JP5866783B2 - Circuit board manufacturing method - Google Patents

Description

The present invention relates to a circuit board manufacturing method . In particular, the present invention relates to a method of manufacturing an active matrix substrate by applying a functional organic material using a printing method.

  Conventionally, in order to manufacture an active matrix substrate using a silicon semiconductor, a thin film formation process, a photolithography process, and an etching process are used as basic cycles, and this basic cycle is repeated a plurality of times. First, after the thin film is formed on the entire substrate, a photoresist pattern corresponding to the required thin film pattern is made, and most of the thin film is removed by the etching process based on the pattern, and the remaining photoresist pattern is It was removed and used as a basic cycle. That is, in this manufacturing method, most of the thin film material and all of the photoresist material have to be finally discarded, so to speak, it can be said that it is based on grand waste. In addition, a vacuum process is required for the film forming process and the etching process. These processes require a long processing time, poor productivity, and a large-scale manufacturing apparatus.

  Therefore, a method of manufacturing an active matrix substrate by a printing method has been studied as a manufacturing method that does not use the above basic cycle as much as possible, has excellent productivity, and avoids the use of a large-scale manufacturing apparatus as much as possible. Although there are various printing methods, the inkjet method is considered suitable for manufacturing an active matrix substrate. This is because the ink jet method forms the pattern in a non-contact manner on the substrate only among the various printing methods, and the probability of occurrence of defects is the lowest. This is because various printing methods other than the ink jet method make it difficult to eliminate dust entrapment and physical defects because the printing plate is brought into contact with the substrate.

  In general, an active matrix substrate is provided with a plurality of wiring layers, and these wiring layers are separated by an insulating film. In places where electrical continuity is required between the wiring layers, via holes are opened to connect the two wirings. Even when an active matrix substrate is manufactured by a printing method, conduction between the wiring layers is required. For example, in Patent Document 1, via holes are formed using a photolithography process and a dry etching process. In Patent Document 2, a via hole is formed by irradiating a laser beam on an insulating film.

JP 2008-277371 A JP 2007-266237 A

  However, in the conventional manufacturing method represented by Patent Document 1, the photolithography process has a significant effect on the functional organic material used for the active matrix substrate, and the active matrix substrate having excellent characteristics can be stably formed. There was a problem that it was difficult to manufacture. This is because the functional organic material may be irradiated with strong short-wavelength light during exposure during the photolithography process, and the functional organic material may be photodegraded. Moreover, it is because there exists a possibility that a developing solution may permeate | transmit a functional organic material at the time of image development in a photolithography process, and a functional organic material may change chemically.

  Moreover, in the conventional manufacturing method represented by patent document 2, there existed a subject that productivity was bad and the yield was low besides the subject that manufacturing cost would rise because the laser apparatus was utilized. Normally, it is necessary to irradiate a laser beam at the same point several times to the opening of the via hole. However, since there are tens of thousands to millions of via holes in the active matrix substrate, opening them while aligning several to several hundreds with a laser device is extremely long. Time is spent. In addition, electrical continuity cannot be obtained with only slight fluctuations in the laser output. For example, if the laser output is slightly weak, the via hole cannot be opened (an insulating film remains at the bottom of the via hole). On the other hand, if it is too strong, even the electrode to be conductive is ablated. Furthermore, because of the use of laser ablation, the generation of dust is unavoidable, and the yield is lowered as a result of soiling the active matrix substrate.

  In other words, there is no conventional via hole formation method suitable for the printing method, and it is therefore difficult to stably produce a circuit board having excellent characteristics at a high yield by the printing method. was there.

  In addition, the photolithography process and the etching process take time, and a large-scale investment is required for the manufacturing apparatus. Therefore, establishment of a manufacturing method using a printing method with excellent productivity is desired. However, in the printing method, since the printing plate is brought into contact with the substrate, it is difficult to completely eliminate dust entrainment and physical damage. In particular, it has been difficult to print components of thin film transistors that require film thickness control on the order of nanometers. For this reason, attention has been focused on the inkjet method that can form a pattern in a non-contact manner. However, the inkjet method has a problem in terms of low resolution. For this reason, there is a limit in manufacturing the source / drain electrodes, driver connection wirings, and the like using the inkjet method. In order to electrically connect the source / drain electrode and the pixel electrode, it is necessary to form a via hole penetrating the gate insulating film and the interlayer insulating film. However, it is difficult to fabricate using only the ink-jet method. Lithography process, dry etching process, and laser beam irradiation were used.

  For example, after forming a gate electrode, a photoresist is applied as an interlayer insulating layer, exposure / development is performed, and dry etching is performed to form a via hole in the gate insulating film. Alternatively, after forming the gate electrode, the vapor deposition of parylene mac as an interlayer insulating layer is performed, and a via hole penetrating the interlayer insulating layer and the gate insulating film is formed using an excimer laser. For this reason, a method for effectively producing a via hole by a printing technique is desired.

  The present invention has been made in view of the above-described problems of the prior art, and a method of manufacturing a circuit board capable of efficiently producing via holes penetrating a plurality of laminated interlayer insulating films by a printing technique. One of the purposes is to provide.

The method for manufacturing a circuit board according to the present invention includes a first conductor forming step of forming a first conductor on a substrate, and a first insulating film that forms a first insulating film so as to cover the first conductor A film forming step, a through hole forming step of forming a through hole by dissolving the first insulating film on the first conductor, and a metal film formed on the first conductor corresponding to the through hole A metal film forming step, a liquid repellency step for repelling the surface of the metal film, a precursor resin is printed in a region other than the through hole, and the precursor resin is cured after printing to form a second insulating film. wherein a second insulating film forming step of forming, a, in the second insulating film forming step, a via hole exposing the metal layer and having a smaller diameter than the diameter of the through hole in the through hole is formed It is characterized by that.

  According to this, a pattern such as a via hole can be efficiently formed by a printing method (inkjet method), and the quality of the first insulating film other than the via hole can be kept high. In addition, the electronic elements manufactured on the circuit board are not adversely affected. Therefore, a circuit board exhibiting excellent circuit characteristics can be stably manufactured with a high yield by a printing method.

Further, in the metal film formation step, a conductive method including forming a metal film by dropping a conductive ink containing a plurality of metal particles in a dispersion medium into the through hole may be used.
According to this, a metal film can be easily formed using an inkjet method.

Moreover, it is good also as a manufacturing method whose particle size of the said metal particle is 10-40 nm.
According to this, a low resistance metal film can be obtained by fusing at a low temperature.

In the metal film forming step, the metal film is formed on the surface of the first conductor corresponding to the through hole via the second insulating film having a thickness of 20 μm or less covering the surface. It is good.
According to this, dielectric breakdown is easily caused by applying a voltage, and conduction is obtained between the metal film and the first conductor. This leads to improved yield.

The metal particles may be made of any one of gold, silver, copper, nickel, platinum, and palladium.
According to this, since these metal particles are particularly excellent in conductivity, it is possible to improve the conductivity of the obtained metal film as a whole.

Further, in the second insulating film forming step, a precursor resin may be printed in a region other than the through hole, and the precursor resin may be cured after printing to form the second insulating film.
According to this, a via hole can be easily opened in the circuit board by a printing method, and an electronic element manufactured on the circuit board is not adversely affected. Therefore, a circuit board exhibiting excellent circuit characteristics can be stably manufactured with a high yield by a printing method.

The first insulating film may be a manufacturing method that is soluble in any of ether solvents, ketone solvents, ester solvents, and fluorine solvents.
According to this, an insulating solvent soluble in an ether solvent, a ketone solvent, an ester solvent, or a fluorine solvent, an ether resin, a ketone resin, an ester resin, or a fluorine resin Since the insulating material consisting of can be used for the first insulating film forming step, the first insulating film can be formed by a printing method. In addition, since the options for the first insulating film are wide, the function of the circuit board can be maximized. Further, when the first insulating film is used as the gate insulating film of the transistor, the first insulating film material does not dissolve the organic semiconductor film, so that the interface between the semiconductor film and the gate insulating film is smooth, and the intermediate transition layer. It becomes a beautiful thing that does not exist. As a result, a thin film transistor having excellent characteristics can be manufactured over a circuit board.

The first insulating film may be a manufacturing method that is hardly soluble in an alcohol solvent.
According to this, an alcohol-based material or a material that is soluble in an alcohol-based solvent in the lyophobic process, the second conductor forming process, and the second insulating film forming process performed after the first insulating film forming process. Can be used. That is, using these materials, the lyophobic process, the second conductor forming process, and the second insulating film forming process can be performed by a printing method. Furthermore, since the first insulating film is not damaged during these steps, the first insulating film can be maintained without deteriorating the function required for the circuit board.

Further, the first insulating film may be a manufacturing method that is hardly soluble in the precursor resin.
According to this, the first insulating film is not damaged by the precursor resin during the second insulating film forming step, and the first insulating film can be maintained without deteriorating the function required for the circuit board.

Further, the through hole formation step, the through constituted by the first solvent capable of dissolving the insulating film viewing including the solvent dropping step of dropping the first insulating film, raised parts of the peripheral edge is the first insulating film It is good also as a manufacturing method which forms a hole .
According to this, since the solvent can be dropped by the inkjet method, according to this configuration, a fine through hole can be easily formed by the printing method.

The liquid repellent step may be a manufacturing method in which the surface of the first conductor is brought into contact with a solution containing a thiol compound or a disulfide compound.
According to this, since the sulfur atom of the thiol compound or disulfide compound is quickly bonded to the metal atom, only the surface of the first conductor can be selectively made liquid-repellent easily in a short contact of several seconds to several minutes. Can do.

Moreover, it is good also as a manufacturing method in which the said thiol compound contains a fluorinated alkyl chain.
According to this, since the fluorinated alkyl chain lowers the surface tension, according to this configuration, the liquid repellency of the surface to which the thiol compound is bonded can be made extremely high.

The disulfide compound may be a production method containing a fluorinated alkyl chain.
According to this, since the fluorinated alkyl chain lowers the surface tension, according to this configuration, the liquid repellency of the surface to which the disulfide compound is bonded can be made extremely high.

The precursor resin may be a production method including a monomer having a hydroxyl group.
According to this, the second insulating film is formed on the first insulating film, but since the first insulating film is stable with respect to the alcohol-based material, according to this configuration, the precursor resin is used for the first insulating film. It is possible to avoid damaging the film (melting the first insulating film).

The precursor resin may be a production method that is soluble in an alcohol solvent.
According to this, since the precursor resin can be diluted with an alcohol solvent, the concentration of the solution can be adjusted relatively freely, and various printing methods can be applied to the second insulating film forming step. In addition, since the first insulating film is stable with respect to the alcohol-based material, it is possible to avoid the second insulating film forming step from damaging the first insulating film (melting the first insulating film).

Further, the precursor resin may be a photocurable resin.
According to this, the second insulating film can be formed quickly and easily by irradiating light after printing the precursor resin.

The precursor resin may be a manufacturing method that is a thermosetting resin.
According to this, after printing precursor resin, a 2nd insulating film can be easily formed by simple heat processing.

The circuit board may include a transistor including a gate insulating film, and the first insulating film may function as the gate insulating film.
According to this, a circuit board having a high function circuit can be realized. Further, since the circuit board is manufactured by a printing method except for the first conductor forming step, it is estimated that the productivity is very high and a circuit board having a high-function circuit can be manufactured in one day. The process is easy to automate, and the main printing method is the ink jet method, which reduces waste.
The electro-optical device of the present invention includes a circuit board manufactured by using the circuit board manufacturing method described above.
An electronic apparatus according to an aspect of the invention includes the electro-optical device described above.

Sectional drawing which showed typically the manufacturing method of the circuit board concerning Embodiment 1. FIG. Sectional drawing which showed typically the manufacturing method of the circuit board concerning Embodiment 1. FIG. Sectional drawing which showed typically the manufacturing method of the circuit board concerning Embodiment 1. FIG. (A) is a top view corresponding to FIG.2 (f), (b) is a top view corresponding to FIG.2 (g). FIG. 3C is a plan view schematically showing the circuit board manufacturing method according to the first embodiment, FIG. 3C is a plan view corresponding to FIG. 3I, and FIG. 3D is a plan view corresponding to FIG. . The figure explaining the principle of a through-hole formation process in the manufacturing method of the circuit board concerning Embodiment 1. FIG. The figure which shows how the conductive ink spreads. The figure explaining in detail the state at the time of completion | finish of a liquid repellent process in the manufacturing method of the circuit board concerning Embodiment 1. FIG. Sectional drawing which shows typically the active matrix substrate of a bottom gate structure. The top view of the manufacturing method of the circuit board concerning the modification 2. FIG. FIG. 2 is a plan view schematically showing an active matrix substrate manufactured using the circuit board manufacturing method described in detail in the first embodiment. FIG. 3 is a cross-sectional view schematically showing an electro-optical device using the above active matrix substrate. FIG. 4 is a perspective view schematically showing an electronic apparatus using the above-described electro-optical device, where (a) is a front perspective view and (b) is a rear perspective view.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following drawings, the scales are different for each layer and each member so that each layer and each member has a size that can be recognized on the drawing.

(Embodiment 1)
1, 2, and 3 are cross-sectional views schematically showing a circuit board manufacturing method according to the first embodiment. 4 and 5 are plan views schematically showing the circuit board manufacturing method according to the first embodiment. 1 to 3 correspond to the cross-sections AA ′ and BB ′ of FIGS. 4 and 5, and for the sake of convenience, the positions of AA ′ and BB ′ only in FIG. Is described. Hereinafter, a method for manufacturing a circuit board will be described with reference to FIGS.

"Overview"
First, the outline will be described with reference to FIG.
The present invention relates to a method of manufacturing a circuit board 1 including two types of conductive layers and two types of insulating layers that separate them. The circuit board 1 is mainly manufactured using a printing method, and relates to a technique for opening two via holes 31 in two types of insulating layers and electrically connecting the two types of conductive layers to each other so as to be suitable for the manufacturing method. In FIG. 3 (j), the two types of conductive layers are a source / drain electrode (first conductor) 11 and a pixel electrode (third conductor) 13. The two types of insulating layers are a gate insulating film (first insulating film) 21 and an interlayer insulating film (second insulating film) 22. The gate insulating film 21 covers a first conductor such as the source / drain electrode 11, an interlayer insulating film 22 is provided thereon, and a pixel electrode 13 is further formed thereon. A via hole 31 is opened on the source / drain electrode 11, and the source / drain electrode 11 and the pixel electrode 13 are connected via the via hole 31.
The gate electrode 12 and the like are formed of the second conductor, and the gate electrode 12 and the pixel electrode 13 are insulated by the interlayer insulating film 22. That is, the first insulating film insulates the first conductor from the second conductor, and the second insulating film insulates the second conductor from the third conductor.

The following steps are performed to manufacture such a circuit board 1.
First, as the first conductor forming step, the source / drain electrodes 11 and the like are formed on the substrate.
Next, as the first insulating film forming step, the gate insulating film 21 is formed so as to cover the first conductor.
Next, as a through hole forming step, a through hole 32 is opened in the gate insulating film 21 on the source / drain electrode 11 to expose the surface of the source / drain electrode 11. Thereafter, a conductive film 43 is formed in the surface of the source / drain electrode 11 by discharging the conductive ink 43 into the through hole 32. Then, a lyophobic process for lyophobizing the surface of the metal film 40 is performed.
Next, as a second insulating film forming step, the precursor resin of the interlayer insulating film 22 is printed in a region other than the through holes 32, and after the printing, the precursor resin is cured to form a second insulating film. The precursor resin has a low viscosity and spreads and spreads on the substrate surface during printing, but the portion where the metal film 40 is opened (exposed) has been subjected to lyophobic treatment, so it cannot be applied, and that portion is the precursor resin. Is not applied. Thus, the via hole 31 is easily and reliably formed. After the via hole 31 is formed, the pixel electrode 13 is formed, and the two kinds of conductive layers are electrically connected.

Hereinafter, the manufacturing method of the circuit board 1 will be described in detail for each process.
In the present embodiment, as a preferred example, a case where an active matrix substrate having an upper gate type and having a thin film transistor (organic TFT) using an organic substance as a semiconductor film is applied to the circuit substrate 1 will be described.

[First Conductor Forming Step and First Insulating Film Forming Step]
FIG. 1A shows the process up to the first insulating film forming process in the manufacturing process of the circuit board of the present embodiment. The substrate 10 is a polyethylene naphthalate (PEN) film. As the substrate 10, any substrate such as a glass substrate, a metal substrate such as aluminum or stainless steel, a semiconductor substrate such as silicon or GaAs, or a plastic substrate can be used. However, the organic TFT can be formed at a low temperature with a simple method. Of these, it is preferable to use a plastic substrate that is inexpensive, lightweight, and flexible.
In the case where a glass substrate is used as the substrate 10, an organic resin layer may be formed on the surface thereof.

  Examples of plastic substrates other than PEN films include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin, modified polyolefin, polyvinyl chloride, poly Vinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylbenten-1), ionomer, acrylic resin, polymethyl methacrylate, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer Polyesters such as polymers, polio copolymers (EVOH), polyethylene terephthalate, polybutylene terephthalate, precyclohexane terephthalate (PCT), polyethers, polyether keto , Polyether ether ketone, polyether imide, polyacetal, polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluororesins, styrene, polyolefin, Various thermoplastic elastomers such as polyvinyl chloride, polyurethane, fluoro rubber, chlorinated polyethylene, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, polyurethane, etc. A copolymer, a blend, a polymer alloy, and the like. Among these, a laminate in which one kind or two or more kinds are laminated can be used.

  A first conductor made of gold (Au) is provided on the substrate 10, and an electrode pad (first conductor) 111 and a source / drain electrode (first conductor) 11 are connected to the outside using these first conductors. , And data lines (not shown) and other wirings are formed. As the first conductor material, a material capable of bonding with a sulfur atom of a thiol compound or a disulfide compound is used. Besides gold, Cr, Al, Ta, Mo, Nb, Cu, Ag, Pt, Pd, Ni , And alloys using these metals are used. In addition to these, an oxide conductor such as indium tin oxide (ITO), tin oxide, or zinc oxide may be used as the first conductor material. These metal films and oxide conductors are patterned into a predetermined shape through a photolithography process and a wet or dry etching process after depositing a uniform thin film by vacuum deposition or sputtering. Alternatively, for a material that is difficult to etch, a metal film may be deposited (mask deposition) through a mask having holes in a predetermined shape. In addition, a dispersion of silver (Ag) nanocolloid may be printed by microcontact printing or convex plate reverse printing. This corresponds to the first conductor forming step. Here, gold was vacuum-deposited on the entire surface of the PEN film, and then the first conductor was formed through a photolithography process and a wet etching process. Note that a mixed solution of iodine and alkali iodide (ammonium iodide) was used for wet etching of gold.

  After the first conductor forming step, a semiconductor film forming step for printing the organic semiconductor film 41 is performed. A semiconductor material is printed by an inkjet method so as to connect the source / drain electrodes 11 (fill the channel formation region). Here, the organic semiconductor film 41 is poly (9,9-dioctylfluorene-codithiophene) (F8T2), and is a polymer organic semiconductor exhibiting P-type semiconductor characteristics. Other P-type polymer organic semiconductor materials that can be used include poly (3-hexylthiophene) (P3HT), poly [5,5′-bis (3-dodecyl-2tinyl) -2,2 ′. -Bithiophene] (PQT-12), PBTTT and the like. When a soluble low molecular weight organic semiconductor material that can be printed is used, BTBT, thiophene oligomer, and the like can be given. Organic semiconductors have a π bond, so they are most soluble in aromatic hydrocarbons (toluene, xylene, mesitylene, cyclohexylbenzene, etc.), and then consist of cyclic saturated hydrocarbons (cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, etc.) It is dissolved in a solvent and printed. The concentration of the semiconductor material at the time of dissolution is desirably in the range of 0.3% to 2.5%, and the ideal range is 0.5% to 1.5%. Since the first insulating film is applied in the next step, the organic semiconductor desirably has high solvent selectivity.

  Specifically, it is well soluble in aromatic hydrocarbons and cyclic saturated hydrocarbons for printing semiconductor films as described above, and water, alcohol-based solvents, ether-based to be stable after the next step. It is desired to be insoluble in solvents, ketone solvents, ester solvents, and fluorine solvents. From the viewpoint of solvent selectivity, a polymer type organic semiconductor material is preferable to a soluble low molecular weight organic semiconductor material. The F8T2 used here dissolves well in decalin and is stable to ketone solvents and ester materials. The semiconductor film was formed by printing F8T2 dissolved in decalin at a concentration of 2% by an inkjet method. The thickness of the semiconductor film is preferably in the range of 10 nm to 200 nm, and the ideal range is 30 nm to 60 nm. The thickness here was 50 nm.

  A first insulating film forming step is performed after the semiconductor film forming step. A gate insulating film 21 that is a first insulating film is provided to cover the organic semiconductor film 41. Here, polymethyl methacrylate (PMMA) having a thickness of 500 nm was formed by spin coating. In this way, the gate insulating film 21 is uniformly coated with the insulating polymer over the entire substrate. Since the organic semiconductor film 41 must not be dissolved at this time, the organic semiconductor material is insulatively soluble in a solvent in which the organic semiconductor material is hardly soluble (alcohol solvent, ether solvent, ketone solvent, ester solvent, fluorine solvent). Use functional polymers. In addition, the liquid repellency step, the second conductor forming step (gate electrode forming step), the second insulating film forming step (application and curing of the precursor resin in the interlayer insulating film forming step), etc. The gate insulating film 21 must be stable with respect to various processes to be performed. In these steps, alcoholic materials, glycols, and glycerin are used, so that the insulating polymer needs to be stable against these. That is, the first insulating film is hardly soluble in alcohol solvents and materials (not easily soluble), and is soluble (soluble in any of ether solvents, ketone solvents, ester solvents, and fluorine solvents). ) Material. Specifically, acrylic polymers such as PMMA, perfluorinated polymers represented by Cytop (trade name of Asahi Glass), or fluorine-based aromatics as disclosed in JP 2010-74088 A Polymers, and phenolic polymers such as polyvinylphenol (PVP) and novolak resins can be used. Since acrylic polymers have ester groups, they are well soluble in ester solvents such as butyl acetate and hardly soluble in alcoholic materials such as ethanol and propylene glycol. Although all fluorinated polymers can be dissolved in fluorinated solvents, they are insoluble (not soluble) in many solvents such as alcohol-based materials. In addition, fluorine aromatic polymers have carbonyl groups and ester groups, so they are well soluble in ketone solvents and ester solvents in addition to fluorine solvents, but only slightly soluble in alcohol solvents such as ethanol. Indicates.

  Since the phenolic polymer is soluble in alcohol, it cannot be used as it is for the first insulating film, but can be applied by insolubilization. That is, first, a crosslinking agent is mixed with a phenol polymer and applied. Next, after completing the through-hole forming step, the chemical reaction is accelerated by heating or the like to crosslink. Thus, the first insulating film is insolubilized and becomes stable with respect to the subsequent steps.

  Olefin polymers can be used as ether solvents, ketone solvents, and ester solvents by copolymerizing with materials having polar functional groups such as hydroxyl groups and carbonyl groups, or by adding these as side chains. Can be dissolved. Therefore, the olefin polymer subjected to such treatment can also be used as the first insulating film. In this case, a cycloolefin polymer is suitable.

  As will be described later, the precursor resin is synthesized with a monomer to which a hydroxyl group has been added to form a second insulating film. However, since the first insulating film is stable to alcohol-based materials, Slightly soluble. The thickness of the first insulating film is preferably in the range of 100 nm to 1000 nm, and more preferably in the range of 200 nm to 800 nm.

[Through hole forming step]
FIG. 1B and FIG. 1C show a through hole forming process in the process of manufacturing the circuit board of the present embodiment. As shown in FIG. 1B, the through hole forming process starts with a solvent dropping process in which a solvent that dissolves the first insulating film is dropped onto the first insulating film. Specifically, γ-butyrolactone is dropped onto the first insulating film by an inkjet 51 at a location where a through hole is to be opened. In FIG. 1B, γ-butyrolactone droplets 52 having a volume of about 5 pL to 10 pL were dropped several times on the electrode portion 113 of the source / drain electrode 11.
Here, a cycle in which 4 drops of a polymer solution of about 5 to 10 pL were continuously discharged to the same spot and dried for several seconds was repeated about 3 times. In this manner, for example, the through hole 32 is formed in the first insulating film (gate insulating film 21) having a thickness of 900 nm. Alternatively, the through-hole 32 may be formed by repeating a cycle in which only one droplet 52 of a polymer solution of about 5 to 10 pL is discharged to the same point and dried for several seconds. Thereby, the through-hole 32 having a smaller diameter can be formed.

  The through hole 32 has an outer diameter D1 of less than 100 μm and an inner diameter D2 of less than 60 μm, and exposes a part of the surface of the source / drain electrode 11.

  As the solvent used in the through-hole forming step, a solvent capable of dissolving the first insulating film (any one of an ether solvent, a ketone solvent, an ester solvent, and a fluorine solvent) is used. It is desirable to use a solvent having a viscosity in the range of 1 mPa · s to 5 mPa · s. If the viscosity is 1 mPa · s or more, the solvent can be easily dropped by the inkjet 51, and if it is 5 mPa · s or less, a micro flow is generated in the solution, and the through hole 32 can be opened. Furthermore, in order to form fine through holes, the surface tension of the solvent is preferably 35 mN / m or more, ideally 40 mN / m or more. Moreover, in order to form a deep through-hole, it is preferable that the boiling point of a solvent is higher than 180 degreeC. Here, the dropped γ-butyrolactone was a cyclic ester, the viscosity was 1.7 mPa · s, the surface tension was 44 mN / m, and the boiling point was 207 ° C. Although it depends on the solvent evaporation rate determined by the temperature and wind speed during the through hole formation process, these conditions are satisfied and the normal working environment (temperature 20 ° C. to 30 ° C., relative humidity 30% to 80%, air With a downflow air volume of 0.01 m / s to 0.1 m / s, when a droplet 52 of about 20 pL is dropped once, a hole with a depth of about 200 nm to 400 nm can be formed, and a droplet 52 of about 40 pL is formed. When dropped once, a hole having a depth of about 400 nm to 600 nm can be formed. Therefore, if the first insulating film has a thickness of less than about 400 nm and a droplet 52 of about 40 pL is used, a through-hole reaching the source / drain electrode 11 can be formed by a single solvent drop. When the first insulating film is thicker or the solubility is insufficient, the droplet 52 is dropped at the same position a plurality of times to form a through hole.

Here, the formation principle of the through hole 32 will be described in detail.
[Principle of through-hole formation]
FIG. 6 is a diagram for explaining the principle of the through-hole forming step in the circuit board manufacturing method according to the first embodiment. Here, the principle of through-hole formation will be described.
In order to open the through hole 32 in the gate insulating film (first insulating film) 21, a solvent droplet 52 is dropped on the gate insulating film 21 by an inkjet method. At this time, as shown in FIG. 6A, the solvent dropped on the gate insulating film 21 spreads to a certain diameter depending on the wettability. The solvent evaporates while dissolving the gate insulating film 21 below. When the solvent evaporates, a micro flow toward the outer edge of the droplet 52 is generated as indicated by the arrow in FIG. This is because the contact line (outer edge) of the droplet 52 is pinned (fixed) and cannot be easily moved. As a result, the evaporation of the solvent in the vicinity of the contact line is compensated by the movement of the liquid from the center, and a micro flow from the center toward the outer edge portion is generated. The polymer (component of the gate insulating film 21) dissolved in the solvent is also collected in the vicinity of the contact line along the minute flow. Thus, a crater-like through hole 32 as shown in FIG. 6C is formed.

  Based on the above principle, in order to open the through-hole 32 by this method, (1) the first insulating film is easily dissolved in the dropped solvent, and (2) the contact angle between the solvent and the first insulating film is 15 °. (3) The drying speed of the solvent is slow, the first insulating film dissolves in the solvent, and there is time to move it in a micro flow (ie, the boiling point of the solvent 4) that the viscosity of the solvent is low to some extent and that the liquid can move is important.

  According to experiments, butyl acetate and PGMEA, which have excellent solubility, are too low in viscosity, making it difficult to discharge the solution by a simple ink jet method (the drive waveform needs to be optimized). When the surface tension is approximately 40 mN / m, the contact angle with respect to PMMA is slightly less than 15 °, and the diameter of the outer peripheral edge (vertical portion raised in FIG. 6 (c)) and the diameter of 20 pL droplet 52 is approximately 100 μm. Through holes 32 could be formed by forming openings of 20 μm to 30 μm (bottom portions where the electrodes were exposed in FIG. 6C). Diclohexanol acetate exhibits excellent solubility, but since the boiling point is as low as 173 ° C., only about 10 nm can be dug by one drop. Accordingly, the boiling point is preferably about 180 ° C. or higher.

As described above, after the solvent dropping step, as shown in FIG. 1C, the through hole 32 is formed at the position where the solvent is dropped. That is, the through hole 32 is opened at a position to be connected to the third conductor on the surface of the first conductor. However, a complete through hole 32 may not be formed in many through holes 32 that range from tens of thousands to millions. At first glance, even though the through-hole 32 appears to reach the bottom, a very thin insulating thin film may remain on the surface of the first conductor. In order to remove this, an etching process for uniformly etching the first insulating film is performed after the solvent dropping process. Here, the entire substrate was exposed to oxygen plasma, and the polymer layer possibly remaining on the surface of the first insulating film and the surface of the first conductor was scraped off. Specifically, the substrate was exposed to oxygen plasma of 40 W / cm ² for 2 minutes. Thereby, the polymer layer remaining in a thin skin state can be completely removed.

  The etching process may be ozone irradiation treatment in addition to the above-described oxygen plasma treatment. Further, it may be rinsed with a solvent whose solubility is controlled. At this time, a solvent that is insoluble in the semiconductor film and soluble in the first insulating film (soluble solvent, such as an ether solvent, a ketone solvent, or an ester solvent), and the semiconductor film also have the first insulation. The film is rinsed for a short time with a mixed solvent in which a solvent that is also insoluble in the membrane (an insoluble solvent such as an alcohol solvent) is mixed at an appropriate ratio. As an example of the mixed solvent, the volume ratio of the insoluble solvent to the soluble solvent is set to a ratio of about 1: 1 to 10: 1. For example, it is possible to obtain a solvent in which the solubility is controlled by mixing ethanol at 2 with acetone at 1. When the substrate is immersed in this mixed solvent for about 1 to 5 minutes, the thin insulating polymer layer is removed cleanly. In addition to being immersed in the mixed solvent, the mixed solvent may be supplied to the substrate surface in a shower form or a spin coat form.

  As described above, when a reactive material (such as a phenolic polymer with a cross-linking agent) is used for the first insulating film, a heat treatment that accelerates the reaction is performed after the etching process.

[Metal film forming process]
FIG. 1D shows a metal film forming process in the manufacturing process of the circuit board of the present embodiment.
As shown in FIG. 1D, a conductive film 43 is dropped into the through hole 32 formed in the first insulating film, and a predetermined film is formed on the surface of the source / drain electrode 11 exposed in the through hole 32. A thick metal film 40 is formed. As the conductive ink, a silver colloid ink in which silver fine particles are dispersed and held in an aqueous or organic dispersion medium is used. Here, it is desirable to use nanoparticles having a particle size of 10 to 40 nm.

As shown in FIGS. 7A to 7C, the conductive ink dropped into the through hole 32 wets and spreads on the exposed electrode surface.
The method of spreading and spreading the conductive ink varies depending on whether or not the through-hole is completely penetrated, the amount of the conductive ink dropped, and the like.

As shown in FIG. 7A, for example, when a plasma treatment is performed on a first insulating film of a hydrophobic polymer in a carbon fluoride such as CF ₄ , the surface of the organic insulator is fluorinated. Therefore, the first insulating film repels the conductive ink and selectively wets the exposed portion of the source / drain electrode 11 exposed in the through hole 32 that completely penetrates the first insulating film. When there is a difference in wettability with respect to the conductive ink 43 between the through hole 32 and the first insulating film, the conductive ink 43 is confined in the through hole 32 by being surrounded by a low wettability region. It becomes.

  As shown in FIGS. 7B and 7C, when there is no difference in wettability with respect to the conductive ink 43 between the through hole 32 and the first insulating film, the shape of the through hole 32 itself, that is, the through hole The conductive ink 43 is confined in the through-hole 32 by the raised portion of the first insulating film constituting the periphery of 32. Here, the case where there is no difference in wettability with respect to the conductive ink 43 between the through hole 32 and the first insulating film means that the through hole 32 does not completely penetrate the first insulating film (that is, the through hole 32 is penetrated). In the state where the insulating thin film remains at the bottom of the hole 32), or the oxygen plasma treatment is performed as described above to completely penetrate the through hole 32, both the first insulating film and the source / drain electrode 11 have wettability. The state where it is high is mentioned.

  In this embodiment, after the conductive ink 43 is applied in the through-hole 32 by the inkjet 51, the silver metal film 40 is obtained by heating and baking at 80 to 150 ° C. Note that a screen printing method or a dispenser method can be used instead of the ink jet method.

  If at least part of the through-hole 32 penetrates the first insulating film, conduction between the source / drain electrode 11 and the metal film 40 can be obtained. However, in the case where a thin thin film of an insulator remains in the through hole 32 and the surface of the first conductor to be exposed in the through hole 32 is covered with the insulating thin film, in principle, conduction cannot be obtained. . However, since the thickness of this insulating thin film is as very thin as 20 nm, by applying a voltage after completion of the insulating thin film, the insulating thin film easily causes dielectric breakdown and a conductive state can be obtained.

[Liquid repellency process]
FIG. 2E shows a lyophobic process in the manufacturing process of the circuit board of this embodiment.
FIG. 8 is a diagram illustrating in detail the state at the end of the liquid repellent process in the circuit board manufacturing method according to the first embodiment. As shown in FIG. 2E, in the liquid repellent step, the surface of the first conductor is brought into contact with a solution 61 containing a thiol compound or a disulfide compound. The simplest method is to immerse the substrate on which the through-holes are formed in a solution 61 containing a thiol compound or a disulfide compound for a short time of about several seconds to several minutes. Since the sulfur atom of the thiol compound or disulfide compound is quickly bonded to the metal atom forming the first conductor, the first conductor (the source / drain electrode exposed in the through hole 32) can be easily obtained by such a short contact treatment. The surface of 11) is made liquid repellent. It is more preferable that the thiol compound or disulfide compound contains a fluorinated alkyl chain (fluorinated alkyl thiol or fluorinated alkyl disulfide, hereinafter, abbreviated as fluorinated alkyl thiol 62), resulting in increased liquid repellency. Here, a fluorinated alkylthiol 62 represented by a chemical formula of HS— (CH ₂ ) ₆ — (CF ₂ ) ₇ —CF ₃ was used. Specifically, perfluoroalkylthiol was used.

  As shown in FIG. 8B, the sulfur of the thiol compound or disulfide compound is firmly bonded to a metal such as gold, and the surface covered with the fluorinated alkylthiol 62 is covered with the fluorinated alkyl chain, and the surface energy is increased. Lower. As a result, the contact angle of the metal surface with water increases from about 100 ° to about 140 °. Thus, the lyophobic treatment is a treatment that lowers the surface energy of the first conductor to make the contact angle with water 90 ° or more.

  The fluorinated alkyl thiol 62 is dissolved in an alcohol solvent (ethanol, isopropyl alcohol, butanol, etc.) at a concentration of 0.005% to 1%. The concentration is more preferably in the range of 0.05% to 0.5%. When the substrate is immersed in a solution having a concentration of about 0.2%, as shown in FIG. 8A, the surface of the source / drain electrode 11 exposed in the through-hole 32 almost instantaneously (with an electrode of 1 second or less) Covered with fluorinated alkylthiol 62 in a short time). However, from the standpoint of stably performing the process, the immersion time is preferably 1 minute or longer. Further, from the standpoint of improving productivity and minimizing substrate damage due to immersion, the immersion time is desirably 3 minutes or less. Here, the above-mentioned alkylthiol was dissolved in ethanol at a concentration of 0.2%.

  Since the fluorinated alkyl thiol 62 is also dissolved in the fluorine-based solvent, it may be used as a diluted solvent for the fluorinated alkyl thiol 62. However, in this case, the first insulating film is hardly soluble in both alcohol solvents and alcohol materials and fluorine solvents, and is soluble in either ether solvents, ketone solvents, or ester solvents. Must be a polymeric material exhibiting Specifically, it is an acrylic polymer, a fluorine-based aromatic polymer, a phenol-based polymer, or an olefin-based polymer.

The thiol compound or disulfide compound does not necessarily have to be substituted with fluorine in the main chain extending from the sulfur atom. If the main chain has a contact angle with respect to water of 90 ° or more, it can be used for the liquid repellency step without using fluoride. When the main chain extending from the sulfur atom is fluorinated, the contact angle with water can be easily increased to 110 ° or more, and excellent liquid repellency can be exhibited. The fluorinated alkyl thiol 62 includes
_{HS- (CH 2) k-O-} (CH 2) l- (CF 2) m-CF 3 or _{HS- (CH 2) k + l-} (CF 2) m-CF 3
A material represented by the chemical formula can be used. In order to form a dense SAM film by introducing a soft and small volume alkyl chain to a hard and large volume fluorinated alkyl, the value of k + 1 is preferably in the range of 4 to 16, The value of is preferably in the range of 0 to 3. In order to exhibit excellent liquid repellency, the value of m needs to be 1 or more, and in order to dissolve in an alcohol solvent, the value of m is preferably 11 or less. When the value of m is 12 or more, the solubility in an alcohol-based solvent is lowered, making it difficult to use in the liquid repellency step. Instead of fluorinated alkyl, some or all of these may be substituted with fluorinated alicyclic hydrocarbons.

  Here, the substrate is immersed in a solution containing the fluorinated alkylthiol 62, but some of the exposed first conductors are made liquid repellent and the rest are not to be made liquid repellent. The solution 61 containing a thiol compound or a disulfide compound may be dropped by the ink jet method only in the through-hole 32 to be made liquid repellent.

  As described above, when an oxide conductor such as indium tin oxide (ITO), tin oxide, or zinc oxide is used as the first conductor material, the oxide is used instead of the thiol compound or disulfide compound. It is made liquid repellent using a compound such as adsorbed phosphoric acid, phosphonic acid, fatty acid, or organosilane. Specifically, a phosphoric acid ester having a fluorinated alkyl group, or a phosphoric acid ester salt having a fluorinated alkyl group, an ether of an alcohol having a fluorinated alkyl group and phosphoric acid, a phosphonic acid having a fluorinated alkyl group, Phosphonic acid ester having fluorinated alkyl group, phosphonic acid ester salt having fluorinated alkyl group, compound having carboxy group and fluorinated alkyl group (fatty acid having fluorinated alkyl group), silane cup having fluorinated alkyl group A compound such as a ring agent is used.

  Further, although water repellency can be achieved even with alkylthiols not substituted with fluorine, the water repellency is inferior to that of fluorinated alkyl chains. The number of fluorinated carbons is desirably 2 or more and 12 or less per molecule. When the number of carbon atoms exceeds 12, solubility in alcohol or the like decreases. It is desirable to have a normal alkyl chain between the fluorinated alkyl group and the thiol group or disulfide group. It is considered that a dense SAM film is easily formed by including a soft and small volume alkyl chain with respect to a hard and large volume fluorinated alkyl group. Here, the length of the alkyl chain is preferably 4 or more and 16 or less.

[Hydrophilic electrode forming step]
FIG. 2F shows a hydrophilic electrode forming process during the manufacturing process of the circuit board of the present embodiment. FIG. 4A is a plan view corresponding to FIG. In the hydrophilic electrode forming step, as shown in FIG. 2 (f), the first insulating film at the place to be connected to the second conductor is removed from the first conductor to remove the hydrophilic (repellent). This is a step of forming a through-hole having an electrode surface that is not liquid.

  The circuit board 1 may require connection between the first conductor and the second conductor. For example, in the electrode pad 111 that connects the scanning line to an external control circuit, there are cases where it is desired to connect the electrode pad of the first conductor and the scanning line of the second conductor. For example, when configuring a series circuit of inverters or a pixel circuit of an organic EL display, the output (drain electrode, first conductor) of one transistor is connected to the input (gate electrode, second conductor) of another transistor. May be. As described above, depending on the circuit board 1, there is a case where the connection between the first conductor and the second conductor is necessary. At this time, this hydrophilic electrode forming step is performed. This is because the electrical connection stability between the first conductor and the second conductor is increased, and the next second conductor forming step is desired to be performed by a printing method. When the surface of the first conductor is liquid repellent, poor connection is likely to occur. Therefore, it is desirable that the surface of the first conductor is hydrophilic in order to obtain an electrical connection with a high yield. In addition, since the ink for a conductor using water or an alcohol solvent is used in the printing method of the second conductor, if the surface of the first conductor is liquid repellent, the conductor ink is repelled and the through hole is formed. The first conductor cannot be drawn on the part. For these reasons, it is desirable that the surface of the first conductor where the connection between the first conductor and the second conductor is required be hydrophilic.

  In the hydrophilic electrode forming step, as shown in FIG. 2 (f), a droplet 52 of a solvent that dissolves the first insulating film is applied to the first electrode on which the hydrophilic electrode is to be formed (for example, using an inkjet 51). It is a step of forming a hydrophilic electrode opening by dropping it on the first insulating film on the electrode pad 111). Here, using the same solvent (γ-butyrolactone) as in the through-hole forming step, a hydrophilic electrode opening was provided by the same method (a predetermined amount of solvent was dropped by the inkjet 51 a predetermined number of times). Thus, as shown in FIG. 2 (f) and FIG. 4 (a), the through hole 32 is provided at a site where a hydrophilic electrode opening is required, such as on the electrode pad 111.

  As described above, when the liquid repellent process can be selectively made liquid repellent by using the ink jet method, this hydrophilic electrode forming process is not necessary. In that case, all the through-holes 32 are opened during the through-hole forming step, and the liquid-repellent electrode surface and the hydrophilic electrode surface are separately formed using the ink jet method during the liquid-repellent step. Specifically, since the electrode surface that is not subjected to any treatment is hydrophilic, the fluorinated alkylthiol 62 is dropped only in the through-hole 32 where the liquid-repellent electrode surface is desired.

[Second conductor forming step]
FIG. 2G shows a second conductor forming process during the manufacturing process of the circuit board 1 of the present embodiment. FIG. 4B is a plan view corresponding to FIG. The second conductor forming step is a step of forming the second conductor on the first insulating film after the liquid repellent step.

  As shown in FIG. 2G, the second conductor is formed by dropping the conductor ink 53 with the ink jet 51 and then firing it, thereby scanning the gate electrode (second conductor) 12 or a scan (not shown). A pattern of a second conductor called a line is formed. As the conductor ink 53, it is desirable to use an ink in which silver nanoparticles that can be baked at a low temperature are dispersed. Here, a conductor ink 53 (hereinafter abbreviated as silver ink) in which silver nanoparticles are dispersed in a mixed solvent of water and propanediol was used. In order to print a thin line with a line width of about 40 μm with the inkjet 51, it is desirable that the surface tension of the conductor ink 53 be in the range of 40 mN / m to 60 mN / m. In this way, the wetting and spreading of the ink dropped on the organic insulator can be controlled to be small, and a thin wiring is drawn.

  Further, in order to print with the ink jet 51, it is necessary that the viscosity of the conductor ink 53 is adjusted within a range of 1 mPs · s to 20 mPs · s. Furthermore, in order to prevent functional deterioration of organic substances such as semiconductor materials during firing of the conductor ink 53, it is desirable that the conductor ink 53 can be fired under processing conditions within a temperature range of 80 ° C. to 150 ° C. The silver ink used here became a sufficiently low conductor having a specific resistance of 50 μΩcm or less after firing by performing a heat treatment at 100 ° C. for 30 minutes in the air.

  As the dispersion medium for the conductor ink 53, water or glycol having a large surface tension of 72 mN / m, or a substance containing a mixed solvent thereof is preferable because of its large surface tension. When it is difficult to draw a continuous line because the viscosity is too low or the surface tension is too high with water alone, an alcohol solvent, a diol solvent, or a glycerin solvent is added to water.

  In addition to silver ink, ink in which carbon (carbon black, graphite, carbon nanotube, fullerene, graphene, or the like) is dispersed in the above-described dispersion medium can also be used. In the present embodiment, since the surface of the second conductor was not desired to be liquid repellent, the liquid repellent step was performed prior to the second conductor forming step. In the case of using an ink in which carbon is dispersed, the surface of the carbon ink is not liquid repellent even if a liquid repellent process is performed. Therefore, in this case, a liquid repellent process may be performed after the second conductor forming process.

  As shown in FIG. 4B, silver ink is printed from the electrode pad 111 having a hydrophilic electrode opening to the scanning line and the gate electrode 12. Thereby, the electrode pad 111 made of the first conductor and the scanning line and the gate electrode 12 can be connected. The wiring and electrode pads connected to the external control circuit are formed with the pattern of the first conductor using the photolithography process, so high-density wiring with a line and space of 50 μm or less is possible. This is useful for miniaturization of electronic equipment using the circuit board 1.

[Second insulating film forming step]
FIGS. 3H and 3I show the second insulating film forming step in the process of manufacturing the circuit board of this embodiment. FIG. 5C is a plan view corresponding to FIG. If there is a second conductor on the circuit board, the second insulating film formation step is performed after the second conductor formation step.

  The second insulating film is an interlayer insulating film and mainly electrically separates the second conductor and the third conductor. To form the second insulating film, as shown in FIG. 3 (h), first, the precursor resin of the interlayer insulating film is printed so as to avoid the through holes 32, and then as shown in FIG. 3 (i). In addition, the reaction of the precursor resin is promoted to form a second insulating film. The precursor resin contains a monomer having a hydroxyl group and is soluble in an alcohol solvent. The precursor resin is preferably a photocurable resin. Here, an ultraviolet curable resin (hereinafter abbreviated as UV ink 54) containing a hydroxy-type acrylic monomer (acrylic acid or an ester of methacrylic acid and a polyhydric alcohol) that is soluble in an alcohol solvent is used as a precursor resin. did.

  As shown in FIG. 3 (h), first, the UV ink 54 is dropped by the inkjet 51 in a region other than the through hole 32 (that is, a region where the first insulating film and the second conductor are present). The precursor resin such as the UV ink 54 is prepared to be suitable for the ink jet 51 and contains a monomer as a main component. The polymer component is not included in the precursor resin, or a small amount is included. It is desirable that the monomer contains an —OH group in order to increase the polarity. As such a monomer, diethylene glycol mono 2-ethylhexyl ether acrylate, tetraethylene glycol monophenyl ether acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, or the like may be used. . Since such an acrylic monomer contains an —OH group, the polarity is high, and the solubility parameter (SP value) is 9.5 or more. Therefore, the polymer of the gate insulating film 21 is not dissolved, and the adhesiveness with the gate insulating film 21 is high.

  In this way, the precursor resin is a monomer having an SP value of 9.5 or more, which has a surface tension equivalent to that of an organic solvent (20 mN / m to 35 mN / m) and a viscosity equivalent to 10 mPa · s to 30 mPa · s. So that it can be easily discharged by the inkjet 51. Since the surface tension is relatively low and the viscosity is low, the UV ink 54 spreads uniformly on the organic insulator or metal material to a diameter of 5 times or more after landing. On the other hand, since the wetting angle is 45 ° or more on the liquid-repellent surface of the metal film 40 formed in the through hole 32, wetting and spreading of the precursor resin is suppressed. That is, the precursor resin spreads over the first insulating film and the second conductor without covering the surface of the lyophobic metal film 40 with the UV ink 54. That is, the wetting and spreading of the precursor resin stops near the boundary of the lyophobic metal film 40, and the via hole 31 having a diameter smaller than the diameter (outer diameter) of the through hole 32 is formed. In this way, the second insulating film is formed.

  The thickness of the second insulating film is controlled by adjusting the dropping amount of the UV ink 54. When the interlayer insulating film 22 of the TFT formed on the film is used as the second insulating film as in this embodiment, the first conductor or the first conductor or the In terms of minimizing the parasitic capacitance between the second conductor and the third conductor, the thickness of the interlayer insulating film 22 is preferably 1 μm or more. When the thickness of the interlayer insulating film 22 exceeds 20 μm, the substrate is warped due to the influence of the volume change when the UV ink 54 is cured. If the amount of ink dropped is too large, the wetting angle on the surface of the metal film 40 will be exceeded, and it will not be possible to maintain a state in which the UV ink 54 does not cover the surface of the liquid-repellent metal film 40. . The wetting angle of the precursor resin on the organic insulator is 45 ° or more and 70 ° or 90 ° or less. When the thickness of the liquid film exceeds 20 μm, the contact angle that is theoretically determined from the weight of the liquid and the surface tension exceeds the previous wetting angle. In this case, since the surface of the lyophobic metal film 40 is also covered with the precursor resin, it is necessary to suppress the dripping amount so that the theoretically determined contact angle does not exceed the previous wetting angle.

  Next, as shown in FIG. 3I, the UV ink 54 is irradiated with ultraviolet rays 55 to cure the UV ink 54, thereby forming the via hole 31. In order to completely cure, heat treatment may be performed in addition to ultraviolet irradiation. Since the ultraviolet ray 55 is irradiated after printing the UV ink 54, a flat second insulating film is obtained except on the metal film 40. Here, after the UV ink 54 is printed, the ultraviolet rays 55 are collectively irradiated. However, the ultraviolet rays 55 may be irradiated simultaneously with the printing of the UV ink 54. In this case, wetting and spreading are suppressed by a chemical reaction, and the controllability of not applying the UV ink 54 to the surface of the metal film 40 is increased. By providing an ultraviolet irradiation device using an LED as a light source adjacent to the inkjet head, a small-sized device can be realized.

  The UV ink 54 is not limited to an acrylic monomer, and an epoxy monomer or the like may be used. Further, the precursor resin is not limited to the UV ink 54, and may be a thermosetting resin. In these cases as well, the precursor resin must not dissolve the gate insulating film, so that the polarity is increased by introducing a hydroxyl group into the epoxy monomer or thermosetting resin.

  In order to form the second insulating film having a thickness of 1 μm or more by the inkjet method, in addition to the method using the curable monomer described above, a method using a dispersion system of surface-treated fine particles and a polymer material is used. There may be. For example, silica fine particles are surface-treated with a surfactant such as lecithin so as to be dispersed in an organic solvent, and this is mixed with a polymer resin for a binder to obtain a dispersion. This dispersion becomes a low-viscosity precursor resin and can be printed by an ink jet method. However, after it is dried, the thickness of the second insulating film can be made relatively large, such as 1 μm or more.

[Third conductor forming step]
FIG. 3J illustrates a third conductor forming step in the process of manufacturing the circuit board according to the present embodiment. FIG. 5D is a plan view corresponding to FIG. After the second insulating film is formed, a third conductor is formed in a region including the via hole 31. Here, the third conductor is the pixel electrode 13.

  The pixel electrode 13 is formed by screen printing using carbon ink. Screen printing has high printing speed and excellent productivity. On the other hand, since printing is performed with the screen in contact with the substrate, there is a risk of damaging the thin film layer when this printing method is used in the production of organic TFTs. However, in this embodiment, since the hardened thick second insulating film covers the outermost surface, even a method of printing by contact such as screen printing does not lead to defects of the organic TFT, and has excellent productivity. You can enjoy the advantage of easy printing process. Moreover, since the reaction of the second insulating film is completed, the solvent of the carbon ink is not particularly limited.

  In the carbon ink, carbon (carbon black, graphite, carbon nanotube, fullerene, graphene, etc.) is dispersed in an organic solvent. As the organic solvent, a ketone solvent, an ester solvent, an ether solvent, or the like is used. The viscosity of the carbon ink is adjusted from 2000 mPa · s to 20000 mPa · s so as to be suitable for screen printing. In this case, even if printing is performed on the surface of the liquid-repellent first electrode, the carbon ink is not repelled and is electrically connected. Further, since most of the pixel electrode 13 is formed on the interlayer insulating film 22, the pixel electrode 13 is not peeled off. However, considering the reliability of the electrical connection and the yield, etc., before the printing of the pixel electrode 13, plasma treatment such as oxygen plasma or ozone irradiation treatment is performed to remove the alkyl fluoride thiol 62 from the surface of the first electrode. It is desirable to keep it. The circuit board 1 having the organic TFT is manufactured through the above steps.

As described above, according to the circuit board manufacturing method according to the present embodiment, the following effects can be obtained.
A pattern such as a via hole can be efficiently formed by a printing method (inkjet method), and the quality of the first insulating film other than the via hole can be kept high. In addition, the electronic elements manufactured on the circuit board are not adversely affected. Therefore, a circuit board exhibiting excellent circuit characteristics can be stably manufactured with a high yield by a printing method.

  Further, the metal film 40 is formed by dropping a conductive ink 43 made of a metal colloid into the through hole 32 formed by the inkjet 51. Some of the many through holes 32 formed in the first insulating film may not be complete through holes. However, since this insulating thin film is very thin, the metal film 40 is formed thereon. When a voltage is applied after completion, the insulating thin film easily breaks down, and conduction between the source / drain electrode 11 and the metal film 40 is obtained. Therefore, even if the formation failure of the through hole 32 occurs, the process for removing the insulating thin film can be omitted, so that the yield can be improved and the manufacturing time can be shortened.

  Further, since the particle size of the metal particles is 10 to 40 nm, the low resistance metal film 40 is obtained by adhesion at a low temperature. Furthermore, although silver particles are used as the metal particles, the present invention is not limited to this, and metal particles made of any of gold, copper, nickel, platinum, and palladium may be used. Since these metal particles are particularly excellent in conductivity, the overall conductivity of the obtained metal film 40 can be improved.

  A through hole 32 is opened in the first insulating film on the first conductor by a printing method to expose the surface of the first conductor, and the surface of the first conductor is made liquid repellent. Since the second insulating film is formed by printing the precursor resin in the region, the via hole 31 can be easily opened in the circuit board 1 by the printing method. In addition, since the electronic device manufactured on the circuit board 1 is not adversely affected, the circuit board 1 exhibiting excellent circuit characteristics can be stably manufactured by a printing method with a high yield.

  In addition, since the second conductor is formed on the first insulating film after the lyophobic process, only the portion where the through hole 32 is opened in the first conductor is selectively lyophobic, and the second conductor is Not repellent. Thus, in the next second insulating film forming step, the precursor resin can be printed uniformly on the second conductor, and the second conductor can be electrically insulated by the second insulating film.

  In addition, since the third conductor is formed in the region including the through hole 32 after the second insulating film formation step, electrical conduction can be established between the first conductor and the third conductor. The circuit board 1 having a complicated and highly functional circuit can be manufactured by a printing method.

  In addition, since the organic semiconductor film 41 is printed after the first conductor forming step and then the first insulating film forming step is performed, an organic thin film transistor can be formed on the circuit board 1. Furthermore, a high-performance thin film transistor can be manufactured with a high degree of process freedom in the first conductor formation step. In addition, since the photolithography process and the etching process can be used prior to the formation of the organic semiconductor film 41 and the gate insulating film 21, the channel formation region length can be extremely reduced to several microns or less, It becomes possible to provide a thin film transistor circuit taking advantage of the scaling advantage on the circuit board 1.

  Further, since the organic semiconductor film 41 is hardly soluble in ether solvents, ketone solvents, ester solvents, and fluorine solvents, an ink containing an organic semiconductor is used. Ready. That is, the organic semiconductor can be printed in a shape required for the circuit board 1 by a printing method such as the inkjet 51.

  In addition, since the first insulating film is soluble in any of ether solvents, ketone solvents, ester solvents, and fluorine solvents, the first insulating film can be formed by a printing method. In addition, since the options for the first insulating film are wide, the function of the circuit board 1 can be maximized. Further, when the first insulating film is used as the gate insulating film 21 of the transistor, the first insulating film material does not dissolve the organic semiconductor film 41, so that a thin film transistor having excellent characteristics is manufactured on the circuit substrate 1. Can do.

  In addition, since the first insulating film is hardly soluble in an alcohol-based solvent, the first insulating film can be used for an alcohol-based material or an alcohol-based solvent in a liquid repellent process, a second conductor forming process, and a second insulating film forming process. A soluble material can be used, and further, the first insulating film is not damaged during these processes. Therefore, the first insulating film can be maintained without deteriorating the function required for the circuit board 1.

  In addition, since the first insulating film is hardly soluble in the precursor resin, the first insulating film is not damaged by the precursor resin during the second insulating film forming step. The function required for the substrate 1 can be maintained without deteriorating.

  Further, in the through-hole forming step, a solvent that dissolves the first insulating film is dropped onto the first insulating film, so that the fine through-hole 32 can be easily formed by a printing method.

  In addition, the through hole forming step includes an etching step for uniformly etching the first insulating film, and the etching step is performed after the solvent dropping step. Can be formed.

  In the liquid repellency step, the surface of the first conductor is brought into contact with the solution 61 containing the thiol compound or disulfide compound, so that only the surface of the first conductor can be easily touched in a short time of several seconds to several minutes. It can be selectively made liquid repellent.

  Moreover, since the thiol compound contains a fluorinated alkyl chain, the liquid repellency of the surface to which the thiol compound is bonded can be extremely increased.

  Further, since the disulfide compound contains a fluorinated alkyl chain, the liquid repellency of the surface to which the disulfide compound is bonded can be extremely increased.

  In addition, since the precursor resin contains a monomer having a hydroxyl group and the first insulating film is stable with respect to the alcohol-based material, the precursor resin can be prevented from damaging the first insulating film.

  Further, since the precursor resin is soluble in an alcohol solvent, the concentration of the solution can be adjusted relatively freely, and various printing methods can be applied to the second insulating film forming step. Furthermore, since the first insulating film is stable with respect to the alcohol-based material, the second insulating film forming step can be prevented from damaging the first insulating film.

  Moreover, since the precursor resin is a photocurable resin, the second insulating film can be formed quickly and easily by light irradiation.

  Further, since the precursor resin is a thermosetting resin, the second insulating film can be easily formed by a simple heat treatment.

  Further, since the circuit board 1 includes a transistor including the gate insulating film 21, and the first insulating film functions as the gate insulating film 21, the circuit board 1 having a high-function circuit can be realized.

  As described above, the preferred embodiments according to the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the examples. It is obvious for those skilled in the art that various changes or modifications can be conceived within the scope of the technical idea described in the claims. It is understood that it belongs to.

  In the previous embodiment, the top gate structure has been described. However, the structure is not limited to this structure, and a bottom gate structure may be used. FIG. 9 is a cross-sectional view schematically showing an active matrix substrate having a bottom gate structure. As shown in the figure, an interlayer insulating film 23 may be formed on the gate insulating film 21 with a predetermined thickness so as to cover the organic semiconductor film 41 and the source / drain electrode 11. By protecting the organic semiconductor film 41 with a polymer film of a quality that can also be used for the gate insulating film 21, the number of traps and the leakage current can be controlled.

  FIG. 10 is a plan view of the circuit board manufacturing method according to the second modification. Hereinafter, the circuit board 1 according to this modification and the manufacturing method thereof will be described. This modified example (FIG. 10) differs from the first embodiment (FIG. 4B) in that the circuit board 1 is provided with a capacitance electrode. The rest of the configuration is almost the same as in the first embodiment, and a duplicate description is omitted.

  In this modification, a storage capacitor is formed in the pixel circuit. The storage capacitor includes a first capacitor electrode, a second capacitor electrode 121, and a dielectric film sandwiched between these electrodes. The first capacitor electrode is connected to a pixel electrode (not shown), and the second capacitor electrode 121 is connected to a reference potential such as a ground potential or a common electrode potential. In the circuit board 1, a source / drain electrode 11 is formed of a first conductor, one of which is connected to a signal line 73 and the other is connected to a pixel electrode (not shown), but the first capacitor electrode is the other source. Also used as the drain electrode 11. The dielectric film is the same first insulating film as the gate insulating film. As shown in FIG. 10, the second capacitor electrode 121 is formed of the same second conductor as the gate electrode 12. In order to connect the second capacitor electrode 121 to the reference potential, the capacitor common line 112 and a plurality of capacitor electrodes are connected. The capacitor common line 112 is formed of a first conductor, and is connected to the second capacitor electrode 121 through the through hole 32 provided in the capacitor common line 112. Therefore, the electrode surface of the through hole 32 is hydrophilic. The circuit board 1 having such a configuration is manufactured by the manufacturing method described in detail in the first embodiment.

  When the pixel circuit has a storage capacitor in the electrophoretic display, a voltage is applied to the electrophoretic material throughout the frame period, so that a high-contrast image can be easily displayed.

"Electro-optical device"
FIG. 11 is a plan view schematically showing an active matrix substrate manufactured using the circuit substrate manufacturing method described in detail in the first embodiment.

  Pixel circuits are arranged in a matrix on the active matrix substrate 81 to form a pixel region 71. Each pixel circuit is provided with an organic TFT 72 and a pixel electrode 13, and display information from the signal line 73 to the pixel electrode 13 is controlled by a switching operation of the organic TFT 72. Specifically, the gate electrode 12 of the organic TFT 72 is connected to the scanning line 74, one of the source / drain electrodes 11 is connected to the signal line 73, and the other of the source / drain electrodes 11 is connected to the pixel electrode 13. The plurality of scanning lines 74 are connected to the scanning line electrode pads 111 and connected to an external control circuit made of a silicon chip. Similarly, a plurality of signal lines 73 are also collected on the signal line electrode pads 111 and connected to an external control circuit made of a silicon chip.

  As shown in FIG. 3J, the source / drain electrodes 11, the signal lines 73, and the electrode pads 111 are formed of the first conductor, the gate insulating film 21 becomes the first insulating film, and the gate electrodes 12 and the scanning lines 74 are formed. Is formed of the second conductor, the interlayer insulating film 22 is the second insulating film, and the pixel electrode 13 is formed of the third conductor. The manufacturing method of the circuit board 1 described in detail in the first embodiment is applied to manufacture the active matrix substrate 81 having such a configuration.

  FIG. 12 is a cross-sectional view schematically showing an electro-optical device using the above-described active matrix substrate.

  The electro-optical device 80 includes an active matrix substrate 81 and a front substrate 82, and an electro-optical material is sandwiched between the substrates. The electro-optic material is an electrophoretic material 83, and therefore the electro-optic device 80 is an electrophoretic display. A common electrode 86 is formed on the surface of the front substrate 82. The electro-optic material is uniformly disposed on almost the entire surface of both substrates. The common electrode 86 is also formed on almost the entire surface of the front substrate 82. A flexible printed circuit (FPC 84) is connected to the electrode pad 111. A display signal from an external control circuit is supplied to each pixel electrode 13 via the FPC 84 and the organic TFT 72 of each pixel. A protective sheet 85 is attached to the outside of the active matrix substrate 81 and the front substrate 82 to enhance the mechanical durability and chemical stability of the electro-optical device 80.

  Since such an electro-optical device 80 includes the above-described active matrix substrate 81, the display quality is high. Furthermore, since the active matrix substrate 81 is manufactured by the above-described manufacturing method of the circuit board 1, the productivity is very high, and both resources and energy are utilized with high efficiency.

"Electronics"
FIG. 13 is a perspective view schematically showing an electronic apparatus using the above-described electro-optical device, where (a) is a front perspective view and (b) is a rear perspective view. Here, the electronic device is an electronic book 90.

  As illustrated in FIG. 13A, the electronic book 90 includes an electro-optical device 80 and a housing 91. The electro-optical device 80 has a flat rectangular shape. The casing 91 is disposed on the outer edge portion of the electro-optical device 80 and holds the electro-optical device 80. That is, the housing 91 is a holding unit for the display device. The holding part is gripped by the user's hand during use.

  The electro-optical device 80 has a vertically long rectangle, and the casing 91 has a thin flat plate shape. As shown in FIG. 13A, a housing upper part 92 (an upper part of the housing 91) is provided on the front surface serving as the display surface, and on the back surface opposite to the display surface as shown in FIG. Is provided with a casing lower portion 93 (a lower part of the casing 91). The casing upper part 92 and the casing lower part 93 are both thin flat plates, and are overlapped to form a casing 91. As can be seen by comparing FIG. 13A and FIG. 13B, the width (width WF) of the housing 91 on the front side is narrower than the width (width WB) of the housing 91 on the back side. ing.

  Various circuits (control circuit) for controlling the electro-optical device 80, a power source, and the like are housed in the lower portion 93 of the housing, and as a result, the housing 91 is a major part of more than half of the weight of the electronic book 90. Occupies a proportion. For these reasons, the center of gravity of the electronic book 90 is located in the housing lower part 93.

  Various types of information are displayed on the display unit of the electro-optical device 80. An operation switch 94 is provided in the center of the casing 91, and information displayed on the display unit is updated through the switch operation.

  The electro-optical device 80 is light and flexible. For this reason, it is relatively strong against external impact, and it is not necessary to cover and protect the entire electro-optical device 80 with the casing 91. Thus, the housing 91 can be provided on the outer edge portion of the electro-optical device 80. Since the housing 91 does not cover the entire display device and there is no need to dispose a metal reinforcing member or the like, the entire electronic book 90 is made thin and light.

  DESCRIPTION OF SYMBOLS 1 ... Circuit board, 10 ... Board | substrate, 11 ... Source-drain electrode (1st conductor), 21 ... Gate insulating film (1st insulating film), 22 ... Interlayer insulating film (2nd insulating film), 32 ... Through-hole, 40 ... Metal film, 43 ... Conductive ink, 61 ... Solution, 111 ... Electrode pad (first conductor)

Claims (19)

A first conductor forming step of forming a first conductor on the substrate;
A first insulating film forming step of forming a first insulating film so as to cover the first conductor;
A through hole forming step of forming a through hole by dissolving the first insulating film on the first conductor;
Forming a metal film on the first conductor corresponding to the through hole; and
A liquid repellency step for lyophobic the surface of the metal film;
Printing a precursor resin in a region other than the through-hole, and curing the precursor resin after printing to form a second insulating film, and a second insulating film forming step,
In the second insulating film forming step, a via hole having a diameter smaller than the diameter of the through hole and exposing the metal film is formed in the through hole. In the metal film forming step,
2. The method of manufacturing a circuit board according to claim 1, wherein the metal film is formed by dropping a conductive ink containing a plurality of metal particles in a dispersion medium into the through hole. The method for manufacturing a circuit board according to claim 2, wherein the metal particles have a particle size of 10 to 40 nm. In the metal film forming step,
4. The circuit board manufacturing method according to claim 1, wherein the metal film is formed on a surface of the first conductor exposed in the through hole. 5. In the metal film forming step,
The metal film is formed on the surface of the first conductor corresponding to the through-hole through the second insulating film having a thickness of 20 μm or less covering the surface. The manufacturing method of the circuit board as described in any one of Claims.   4. The method for manufacturing a circuit board according to claim 2, wherein the metal particles are made of any one of gold, silver, copper, nickel, platinum, and palladium. In the second insulating film forming step,
The precursor resin is printed in a region other than the through hole, and the second insulating film is formed by curing the precursor resin after printing. A method of manufacturing a circuit board. The circuit board according to claim 1, wherein the first insulating film is soluble in any of an ether solvent, a ketone solvent, an ester solvent, and a fluorine solvent. Manufacturing method. The method for manufacturing a circuit board according to claim 1, wherein the first insulating film is hardly soluble in an alcohol-based solvent. The method for manufacturing a circuit board according to claim 1, wherein the first insulating film is hardly soluble in the precursor resin. The through-hole forming step includes a solvent dropping step of dropping a solvent for dissolving the first insulating film onto the first insulating film, and forming the through-hole having a peripheral edge formed by a raised portion of the first insulating film The method for manufacturing a circuit board according to any one of claims 1 to 10, wherein: The method for manufacturing a circuit board according to claim 1, wherein in the liquid repellent step, the surface of the first conductor is brought into contact with a solution containing a thiol compound or a disulfide compound. The method for producing a circuit board according to claim 12, wherein the thiol compound includes a fluorinated alkyl chain. The method for manufacturing a circuit board according to claim 12, wherein the disulfide compound includes a fluorinated alkyl chain. The method of manufacturing a circuit board according to claim 1, wherein the precursor resin contains a monomer having a hydroxyl group. The method of manufacturing a circuit board according to claim 1, wherein the precursor resin is soluble in an alcohol solvent. The method of manufacturing a circuit board according to claim 1, wherein the precursor resin is a photocurable resin.   The method for manufacturing a circuit board according to claim 1, wherein the precursor resin is a thermosetting resin. The circuit board includes a transistor including a gate insulating film,
The method for manufacturing a circuit board according to claim 1, wherein the first insulating film functions as the gate insulating film.

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