name: AG-IJ-G-100-S1, manufactured by Cabot Corporation, average primary particle size of 40 nm) was adjusted to a solid content of 15% by mass.
Subsequently, after a corona discharge treatment was performed on a polyethylene terephthalate base material (trade name: Toyobo Ester Film E5000, manufactured by Toyobo Co., Ltd.) having a film thickness of 100 μm, the base material was fixed to a glass substrate with an adhesive tape, and spin Silver fine particles were applied using a coating method.
Then, it dried naturally and produced the printed matter 100.

Subsequently, the printed material 100 was put into the processing chamber 31, and microwave surface wave hydrogen plasma was irradiated at a pressure of 20 Pa and a microwave power of 600 W for 40 seconds, and then the printed material 100 was taken out from the processing chamber 31.
There was no damage such as deformation and discoloration in the printed matter.
The film thickness of the fine particle layer was 1.0 μm.

Metallic luster was observed on the surface of the printed material 100, and the volume resistivity of the conductive pattern of the printed material 100 was measured. As a result, the resistance was reduced to 5.27 × 10 ⁻⁶ Ω · cm.
There was no peeling of the fine particle sintered layer from the substrate, and adhesion was good.
When the surface of the printed material 100 was observed with a scanning electron microscope, a structure in which the fine particles were melted and sintered and fused was observed.
When the cross section was observed, it was a high-density film that was uniform and free of voids.

  Since silver fine particles are reduced by heating in the atmosphere, reducing plasma is considered unnecessary for reduction, but since organic components in the coating film are removed by hydrogen plasma, they can be efficiently melted in a short time. It was confirmed that the wear progressed.

  It can be applied to printed wiring boards, RFID tag antennas, membrane switch wiring, electromagnetic shielding materials, electrodes for flat panel displays, wiring, electrodes of batteries such as solar cells, radio wave reflectors, antennas, anti-fogging plates, etc. .

It is a simplified sectional view of the pattern formation device shown as an embodiment. 1 is a simplified perspective view of a pattern forming apparatus shown as apparatus example 1. FIG. 1 is a simplified cross-sectional view illustrating a pattern forming apparatus according to an apparatus embodiment 1. FIG. It is a perspective view which shows the process stand with which the pattern formation apparatus of apparatus Example 1 is equipped, a pushing up lever, a carrying-in movement board, and printed matter. FIG. 3 is a simplified view of a processing table portion illustrating a printed material carrying-in operation in the pattern forming apparatus according to the apparatus embodiment 1; It is a simplified sectional view showing an example in which a cooling pipe is provided as a cooling means on the above-described processing table. It is a simplified diagram of a processing stand portion showing a configuration in which the above-described push-up bar is used as a suction unit for printed matter. It is a simplified view of a processing table portion showing a configuration in which the surface of the processing table described above is gently bulged to more accurately join a printed material. FIG. 3 is a simplified view of a processing table portion showing a configuration in which a large number of suction holes are provided in the processing table and the printed material is sucked and held. It is sectional drawing of the processing stand shown in FIG. It is a simple perspective view of the pattern formation apparatus shown as apparatus Example 2. It is a simplified sectional view showing a pattern forming apparatus of apparatus example 2. FIG. 6 is a simplified cross-sectional view of a pattern forming apparatus shown as an improved example of the apparatus embodiment 2.

Explanation of symbols

11 Processing chamber 12 Processing table 14 Microwave irradiation window 15 Waveguide 21 Hydrogen supply path 24 Vacuum pump path 31 Processing chamber 32 Processing tables 35a, 35b, 35c Waveguides 36a, 36b, 36c Irradiation window 37 Hydrogen supply path 38 Vacuum Pump path 42 First spare chamber 43 Second spare chamber 44, 45 Shutter 46 Carry-in moving plate 48 Push-up rod 50 Carry-out moving plate 71 Processing chamber 72 Take-up reel 73 Take-up reel 74 Processing rollers 77-80 Cooling rollers 74a, 74b, 74c Processing roller 100, 200 Printed matter

Claims (34)

A method of drawing a pattern on a non-conductive substrate using a fine particle dispersion in which fine particles are dispersed, and sintering the fine particles of the pattern to form a conductive pattern,
For drawing the pattern, a fine particle dispersion in which fine particles of metal or metal compound are dispersed is used.
The sintering process uses an electrodeless plasma generating means for supplying microwave energy from an irradiation window of a processing chamber consisting of a decompression chamber and generating surface wave plasma along the irradiation window in the processing chamber,
A method for forming a conductive pattern, comprising exposing the drawing pattern to microwave surface wave plasma having a low electron temperature and a high electron density to sinter the fine particles of the pattern. In the formation method of the electroconductive pattern of Claim 1,
A method for forming a conductive pattern, wherein a fine particle dispersion in which fine particles made of a noble metal are dispersed is used for drawing the pattern. In the formation method of the electroconductive pattern of Claim 1,
For drawing the pattern, a fine particle dispersion in which fine particles of a base metal or a base metal whose surface is at least oxidized is dispersed,
In the sintering process, electrodeless plasma generation is performed in which reducing gas is supplied together with microwave energy into the processing chamber, and surface wave plasma is generated in the processing chamber near the irradiation window in the reducing gas atmosphere. Using means,
A method for forming a conductive pattern, wherein the drawing pattern is exposed to a microwave surface wave plasma generated in an atmosphere of a reducing gas to perform reduction treatment and sintering treatment of fine particles of the pattern. In the formation method of the conductive pattern according to claim 3,
The pattern is drawn using a fine particle dispersion in which copper fine particles or copper fine particles whose surface is at least oxidized are dispersed. In the formation method of the electroconductive pattern in any one of Claims 1 thru | or 4,
The method for forming a conductive pattern, wherein the substrate is made of a glass material or a synthetic resin material. In the formation method of the conductive pattern according to claim 5,
The method for forming a conductive pattern, wherein the substrate is made of a resin film having a high transmittance. In the formation method of the conductive pattern according to claim 5 or 6,
The method for forming a conductive pattern, wherein the substrate is made of a synthetic resin material having a melting point of 280 ° C or lower. In the formation method of the electroconductive pattern in any one of Claims 1 thru | or 7,
A method of forming a conductive pattern comprising a step of forming an easy-adhesive component on the base material or modifying the base material before drawing the pattern. In the formation method of the electroconductive pattern in any one of Claim 3 thru | or 8,
A method for forming a conductive pattern, wherein a reducing gas such as hydrogen gas is used. In the formation method of the electroconductive pattern of Claim 1,
The plasma generating means supplies microwave energy having a frequency of 2450 MHz from the irradiation window of the processing chamber, and the electron temperature is about 1 eV or less and the electron density is about 1 × 10 ¹¹ to 1 × 10 ¹³ cm ⁻³ in the processing chamber. A method for forming a conductive pattern, characterized by generating a microwave surface wave plasma.   A conductive substrate patterned by the method for forming a conductive pattern according to claim 1. In a pattern forming apparatus for drawing a pattern on a non-conductive substrate using a fine particle dispersion in which fine particles made of metal or a metal compound are dispersed, and sintering the fine particles present in the pattern to form a conductive pattern ,
An electrodeless plasma generating means for supplying microwave energy from an irradiation window of a processing chamber configured as a decompression chamber and generating surface wave plasma along the irradiation window in the processing chamber;
A processing table for arranging the substrate on which the pattern is drawn in the processing chamber;
A substrate on which a pattern is drawn is placed on the processing table, and the drawing pattern is exposed to microwave surface wave plasma having a low electron temperature and a high electron density in the processing chamber to sinter the fine particles of the drawing pattern, thereby conducting the conductive process. A pattern forming apparatus for forming a characteristic pattern. The pattern forming apparatus according to claim 12, wherein
A substrate on which a pattern is drawn using a dispersion of noble metal fine particles is placed on the processing table, exposed to microwave surface wave plasma, and the fine particles present in the pattern are sintered to form a conductive pattern. A pattern forming apparatus. The pattern forming apparatus according to claim 12, wherein
Supplying reducing gas together with microwave energy to the processing chamber, comprising plasma generating means for generating surface wave plasma in the atmosphere of reducing gas,
A substrate on which a pattern is drawn using a dispersion of base metal fine particles or copper fine particles whose surface is at least oxidized is placed on the processing table and exposed to microwave surface wave plasma to reduce the fine particles present in the drawn pattern. A pattern forming apparatus characterized by forming a conductive pattern by sintering. The pattern forming apparatus according to claim 14, wherein
A substrate on which a pattern is drawn using a dispersion of copper fine particles or copper fine particles whose surface is at least oxidized is placed on the processing table and exposed to microwave surface wave plasma, and the fine particles present in the pattern are reduced. A pattern forming apparatus characterized by forming a conductive pattern by sintering. In a pattern forming apparatus for drawing a pattern on a non-conductive substrate using a fine particle dispersion in which fine particles made of metal or a metal compound are dispersed, and sintering the fine particles present in the pattern to form a conductive pattern ,
An electrodeless plasma generating means for supplying microwave energy from an irradiation window of a processing chamber configured as a decompression chamber and generating surface wave plasma along the irradiation window in the processing chamber;
A processing table for arranging the substrate on which the pattern is drawn in the processing chamber;
A first auxiliary chamber associated with the carry-in port of the processing chamber, a second auxiliary chamber associated with the carry-out port,
A loading mechanism for depressurizing the first preliminary chamber and opening a loading port, and feeding a substrate on which a pattern is drawn from the first preliminary chamber onto a processing table in a treatment chamber;
A decompression mechanism that decompresses the second preliminary chamber and opens the carry-out port, and feeds the substrate on which the pattern is drawn from the treatment table in the treatment chamber to the second preliminary chamber,
Microwave surface wave plasma with a low electron temperature and a high electron density in the processing chamber for fine particles existing in the drawing pattern by carrying in a series of carry-in by the carry-in mechanism, plasma treatment at the processing table, and carry-out by the carry-out mechanism. And forming a conductive pattern by subjecting the fine particles of the drawing pattern to a sintering process. The pattern forming apparatus according to claim 16, wherein
A substrate on which a pattern is drawn using a dispersion of noble metal fine particles is carried in by the carry-in mechanism, exposed to microwave surface wave plasma on the processing table, carried out by the carry-out mechanism, and fine particles present in the drawn pattern are sintered. And forming a conductive pattern. The pattern forming apparatus according to claim 16, wherein
Supplying reducing gas together with microwave energy to the processing chamber, comprising plasma generating means for generating surface wave plasma in the atmosphere of reducing gas,
A base material on which a pattern is drawn using a dispersion of base metal fine particles or base metal fine particles whose surface is at least oxidized is carried in by the carry-in mechanism, exposed to microwave surface wave plasma in a processing table, and carried out by a carry-out mechanism. A pattern forming apparatus characterized in that fine particles present in a drawing pattern are reduced and sintered to form a conductive pattern. The pattern forming apparatus according to claim 18, wherein
A substrate on which a pattern is drawn using a dispersion of copper fine particles or copper fine particles whose surface is at least oxidized is carried in by the carry-in mechanism, exposed to microwave surface wave plasma in a processing table, and carried out by a carry-out mechanism. A pattern forming apparatus characterized in that fine particles present in a drawing pattern are reduced and sintered to form a conductive pattern. The pattern forming apparatus according to any one of claims 12 to 19,
The pattern forming apparatus according to claim 1, further comprising a cooling unit that cools the back surface of the substrate on which the pattern is drawn. The pattern forming apparatus according to any one of claims 12 to 19,
The pattern forming apparatus, wherein the processing table is provided with suction holding means for sucking the drawn base material into the air and bonding the printed material to the processing table. The pattern forming apparatus according to any one of claims 12 to 19,
A pattern forming apparatus, wherein a base surface of the processing base is formed on a gently bulging surface. The pattern forming apparatus according to any one of claims 12 to 19,
A pattern forming apparatus comprising driving means for rotating the processing table. The pattern forming apparatus according to claim 18 or 19,
An apparatus for forming a pattern, characterized in that the second preliminary chamber is provided with means for supplying an oxidation-suppressing gas for suppressing oxidation of the sintered conductive pattern before taking out the drawn substrate. In a pattern forming apparatus for drawing a pattern on a non-conductive substrate using a fine particle dispersion in which fine particles made of metal or a metal compound are dispersed, and sintering the fine particles present in the pattern to form a conductive pattern ,
Supplying microwave energy from the irradiation window of the processing chamber configured as a decompression chamber, and comprising electrodeless plasma generating means for generating surface wave plasma along the irradiation window in the processing chamber,
Further, in the processing chamber, a winding reel in which a long-diameter flexible base material on which a pattern is drawn is wound, a take-up reel on which the flexible base material is wound, and a microwave surface provided on the drawing pattern provided between these two reels. A plasma processing roller for irradiating wave plasma,
While moving the flexible substrate supplied from the take-up reel to the take-up reel through the plasma processing roller, the fine particles present in the drawing pattern are converted into microwave surface wave plasma having a low electron temperature and a high electron density. A pattern forming apparatus characterized in that a conductive pattern is formed by continuously performing a sintering process by exposure. The pattern forming apparatus according to claim 25, wherein
While a long flexible substrate with a pattern drawn using a dispersion liquid in which noble metal fine particles are dispersed is supplied from the take-up reel and moved to the take-up reel through the plasma processing roller, the fine particles present in the draw pattern are removed. A pattern forming apparatus characterized in that it is exposed to microwave surface wave plasma and continuously subjected to a sintering process to form a conductive pattern. The pattern forming apparatus according to claim 25, wherein
Supplying reducing gas together with microwave energy to the processing chamber, comprising plasma generating means for generating surface wave plasma in the atmosphere of reducing gas,
A long flexible base material on which a pattern is drawn using a dispersion in which fine particles of base metal or base metal whose surface is at least oxidized is dispersed is supplied from the take-up reel and moved to the take-up reel through the plasma processing roller. In the meantime, a pattern forming apparatus is characterized in that fine particles present in a drawing pattern are exposed to microwave surface wave plasma, and a reduction process and a sintering process are continuously performed to form a conductive pattern. The pattern forming apparatus according to claim 27, wherein
A pattern forming apparatus, wherein the flexible base material is obtained by drawing a pattern on a long base material using a fine particle dispersion liquid in which copper fine particles or copper fine particles whose surfaces are at least oxidized are dispersed. The pattern forming apparatus according to any one of claims 25 to 28,
A pattern forming apparatus, wherein the plasma processing roller is provided with cooling means for cooling the back surface of the flexible substrate. The pattern forming apparatus according to any one of claims 25 to 28,
A pattern forming apparatus, wherein a cooling roller for lowering a temperature while guiding a flexible base material is disposed between a plasma processing roller and a take-up reel. The pattern forming apparatus according to any one of claims 25 to 28,
The driving means for driving the take-up reel, the take-up reel, and the plasma processing roller is provided with a forward / reverse drive means for rotating the plasma wave processing roller forward and backward within a small range together with the take-up reel and the take-up reel. A characteristic pattern forming apparatus. In the pattern formation apparatus in any one of Claim 12, 16, 25,
The plasma generating means supplies microwave energy having a frequency of 2450 MHz from the irradiation window of the processing chamber, and the electron temperature is about 1 eV or less and the electron density is about 1 × 10 ¹¹ to 1 × 10 ¹³ cm ⁻³ in the processing chamber. A pattern forming apparatus characterized by generating a microwave surface wave plasma. In the pattern formation apparatus in any one of Claim 14, 15, 18, 19, 27, 28,
A pattern forming apparatus using a reducing gas such as hydrogen gas. 34. A conductive substrate patterned in the pattern forming apparatus according to claim 12.

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