JP4312036B2 - Solution injection type manufacturing apparatus, fine particle-containing solution, pattern wiring board, and device board - Google Patents

Description

  The present invention relates to an apparatus for forming a wiring board or a functional device by injecting a fine particle-containing material by using a discharge apparatus and forming a wiring board or a functional device, a material used therefor, and a patterned wiring board or a functional device board formed by the apparatus About.

  In recent years, various devices such as a light emitting device / medium and an optical processing device / medium using fine particles / ultrafine particles have been studied. For the application of such fine particles to devices, high density integration obtained by depositing a film or layer of fine particle-containing material on a solid substrate is important. The thin film in which the fine particles are densely integrated is specifically reported to be applied to Non-Patent Document 1, Non-Patent Document 2, Non-Patent Document 3, Non-Patent Document 4, Non-Patent Document 5, Non-Patent Document 6, and the like. Has been.

  On the other hand, as a method of forming an inorganic compound thin film having excellent orientation, molecular beam epitaxy (MBE), cluster ion beam, ion beam irradiation vacuum deposition, chemical vapor deposition (CVD), physical vapor deposition ( PVD), liquid phase epitaxy (LPE) and the like are known. As a method for forming an organic compound thin film, a Langmuir-Blodgett method (LB method) or the like is known. In general, what is called a quantum dot can be manufactured using a process in which a source material sublimated in a high vacuum using a vacuum apparatus such as the MBE method described above forms dots on a solid substrate in a self-organizing manner. it can.

  However, in the above method, it is difficult to control the distance between dots and the size distribution, and there is a problem that it takes a great deal of cost to control to a desired structure. Therefore, as a technique that can solve such a problem, it has been proposed to form a film of a material containing fine particles by an ink jet principle, that is, a liquid jet head. For example, in Patent Document 1, an emulsion containing nanoparticles is inkjet-coated on a solid substrate, and a photoluminescence intensity is increased or increased and stored as a function of irradiation time or irradiation amount of excitation light. There has been proposed a method of forming a thin film comprising an aggregate of fine particles (nanoparticles) on a solid substrate.

  In addition to such functional elements, studies have been made to apply the same principle to circuit board fabrication. For example, the following methods are conventionally known as a method for manufacturing a circuit board.

(1) A method in which a copper-clad laminate is coated with a resist, and a copper line pattern is formed by exposure of a circuit pattern, dissolution and removal of an unexposed resist, and etching of a resist removal portion by a photolithographic method.
(2) A method of forming a conductive pattern by printing a conductive paste on a ceramic substrate by screen printing in a desired circuit pattern and then heat-treating it in a non-oxidizing atmosphere to sinter metal fine particles in the conductive paste.
(3) A thin conductive layer is formed on the insulating substrate by vapor deposition of a conductive metal, and a resist is coated on the conductive layer, and exposure of the circuit pattern, dissolution and removal of the unexposed resist by the photolithography method, resist A method of forming a copper wire pattern by etching the removed portion.

  However, since these methods are unsuitable for forming fine patterns, for example, in Patent Document 2, a circuit pattern is directly drawn with a metal paste on a substrate using an inkjet head, There have been proposed a wiring pattern forming method and a circuit board manufacturing method that are easy to form a fine pattern, do not require waste liquid treatment, have a simple production process, and require less equipment and production costs.

On the other hand, the present inventor has also proposed an invention for manufacturing an electron source substrate using the ink jet principle as Patent Document 3.
In this way, various proposals using the ink jet principle have begun to be made, but the idea of manufacturing various devices or pattern substrates by such means is still new, and more specific methods are still unknown. The fact is that there are many parts and they are groping. In addition, even though the ink jet principle is used, there are still problems to be investigated when forming a pattern on a non-liquid-absorbing substrate instead of paper, such as an ink jet printer that attaches ink to paper and the present invention. There are many.
JP 2000-126681 A JP 2002-134878 A JP 2001-319567 A Light emitting device (LED) (Alivisatos et al.) Photoelectric conversion element (Greenham, NC, et al., Phys. Rev. B, 54, 17628 (1996)) Ultra-high speed detector (Bhargava) Electroluminescent displays and panels (Bhargava, Alivisatos et al.) Nanostructured memory device (Chen et al.) Multicolor device consisting of nanoparticle arrays (Dushkin et al.)

The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a novel solution injection manufacturing apparatus for manufacturing a high-quality and high-precision pattern wiring board or device board. It is in.
The second object is to propose a condition for manufacturing a high-quality and high-precision pattern wiring board or device board using the solution jet type jet manufacturing apparatus having such a configuration.
A third object of the present invention is to provide a solution injection type injection manufacturing apparatus having another configuration for manufacturing a high-quality and high-precision pattern wiring board or device substrate.
A fourth object is to propose conditions for manufacturing a high-quality and high-precision pattern wiring board or device board using the solution jet manufacturing apparatus of the third configuration.

A fifth object is to provide a means for ensuring the reliability of the solution jet manufacturing apparatus having such a novel configuration.
A sixth object is to provide a fine particle-containing solution that can be used in the solution jet manufacturing apparatus having such a novel configuration and can maintain the reliability of the apparatus.
A seventh object is to provide a highly accurate and high quality pattern wiring board manufactured by the solution jet manufacturing apparatus having such a novel configuration.
In addition, an eighth object is to provide a device substrate provided with a high-precision and high-quality function manufactured by the solution jet manufacturing apparatus having such a novel configuration.

A ninth object is to provide a highly accurate, high quality and highly reliable pattern wiring board manufactured by the solution jet manufacturing apparatus having such a novel configuration.
A tenth object is to provide a highly accurate, high quality and highly reliable pattern wiring board manufactured by a solution jet manufacturing apparatus having such a novel configuration.
The eleventh object is to provide a highly accurate and high-quality and highly reliable pattern wiring board manufactured by the solution jet manufacturing apparatus having such a novel configuration.
A twelfth object of the present invention is to provide a device substrate having a highly accurate, high quality and reliable function manufactured by the solution jet manufacturing apparatus having such a novel configuration.

Furthermore, the thirteenth object is to provide a device substrate having another configuration provided with a highly accurate and high-quality and reliable function manufactured by the solution jet manufacturing apparatus having such a novel configuration. .
In addition, a fourteenth object is to provide a device substrate having still another configuration to which a highly accurate and high quality reliable function is provided, which is manufactured by the solution jet manufacturing apparatus having such a novel configuration. is there.
A fifteenth object is to provide a highly accurate and high quality pattern wiring board manufactured by the solution jet manufacturing apparatus having such a novel configuration.
A sixteenth object is to provide a device substrate having a high-precision and high-quality function of another configuration manufactured by the solution jet manufacturing apparatus having such a new configuration.

In order to achieve the above object, according to the present invention, first, an ink jet principle jet having an ejection port having a size of Φ20 μm or less on an electrode pattern formed on a flexible substrate having no liquid absorbing action and on the flexible substrate. the fine particle-containing solution was injected imparted by the head, said forming a pattern by dots on the flexible substrate and the electrode pattern on the flexible substrate, to evaporate the volatile components of the pattern in the dot after applying, the flexible solids In a solution injection type manufacturing apparatus for forming a pattern wiring or an electronic device by remaining on a substrate and an electrode pattern, when the size of the fine particles is Dp and the diameter of the discharge port is Do, 0.0001 ≦ Dp /Do≦0.01, and the ejection head has an acting force due to mechanical displacement. The solution is injected and the shape of the solution during flight, said a generally rounded drop shape just prior to adhering the flexible substrate surface, or a columnar shape extending in the flight direction of 3 times within the length of its diameter A solution injection type manufacturing apparatus that is columnar and is not accompanied by a plurality of minute droplets behind a flying solution, wherein the discharge port is an opening made of a material harder than fine particles in the fine particle-containing solution, a upstream portion of the discharge port, provided with a filter closest to the discharge port, with the filter is a filter that traps more than 30 times the size of foreign matter particles particle size of the solution, the The fine particle diameter was set to be equal to or less than the surface roughness of the flexible substrate .

Second, in the first solution injection type manufacturing apparatus, the flying distance of the solution is within 3 mm, and the spraying speed of the solution is faster than the relative movement speed of the flexible substrate and the jet head. did.

Thirdly, a fine particle-containing solution is sprayed and applied on an electrode pattern formed on a flexible substrate having no liquid absorbing action and on the flexible substrate by an ejection head based on an ink jet principle having a discharge port having a size of Φ20 μm or less. the dot pattern is formed by the flexible substrate and on the electrode pattern on the flexible substrate, to evaporate the volatile components of the pattern in the dot after applying, to leave the solid in the flexible substrate and the electrode pattern on the In the solution injection type manufacturing apparatus for forming a pattern wiring or an electronic device by this, when the size of the fine particles is Dp and the diameter of the discharge port is Do, 0.0001 ≦ Dp / Do ≦ 0.01, Jet head grows bubbles in the solution instantly generated by heat Together ejects the solution in the utility, the shape of the solution during flight, a slender columnar extending in flight direction and columnar 5 times the length of its diameter, relative to the said flexible substrate and the ejection head In the solution injection type manufacturing apparatus in which the moving speed is set to 1/3 or less of the jetting and flying speed of the solution, the discharge port is an opening made of a material harder than the fine particles in the fine particle-containing solution. a upstream portion, provided with a filter closest to the discharge port, with the filter is a filter that traps more than 30 times the size of foreign matter particles diameter of said solution, said fine particle size Was less than the surface roughness of the flexible substrate .

  Fourthly, in the third solution jet manufacturing apparatus, the solution at the time of flight has a shape of an elongated column and is allowed to fly at high speed so as to be accompanied by a plurality of minute droplets.

The Fifth, flexible on the electrode pattern formed on a substrate and the flexible substrate without the liquid absorbing action, discharge port diameter is a fine particle-containing solution was injected imparted by jet head following inkjet principle [phi] 20 [mu] m, the flexible substrate A pattern wiring is formed by forming a pattern with dots on the electrode pattern on the flexible substrate and on the flexible substrate, volatilizing volatile components in the pattern with the dots after application, and leaving the solid content on the flexible substrate and the electrode pattern. Alternatively, in a fine particle-containing solution used in a solution injection type manufacturing apparatus for forming a device, when the size of the fine particles in the fine particle-containing solution is Dp and the discharge port diameter is Do, 0.0001 ≦ Dp / Do ≦ 0.0. 01, and a softer material than the member constituting the discharge port. Together with the fine particle size was less than the surface roughness of the flexible substrate.

Sixthly, a fine particle-containing solution is sprayed onto an electrode pattern formed on a flexible substrate having no liquid absorbing action and onto the flexible substrate by an ink jet principle jet head having an ejection port diameter of Φ20 μm or less, and the flexible substrate A pattern wiring is formed by forming a pattern with dots on the electrode pattern on the flexible substrate and on the flexible substrate, volatilizing volatile components in the pattern with the dots after application, and leaving the solid content on the flexible substrate and the electrode pattern. Alternatively, in a pattern wiring board manufactured by a solution injection type manufacturing apparatus for forming a device, when the size of the fine particles in the pattern of the dots is Dp and the discharge port diameter is Do, 0.0001 ≦ Dp / Do ≦ 0 .01 and by the dot The fine particles in the pattern are made of a material softer than the member constituting the discharge port, and the fine particle diameter is set to be equal to or less than the surface roughness of the flexible substrate .

Seventhly, the flexible substrate is sprayed with a fine particle-containing solution on an electrode pattern formed on a flexible substrate having no liquid-absorbing action and on the flexible substrate by a jet head having an ejection orifice diameter of Φ20 μm or less. A pattern wiring is formed by forming a pattern with dots on the electrode pattern on the flexible substrate and on the flexible substrate, volatilizing volatile components in the pattern with the dots after application, and leaving the solid content on the flexible substrate and the electrode pattern. Alternatively, in a device substrate provided with a function manufactured by a solution injection type manufacturing apparatus for forming a device, when the size of fine particles in the pattern of the dots is Dp and the discharge port diameter is Do, 0.0001 ≦ Dp /Do≦0.01, and Fine pattern in accordance DOO, along with a softer material than the member constituting the discharge port, the fine particle size was less than the surface roughness of the flexible substrate.
Eighthly, in the sixth patterned wiring board, the electrode pattern is constituted by a rectangular pattern or a combination of rectangular patterns.

Further Ninth, the pattern wiring board of the eighth, the corner portion of the front Symbol electrodes pattern was beveled shape.

The Tenth, the pattern wiring board of the eighth, the corner portions of the conductive Gokupa turn covered by the dot pattern of the fine particle-containing solution.

Further to the 11, in the sixth pattern wiring substrate, prior Symbol electrodes pattern, a solution containing fine particles of conductive material by ejecting head of an ink jet principle injected grant, volatilization of the pattern by dots after application The components were volatilized and formed by a solid dot pattern.

Further to the 12, in the seventh device substrate, prior Symbol electrodes pattern was so constituted by a combination of a rectangular pattern or a rectangular pattern.

Thirteenthly, in the twelfth device substrate, the corner portion of the electrode pattern is chamfered.
Further to the 14, in the device substrate of the first 12, the corner portions of the front Symbol electrodes pattern was covered by the dot pattern of the fine particle-containing solution.

Also in the first 5, in the device substrate of the seventh, before Symbol electrodes pattern, a solution containing fine particles of conductive material by ejecting head of an ink jet principle injected grant, volatilization of the pattern by dots after application The components were volatilized and formed by a solid dot pattern.

More first 6, in the sixth pattern wiring board, the pattern by the dot is band-shaped pattern by a combination of parallel dot on each of two directions perpendicular to turn the two directions of the belt-like pattern The outer area of the area was curved.

Also in the first 7, the in the seventh device substrate, the pattern by the dot is band-shaped pattern by a combination of parallel dot on each of two orthogonal directions, a region that bends in the two directions of the belt-like pattern The outer region of the curve was curved.

In a solution injection type manufacturing apparatus that manufactures a pattern wiring board or a device substrate by spraying and applying a fine particle-containing solution by a jet head having a size of Φ20 μm or less onto a substrate having no liquid absorbing action, realizing high- precision pattern formation, In addition, the size of the fine particles and the discharge port diameter were optimized to achieve stable injection without clogging.
Also, droplets that are easy to form good pattern dots are ejected and formed, and the material of the discharge port and the hardness of the fine particles used are optimized, so a highly accurate and high quality pattern wiring board or device using a new method The substrate can be manufactured stably at low cost. Further, since the position of the filter and the mesh size were optimized, it was possible to obtain a highly reliable solution jet manufacturing apparatus free from clogging by foreign matters.

  Further, since the solution flight conditions are optimized in the solution injection type manufacturing apparatus, a high-quality and high-precision pattern wiring board or device board can be manufactured.

In addition, high precision pattern formation is realized in solution injection type manufacturing equipment that manufactures a pattern wiring board or a device substrate by spraying and applying a solution containing fine particles onto a substrate that does not absorb liquid by a jet head having a size of Φ20 μm or less. In addition, the size of the fine particles and the outlet diameter were optimized to achieve stable injection without clogging. In addition, a solution that easily forms good dots is ejected and formed, and the relationship between the ejection speed of the solution and the relative movement speed of the substrate and the ejection head is optimized, and the discharge port material and the fine particles to be used As a result, the high-precision and high-quality pattern wiring board or device board can be manufactured at low cost and stably. Further, since the position of the filter and the mesh size were optimized, it was possible to obtain a highly reliable solution jet manufacturing apparatus free from clogging by foreign matters.

  Moreover, since the conditions for high-speed flight of the solution have been optimized in the solution injection type manufacturing apparatus, it has become possible to manufacture a high-quality and high-precision pattern wiring board or device board.

Further, in the fine particle-containing solution used in the solution injection type production apparatus, microparticles in the microparticle-containing solution, thereby optimizing the magnitude and the discharge diameter of the particles. Thus consisting softer material than the members constituting the discharge opening In such a new solution injection type manufacturing apparatus, stable injection without clogging is realized, highly accurate pattern formation is realized, and the discharge port of the injection head is scratched or worn, The jet performance is never deteriorated, and a substrate on which pattern wiring or a device is formed can be stably manufactured.

Further, the pattern wiring board which is manufactured by solution injection type production apparatus, fine particles in the formed pattern. Thus consisting softer material than the members constituting the discharge opening, to realize highly accurate pattern formation, Furthermore, there is no possibility that the ejection port of the ejection head is scratched or worn to cause deterioration of the ejection performance, and a highly accurate and high quality pattern wiring board can be stably manufactured.

Further, in the device substrate which is provided with a function that is produced by solution injection type production apparatus, fine particles in the formed pattern. Thus consisting softer material than the members constituting the discharge opening, highly accurate pattern formation In addition, there is no possibility that the ejection performance of the ejection head is scratched or worn, causing degradation of the ejection performance, and stable production of device substrates with high-precision and high-quality functions. I can do it now.
Further, in the pattern wiring board manufactured by the solution injection type manufacturing apparatus, the electrode pattern in the electrode region is constituted by a rectangular pattern or a combination of rectangular patterns, so that high-accuracy and high-quality discharge and damage due to it occur. It has become possible to stably produce a highly reliable pattern wiring board that does not have high reliability.

Further, the pattern wiring board which is manufactured by solution injection type production apparatus, since the corner portion of the electrode pattern of the electrode regions and the chamfered shape, high accuracy and high-quality discharge as well as reliability is not caused such damage by it High pattern wiring boards can be manufactured stably.

Further, the pattern wiring board which is manufactured by solution injection type production apparatus, since the corner portion of the electrode pattern of the electrode regions covered by the dot pattern of the fine particle-containing solution, such as high-precision and high-quality discharge and damage from it A highly reliable pattern wiring board that does not occur can be manufactured stably.

Further, the pattern wiring board which is manufactured by solution injection type production apparatus, the electrode pattern of the electrode regions, a solution containing fine particles of conductive material by ejecting head of an ink jet principle injected impart a pattern in the dot after giving Since the volatile components were volatilized and formed with a solid dot pattern, it was possible to stably manufacture a highly reliable pattern wiring board that does not cause high-accuracy and high-quality discharge and damage caused thereby.

Further, in the device substrate which is provided with a function that is produced by solution injection type production apparatus, the electrode pattern of the electrode regions, than Ru is configured by a combination of rectangular patterns or rectangular pattern, high-precision and high-quality discharge and it It is now possible to stably manufacture device substrates that have been provided with highly reliable functions that do not cause damage due to the above.
In addition, in the device substrate provided with the function manufactured by the solution injection type manufacturing apparatus, the corner portion of the electrode pattern in the electrode region has a chamfered shape, so that high-precision and high-quality electric discharge and damage due to it do not occur. A device substrate having a highly reliable function can be manufactured stably.

Further, in the device substrate which is provided with a function that is produced by solution injection type production apparatus, since the corner portion of the electrode pattern of the electrode regions covered by the dot pattern of the fine particle-containing solution, a high-precision and high-quality discharge and it It is now possible to stably manufacture device substrates that have been provided with highly reliable functions that do not cause damage due to the above.

Further, in the device substrate provided with the function manufactured by the solution injection type manufacturing apparatus, the electrode pattern of the electrode region is applied by spraying a solution containing fine particles of the conductive material by an injection head of the ink jet principle, and after the application Volatile components in the pattern due to dots are volatilized and formed with a solid dot pattern, which stabilizes the device substrate with a highly reliable function that does not cause high-precision and high-quality discharge and damage due to it. Can now be manufactured.

In the pattern wiring board manufactured by the solution injection type manufacturing apparatus, the dot pattern is a belt-like pattern formed by a combination of dots parallel to each of the two orthogonal directions, and the outside of the region bent in the two directions of the pattern. Since the area is curved, it is possible to stably manufacture a highly reliable pattern wiring board that is high-precision and high-quality and that does not cause discharge and damage due to the bending area. It was.

Further, in the device substrate which is provided with a function that is produced by solution injection type production apparatus, the pattern by the dot is band-shaped pattern by a combination of parallel dot to each of two orthogonal directions in the two directions of the pattern Since the outer area of the bending area is curved, the device board is a high-precision and high-quality device board that has a reliable function that does not cause discharge and damage in the bending area. Can now be manufactured.

  FIG. 1 shows an example in which a pattern is formed by a technique of the present invention on a glass substrate, a plastic substrate, a semiconductor substrate such as Si, a glass / epoxy substrate, a flexible substrate, or the like. FIG. 1A shows a state in which terminals 2 and 3 are formed on such a substrate 10, and a dotted line portion 1 'in the drawing is a region where a wiring pattern 1 as described later is generated. FIG. 1B shows an example in which a wiring pattern 1 is formed by jetting and drawing a solution containing fine conductive fine particles by the droplet jetting principle.

Here, as a means for applying a solution containing fine conductive fine particles, an inkjet technique is applied in the present invention. The specific method will be described below.
FIG. 2 is a view for explaining an embodiment of a manufacturing apparatus for forming a patterned wiring board or functional device of the present invention. In the figure, 11 is an ejection head unit (ejection head), 12 is a carriage, 13 is A substrate holding table, 14 is a substrate such as a wiring substrate or a functional element substrate, or a substrate forming a functional device, 15 is a supply tube for a solution containing fine conductive fine particles, 16 is a signal supply cable, and 17 is an ejection head. A control box (including a solution tank), 18 is an X-direction scan motor for the carriage 12, 19 is a Y-direction scan motor for the carriage 12, 20 is a computer, 21 is a control box, 22 ( _22X1 , _22Y1 , _22X2 , _22Y2) ) Is a substrate positioning / holding means. In this case, the ejection head 11 is moved by carriage scanning on the front surface of the substrate 14 placed on the substrate holder 13 and ejects a solution containing fine conductive fine particles.

FIG. 3 is a schematic diagram showing a configuration of a droplet applying apparatus applied to manufacture of a patterned wiring board or functional device formation of the present invention, and FIG. 4 is a schematic diagram of a main part of an ejection head unit of the droplet applying apparatus of FIG. It is a block diagram.
The configuration of FIG. 3 is different from the configuration of FIG. 2 in that the substrate 14 side is moved to form a wiring pattern or a functional device on the substrate. 3 and 4, 31 is a head alignment control mechanism, 32 is a detection optical system, 33 is an ejection head, 34 is a head alignment fine movement mechanism, 36 is an image identification mechanism, 37 is an XY direction scanning mechanism, and 38 is a position detection mechanism. , 39 is a position correction control mechanism, 40 is an ejection head drive / control mechanism, 41 is an optical axis, 42 is an element electrode, 43 is a droplet, and 44 is a droplet landing position.

The droplet applying device (ejection head 33) of the ejection head unit 11 may be any mechanism as long as it can discharge an arbitrary amount of droplets, and in particular, an ink jet principle capable of forming droplets of about 0.1 pl to several hundred pl. The mechanism is desirable.
Examples of the ink jet method include a method disclosed in US Pat. No. 3,683,212 (Zoltan method), a method disclosed in US Pat. No. 3,747,120 (Stemme method), and US Pat. No. 3,946,398. As in the disclosed method (Kyser method), an electrical signal is applied to the piezo-vibration element, this electrical signal is converted into mechanical vibration of the piezo-vibration element, and droplets are discharged from a fine nozzle according to the mechanical vibration. Is generally called a drop-on-demand system.

As other methods, there are methods (Sweet method) disclosed in US Pat. No. 3,596,275, US Pat. No. 3,298,030, and the like. This generates a recording liquid droplet with a controlled charge amount by a continuous vibration generation method, and the generated charge amount controlled droplet flies between deflection electrodes to which a uniform electric field is applied. Thus, recording is performed on a recording member, which is usually called a continuous flow method or a charge control method.
As another method, there is a method disclosed in Japanese Patent Publication No. 56-9429. This is a method in which bubbles are generated in a liquid and droplets are ejected and ejected from fine nozzles by the action force of the bubbles, which is called a thermal ink jet method or a bubble jet (R) method.

There are a drop-on-demand method, a continuous flow method, a thermal ink jet method, and the like as a method for ejecting droplets as described above.
In the present invention, in the manufacturing apparatus (FIG. 2) for forming such a patterned wiring board or functional device, the substrate 14 is determined by adjusting the holding position by the substrate positioning / holding means 22 of this apparatus. Although simplified in FIG. 2, the substrate positioning / holding means 22 is brought into contact with each side of the substrate 14 and can be finely adjusted in the submicron order in the X direction and the Y direction orthogonal thereto. These are connected to the ejection head control box 17, the computer 20, the control box 21, etc., and the positioning information, fine adjustment displacement information, etc., the position information of the droplet application, the timing, etc. can be constantly fed back.

  Further, in the manufacturing apparatus for forming the pattern wiring board or the functional device of the present invention, in addition to the position adjusting mechanism in the X and Y directions, a rotational position adjusting mechanism (not shown because it is located under the substrate 14) is not shown. Have. In relation to this, the shape of the patterned wiring board or functional device forming substrate of the present invention and the arrangement of the functional device group to be formed will be described.

  The patterned wiring board or functional device forming substrate of the present invention is a glass substrate, a ceramic substrate, various plastic substrates including PET, a semiconductor substrate such as Si, a glass / epoxy substrate, a polyimide film, depending on the purpose and application. A flexible substrate made of a polymer film such as a polyamideimide film, a polyamide film, or a polyester film is preferably used. For example, various plastic substrates and polymer films are effective for pattern wiring substrates or functional devices that require weight reduction.

  However, in the present invention, the ink jet principle is used for applying the fine particle-containing solution, but these substrates applied to the present invention do not have a liquid absorbing action of absorbing the ink solvent as in paper. This is the difference between an ink jet recording apparatus and a solution jet manufacturing apparatus using the ink jet principle as in the present invention.

  The shape of various plastic substrates and polymer films used for the pattern wiring substrate or functional device forming substrate of the present invention is the functional device forming substrate that is economically produced, supplied, or finally manufactured. Because of its use, it is rectangular. That is, the two vertical and horizontal sides constituting the rectangular shape are substrates in which the two vertical sides are parallel to each other, the two horizontal sides are parallel to each other, and the vertical and horizontal sides form a right angle.

  In the present invention, the functional device groups to be formed are arranged in a matrix for such a substrate, and the two orthogonal directions of the matrix are parallel to the direction of the vertical side or the horizontal side of the substrate. The functional device group is arranged so that The reason why the functional device groups are arranged in a matrix and the reason why the vertical and horizontal sides of the substrate are parallel to two orthogonal directions of the matrix will be described below.

  As shown in FIG. 2 or FIG. 3, in the present invention, after the positional relationship between the substrate 14 and the solution ejection port surface of the ejection head unit 11 is first determined, the position control is not particularly performed. That is, the ejection head unit 11 ejects the solution while performing a relative movement in the X and Y directions parallel to the formation surface of the functional device group while maintaining a certain distance from the substrate 14. In other words, the X direction and the Y direction are two directions orthogonal to each other. When the substrate is positioned, the vertical direction or the horizontal side of the substrate is formed so as to be parallel to the Y direction or the X direction. In the functional device group, the two directions of the matrix arrangement are parallel to each other, so that it is possible to form a highly accurate device group only by a mechanism that performs ejection while performing relative movement. In other words, if a substrate shape, a matrix arrangement of functional device groups, and a relative movement device in two directions of X and Y orthogonal to each other as in the present invention are used, positioning of the substrate before droplet ejection for device formation is performed. If performed accurately, a highly accurate matrix arrangement of functional device groups can be obtained.

  Here, the description will be returned to the rotational position adjustment mechanism. As described above, in the present invention, the substrate is accurately positioned before the droplet ejection for device formation is performed, only the relative movement in the X and Y directions is performed, and other controls are not performed. It is intended to obtain a matrix-like arrangement. In this case, a problem is a shift in the rotation direction (the rotation direction with respect to the axis perpendicular to the plane determined by the two directions X and Y) when the substrate is first positioned.

  In order to correct this shift in the rotational direction, the present invention has a rotational position adjusting mechanism (not shown) that is not shown (not shown) as described above. Thus, when the displacement in the rotational direction is also corrected and the sides of the substrate are positioned, the apparatus of the present invention can obtain a highly accurate matrix arrangement of functional device groups by relative movement only in the X and Y directions.

The rotation position adjusting mechanism has been described as a mechanism different from 22 (22 _X1 , 22 _Y1 , 22 _X2 , 22 _Y2 ) in the substrate positioning / holding means of FIG. However, it is also possible to provide the substrate positioning / holding means 22 with a rotational position adjusting mechanism. For example, the substrate positioning / holding means 22 is brought into contact with the side of the substrate 14 so that the entire position of the substrate positioning / holding means 22 can be adjusted in the X direction or the Y direction. The angle adjustment is possible if two screws provided at a distance are moved independently at a portion that contacts the side of the substrate 14. This rotational position control information is also connected to the ejection head control box 17, the computer 20, the control box 21, etc. in the same manner as the positioning information and fine adjustment displacement information in the X and Y directions, and the droplet application position information, Timing, etc. can be constantly fed back.

  The above description is based on the premise that the substrate suitably used in the present invention is basically a rectangular shape, except that a semiconductor substrate such as Si is supplied as a round wafer, In that case, the substrate positioning / holding means 22 may be brought into contact with one straight side called an orientation flat (orientation flat) indicating the direction of the crystal orientation axis.

  Next, other means and configuration of positioning according to the present invention will be described. In the above description, the substrate positioning / holding means 22 is brought into contact with the side of the substrate 14 so that the position of the entire substrate positioning / holding means 22 can be adjusted in the X direction or the Y direction. An example in which the belt-like pattern is provided in two directions orthogonal to each other on the substrate, not on the side of the substrate 14 will be described. As described above, in the present invention, functional device groups are formed in a matrix on a substrate. Here, however, the above-described two orthogonal band-like patterns are defined as two orthogonal directions of the matrix. It forms so that it may become parallel. Such a pattern can be easily formed on a substrate by a photofabrication technique.

  The present invention is applied to the case of forming a wiring pattern as shown in FIG. 1 in addition to the case of forming a large number of functional device groups arranged in a matrix. It is formed in two orthogonal directions as in this example, and is formed so as to be parallel to the vertical and horizontal directions (X direction and Y direction) of the substrate, respectively. The wiring pattern may be formed as a pattern for the purpose of such positioning at a position that does not hinder the original function of the substrate of the present invention, or the element electrode 42 (FIG. 4) or each device. The wiring patterns such as the X-direction wiring and the Y-direction wiring may be regarded as the two-direction belt-like patterns of the present invention. If such a belt-like pattern is provided, pattern detection can be performed by a detection optical system 32 using a CCD camera and a lens as will be described later with reference to FIG.

  Next, in the Z direction, which is a direction perpendicular to the X and Y directions, in the present invention, after the positional relationship between the substrate 14 and the solution ejection surface of the ejection head unit 11 is first determined, the position is particularly important. There is no control. That is, the ejection head unit 11 ejects a solution containing fine conductive fine particles while performing relative movement in the X and Y directions while maintaining a certain distance (1 to 3 mm) with respect to the substrate 14. At the time of ejection, the position control of the ejection head unit 11 in the Z direction is not particularly performed. The reason for this is that if the control is performed at the time of jetting, not only the mechanism and the control system become complicated, but also the formation of the functional device by applying droplets to the substrate 14 becomes slow, and the productivity is significantly reduced. .

  Instead, according to the present invention, the flatness of the substrate 14 and the flatness of the device that holds the substrate 14 and the accuracy of a carriage mechanism that relatively moves the ejection head unit 11 in the X and Y directions are improved. As a result, the Z-direction control during ejection is not performed, and the relative movement of the ejection head unit 11 and the substrate 14 in the X and Y directions is performed at high speed, thereby improving productivity. As an example, the variation in the distance between the substrate 14 and the solution ejection port surface of the ejection head unit 11 at the time of application of the solution of the present invention (during ejection) is suppressed to 2 mm or less (the size of the substrate 14 is 100 mm × 100 mm or more). 4000mm x 4000mm or less).

  Although the apparatus is configured so that the plane determined by the two directions of the X and Y directions is normally maintained (horizontal to the vertical direction), the substrate 14 is small (for example, 500 mm × 500 mm or less). ) Does not necessarily need to be horizontal in the plane determined by the two directions of X and Y, and it is sufficient that the positional relationship of the arrangement of the substrates 14 is most efficient for the apparatus.

  Next, the configuration of the ejection head unit 11 will be described with reference to FIG. In FIG. 4, reference numeral 32 denotes a detection optical system that captures image information on the substrate 14. The detection optical system 32 is close to the ejection head 33 that ejects the droplet 43, and the optical axis 41 and the focal position of the detection optical system 32 and the ejection head 33. The droplets 43 are arranged so that the landing positions 44 of the droplets 43 coincide with each other.

  In this case, the positional relationship between the detection optical system 32 and the ejection head 33 shown in FIG. 3 can be precisely adjusted by the head alignment fine movement mechanism 34 and the head alignment control mechanism 31. The detection optical system 32 uses a CCD camera and a lens.

  In FIG. 3, reference numeral 36 denotes an image identification mechanism for identifying image information captured by the previous detection optical system 32, and has a function of binarizing the contrast of the image and calculating the center of gravity position of the binarized specific contrast portion. I have it. Specifically, VX-4210, a high-precision image recognition device manufactured by Keyence Corporation can be used. A means for giving position information on the functional element substrate 14 to the image information obtained thereby is a position detection mechanism 38. For this purpose, a length measuring device such as a linear encoder provided in the XY direction scanning mechanism 37 can be used. The position correction control mechanism 39 corrects the position based on the image information and the position information on the functional element substrate 14, and this mechanism corrects the movement of the XY direction scanning mechanism 37. It is done. Further, the ejection head 33 is driven by the ejection head control / drive mechanism 40, and droplets are applied onto the functional element substrate 14. Each control mechanism described so far is centrally controlled by the control computer 35.

  Incidentally, FIG. 4 shows a diagram in which droplets are ejected obliquely onto the substrate surface. This is because the droplets fly obliquely in this manner in order to illustrate the detection optical system 32 and the ejection head 33 together. However, in actuality, spraying is performed so that it is substantially perpendicular to the substrate.

  In the above description, the ejection head unit 11 is fixed, and the functional element substrate 14 is moved to an arbitrary position by the XY-direction scanning mechanism 37 so that the ejection head unit 11 and the functional element substrate 14 are moved relative to each other. Although realized, it goes without saying that the functional element substrate 14 may be fixed and the ejection head unit 11 may scan in the XY directions as shown in FIG. In particular, when applied to the production of a medium-sized substrate of about 200 mm × 200 mm to a large substrate of 2000 mm × 2000 mm or larger, the functional element substrate 14 is fixed as in the latter, and the ejection head unit 11 is orthogonal to X, Y It is better to adopt a configuration in which scanning is performed in the two directions, and droplet application of the solution is sequentially performed in the two orthogonal directions.

  When the substrate size is about 200 mm × 200 mm or less, the ejection head unit for applying droplets is a large array multi-nozzle type capable of covering the range of 200 mm, and the relative movement between the ejection head unit and the substrate is orthogonal 2. It is possible to perform relative movement only in one direction (for example, only in the X direction) without performing in the direction (X direction, Y direction), and the mass productivity can be increased, but the substrate size is 200 mm × 200 mm. In the above case, it is difficult to technically / cost-effectively produce such a large array multi-nozzle type ejection head unit that can cover a range of 200 mm. Scanning is performed in two directions of X and Y that are orthogonal to each other, and liquid droplet application is sequentially performed in these two orthogonal directions. It is better to have a configuration to do so.

  In particular, as a final substrate, even when a substrate smaller than 200 mm × 200 mm is manufactured, when a plurality of large substrates are manufactured, the original substrate is 400 mm × 400 mm to 2000 mm. Since a nozzle of 2000 mm or more is used, the ejection head unit 11 scans in two orthogonal X and Y directions, and solution droplet application is sequentially performed in the two orthogonal directions. It is better to have a configuration that does this.

As the material of the droplet 43, a solution containing fine conductive fine particles is used. For example, Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os A solution containing fine metal particles such as Ir, Fe, Mn, Ge, Sn, Ga, and In is preferably used.
In particular, when fine metal particles such as Au, Ag, and Cu are used, it is possible to form a fine circuit pattern that has low electrical resistance and is resistant to corrosion.
In the present invention, the solution containing such fine conductive fine particles includes an aqueous solution and an oily solution.

An aqueous solution obtained by dispersing such fine conductive fine particles in a dispersion medium mainly composed of water can be prepared by the following method, for example.
That is, a water-soluble polymer is dissolved in an aqueous metal ion source solution such as chloroauric acid or silver nitrate, and an alkanolamine such as dimethylaminoethanol is added with stirring. Metal ions are reduced in several tens of seconds to several minutes, and metal fine particles having an average particle diameter of 0.5 μm (500 nm) or less are precipitated. After removing chloride ions and nitrate ions by a method such as ultrafiltration, a concentrated conductive fine particle-containing solution can be obtained by concentration and drying. This conductive fine particle-containing solution can be stably dissolved and mixed in water, an alcohol solvent, a sol-gel process binder such as tetraethoxysilane or triethoxysilane.

An oily solution obtained by dispersing fine conductive fine particles in a dispersion medium mainly composed of oil can be prepared, for example, by the following method.
That is, an oil-soluble polymer is dissolved in a water-miscible organic solvent such as acetone, and this solution is mixed with an aqueous metal ion source solution. The mixture is heterogeneous, but when alkanolamine is added while stirring the mixture, the metal fine particles are precipitated on the oil phase side in a form dispersed in the polymer. When this is concentrated and dried, a concentrated conductive fine particle-containing solution similar to the aqueous system is obtained. This conductive fine particle-containing solution can be stably dissolved and mixed in aromatic solvents, ketone solvents, ester solvents and the like, polyesters, epoxy resins, acrylic resins, polyurethane resins, and the like.

The concentration of the conductive fine particles in the dispersion medium of the conductive fine particle-containing solution can be a maximum of 80% by weight, but is appropriately diluted depending on the application.
Usually, the content of the conductive fine particles in the conductive fine particle-containing solution is 2 to 50% by weight, the content of the surfactant and the resin is 0.3 to 30% by weight, and the viscosity is suitably 3 to 30 centipoise.

  In any material, the present invention performs pattern wiring formation or functional device formation by volatilizing a volatile component in a solution and leaving a solid content on a substrate. This solid material generates the function of each pattern or device, and the solvent (volatile component) is a vehicle for ejecting droplets by the ink jet principle.

Other examples of the material of the droplet 43 include a group I-VII compound semiconductor such as CuCl, a group II-VI compound semiconductor such as CdS and CdSe, a group III-V compound semiconductor such as InAs, and a group IV semiconductor. Nano-particles such as semiconductor crystals, metal oxides such as TiO ₂ , SiO, SiO ₂ , phosphors, inorganic compounds such as fullerenes and dendrimers, organic compounds such as phthalocyanines and azo compounds, or composite materials thereof. Examples of the contained solution.

The nanoparticles to be used in the present invention are usually fine particles having a particle size of 0.0005 to 0.2 μm (0.5 to 200 nm), preferably 0.0005 to 0.05 μm (0.5 to 50 nm). More strictly, it is determined in consideration of the dispersion stability of fine particles during production of the solution, the occurrence of clogging at the time of injection described later, and the surface roughness of the substrate on which the pattern is formed.
The surface of these nanoparticles may be chemically or physically modified within the range not impairing the object of the present invention, and additives such as surfactants, dispersion stabilizers and antioxidants may be added. good. Such nanoparticles can be obtained by colloidal chemical methods such as reverse micelle method (Lianos, P. et al., Chem. Phys. Lett., 125, 299 (1986)) and hot soap method (Peng, X. et al , J. Am. Chem. Soc., 119, 7019 (1997)).

The nanoparticle-containing solution that can be suitably used in the present invention is a dispersion in which the above-mentioned nanoparticles are dispersed in an emulsion (O / W emulsion) in which the continuous phase is an aqueous phase and the dispersed phase is an oil phase.
The aqueous phase is mainly water, but a water-soluble organic solvent may be added to water. Examples of water-soluble organic solvents include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (# 200, # 400), glycerin, alkyl ethers of the glycols, N-methylpyrrolidone, 1,3- Examples thereof include dimethyl imidazolinone, thiodiglycol, 2-pyrrolidone, sulfolane, dimethyl sulfoxide, diethanolamine, triethanolamine, ethanol, isopropanol and the like. The amount of water-soluble organic solvent used in the aqueous dispersion medium is usually preferably 30% by weight or less, and more preferably 20% by weight.

  The content of the nanoparticles in the dispersion varies depending on the desired film (layer) structure or particle arrangement structure and film (layer) thickness, but is usually in the range of 0.01 to 15% by weight with respect to the total weight of the dispersion. Although it is used, it is more preferably in the range of 0.05 to 10% by weight. If the content of the nanoparticles is too small, there is a possibility that the device function cannot be expressed sufficiently. Conversely, if the content is too large, the ejection stability at the time of ejecting droplets by the ink jet principle is impaired.

  Further, the nanoparticle-containing solution that is preferably used in the present invention and ejected by the ink jet principle preferably has a surfactant and a solvent for dispersing nanoparticles coexist in the dispersion. Examples of the surfactant include an anionic surfactant (sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium laurate, ammonium salt of polyoxyethylene alkyl ether sulfate, etc.), nonionic surfactant (polyoxyethylene alkyl). Ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl amines, polyoxyethylene alkyl amides, etc.), and these may be used alone or in combination of two or more. be able to.

The amount of the surfactant is usually in the range of 0.1 to 30% by weight, more preferably in the range of 5 to 20% by weight, based on the total weight of the solution. When the amount of the surfactant is less than this range, oil-water separation occurs in the aqueous dispersion, and there is a case where a uniform pattern cannot be coated by applying droplets. On the contrary, when the amount is more than this range, the viscosity of the aqueous dispersion medium tends to be too high.
The solvent for dispersing the nanoparticles is usually a liquid such as toluene, hexane, pyridine, chloroform, and preferably volatile. The amount of the dispersing solvent is usually used in the range of about 0.1 to 20% by weight, but more preferably in the range of 1 to 10% by weight. If the amount of the dispersing solvent is less than this range, the amount of ultrafine particles that can be contained in the aqueous medium decreases. On the other hand, if it is more than this range, oil-water separation may occur in the aqueous dispersion medium.

Furthermore, the organic compound can be dissolved in the dispersion. Examples of such organic compounds include trioctylphosphine oxide (TOPO), thiophenol, photochromic compounds (spiropyran, fulgide, etc.), charge transfer complexes, electron-accepting compounds, and the like that are solid at room temperature are preferable. . In this case, the amount of the organic compound in the dispersion is at least 1/10000, preferably about 1/1000 to 10 times the weight of the nanoparticles.
In addition, a surfactant, a dispersion stabilizer, an additive such as an antioxidant, or a binder such as a polymer or a material that gels in the coating / drying process may be added to the suspension as long as the object of the present invention is not impaired. good.

A droplet containing such a nanoparticle-containing solution is applied onto a substrate by the ink jet principle and dried to form a pattern wiring or a functional device. In the present invention, for example, it may be first air-dried at −20 to 200 ° C., preferably about 0 to 100 ° C. for 1 hour or more, preferably 3 hours or more, and then dried under reduced pressure as necessary. good. The degree of vacuum at this time may be 1 × 10 ⁵ Pa or less, preferably about 1 × 10 ⁴ Pa or less, and the temperature is usually −20 to 200 ° C., preferably 0 to 100 ° C. The decompression time is about 1 to 24 hours.

  Although the thickness of the nanoparticle thin film obtained by said method is not specifically limited, Usually, the diameter of a nanoparticle is 1 mm, Preferably it is the diameter of a nanoparticle-about 100 micrometers. In the nanoparticle thin film, the nanoparticles are preferably present at a density of a certain level or more. In this sense, the average interparticle distance between individual nanoparticles in the nanoparticle aggregate is usually within 10 times the particle diameter, and more preferably within 2 times the particle diameter. If this average interparticle distance is too large, the nanoparticles will not exhibit collective function.

Next, a liquid jet head suitably applied to the present invention will be described with reference to FIGS. This example is an example of 7 nozzles.
This liquid ejecting head is provided with a piezo element 46 as an energy acting part in a flow path 45 into which a solution 47 is introduced. When a pulsed signal voltage is applied to the piezo element 46 to distort the piezo element 46 as shown in FIG. 5A, the volume of the flow path 45 is reduced and a pressure wave is generated. A droplet 43 is discharged from 48. FIG. 5B shows a state in which the piezoelectric element 46 is no longer distorted and the volume of the flow path 45 is increased.

  Here, the solution 47 introduced into the flow path 45 immediately before the nozzle 48 has passed through the filter 49. In the present invention, the filter 49 is thus provided in the ejection head, and the filter removal function is provided in the vicinity of the nozzle 48. By doing so, foreign particles larger than those other than the conductive fine particles or nanoparticles in the solution of the present invention are trapped so as not to cause deterioration in the performance of the pattern or device formed on the substrate. . Such a filter 49 can be incorporated into the ejection head 11 as shown in FIG. The ejection head 11 itself can also be made compact.

  As such a filter 49, for example, a stainless mesh filter is preferably used. Alternatively, resin materials such as Teflon (R) (tetrafluoroethylene) and polypropylene are also preferably used. In short, a material that does not corrode or dissolve in the solution of the present invention is appropriately selected. The pore size (filter mesh size) is selected so that foreign matter having a size of 30 times or more the particle size of the fine particles in the solution can be trapped.

  More specifically, as described above, in the present invention, the particle size is usually 0.0005 to 0.2 μm (0.5 to 200 nm), preferably 0.0005 to 0.05 μm (0.5 to 50 nm). ) Is used, so that the filter can trap foreign matter having a size of 0.015 to 0.6 μm, preferably 0.015 to 1.5 μm or more. The problem of clogging the outlet (nozzle) can be avoided. In addition, regarding the filter mesh size (the size of foreign matter that can be trapped), strictly speaking, there is a definition of whether the removal rate refers to the absolute removal rate or the average removal rate, but here the concept of the absolute removal rate In the above mesh size.

  Further, although the position of the filter 49 is shown in FIG. 6 as an example of being incorporated in the ejection head 11, it is not essential to be incorporated in the ejection head 11. Since the filter may be provided at a plurality of locations, in the present invention, the mesh size of the filter that is upstream of the discharge port (nozzle) 48 and closest to the discharge port (nozzle) 48 is within the above range. That is the point. The filter 49 is not only provided in the jet head having the above-described configuration, but is similarly applied to a thermal type (bubble type) liquid jet head, which will be described later, or another type of jet head.

Next, another example of a liquid jet head suitably applied to the present invention will be described with reference to FIG. This example is an example of a thermal type (bubble type) liquid jet head, and the driving force of droplet jetting is the growth action force of film boiling bubbles generated instantaneously in a solution.
The liquid ejecting head shown here is of a type in which droplets are ejected from a short channel portion in which a solution flows, and is called an edge shooter type.

  Here, an example in which the number of nozzles of the liquid ejecting head is four is shown. This liquid ejecting head is formed by bonding a heating element substrate 66 and a lid substrate 67. The heating element substrate 66 is formed on a silicon substrate 68 by an individual electrode 69, a common electrode 70, and an energy application unit by a wafer process. It is comprised by forming the heat generating body 71 which is.

  On the other hand, the lid substrate 67 has a groove 74 for forming a flow path for introducing a solution containing a functional material, and a recess for forming a common liquid chamber for containing the solution introduced into the flow path. A region 75 is formed, and the heat generating substrate 66 and the lid substrate 67 are joined as shown in FIG. 7 to form the flow path and the common liquid chamber. In the state where the heating element substrate 66 and the lid substrate 67 are joined, the heating element 71 is located on the bottom surface of the channel, and the solution introduced into these channels at the end of the channel. The nozzle 65 for ejecting a part of the nozzle as a droplet is formed. Here, the nozzle shape is rectangular, but it may be round.

  Further, in consideration of jetting stability, a nozzle plate may be separately provided on the end face (the area of the nozzle 65) to have a desired nozzle diameter and nozzle shape (for example, a round shape). In this case, for example, Ni is used as the nozzle plate, and a highly accurate object can be formed by a technique such as electroforming. Alternatively, it is also a good method to use a resin film (substrate) having nozzle holes drilled by excimer laser processing.

The lid substrate 67 is provided with a solution inlet 76 for supplying a solution into the supply liquid chamber by a supply means (not shown).
In the present invention, a single functional element is formed by a plurality of droplets, or a pattern for forming a functional element or the like is formed by overlapping or contacting dots with a plurality of droplets. Therefore, when such a multi-nozzle type liquid jet head is used, a functional element can be formed very efficiently. In this example, a four-nozzle liquid ejecting head is shown, but the present invention is not necessarily limited to four nozzles. Needless to say, the larger the number of nozzles, the more efficiently the functional elements are formed. However, this is not simply a matter of increasing the number, and if it increases, the liquid jet head becomes expensive, and the probability of clogging of the jet nozzle increases. The balance of the production efficiency of the conductive element).

  FIG. 8 is a view of the multi-nozzle type liquid jet head manufactured as described above as viewed from the nozzle side. In the present invention, such a multi-nozzle type liquid jet head is provided for each solution to be jetted and mounted on a carriage as shown in FIG. FIG. 10 is a perspective view thereof.

In FIGS. 9 and 10, the multi-nozzle type liquid jet heads are labeled A, B, C, and D, respectively, but each of the liquid jet heads A, B, C, and D has a nozzle portion of each liquid jet head. A different type of conductive fine particle-containing solution or nanoparticle-containing solution can be ejected for each liquid ejecting head while being configured separately for each ejecting head.
In the present invention, a functional device is manufactured by spraying a conductive fine particle-containing solution or a nanoparticle-containing solution, but not only a single solution is sprayed, Since various types of solutions can be ejected, for example, a device structure in which a solution for forming an electrode pattern and a solution for forming a functional device are combined can be easily formed.

  Next, other features of the present invention will be described. As described above, the present invention performs pattern wiring formation or functional device formation, and the solution used for the formation is a nanoparticle-containing solution. The present invention also relates to a technique for forming a pattern on a substrate by ejecting the solution from a fine discharge port by a technique equivalent to the so-called inkjet ejection principle. However, in the ink used in the conventional ink jet recording field, the dye is dissolved in the solution, whereas in the solution used in the present invention, the nanoparticles are only dispersed in the solution, so clogging occurs. Cheap.

Further, in the present invention, the pattern or device applications requiring, not in the conventional fine discharge port diameter, for example, an injection head as discharge port diameter is Φ20μm less (approximately 300 [mu] m ² or less if referred to the area) This clogging is a very serious problem.

  By the way, clogging originates from the principle itself that a solution is ejected from a fine discharge port. That is, it occurs because the discharge port is fine. Therefore, there is a close relationship between the size of the discharge port and the size of the nanoparticles, which can be called foreign matter in the solution.

  In view of this point, the present invention pays attention to the size of the discharge port and the size of the nanoparticles, and finds out the relationship between the difficulty of clogging and the occurrence thereof. As described above, the present invention usually contains fine particles having a particle size of 0.0005 to 0.2 μm (0.5 to 200 nm), preferably 0.0005 to 0.05 μm (0.5 to 50 nm). A solution is used.

  The fine particles are fine as described above, but generally, when undergoing a process of prescribing as a final fine particle-containing solution, the fine particles are aggregated and form a cluster having a size of 0.05 to 5 μm (if another expression is used). A bunch of potatoes). Assuming that 100 to 1000 fine particles originally present independently existed in a straight line (one line) after the above process, the length is 0.05 to 5 μm, or It becomes 0.5-50 micrometers, and becomes a size which may affect nozzle clogging.

  Actually, it is not only connected in such a straight line (anisotropic), but also becomes a cluster-like aggregate, and several hundred to several thousand pigments are considered to be collected isotropically. It is done. When these particles pass through fine discharge ports (nozzles), the fine particle agglomerates that have become cluster-like agglomerates are applied to a solution injection type production apparatus such as the present invention depending on the size. In this case, it is predicted that the fine particle aggregates in the solution cause clogging of the discharge port.

In practice, how many fine particles gather together to cause clogging of the discharge port? In the present invention, this is experimentally investigated.
In this regard, the inventor assumed a case where 400 particles of 0.05 μm were connected in a row. In this case, the maximum length is 20 μm, and it is considered that there is a possibility of clogging of the discharge port if such a size exists in the vicinity of the discharge port. If the discharge port diameter is Φ20 μm or less, It was found by experiment how clogging occurs.

Specifically, a solution with a changed nanoparticle diameter was prepared, and after using a jet head with a known discharge port size, droplet ejection was performed for a certain period of time, then left for a certain period of time, and droplet ejection was resumed. The discharge port was checked for clogging. In that case, not only a complete blockage of the outlet, but also a partial clogging and a prior indication (a slight clogging) were considered as clogging and tested.
The used ejection head uses a piezo element as shown in FIGS. 5 and 6 as a driving force for droplet ejection. That is, the mechanical displacement of the piezo element, which is an electro-mechanical conversion element, is taken as the displacement of the diaphragm of the liquid chamber, and droplets are ejected from the fine discharge port by the displacement acting force.

  Although not shown in the figure, an ejection head having a structure in which a nozzle plate in which nozzle holes are separately drilled is provided on one nozzle surface was used. In addition, the number of nozzles is also shown in a simplified example of seven nozzles, but actually, the number of nozzles (discharge ports) is 64, and the arrangement density is 100 dpi. The driving voltage for droplet ejection was 20 V, and the driving frequency was 10 kHz. The ejection heads were prepared from H1 to H4 (respective ejection port diameters were set to H1 = Φ20 μm, H2 = Φ15 μm, H3 = Φ10 μm, H4 = Φ5 μm). Further, the nozzle plate was formed by Ni electroforming, and the thickness of the discharge port portion was all 25 μm.

  The solution used was prepared as follows. That is, a water-soluble polymer was dissolved in silver nitrate, dimethylaminoethanol was added with stirring, and metal ions were reduced in 3 minutes to precipitate Ag fine particles having an average particle size of 0.5 μm (500 nm) or less. Thereafter, chlorine ions and nitrate ions were removed with an ultrafiltration membrane, and concentrated and dried to obtain a concentrated Ag fine particle-containing solution.

  Further, this Ag fine particle-containing solution was dissolved in acetone, alkanolamine was added while stirring, and Ag fine particles were dispersed in the polymer and precipitated on the oil phase side. This concentrated and dried concentrated Ag fine particle-containing solution was dissolved and mixed in a mixed solvent of water, alcohol and ethylene glycol to obtain a spray solution. In addition, in order to produce the solution which changed the magnitude | size of Ag microparticles | fine-particles, the centrifuge was used and the average particle diameter of Ag microparticles | fine-particles was prepared to 0.0001 micrometer-0.5 micrometer. However, those having an average particle size of 0.0003 μm or less were made, but could not be evaluated because they were not stable. The content of Ag fine particles in each solution was 10% by weight, and the resin content in the solution was 20% by weight. Moreover, the amount of ethylene glycol added was adjusted, and the viscosity of each solution was unified to 20 centipoise.

  In the test, each solution having a different Ag fine particle size was combined with H1 to H4 having a different discharge port size, and after droplet ejection was continuously performed for 10 minutes, the solution was left in an atmosphere of a temperature of 40 ° C. and a humidity of 30% for 10 hours. Thereafter, the injection was resumed, and the occurrence of clogging was examined. The results are shown in Tables 1 to 4.

  Table 1 shows head H1 (discharge port diameter Do = Φ20 μm), Table 2 shows head H2 (discharge port diameter Do = Φ15 μm), Table 3 shows head H3 (discharge port diameter Do = Φ10 μm), and Table 4 shows head H4. The case of (discharge port diameter Do = Φ5 μm) is shown. Judgment ○ indicates that it can be used practically well, Δ indicates that it can be used but is not very preferable, and X indicates that it is not practical at all.

  From the above results, when an ejection head having a discharge port diameter of Φ5 μm to Φ20 μm is used, there is no clogging if the Ag fine particle diameter Dp and the discharge port diameter Do satisfy the relationship of Dp / Do ≦ 0.01. It can be seen that stable droplet ejection can be obtained. Incidentally, although it is the lower limit value of Dp / Do, it is difficult for the Ag fine particle diameter Dp to be 0.0003 μm or less considering that such very fine particles are stably dispersed in the solution. Further, in order to stably eject droplets to all ejection heads having a discharge port diameter of Φ20 μm or less, the lower limit value of Dp / Do may be set to 0.0001 with a margin. That is, if the Ag fine particle diameter Dp and the discharge port diameter Do satisfy the relationship of 0.0001 ≦ Dp / Do ≦ 0.01, the pattern by droplet discharge using a discharge head having a discharge port diameter of Φ20 μm or less. It can be seen that a stable dispersion capable of forming or forming a device can be produced, and clogging of the discharge port (nozzle) can be prevented.

  When the discharge port diameter is larger than Φ20 μm, for example, Φ100 μm, there is no problem because the discharge port is sufficiently large even if the fine particles are aggregated. In fact, although no data is shown here, in the case where the discharge port diameter is Φ100 μm, the clogging problem did not occur when a fine particle-containing solution of 0.0005 to 0.05 μm was used.

In the experiment, a round discharge port (nozzle) was used. However, in the case of other shapes, the areas may be compared. For example, in the case of a rectangular discharge port of 18 μm × 18 μm, the round shape Φ20 μm of the present invention is used. It is almost the same as a nozzle. In other words, the present invention is an ejection head using a nozzle having an area of approximately 300 μm ² or less, and its lower limit value is a nozzle of approximately 20 μm ² (discharge port diameter is Φ5 μm). Alternatively, it is applied when forming a device.

  In the experiment, an ejection head using a piezoelectric element as a driving force for droplet ejection was used. However, the ejection head used in the manufacturing apparatus of the present invention is not limited to this, and an electrostatic force between two electrodes is used as the driving force. In addition, an electrostatic system that generates mechanical displacement of the diaphragm of the liquid chamber can also be used satisfactorily. Since these impart mechanical action force to the liquid, there is an advantage that the liquid to be used is less restricted. Moreover, since this mechanical displacement can be displaced in an analog manner, the shape of the flying droplet can be made round by controlling the drive waveform. For example, in the present invention, the driving waveform is controlled to form flying droplets close to a round shape to obtain a good dot pattern, which will be described later.

  Furthermore, the problem of clogging caused by the principle of injecting the fine particle-containing solution from the micro discharge port itself is the growth of film boiling bubbles generated instantaneously by heat in the solution using a thermal head as described later. This is a problem common to the ejection head based on the principle that the fine particle-containing solution is ejected from the minute ejection port by using the acting force, and the above result can be applied to the ejection head using the film boiling bubbles as it is. Alternatively, a charge control method (continuous flow method) in which electric charges are applied to droplets that are continuously ejected and the droplets are deflected according to the amount of electric charges can be used.

In addition, since the method of generating film boiling bubbles using a thermal head or the like uses heat, the solution to be used may be thermally deteriorated, so that the solution that can be used to some extent is limited.
On the other hand, the method of generating film boiling bubbles using a thermal head or the like allows high density and highly integrated arrangement of the heating element part and the discharge port part due to its structure, with an arrangement density of 600 dpi to 1200 dpi or more. Moreover, the number of discharge ports (nozzles) of 500 to 10000 can be easily realized, and is suitable for a manufacturing apparatus with high production efficiency.

  Next, other features of the present invention will be described. As described above, according to the present invention, a solution containing fine particles is made to stably eject a droplet from a minute discharge port without causing clogging. Here, after the droplet is ejected, the droplet adheres onto the substrate. The result of examining how to form a good pattern or device is shown.

  As described above, in the present invention, the ejection head unit 11 performs pattern movement while maintaining a certain distance from the substrate 14 or performing relative movement in the X and Y directions parallel to the formation surface of the functional device group. Alternatively, a functional device group is formed. That is, the ejection head unit 11 translates relative to the substrate surface with respect to the substrate 14, or the substrate 14 translates relative to the ejection head unit 11.

  At that time, each time the fine particle-containing solution for forming the pattern or functional device group is ejected, the relative movement is stopped and the ejection is performed, so that a highly accurate pattern or functional device group can be formed. However, since the productivity is remarkably lowered, the solution is sequentially ejected without stopping the relative movement. In that case, the relative movement speed (for example, the X-direction movement speed of the carriage 12 in FIG. 2) should not be determined merely by improving productivity, but from the viewpoint of forming a highly accurate pattern or functional device group. Must also be considered.

  In the present invention, as a result of intensive studies on this point, it has been found that it is necessary to optimize the relationship between the jet flight speed and the relative movement speed when jetting such a fine particle-containing solution. In the case of forming a pattern or a functional device group by ejecting the fine particle-containing solution while performing the relative movement in the X and Y directions while keeping the ejection head unit 11 at a certain distance from the substrate 14 as described above. The droplets of the solution are deposited and formed on the substrate 14 at the speed of the combined vector of the relative speed and the jet flight speed. As for the positional accuracy, the droplet is attached to the target position by appropriately selecting the ejection timing in consideration of the distance between the substrate 14 and the solution ejection port surface of the ejection head unit 11 and the speed of the combined vector. Can be made.

  However, even if the target can be attached to the target position, if the relative speed is too high, the attached droplets flow on the substrate 14 by being dragged by the relative speed, and the pattern has a good shape. Or, a functional device group cannot be formed. The present invention has been examined in this regard. An example of the examination results is shown below. In this example, an apparatus as shown in FIG. 2 is used, and the X direction moving speed of the carriage 12 and the ejecting speed of the ejecting head unit 11 are changed. It was investigated whether it was possible.

FIG. 11 shows an example of a pattern used for the test. Here, an Ag fine particle-containing solution is sprayed to form a wiring pattern in which the dot pattern 83 is connected between two rows of adjacent element electrodes (between the ITO transparent electrodes 82), and the pattern formation state is determined. It has been evaluated. Evaluation evaluated the pattern after formation under the microscope, and judged good / bad ((circle) / x). FIG. 11A is good (◯), and each dot pattern does not have a good round shape as shown in FIG. 11B, becomes an oval shape, and the landing position on the substrate is the original aim. Anything that deviates from the position of and touches the adjacent dot pattern is defective (x).
Further, this often occurs due to deterioration of the jetting performance due to the initial stage of clogging or generation of scratches on the discharge port, etc., but it is also defective (×) that micro droplets are scattered around.

  In addition to the evaluation of the shape, the resistance value between the upper and lower ITO transparent electrodes 82 was measured, and the resistance value fluctuation due to the disconnection due to poor dot position accuracy or contact with the adjacent (left and right) dots was evaluated (○ : Resistance value as intended, x: resistance value outside the aim).

  Details of the experimental conditions are shown below. The substrate used is a glass substrate with ITO transparent electrode 82, and the above-mentioned Ag fine particle-containing solution (here, a fine particle diameter of 0.01 μm is used) is combined with the above-mentioned H4 jet head (nozzle diameter Φ5 μm), A dot pattern 83 as shown in FIG. 11 was formed. For simplicity, FIG. 11 shows a diagram in which the space between a pair of ITO transparent electrodes 82 is filled with 4 dots. In practice, however, a dot of about Φ8 μm is formed in one column in the vertical direction. About 1000 pieces are driven at a pitch of about 4 μm to connect the upper and lower ITO transparent electrodes 82 (distance between electrodes: 4 mm). Further, a similar pattern is formed adjacent to the ITO transparent electrode 82 and the ITO transparent electrode 82 with a center-to-center distance of 12 μm.

  The used ejection head is an H4 ejection head having 64 nozzles (discharge ports) and an arrangement density of 100 dpi. The ejection head and the substrate move relative to each other (here, the substrate is fixed and the ejection head is scanned by carriage), the control is controlled in μ order, and the timing of ejection is controlled. As described above, dots are deposited at a pitch of about 4 μm. In addition, pattern formation was performed while maintaining a center-to-center distance of 12 μm.

  The driving voltage for droplet ejection changes the input voltage to the piezo element from 14V to 21V in order to change the ejection speed. The driving frequency was 10 kHz. In an ejection head using such a piezo element, the ejection speed can be changed by changing the input voltage to the piezo element, but at the same time the mass of the ejection droplet also changes, so the drive waveform (rising waveform including striking and The falling waveform was controlled so that the volume of the ejected droplet was always almost constant (1 pl), and only the ejection speed was changed.

  In addition, the droplet shape at the time of droplet flight is separately ejected and observed under the same conditions as the element formation, and the drive waveform is such that the shape becomes a substantially round droplet just before adhering to the substrate surface (3 mm in the present invention example). Were controlled and jetted (FIG. 12). Note that even if a rounded spherical shape is not obtained and the columnar shape extends in the flight direction, it can be easily reduced to a length within three times its diameter (l ≦ 3d) simply by controlling the drive waveform. (FIG. 13). At that time, as will be described later (FIG. 14), a plurality of microscopically behind the flying droplets, which is often seen when bubbles are generated using heat and the solution is jetted and flying by the growth action force of the bubbles. A driving condition (driving waveform) that does not involve a large droplet (satellite microdroplet 81) was selected. The results are shown below.

  From the above results, it can be seen that when the carriage moving speed in the X direction is equal to or higher than the ejection speed, a good pattern cannot be formed, and the resistance value between the electrodes is not intended. In other words, when performing pattern wiring formation or functional device formation by applying droplets of a nanoparticle-containing solution onto a substrate with an apparatus using an ejection head using a piezo element and drying it as in the present invention, It can be seen that the velocity of the droplets ejected from the ejection head must be faster than the carriage movement speed in the X direction.

  Although this example is an example in which the ejection head is scanned by carriage, it is also applied to the case where the ejection head (ejection head unit 11) is fixed and the substrate is moved as shown in FIG. That is, the speed of the ejected droplets must be higher than the relative movement speed of the ejection head and the substrate.

  In addition, the droplet flying condition this time was set to a driving condition (driving waveform) that does not involve a plurality of minute droplets (satellite minute droplets 81) behind the flying droplet as described above (FIG. 14). As a result, the plurality of minute droplets never adhered to unnecessary portions, and a very good pattern formation could be performed.

  Even if the flying droplets are in the form of a column extending in the flying direction, the length of the flying droplets is made within 3 times the diameter (l ≦ 3d) by driving waveform control (FIG. 13). The formed dots also had a shape close to a perfect circle, and a good pattern could be formed.

  In addition, the inkjet ejection principle uses a piezo element as the driving force for droplet ejection as in this example. In addition to the mechanical action force, bubbles are generated using heat and the solution is ejected by the growth action force of the bubbles. There is something to fly. FIG. 14 shows the shape of the solution at the time of flight seen in such a case.

  The difference in flight form as shown in FIG. 12 and FIG. 13 when the piezo element as shown in FIG. 14 and the above-described piezo element is used as the driving force for droplet discharge and jetted by mechanical action force is as follows. That is, in the case of FIG. 14, a part of the solution is heated instantaneously (for several μs) to 300 to 400 ° C. to generate film boiling bubbles, and the bubbles grow instantaneously (for several μs), the pressure rises. In order to inject a solution using (acting force), the piezo element is used as a driving force for droplet discharge, and the injection pressure is higher than that in the case of injecting with a mechanical acting force (in the case of FIGS. 12 and 13), The jet flight speed is also fast.

  As a result, as shown in FIG. 14, when flying, the flying shape of the solution extends in the shape of an elongated column in the flying direction, and has a characteristic of flying at high speed with a plurality of minute droplets (satellite minute droplets 81) behind. ing. For example, the shape at the time of flying the solution is such that when a stable film boiling bubble is generated, the elongated columnar length l extending in the flying direction is at least five times the diameter d, and The speed flies at approximately 5 m / s to 20 m / s.

  As a result, there is an advantage that the jetting is stable and the landing accuracy of the jetted solution on the substrate is high, but on the other hand, if the relative movement speed of the jet head and the substrate is not properly selected, it becomes an elongated column shape in the flight direction. The extended solution in the rear part and a plurality of minute droplets (satellite minute droplets 81) connected to the rear side also prevent good round dot formation.

  In the present invention, also in this regard, the above-described piezo element is used as a driving force for ejecting droplets, and the same examination as the result of examination with an ejection head using a mechanical force is performed. As a result, when using an ejection head that generates bubbles using such heat and ejects the solution with the growth force of the bubbles, it is unique between the ejection speed and the relative movement speed. I found that there is a relationship to be optimized.

  When a jet head that generates bubbles using such heat and jets and flies a solution with the growth action force of the bubbles is used, the jet flying speed is about 5 m / s to 20 m / s. Since it flies at high speed, it becomes a stable flight. That is, as a result of stable flight, the accuracy of landing is considered high.

  However, although it is considered that the accuracy of landing is high, since the solution is elongated and elongated in the flight direction at the time of flight, if the relative movement speed between the ejection head and the substrate is too fast, the relative speed is shifted. As a result, the adhering solution flows on the substrate 14 and does not form a good round dot shape, and a good pattern or functional device group cannot be formed. In addition, a plurality of minute droplets (satellite minute droplets 81) connected to the rear side adhere in a randomly scattered state to a position deviating from the position where they should originally adhere, hindering the formation of good round dots, functional device performance May cause a decrease in The present invention has been examined in this regard.

  An example of the examination results is shown below. Except that the ejection head uses bubbles to generate bubbles and spray the solution with the growth action force of the bubbles, we examined using the ejection head that uses the piezo element as the driving force for droplet ejection. This is the same as the equipment, conditions, etc. That is, whether or not a good pattern can be formed on the substrate 14 by changing the moving speed of the carriage 12 in the X direction and the jetting speed of the jetting head unit 11 using the apparatus shown in FIG. It has been investigated.

  Similarly, the pattern after formation was observed under a microscope to determine whether it was good / bad (O / X). In the case of FIG. 11 (A), good (O) and FIG. 11 (B). In this way, each dot pattern does not have a good round shape but becomes an oval shape, or the landing position on the substrate deviates from the original target position and contacts with the adjacent dot pattern. It is defective (x). Furthermore, the thing in which the micro droplet 84 resulting from a satellite droplet is scattered was also made into a defect (x).

  Along with this evaluation of the shape, the resistance value between the upper and lower ITO transparent electrodes 82 is measured, and the same evaluation is performed for the resistance value fluctuation due to disconnection due to poor dot position accuracy or contact with adjacent (left and right) dots. (○: resistance value as intended, ×: resistance value outside the aim).

  Details of the experimental conditions are shown below. The substrate used is a glass substrate with an ITO transparent electrode 82, and the above-mentioned Ag fine particle-containing solution (here, a fine particle diameter of 0.01 μm is used) is an ejection head (provided that a nozzle having a diameter of 5 μm is used). A dot pattern 83 as shown in FIG. 11 was formed in combination with a Ni nozzle forming multi-nozzle plate provided separately). For simplicity, FIG. 11 shows a diagram in which the space between a pair of ITO transparent electrodes 82 is filled with 4 dots. In practice, however, a dot of about Φ8 μm is formed in one column in the vertical direction. About 1000 pieces are driven at a pitch of about 4 μm to connect the upper and lower ITO transparent electrodes 82 (distance between electrodes: 4 mm). Further, a similar pattern is formed adjacent to the ITO transparent electrode 82 and the ITO transparent electrode 82 with a center-to-center distance of 12 μm.

  The used ejection head is the above-described ejection head (FIG. 7 shows four simplified nozzles), but the number of nozzles (discharge ports) is 64. The arrangement density is 400 dpi. The heating element size is 10 μm × 40 μm, and its resistance value is 102Ω. The head drive voltage was 11 V, the pulse width was 2 μs, and the drive frequency was 14 kHz. The volume of the ejected droplet is approximately 1 pl.

  Under such conditions, the above-described pattern (FIG. 11) is formed on the glass substrate, and after the formation, pattern evaluation is performed. Under the same conditions, a separate injection experiment is performed, and a solution 3 mm away from the discharge port The injection situation of was observed. This is because the test pattern of FIG. 11 was manufactured with a distance between the substrate and the discharge port of 3 mm. As shown in FIG. 14, the flight form was a columnar shape (l = 5d to 20d) that was extremely elongated in the flight direction. Moreover, it was in a state with a plurality of minute droplets behind the flying droplets. The examination results are shown below.

  From the above results, it can be seen that when the moving speed of the carriage in the X direction exceeds 1/3 of the ejection speed, a good element cannot be formed. Although this example is an example in which the ejection head is scanned by carriage, it is also applied to the case where the ejection head is fixed and the substrate is moved as shown in FIG. That is, the relative moving speed of the jet head and the substrate must be 1/3 or less of the jet flight speed of the jetted solution.

  Next, still another feature of the present invention will be described. FIG. 15 shows an example of pattern wiring of a pattern wiring board formed according to the principle of the present invention. This is an example in which a wiring pattern 92 is formed by later spraying a fine particle-containing solution onto a terminal pattern (electrode pattern) 91 formed of a rectangle or a combination of rectangles previously formed on a substrate. In this example, in order to avoid complication of the drawing, the dots of the wiring pattern 92 are arranged so as to be just in contact with each other in the adjacent oblique direction. The arrangement is such that a large number of dots overlap each other), and no uncovered portion is formed in the wiring pattern portion.

  FIG. 16 is an example of one device on a device substrate formed in accordance with the principles of the present invention. This is an example in which a device is formed by later spraying a fine particle-containing solution onto a pair of element electrodes (electrode patterns) 93 formed by a rectangle or a combination of rectangles previously formed on a substrate.

  However, there is one problem here. It is an abnormal discharge in the terminal pattern 91 or the element electrode (electrode pattern) 93 portion that occurs when the circuit pattern or various devices are used after completion. This will be described with reference to FIGS. 15 and 16.

  In the present invention, as shown in FIGS. 15 and 16, a wiring pattern 92 is formed by a dot pattern of a solution containing a metal fine particle material between a plurality (2 in this example) of terminal patterns (electrode patterns) 91, or opposed to each other. Various electronic devices are formed by the dot pattern 94 of the solution containing the metal fine particle material between the element electrodes 93 to be performed. Usually, the terminal pattern 91 and the element electrode (electrode pattern) 93 are thin films such as Al, Au, and Cu. Or an ITO thin film, and formed into a desired pattern shape by photolithography, etching, or the like. Usually, it is often composed of a rectangular pattern or a combination of rectangular patterns.

  This is because the electrode patterns 91 and 93 are formed in a rectangular shape depending on the shape of the photomask when the photolithographic technique is formed (the rectangle is most easily manufactured in terms of cost). 15. Since the corner portions 91C and 93C of the electrode patterns 91 and 93 are pointed as shown in FIG. 16, electric field concentration occurs in those portions. As a result, when applied between both electrodes, there is a problem that abnormal electric discharge occurs in the electric field concentration portion, and good element performance cannot be obtained, or the portion is damaged.

In view of this point, in the present invention, for example, the corner portions of the electrode patterns 91 and 93 are chamfered as shown in FIGS. In this example, c-shaped chamfering when displayed in a mechanical drawing is used, but it goes without saying that it may be r-shaped chamfering.
Such a shape may be such that when the electrode patterns 91 and 93 are formed by a photolithography technique, the shape of the photomask does not have such a sharp corner portion.

  Although the size of the chamfered portion is usually about 1/2 to 1/5 of the dot pattern diameter, that is, c2 μm to c5 μm, or r2 μm to r5 μm, a good electrode pattern in which electric field concentration does not occur is obtained. be able to.

  In the present invention, by eliminating the sharp part of the electrode pattern and eliminating the electric field concentration, there is no abnormal discharge when used as a circuit pattern or various devices, and it is stable even when used for a long time. The quality that you have come to get.

  Next, still another feature of the present invention will be described. 19 and 20 are equivalent to the wiring patterns or electronic devices described with reference to FIGS. In FIG. 15 to FIG. 18, in order to form the electrode pattern (terminal pattern 91, element electrode 93), a thin film of Al, Au, Cu or the like is formed on the substrate in advance, and photolithography, etching or the like is performed. 19 and FIG. 20, the electrode patterns 91 and 93 are formed by the solution injection principle of the present invention.

  That is, a solution containing fine particles of a conductive material such as Ag is used, and the electrode patterns 91 and 93 are formed as a combination of dots in the same manner as the pattern wiring or device pattern formation as described above. The merit of doing in this way is that the problem of abnormal discharge described above can be solved in addition to the point that the manufacturing apparatus of the present invention described with reference to FIGS. As shown in FIG. 19 and FIG. 20, if the electrode patterns 91 and 93 are formed by a dot pattern by solution injection in which metal fine particles of the present invention are dispersed, the outer shape of the dot pattern itself is round. Since there is no pointed portion, it can be automatically chamfered.

  19 and 20, the dot diameter of the electrode pattern portions 91 and 93 is larger than the dot diameter of the wiring pattern 92 or the device pattern (dot pattern 94), but this has the same discharge port diameter. The same ejection head having a dot pattern may be used so that the dot patterns have the same size.

By the way, the wiring pattern 92 by the combination of dots shown in FIG. 15 is formed as a belt-like pattern extending in the longitudinal direction, or the dot pattern 94 is also formed as a belt-like pattern in the device of FIG. The direction in which the belt-like pattern extends is the X direction or the Y direction described with reference to FIGS. 2 to 4, that is, the relative movement direction of the substrate 14 and the ejection head 11 (the movement direction of the carriage 12 on which the ejection head is mounted). Or the movement direction of the substrate 14), the pattern information for controlling the ejection of the solution and the control thereof can be simplified, and high-precision pattern formation can be realized at low cost.
Similarly, these directions, that is, the direction in which the pattern is extended, are positioned or formed by making each side of the rectangular substrate to be used parallel to the direction of the matrix arrangement of the device group to be formed. Can be made with high accuracy.

Next, another example for solving the above problem will be described.
In view of this point, in the present invention, for example, as shown in FIGS. 21 and 22, the wiring pattern 92 or the dot pattern 94 forming the device pattern is covered so that the corner portions of the electrode patterns 91 and 93 are not exposed. . In the example of the wiring pattern 92 in FIG. 21, an example in which the dot pattern row is vertically four rows is shown, but it goes without saying that it may be one row as shown in FIG. 23. The same applies to the device of FIG. 22, and only one dot may be used as shown in FIG.

  In short, if the sharp portions of the electrode patterns 91 and 93 are covered with a dot pattern so that the portions are not exposed on the surface, abnormal discharge due to electric field concentration can be prevented or damage can be prevented, and circuit patterns or various devices can be prevented. As a result, stable quality can be obtained even when used for a long time.

  Next, still another feature of the present invention will be described. FIG. 25 is an enlarged view of a part (corner portion) of the wiring pattern 1 of FIG. In the present invention, in relation to the above-described problem, the corner portion (outer region of the region where the pattern bends at a right angle) 1C of the wiring pattern 1 is prevented from being sharpened.

  This will be described more specifically with reference to FIGS. FIG. 26 shows an example of pattern wiring of a pattern wiring board formed according to the principle of the present invention. In this example, a dot pattern is combined to form a wiring pattern 92 that is bent 90 degrees in the middle. That is, such a wiring pattern 92 is formed into a strip-like pattern parallel to each of two orthogonal directions (arrows in the figure), and is arranged with its direction bent depending on the convenience of the arrangement of the wiring pattern 92. In this case, as shown in part A in the figure, the outer region of the region where the wiring pattern 92 bends in two orthogonal directions is formed in a curved shape. In this way, the bent corners of the wiring pattern 92 can be prevented from being sharpened by forming a dot pattern, and electric field concentration can be avoided.

  FIG. 27 shows a case in which the wiring pattern 92 is formed by arranging the dot pattern in one line. In this case as well, the corner where the wiring pattern 92 is bent is not sharpened by the dot pattern as in the A part in the figure. And concentration of the electric field can be avoided.

  FIG. 28 is an example of one device on a device substrate formed in accordance with the principles of the present invention. This is an example in which a device is formed by later spraying a fine particle-containing solution onto a pair of element electrodes (electrode patterns) 93 formed by a rectangle or a combination of rectangles previously formed on a substrate. Also in this case, in order to obtain a desired device shape, the pattern of the dot pattern 94 (device pattern portion) is formed in a band shape, and the band pattern is a pattern that is bent 90 degrees in the middle. And, as shown in the B part in the figure, the outer area of the area where the dot pattern 94 bends in two orthogonal directions (in the direction of the arrow in the figure) has a curved shape. In this way, the pattern is bent. By forming a dot pattern, the corners can be prevented from being sharpened, and electric field concentration can be avoided.

  FIG. 29 shows a case where the dot pattern 94 is formed in one row, but in this case as well, the corner where the pattern is bent is prevented from being sharpened by the dot pattern as in the B portion in the figure. And concentration of the electric field can be avoided.

By the way, the wiring pattern 92 by the combination of dots shown in FIGS. 15, 21, 23, 26, and 27 is formed as a belt-like pattern extending in the longitudinal direction, or FIGS. 16, 22, 28, and 28. Also in the device of FIG. 29, the dot pattern 94 is formed as a belt-like pattern. The direction in which such a belt-like pattern extends is the X direction or the Y direction described with reference to FIGS. The pattern information for controlling the ejection of the solution and the control thereof are simplified by making the direction parallel to the relative movement direction (the movement direction of the carriage 12 on which the ejection head is mounted or the movement direction of the substrate 14). It is possible to form each pattern with high accuracy at low cost.
Similarly, these directions, that is, the direction in which the pattern is extended, are positioned or formed by making each side of the rectangular substrate to be used parallel to the direction of the matrix arrangement of the device group to be formed. Can be made with high accuracy.

  Next, still another feature of the present invention will be described. The substrate provided with the function of the present invention is manufactured by applying a fine particle-containing solution in which numerous fine particles and nanoparticles are dispersed in a solution, flying in the air on the principle of ink jet, and applying them as droplets on the substrate. However, in order to produce a substrate with a high-precision and high-quality function, the surface of the substrate when a fine pattern is formed by spraying and applying a solution containing nano-particles onto the substrate. It is necessary to optimize the roughness and the size of the nanoparticles.

  In particular, in the present invention, as described above, the ink jet principle is used for applying the fine particle-containing solution. However, the substrate applied to the present invention is a substrate that does not absorb liquid such as paper and absorbs the solvent of the ink. Therefore, the same idea as the ink jet recording apparatus is not valid.

  Specifically, in the present invention, the sprayed fine particle-containing solution remains in a meniscus shape on the substrate. Then, after a certain period of time, the solution is evaporated and dried, and the solid content remains on the substrate. In this case, since the substrate of the present invention does not have a liquid absorbing action like that of ink-jet paper fibers, it does not make much sense to follow the principle of ink adhering to paper as it is in forming a good dot pattern.

In the present invention, it was considered that the surface roughness of the substrate should be examined in order to form a good pattern in consideration of these.
For example, the surface roughness of the substrate is the unevenness of the surface. As shown in FIG. 30, when particles 85 having a size that protrudes from the unevenness adhere to the surface 86 of the substrate, a good pattern or The device will not be obtained. On the other hand, as shown in FIG. 31, if the particle 85 is a particle having a size not larger than the unevenness of the substrate surface 86, a good pattern or device will be obtained. In the present invention, in view of this point, a pattern is formed on a substrate whose surface roughness is known in advance using a solution containing fine particles having different sizes, and the quality of the formed pattern is evaluated.

  In the experiment, Pyrex (R) glass was polished so that the surface roughness was 0.01 s to 0.02 s, and the above Ag fine particle-containing solution (here, the fine particle diameter was 0) on the polished substrate. .0005 μm to 0.2 μm) is used in combination with the aforementioned H4 jet head (nozzle diameter Φ5 μm) to form a pattern in which dots are connected, and the smoothness of the pattern is observed under a microscope. Sensory evaluation was performed, and good to good to bad (◯ to Δ to x) were judged.

Details of the experimental conditions are shown below. The pattern is one row in the vertical direction and about 100 dots of about Φ8 μm are implanted at a pitch of about 4 μm.
The used ejection head is an H4 ejection head having 64 nozzles (discharge ports) and an arrangement density of 100 dpi. The ejection head and the substrate move relative to each other (here, the substrate is fixed and the ejection head is scanned by carriage), the control is controlled in μ order, and the timing of ejection is controlled. As described above, dots are deposited at a pitch of about 4 μm. Went.

  As the driving voltage for droplet ejection, the input voltage to the piezo element was 15 V, and the driving frequency was 10 kHz. The volume of the spray droplet is always about 1 pl. Also, the droplet shape at the time of droplet flight is separately ejected and observed under the same conditions as pattern formation, and the drive waveform is such that the shape becomes a substantially round droplet immediately before adhering to the substrate surface (3 mm in the present invention example). Were controlled and jetted (FIG. 12). Note that even if a rounded spherical shape is not obtained and the columnar shape extends in the flight direction, it can be easily reduced to a length within three times its diameter (l ≦ 3d) simply by controlling the drive waveform. (FIG. 13). At that time, a driving condition (driving waveform) that does not involve a plurality of minute droplets (satellite minute droplets 81) behind the flying droplets was selected.

  As described above, Ag fine particle-containing solutions having different fine particle sizes ranging from 0.0005 μm to 0.2 μm were prepared and used (solution No. is common), but the fine particle size was 0.02 μm or more. Since nozzle clogging started to occur, only those patterns that were well clogged without clogging among the formed patterns were selected and evaluated. The results are shown below.

  From the above results, it can be seen that the fine particles contained in the solution can form a smooth and favorable pattern by setting the size to be less than the surface roughness of the surface on which the pattern of the substrate is formed. On the other hand, when the size of the fine particles is larger than that, the smoothness of the pattern shape is impaired.

  Next, still another feature of the present invention will be described. The substrate provided with the function of the present invention is manufactured by applying a fine particle-containing solution in which numerous fine particles and nanoparticles are dispersed in a solution, flying in the air on the principle of ink jet, and applying them as droplets on the substrate. However, in order to stably manufacture a substrate having a high-quality function over a long period of time, the manufacturing apparatus must stably maintain a certain level of performance. The most important point here is the long-term performance stability of the ejection head.

  As described above, the fine particle-containing solution used in the present invention is a solution in which fine particles are dispersed in a liquid, but the fine particles are present like abrasive grains dispersed in the solution, and this solution is used in large quantities. In such a case, there is a problem that the passage of the solution of the jet head is damaged or worn. Among the passages, scratches and abrasion of the discharge port (nozzle) are particularly problematic because they affect the droplet ejection performance of the solution.

  By the way, the scratches and wear are caused when two objects collide with each other or rub against each other. Therefore, it is considered that they can be solved by appropriately selecting the hardness of each other. In addition, it is true that scratches affect the droplet jetting performance of the jet head, but how much the scratches are affected is considered to be determined by the size of the scratch and the size of the solution path. For example, even if a water discharge hose having an inner diameter of Φ15 mm to Φ20 mm has scratches on the order of nanometers, the water discharge flow rate cannot be greatly affected.

In the present invention, these points are considered, and the hardness of the material of the discharge port, the hardness of the material of the fine particles, and the size of the discharge port are intensively studied.
The used ejection head is the same as the aforementioned H1 ejection head to H3 ejection head. That is, the piezo element 46 as shown in FIGS. 5 and 6 is used as a driving force for droplet discharge, and the mechanical displacement of the piezo element 46 as an electro-mechanical conversion element is used as the displacement of the diaphragm of the liquid chamber. Thus, droplets are ejected from a fine discharge port.

Although not shown in the drawing, an ejection head having a structure in which a nozzle plate having a nozzle hole perforated separately is provided on one surface of the nozzle is used. The number of nozzles is 64, and the arrangement density is 100 dpi.
By using such an ejection head and performing solution ejection for a certain period of time, whether or not the ejection port (nozzle hole) is scratched and the pattern shape (dots) formed due to the deterioration of the solution droplet ejection performance Whether the shape of the pattern was good) and whether the pattern performance was deteriorated (resistance value change) were examined. Multi-nozzle plates were prepared with different materials and nozzle diameters (here rounded). Regarding the pattern performance, the difference in resistance between the pattern formed at the initial stage of injection and the pattern formed after performing the injection for a certain period of time was examined.

The ejection head drive voltage was 20 V, the drive frequency was 10 kHz, and continuous ejection was performed for 100 hours. The ejection port portion after ejection was observed with an SEM to check for scratches.
The discharge port diameters were prepared with Φ20 μm (H1 jet head), Φ15 μm (H2 jet head), and Φ10 μm (H3 jet head), respectively.
As a comparative reference example, one having a discharge port diameter of Φ36 μm (reference head) was also prepared. In this case, the number of discharge ports is 48 and the arrangement density is 60 dpi. The ejection head drive voltage was 30 V, the drive frequency was 3.8 kHz, and continuous ejection was performed for 260 hours.

The thickness of the nozzle plate was 30 μm for the H1 jet head and the H2 jet head, 20 μm for the H3 jet head, and 40 μm for the reference head. The speed of the droplets at the time of jetting was about 7 m / s in any jet head.
The nozzle plate was made of Ni and austenitic stainless steel SUS304. A Ni nozzle made of a multi-nozzle plate by an electroforming method, and a nozzle made of SUS304 made of stainless steel foil was drilled with a nozzle hole by electric discharge machining. When the hardness was measured with a Vickers hardness meter, the Vickers hardness Hv was 58 to 63 in the case of Ni material, and the Vickers hardness Hv was 170 to 190 in the case of SUS304 material.

  The liquid used is an aqueous solution in which fine particles are dispersed in a dispersion medium mainly composed of water as described above. The fine particles are the following seven types (S1 to S7). The element names of the contained fine particles and the Vickers hardness Hv in the bulk state are shown. In addition, this Vickers hardness Hv published the value of the metal data book (edited by the Japan Institute of Metals, revised 3rd edition, published by Maruzen). The fine particle content in each solution was about 8%, and the fine particle diameter was 0.01 μm to 0.02 μm.

  The results of evaluation using these sample solutions and the ejection head are shown below. In the table, scratches ○ indicate that no conspicuous scratches could be confirmed after 100 hours of injection, and × indicates that a number of scratches that affect the nozzle shape or dimensions exist. The pattern shape ○ is a dot pattern formed in a good round shape at the target position (between a pair of electrodes) when the pattern was produced after 100 hours of jetting (FIG. 11A). Is the one where the position is slightly off from the target position, the shape is irregular, or the micro droplets are scattered around (FIG. 11B). XX of the pattern performance is the difference in resistance value between the pattern formed at the initial stage of injection and the pattern formed after performing the injection for a certain period of time, and ○ is the resistance value when the pattern was prepared after 100 hours of injection. The pattern is almost the same as the pattern formed in (Practical level), and x is when the resistance value is abnormally large or short-circuited after 100 hours of spraying (Non-practical level). is there. In the case of the reference head, the ejection time is 260 hours.

  From the above results, it is understood that when the hardness of the contained fine particles is larger than that of the material of the discharge port (S3, S6), the discharge port is damaged. It can also be seen that the pattern shape formed thereby is poor and the pattern performance is also poor. Therefore, it can be seen that when such a pattern is formed by a manufacturing apparatus such as the present invention, it is necessary to select a material that is softer than the member that forms the discharge port for the fine particles.

Some of the scratches do not deteriorate the pattern shape because of the relationship with the size of the discharge port. As in the case of the reference head, when the discharge port diameter is as large as 36 μm (= the area is about 1000 μm ² ), since the discharge port diameter is large even if it is scratched, it is not a scratch that would cause the jetting performance to deteriorate, A sufficiently usable pattern shape is obtained.

On the other hand, when the discharge port diameter is Φ20 μm or less (= the area is 314 μm ² or less), when the area is compared with 1/3 or less of the reference head, even if scratches are similarly caused, It can be seen that the influence on the comparison is great, and a good pattern shape and pattern performance cannot be obtained. This can be explained by the logic of the water discharge hose described above.

  In other words, if a very fine pattern is not formed, the problem of scratches does not affect the pattern performance, so there is no concern. However, according to the experiment of the present invention, a droplet ejecting head having an ejection diameter of Φ20 μm or less In order to prevent clogging, the fine particle size of the fine particle-containing solution is set to 0.0005 to 0.2 μm (0.5 to 200 nm), preferably 0.0005 to 0.05 μm (0.5 to 50 nm). However, when pattern formation is performed, scratches at the discharge port are fatal for obtaining good pattern performance. The critical value of the critical nozzle size is around Φ20 μm. That is, in the case where such a pattern is formed by jetting a solution with an jet head having a nozzle of Φ20 μm or less, it is necessary to select a combination of a solution and a discharge port member that does not damage the nozzle part. That is, as is clear from the above experimental results, the fine particles need to be made of a material that is softer than the member constituting the discharge port.

Note In the experiment, [phi] 20 [mu] m nozzle of a round shape (area of about 314μm ^2), Φ15μm nozzle (area of about 177 .mu.m ^2), but using Φ10μm nozzle (area of about 79μm ^2), other shapes as a nozzle of the ejection head ( For example, when a nozzle having a rectangular shape or the like is used, the areas may be compared. For example, a 18 μm × 18 μm nozzle is equivalent to the round Φ20 μm nozzle of the present invention.

That is, in the present invention, when the discharge port diameter is Φ20 μm or less, it is not necessarily applied only to the round nozzle, and if the nozzle shape is not round, it should be considered as a considerable value in the area comparison. As long as the area of the nozzle opening is 314 μm ² or less, even nozzles having shapes other than circles are included in the scope of the present invention. Needless to say, this is also applied to conditions for obtaining stable droplet ejection without clogging, in which the relationship between the fine particle diameter Dp and the discharge port diameter Do is optimized.

  As is apparent from the above description, the present invention is a technique for manufacturing a pattern wiring board or a device substrate, but a very fine pattern of several tens of μm to several μm is not based on a conventional photolithography technique, Patterns and devices are directly manufactured by a simple apparatus in which droplets of a fine particle-containing solution are directly sprayed onto a substrate by an ejecting head having a minute ejection port that has not been conventionally available. Therefore, an expensive manufacturing apparatus used in a so-called semiconductor manufacturing process is not required, and it can be manufactured stably at a low cost.

It is a figure for demonstrating one Example of the pattern wiring formed by the droplet jet manufacturing apparatus of this invention. It is a figure for demonstrating one Example of the droplet jet manufacturing apparatus which manufactures the pattern wiring board or device board | substrate of this invention. It is a figure for demonstrating the other Example of the droplet jet manufacturing apparatus which manufactures the pattern wiring board or device board | substrate of this invention. It is a schematic block diagram which shows the droplet application apparatus applied to manufacture of the pattern wiring board or device board | substrate of this invention. It is a figure explaining the droplet jetting principle of the jet head using a piezoelectric element suitably used for this invention. It is a figure which shows the structure of the ejection head using a piezoelectric element suitably used for this invention. 2 is an example of a thermal type (bubble type) liquid jet head suitably applied to the present invention. FIG. 5 is a diagram of a multi-nozzle type liquid jet head viewed from the nozzle side. FIG. 4 is a diagram illustrating a unit in which a multi-nozzle liquid ejecting head is stacked for each solution to be ejected. It is a perspective view of the head unitized. It is a figure which shows the example of the test pattern used in order to find the conditions which perform favorable pattern formation with the droplet jet manufacturing apparatus of this invention. It is a figure for demonstrating the example of the droplet flight shape at the time of ejecting with the action force by mechanical displacement with the ejection head used for the droplet ejection manufacturing apparatus of this invention. It is a figure for demonstrating the example of the other droplet flight shape at the time of ejecting with the action force by mechanical displacement with the ejecting head used for the droplet ejecting manufacturing apparatus of this invention. It is a figure for demonstrating the example of the droplet flight shape at the time of ejecting with the action force by a film | membrane boiling bubble. It is a figure for demonstrating the example which forms a pattern wiring combining the dot of a droplet or a solution based on the principle of this invention. It is a figure for demonstrating the example which forms a device combining the dot of a droplet or a solution based on the principle of this invention. It is a figure for demonstrating the example which improved the abnormal discharge in a corner part in the example of FIG. It is a figure for demonstrating the example which improved the abnormal discharge in a corner part in the example of FIG. It is an example of the figure for demonstrating the other which improved the abnormal discharge in a corner part in the example of FIG. It is a figure for demonstrating the other example which improved the abnormal discharge in a corner part in the example of FIG. It is a figure for demonstrating the example which covered the corner part in the example of FIG. 15, and improved abnormal discharge. It is a figure for demonstrating the example which coat | covered the corner part and improved abnormal discharge in the example of FIG. It is a figure for demonstrating the other example which improved the abnormal discharge in a corner part. It is a figure for demonstrating the other example which improved the abnormal discharge in a corner part. It is the figure which expanded a part (corner part) of the wiring pattern of FIG.1 (B). It is a figure for demonstrating one example of the pattern wiring of the pattern wiring board formed by the principle of this invention. It is a figure for demonstrating the other example of the pattern wiring of the pattern wiring board formed by the principle of this invention. It is a figure for demonstrating the example of 1 device of the device substrate formed by the principle of this invention. It is a figure for demonstrating the other example of the device of the device substrate formed by the principle of this invention. It is the figure which showed typically the relationship between microparticles | fine-particles and surface roughness at the time of forming a dot pattern with the solution containing the microparticles | fine-particles larger than the surface roughness of a board | substrate. It is the figure which showed typically the relationship between microparticles | fine-particles and surface roughness at the time of forming a dot pattern with the solution containing the microparticles | fine-particles below the surface roughness of a board | substrate.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Wiring pattern, 2, 3 ... Terminal, 10 ... Board | substrate, 11 ... Ejection head unit (ejection head), 12 ... Carriage, 13 ... Substrate holding base, 14 ... Substrate, 15 ... Supply tube, 16 ... Signal supply cable, DESCRIPTION OF SYMBOLS 17, 21 ... Control box, 18 ... X direction scan motor, 19 ... Y direction scan motor, 20 ... Computer, 22 ... Substrate positioning / holding means, 31 ... Head alignment control mechanism, 32 ... Detection optical system, 33 ... Ejection head , 34... Head alignment fine movement mechanism, 35... Control computer, 36... Image identification mechanism, 37... XY direction scanning mechanism, 38 ... position detection mechanism, 39. ... Optical axis, 42 ... Element electrode, 43 ... Droplet, 44 ... Droplet landing position, 45 ... Flow path, 46 ... Piezo element, 47 ... Solution 48 ... Nozzle, 49 ... Filter, 65 ... Nozzle, 66 ... Heating element substrate, 67 ... Cover substrate, 68 ... Silicon substrate, 69 ... Individual electrode, 70 ... Common electrode, 71 ... Heating element, 74 ... Groove, 75 ... Recess Area, 76 ... Solution inlet, 81 ... Satellite microdroplet, 82 ... Element electrode (ITO transparent electrode), 83 ... Dot pattern, 84 ... Microdroplet, 85 ... Particle, 86 ... Substrate surface.

Claims (17)

On the electrode pattern formed on a flexible substrate having no liquid absorbing effect as well as on the flexible substrate, a fine particle-containing solution was injected imparted by ejecting head of an ink jet principle size has the following discharge opening [phi] 20 [mu] m, the flexible substrate And forming a pattern with dots on the electrode pattern on the flexible substrate, volatilizing the volatile components in the pattern with the dots after application, and leaving the solid content on the flexible substrate and the electrode pattern to form pattern wiring or In a solution jet manufacturing apparatus for forming an electronic device, when the size of the fine particles is Dp and the diameter of the discharge port is Do, 0.0001 ≦ Dp / Do ≦ 0.01, and the jet head is a machine Shape of the solution at the time of flight The a generally rounded drop shape just prior to adhering the flexible substrate surface, or a columnar shape extending in the flight direction a columnar three times within the length of its diameter, a plurality of minute behind the flight solution In the solution injection type manufacturing apparatus in which no droplet is accompanied, the discharge port is an opening made of a material harder than the fine particles in the fine particle-containing solution, and is an upstream portion of the discharge port, A filter is provided at the closest position, and the filter traps a foreign substance having a size of 30 times or more of the fine particle diameter in the solution, and the fine particle diameter is equal to or less than the surface roughness of the flexible substrate. the solution injection type manufacturing apparatus characterized by the. 2. The solution injection mold manufacturing according to claim 1, wherein a flying distance of the solution is set to 3 mm or less, and a spraying speed of the solution is higher than a relative moving speed of the flexible substrate and the spraying head. apparatus. On the electrode pattern formed on a flexible substrate having no liquid absorbing effect as well as on the flexible substrate, a fine particle-containing solution was injected imparted by ejecting head of an ink jet principle size has the following discharge opening [phi] 20 [mu] m, the flexible substrate And forming a pattern with dots on the electrode pattern on the flexible substrate, volatilizing the volatile components in the pattern with the dots after application, and leaving the solid content on the flexible substrate and the electrode pattern to form pattern wiring or In the solution ejection type manufacturing apparatus for forming an electronic device, when the size of the fine particles is Dp and the diameter of the discharge port is Do, 0.0001 ≦ Dp / Do ≦ 0.01, and the ejection head is The solution is generated by the bubble growth action force instantly generated by heat in the solution. With jetting the, the shape of the solution during flight, a slender columnar extending in flight direction and columnar 5 times the length of its diameter, the relative movement speed between the flexible substrate and the ejection head, In the solution injection type manufacturing apparatus, the discharge port is an opening made of a material harder than the fine particles in the fine particle-containing solution, and is an upstream portion of the discharge port. In addition, a filter is provided at a position closest to the discharge port, the filter is a filter for trapping foreign matter having a size of 30 times or more of the particle size of the fine particles in the solution, and the particle size of the flexible substrate A solution injection type manufacturing apparatus characterized by having a surface roughness of or less .   4. The solution jet manufacturing apparatus according to claim 3, wherein the solution at the time of flight has an elongated column shape and is caused to fly at high speed so as to be accompanied by a plurality of minute droplets. On the electrode pattern formed on a flexible substrate having no liquid absorbing effect as well as on the flexible substrate, discharge port diameter is a fine particle-containing solution was injected imparted by jet head following inkjet principle [phi] 20 [mu] m, on the flexible substrate and the flexible substrate A pattern by dots is formed on the upper electrode pattern, a volatile component in the pattern by the dots after application is volatilized, and solid wiring is left on the flexible substrate and the electrode pattern to form a pattern wiring or device. In the fine particle-containing solution used in the solution injection type manufacturing apparatus, when the size of the fine particles in the fine particle-containing solution is Dp and the discharge port diameter is Do, 0.0001 ≦ Dp / Do ≦ 0.01, and the discharge with a softer material than the members constituting the outlet, Serial fine particle size fine particle-containing solution characterized in that it has less surface roughness of the flexible substrate. On the electrode pattern formed on a flexible substrate having no liquid absorbing effect as well as on the flexible substrate, discharge port diameter is a fine particle-containing solution was injected imparted by jet head following inkjet principle [phi] 20 [mu] m, on the flexible substrate and the flexible substrate A pattern by dots is formed on the upper electrode pattern, a volatile component in the pattern by the dots after application is volatilized, and solid wiring is left on the flexible substrate and the electrode pattern to form a pattern wiring or device. In the pattern wiring board manufactured by the solution injection type manufacturing apparatus, when the size of the fine particles in the pattern by the dots is Dp and the discharge port diameter is Do, 0.0001 ≦ Dp / Do ≦ 0.01. , In the pattern by the dots The patterned wiring board is characterized in that the particles are made of a material softer than a member constituting the discharge port, and the particle diameter is set to be equal to or less than the surface roughness of the flexible substrate. On the electrode pattern formed on a flexible substrate having no liquid absorbing effect as well as on the flexible substrate, discharge port diameter is a fine particle-containing solution was injected imparted by jet head following inkjet principle [phi] 20 [mu] m, on the flexible substrate and the flexible substrate A pattern by dots is formed on the upper electrode pattern, a volatile component in the pattern by the dots after application is volatilized, and solid wiring is left on the flexible substrate and the electrode pattern to form a pattern wiring or device. In a device substrate provided with a function manufactured by a solution injection type manufacturing apparatus, when the size of the fine particles in the pattern of the dots is Dp and the discharge port diameter is Do, 0.0001 ≦ Dp / Do ≦ 0.0. 01 and the dot pattern The fine particles in the over emissions, as well as a softer material than the member constituting the discharge port, the fine particle size device substrate, characterized in that it has less surface roughness of the flexible substrate.   The pattern wiring board according to claim 6, wherein the electrode pattern is configured by a rectangular pattern or a combination of rectangular patterns.   The pattern wiring board according to claim 8, wherein a corner portion of the electrode pattern has a chamfered shape.   9. The pattern wiring board according to claim 8, wherein a corner portion of the electrode pattern is covered with a dot pattern of the fine particle-containing solution.   The electrode pattern is formed by spraying a solution containing fine particles of a conductive material by a jet head based on an ink jet principle, volatilizing a volatile component in the pattern by the dots after application, and forming a solid dot pattern. The patterned wiring board according to claim 6.   The device substrate according to claim 7, wherein the electrode pattern is configured by a rectangular pattern or a combination of rectangular patterns.   The device substrate according to claim 12, wherein a corner portion of the electrode pattern has a chamfered shape.   The device substrate according to claim 12, wherein a corner portion of the electrode pattern is covered with a dot pattern of the fine particle-containing solution.   The electrode pattern is formed by spraying a solution containing fine particles of a conductive material by a jet head based on an ink jet principle, volatilizing a volatile component in the pattern by the dots after application, and forming a solid dot pattern. The device substrate according to claim 7.   The pattern of dots is a band-like pattern formed by a combination of dots parallel to each of two orthogonal directions, and an outer area of the band-shaped pattern that is bent in the two directions has a curved shape. Item 7. The patterned wiring board according to Item 6.   The pattern of dots is a band-like pattern formed by a combination of dots parallel to each of two orthogonal directions, and an outer area of the band-shaped pattern that is bent in the two directions has a curved shape. Item 8. The device substrate according to Item 7.

Images