JP2005220395A - Film forming method, film, electronic component and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film-forming method for easily and inexpensively forming a film having a predetermined pattern; the film formed by the film-forming method; an electronic component provided with the film; and electronic equipment provided with the film. <P>SOLUTION: The film-forming method comprises the steps of: making liquid repellency in a region 9 to be film-formed of a substrate 5 having the liquid repellency on the surface at least of a side to be film-formed, lower than that in a region 9' in which the film is not to be formed, by performing predetermined treatment on the region 9; forming a catalyst layer 6 containing a catalyst, selectively in the region 9 of the substrate 5, by using a difference in the water repellency between the region 9 and the region 9'; and forming the film on the catalyst layer 6, by using a catalytic function of the catalyst layer 6. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a film forming method, a film, an electronic component, and an electronic apparatus.

Conventionally, an etching method using a mask containing a resin as a main component has been widely used to form a film having a predetermined pattern (see, for example, Patent Document 1).
Specifically, I: A layer composed of a film-forming material is formed on a substrate. II: A resist material is applied on the layer. III: The resist material is exposed and developed to obtain a resist layer having openings corresponding to unnecessary portions of the layer. IV: The film forming layer exposed in the opening is removed by an etching method using the resist layer as a mask. V: The mask is removed. Thereby, a film formed in a predetermined pattern is obtained.
However, such a method requires time and labor to form the resist layer. As a result, problems such as a long time required for film formation and high costs arise.

JP-A-5-338184

  An object of the present invention is to provide a film forming method capable of easily and inexpensively forming a film having a predetermined pattern, a film formed by such a film forming method, an electronic component and an electronic apparatus including the film.

Such an object is achieved by the present invention described below.
The film forming method of the present invention is a film forming method for forming a film of a predetermined pattern on a substrate,
A film forming region for forming the film of the substrate having liquid repellency at least on a surface on which the film is formed is subjected to a predetermined treatment, and the liquid repellency of the film forming region is set so that the film is not formed. A first step of lowering the liquid repellency of the film forming region;
A liquid containing catalyst is supplied to the surface of the base material, and a catalyst layer is selectively formed in the film formation region by utilizing the difference in liquid repellency between the film formation region and the non-film formation region. A second step of:
And a third step of forming the film on the catalyst layer using the catalytic function of the catalyst layer.
Thereby, a film can be formed easily and inexpensively with high film forming accuracy.

In the film forming method of the present invention, it is preferable that the predetermined treatment in the first step is performed by irradiating the film forming region of the substrate with active energy rays.
Thereby, the liquid repellency of the film formation region is lower than the liquid repellency of the non-film formation region.
In the film forming method of the present invention, the active energy ray is preferably at least one of ultraviolet rays, electron beams and ion beams.
As a result, the liquid repellency of the film forming region can be more easily and reliably lost or reduced to be lower than the liquid repellency of the non-film forming region.

In the film forming method of the present invention, in the first step, the contact angle of pure water with respect to the non-film formation region is A [°], and the contact angle of pure water with respect to the film formation region is B [°]. In this case, it is preferable to satisfy the relationship A−B ≧ 15.
By satisfying the above relationship between the film formation region and the non-film formation region, in the second step, the catalyst in the catalyst solution is adsorbed on the film formation region of the base material with higher selectivity and more accurately. In addition, a catalyst layer corresponding to the shape of the film formation region can be formed.

In the film-forming method of this invention, it is preferable that content of the said catalyst in the said catalyst layer is 50 wt% or more.
Thereby, the catalyst layer can exhibit a sufficient catalytic function, and a film can be more reliably formed in the third step.
In the film forming method of the present invention, the catalyst is preferably mainly composed of at least one of Pd, Ni, Cu, Co, Pt and alloys containing these.
All of these have a high catalytic function, and can function as a catalyst in the third step to reliably form a film.

In the film forming method of the present invention, the film is preferably a metal film mainly composed of a metal material.
The metal film can be efficiently formed with high film forming accuracy by utilizing the catalytic function of the catalyst layer.
In the film forming method of the present invention, in the third step, the metal film is preferably formed by an electroless plating method or a CVD method.
By using the electroless plating method, a metal film (the film of the present invention) can be formed easily and inexpensively with high film forming accuracy without requiring a large-scale apparatus such as a vacuum apparatus. In addition, a dense (high density) metal film can be formed by using the CVD method.

In the film forming method of the present invention, the substrate is obtained by irradiating fluorine plasma to the surface of the base material mainly composed of a resin material at least near the surface on which the film is formed. It is preferable that
According to the method of irradiating with fluorine plasma, the upper surface of the base material can be uniformly fluorinated over almost the entire surface, and a substrate having liquid repellency uniformly (without unevenness) on the upper surface can be obtained.

The film of the present invention is formed by the film forming method of the present invention.
Thereby, a film can be obtained more easily and cheaply with high film forming accuracy.
The electronic component of the present invention includes the film of the present invention.
Thereby, a highly reliable electronic component is obtained.
The electronic device of the present invention includes the electronic component of the present invention.
As a result, a highly reliable electronic device can be obtained.

Hereinafter, a film forming method, a film, an electronic component, and an electronic apparatus of the present invention will be described in detail with reference to the accompanying drawings.
<Film formation method>
First, a preferred embodiment of the film forming method of the present invention will be described.
1 and 2 are views (longitudinal sectional views) for explaining the film forming method of the present invention. In the following description, the upper side in FIGS. 1 and 2 is referred to as “upper” and the lower side is referred to as “lower”.
The film forming method of the present invention is a method of forming a film 8 having a predetermined pattern on a substrate 5, and has liquid repellency on at least the surface on which the film 8 is formed, as shown in FIGS. The film forming region 9 where the film 8 of the substrate 5 is formed is subjected to a predetermined treatment so that the liquid repellency of the film forming region 9 is lower than the liquid repellency of the non-film forming region 9 ′ where the film 8 is not formed. A catalyst layer 6 that selectively contains a catalyst is formed on the film forming region 9 of the substrate 5 by utilizing the liquid adjustment step and the difference in liquid repellency between the film forming region 9 and the non-film forming region 9 ′. A catalyst layer forming step for forming, and a film forming step for forming the film 8 on the catalyst layer 6 by utilizing the catalytic function of the catalyst layer 6. Hereinafter, each process will be described sequentially.

[1] Liquid Repellency Adjustment Step First, a substrate 5 having liquid repellency is prepared on at least the surface (upper surface) on which the film 8 is formed (see FIG. 1A).
The structure of the base material 5 is not particularly limited as long as it has liquid repellency on at least its upper surface. For example, X: at least the upper surface of the base material mainly composed of a resin material in the vicinity of the upper surface , Obtained by irradiating fluorine plasma, Y: obtained by forming a film having liquid repellency on the upper surface of a base material composed of various glass materials and various semiconductor materials such as Si And the like.

In the case of the configuration X, the base material may be a layered structure in which a resin layer is formed on the upper surface of a base portion made of various glass materials or various semiconductor materials such as Si. The whole may be made of a resin material.
Among these, as the base material 5, a material obtained as in the configuration X is particularly preferable. Specifically, an electric field is applied while supplying a gaseous fluorine compound in a state where the base material is set (installed) in a chamber. As a result, the gaseous fluorine compound is turned into plasma and fluorine plasma is generated. This fluorine plasma is irradiated onto the upper surface of the base material, and adsorbs, bonds, etc. to the molecular structure of the resin material that forms the vicinity of the upper surface of the base material. As a result, the vicinity of the upper surface of the base material is fluorinated, and the base material 5 having liquid repellency at least on the upper surface is obtained.

According to this method, the upper surface of the base material can be uniformly fluorinated over almost the entire surface, and the base material 5 having liquid repellency uniformly (without unevenness) can be obtained on the upper surface.
The resin material constituting the surface of the base material is not particularly limited. For example, polyethylene, polyethylene terephthalate (PET), polyethylene naphthalate (PEN) polyimide, polycarbonate, polyethersulfone (PES), aromatic polyester (liquid crystal Polymer), aromatic polyamides, and the like, and one or more of them can be used in combination.

Further, the gaseous fluorine compound is not particularly limited. For example, tetrafluoromethane (CF ₄ ), tetrafluoroethylene (C ₂ F ₄ ), propylene hexafluoride (C ₃ F ₆ ), eight fluorine Butylene chloride (C ₄ F ₈ ) and the like can be mentioned, and one or more of these can be used in combination.
The flow rate when supplying the gaseous fluorine compound is preferably about 10 to 500 sccm, and more preferably about 50 to 300 sccm.

The discharge power is preferably about 100 to 1500 W, and more preferably about 300 to 500 W.
The temperature of the substrate 5 is preferably about 10 to 200 ° C, and more preferably about 50 to 100 ° C.
By setting the flow rate of the gaseous fluorine compound, the discharge power, and the temperature of the base material 5 within the above ranges, at least the vicinity of the upper surface of the base material 5 is configured with a resin material having liquid repellency more easily and reliably. Can be.

Note that the gaseous fluorine compound may be supplied together with an inert gas such as helium gas, argon gas, or neon gas. As a result, fluorine plasma can be generated under a relatively high pressure (for example, under atmospheric pressure), and the fluorine plasma treatment can be performed more easily.
Next, the film forming region 9 where the film 8 of the base material 5 is formed is subjected to a predetermined treatment, and the liquid repellency of the film forming region 9 is set to be higher than the liquid repellency of the non-film forming region 9 ′ where the film 8 is not formed. make low.

The predetermined treatment may be any treatment as long as the liquid repellency of the film formation region 9 is lower than the liquid repellency of the non-film formation region 9 ′, and is not particularly limited. It is preferable to use a method of irradiating the film forming region 9 of the material 5 with the active energy ray 2.
Specifically, using the photomask 7 corresponding to the shape of the non-film formation region 9 ′, the film formation region 9 is irradiated with the active energy ray 2 (see FIG. 1B), and the film formation region 9 is reduced (see FIG. 1C).

By using this treatment method, for example, fluorine atoms existing near the upper surface of the film forming region 9 of the base material 5 are removed, or near the upper surface of the base material 5 of the film forming region 9 (part containing fluorine atoms). As a result, the original base material surface is exposed. Thereby, the liquid repellency of the film forming region 9 is lower than the liquid repellency of the non-film forming region 9 ′.
Examples of the active energy rays 2 include electromagnetic waves such as infrared rays, visible rays, ultraviolet rays, and X-rays, electron rays, ion beams, neutron rays, and particle rays such as α rays. It is preferable to use at least one of electron beam and ion beam. As a result, the liquid repellency of the film forming region 9 can be more easily and reliably lost or reduced to be lower than the liquid repellency of the non-film forming region 9 ′.

I: When using ultraviolet rays as the active energy ray 2 The wavelength of the ultraviolet rays to be irradiated is preferably about 100 to 365 nm, and more preferably about 150 to 200 nm.
Further, the irradiation intensity of the ultraviolet rays is preferably about 0.1 to 100 mW, and more preferably about 1 to 50 mW.

Furthermore, the irradiation time of the ultraviolet rays is preferably about 0.1 to 30 minutes, and more preferably about 1 to 15 minutes.
Note that the irradiation atmosphere at this time may be any atmosphere such as an oxidizing atmosphere, a reducing atmosphere, an inert atmosphere, a vacuum or a reduced pressure state, but is preferably an inert atmosphere.
Next, the temperature of the irradiation atmosphere is preferably about 0 to 100 ° C, more preferably about 20 to 50 ° C.
By setting the wavelength, irradiation intensity, irradiation time, irradiation atmosphere, and irradiation atmosphere temperature of the ultraviolet ray within the above ranges, the liquid repellency of the film formation region 9 is more than the liquid repellency of the non-film formation region 9 ′. It can be made more reliable.

II: When using an electron beam as the active energy ray 2 The acceleration voltage of the irradiated electron beam is preferably about 50 to 300 kV, more preferably about 80 to 150 kV.
The dose of the electron beam is preferably about 10 to 1500 kGy, and more preferably about 50 to 1000 kGy.

Note that the irradiation atmosphere at this time may be any atmosphere such as an oxidizing atmosphere, a reducing atmosphere, an inert atmosphere, a vacuum or a reduced pressure state, but is preferably a vacuum or a reduced pressure state.
Next, the temperature of the irradiation atmosphere is preferably about 0 to 100 ° C, more preferably about 20 to 50 ° C.
By making the acceleration voltage, dose, irradiation atmosphere, and irradiation atmosphere temperature of the electron beam within the above ranges, the liquid repellency of the film formation region 9 is more reliable than the liquid repellency of the non-film formation region 9 ′. Can be low.

III: When an ion beam is used as the active energy ray 2 The acceleration voltage of the ion beam to be irradiated is preferably about 1 to 150 kV, and more preferably about 10 to 50 kV.
The beam current of the ion beam is preferably about 0.01 to 50 nA, more preferably about 0.01 to 20 nA.

Further, the irradiation time of the ion beam is preferably about 0.001 to 50 seconds, and more preferably about 0.01 to 30 seconds.
Note that the irradiation atmosphere at this time may be any atmosphere such as an oxidizing atmosphere, a reducing atmosphere, an inert atmosphere, a vacuum or a reduced pressure state, but is preferably a vacuum or a reduced pressure state.

Next, the temperature of the irradiation atmosphere is preferably 0 to 100 ° C, and more preferably 20 to 50 ° C.
By setting the acceleration voltage, beam current, irradiation time, irradiation atmosphere, and irradiation atmosphere temperature of the ion beam within the above ranges, the liquid repellency of the film forming region 9 is made higher than the liquid repellency of the non-film forming region 9 ′. Can be made more reliable.

The difference in the degree of liquid repellency between the film-forming region 9 and the non-film-forming region 9 ′ can be expressed by various indices, but can be preferably expressed by using a contact angle. Specifically, when the contact angle of pure water with respect to the non-film formation region 9 ′ is A [°] and the contact angle of pure water with respect to the film formation region 9 is B [°], A−B ≧ 15 [° It is preferable to satisfy the following relationship: more preferable to satisfy the relationship of AB ≧ 30 [°], and particularly preferable to satisfy the relationship of AB ≧ 50 [°]. When the film forming region 9 and the non-film forming region 9 ′ satisfy the above relationship, the catalyst in the catalyst solution 10 has a higher selectivity in the film forming region of the substrate 5 in the catalyst layer forming step described later. The catalyst layer 6 adsorbed on the substrate 9 and more accurately corresponding to the shape of the film formation region 9 is formed.
In the present embodiment, the film forming region 9 of the substrate 5 is irradiated with the active energy ray 2 to make the liquid repellency of the film forming region 9 lower than the liquid repellency of the non-film forming region 9 ′. Although explained, it is not limited to this, For example, the film | membrane (lyophilic film) comprised with a material lower than the liquid repellency of non-film | membrane formation area 9 'is formed in the upper surface of the base material 5 of the film formation area 9. You may do it.

[2] Catalyst Layer Forming Step Next, a liquid containing a catalyst (catalyst liquid) is supplied to the upper surface of the substrate 5. Then, the catalyst layer 6 containing the catalyst is selectively formed in the film forming region 9 by utilizing the difference in liquid repellency between the film forming region 9 and the non-film forming region 9 ′.
Examples of methods for supplying the catalyst solution to the substrate 5 include a method of immersing the substrate 5 in the catalyst solution (immersion method), a method of showering (spraying) the catalyst solution on the substrate 5, and a catalyst applied to the substrate 5. Examples of the method include a method of applying a liquid (coating method) and the like. In particular, it is preferable to use a dipping method. According to the dipping method, a large amount of the substrate 5 can be easily processed.
As described above, there are various methods for supplying the liquid to the substrate 5. In the following steps, the case where the dipping method is used as a method for bringing the liquid into contact will be described as a representative.

[2-I] First, a pretreatment for forming the catalyst layer 6 on the film formation region 9 of the substrate 5 is performed on the substrate 5.
This pretreatment is performed, for example, by immersing the base material 5 in a solution containing a cationic surfactant (surfactant solution). And when the base material 5 is taken out from the said solution, since the film formation area 9 has low liquid repellency (high lyophilicity), it will be in the state to which this solution adhered. On the other hand, since the non-film formation region 9 ′ has high liquid repellency, this solution is prevented from adhering to the non-film formation region 9 ′. Further, the solution in the non-film forming region 9 ′ gathers (aggregates) in the film forming region 9 so as to be attracted by the solution attached to the film forming region 9. That is, the solution collects in the film formation region 9 due to the difference in liquid repellency between the film formation region 9 and the non-film formation region 9 ′.

Thereafter, the solvent of the solution aggregated in the film forming region 9 is removed, so that the cationic surfactant adheres to the surface of the film forming region 9 of the substrate 5.
Due to the adhesion of the cationic surfactant, the surface of the film forming region 9 of the substrate 5 is positively charged. As a result, the catalyst used in the electroless plating can be easily adsorbed, and as a result, the adhesion between the film 8 formed in the film forming region 9 and the substrate 5 is improved.

Examples of the cationic surfactant include alkyl ammonium chloride, benzalkonium chloride, benzethonium chloride, stearic acid, and the like, and one or more of these can be used in combination.
The temperature of the surfactant solution during the treatment is preferably about 0 to 70 ° C, more preferably about 10 to 40 ° C.

Moreover, it is preferable that the processing time of the base material 5 in the surfactant solution is about 10 to 90 seconds, and more preferably about 30 to 60 seconds.
In this way, the pretreated base material 5 is washed using, for example, pure water (ultra pure water), ion exchange water, distilled water, RO water or the like.
In the present embodiment, as a pretreatment for forming the catalyst layer 6 on the film forming region 9 of the base material 5, the cationic surfactant is used. For example, aminosilane, vinylsilane, Silane coupling agents such as epoxy silane, isopropyl triisostearoyl titanate, titanium coupling agents such as isopropyl tri (N-aminoethyl-aminoethyl) titanate, zirconium acetylacetonate, acetylacetone zirconium butyrate and the like The pretreatment may be performed using a coupling agent such as an aluminum coupling agent such as a zirconium-based coupling agent, acetoalkoxyaluminum diisopropylate, and aluminum trisacetylacetonate.
In addition, this process can also be abbreviate | omitted as needed.

[2-II] Next, a catalyst layer 6 containing a catalyst is formed on the film formation region 9 of the substrate 5 by utilizing the difference in liquid repellency between the film formation region 9 and the non-film formation region 9 ′. Form.
As this catalyst, various materials such as Pd, Ni, Cu, Co, Pt, Au, Fe, V, Mo and alloys containing these can be used, but Pd, Ni, Cu, Co, Pt and these can be used. It is preferable to use one or two or more of the alloys included. Each of these has a high catalytic function, and functions as a catalyst in the film forming step described later, and can reliably form the film 8.

Further, the content of the catalyst in the catalyst layer 6 is preferably 50 wt% or more, and more preferably 70 wt% or more. Thereby, the catalyst layer 6 can exhibit a sufficient catalytic function. As a result, the film 8 can be more reliably formed in the film forming process described later.
Specifically, when Pd is used as the catalyst, for example, in a solution of an ionic Pd catalyst such as palladium chloride or a colloidal liquid of a Pd alloy such as Sn—Pd (hereinafter referred to as “catalyst-containing solution”). )). When the base material 5 is taken out from the catalyst-containing solution, the catalyst-containing solution collects (aggregates) in the film forming region 9 as in the case of the surfactant solution in the step [2-I] described above. That is, the catalyst-containing solution collects in the film forming region 9 due to the difference in liquid repellency between the film forming region 9 and the non-film forming region 9 ′.

Thereafter, the solvent of the catalyst-containing solution aggregated in the film forming region 9 is removed.
Furthermore, Pd can be exposed on the surface of the film forming region 9 of the substrate 5 by removing elements not involved in the catalyst.
For example, when using a solution of an ionic Pd catalyst such as palladium chloride, the substrate 5 is immersed in the catalyst solution 10 as shown in FIG. Thereafter, by immersing in an acid solution, Sn coordinated to Pd is dissolved and removed, Pd is exposed on the film forming region 9 of the substrate 5, and the catalyst layer 6 is formed (FIG. 1 ( e)).

As the acid solution, for example, a solution containing an acid such as HBF ₄ or HCl and a reducing agent such as glucose, or a solution obtained by further adding sulfuric acid to the solution can be used.
The temperature of the catalyst solution 10 in which the substrate 5 is immersed is preferably about 0 to 70 ° C, and more preferably about 10 to 40 ° C.
Next, the treatment time of the substrate 5 in the catalyst solution 10 is preferably about 10 seconds to 5 minutes, and more preferably about 20 seconds to 3 minutes.

On the other hand, the temperature of the acid solution is preferably about 0 to 70 ° C, and more preferably about 10 to 55 ° C.
In addition, the treatment time of the substrate 5 in the acid solution is preferably about 10 seconds to 5 minutes, and more preferably about 30 seconds to 3 minutes.
In this way, the catalyst layer 6 provided on the film forming region 9 of the substrate 5 is washed using, for example, pure water (ultra pure water), ion exchange water, distilled water, RO water, or the like.

[3] Film Forming Step Next, the film 8 is formed on the catalyst layer 6 using the catalytic function of the catalyst layer 6.
As the film 8, for example, a metal film mainly composed of a metal material, an oxide film mainly composed of an oxide, a carbon film mainly composed of a fibrous carbon substance, and the like can be formed. In particular, it is preferable to form a metal film. The metal film can be formed (film formation) particularly efficiently by utilizing the catalytic function of the catalyst layer 6.

As this metal film (film 8), for example, Ni, Pd, Pt, Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, Yb, Ag, Cu, Co, Al, Cs, At least one of metals such as Rb and alloys containing these can be used as the main material.
A method for forming the film 8 is not particularly limited, but it is preferable to use an electroless plating method or a CVD method. By using the electroless plating method, a metal film can be formed easily and inexpensively with high film forming accuracy without requiring a large-scale apparatus such as a vacuum apparatus. In addition, a dense (high density) metal film can be formed by using the CVD method.
In the following, first, the film forming process of the film 8 by the electroless plating method will be described, and then the film forming process of the film 8 by the CVD method will be described.

[3a] Film Forming Step by Electroless Plating Method When the electroless plating method is used for forming the metal film, the substrate 5 is immersed in the plating solution 11 (see FIG. 2 (f)). As a result, the metal element is deposited on the catalyst existing in the catalyst layer 6 in the film formation region 9, and a film 8 corresponding to the shape of this region is formed (see FIG. 2G).
As the metal salt, for example, sulfate, nitrate and the like are preferably used.

  As the reducing agent, for example, those containing at least one of hydrazine, ammonium hypophosphite, sodium hypophosphite and the like as a main component are preferable. By using these as the reducing agent, the film forming speed of the film 8 becomes appropriate, and the film thickness can be easily controlled within the optimum film thickness range required for the film 8. Further, the formed film 8 has a uniform film thickness and good surface properties (high film surface morphology).

The content of the metal salt in the plating solution 11 (addition amount of the metal salt to the solvent) is preferably about 1 to 50 g / L, and more preferably about 5 to 25 g / L. If the content of the metal salt is too small, it may take a long time to form the film 8. On the other hand, even if the content of the metal salt is increased beyond the upper limit, no further increase in effect can be expected.
Further, the content of the reducing agent in the plating solution 11 (addition amount of the reducing agent to the solvent) is preferably about 10 to 200 g / L, and preferably about 50 to 150 g / L. When there is too little content of a reducing agent, there exists a possibility that efficient reduction | restoration of a metal ion may become difficult depending on the kind etc. of reducing agent. On the other hand, even if the content of the reducing agent is increased beyond the upper limit, no further increase in effect can be expected.

It is preferable to mix (add) a pH adjusting agent (pH buffering agent) to the plating solution 11. As a result, it is possible to prevent or suppress the pH of the plating solution 11 from being lowered as the electroless plating progresses. As a result, it is possible to effectively reduce the deposition rate and change the composition and properties of the film 8. Can be prevented.
Examples of the pH adjuster include various agents, and those having at least one of ammonia water, trimethylammonium hydride, sodium hydroxide, sodium carbonate and ammonium sulfide as a main component are preferable. Since these things are excellent in a buffering effect, the said effect is exhibited more notably by using these things as a pH adjuster.

The pH of the plating solution 11 during the immersion (plating treatment) in the plating solution 11 is preferably about 5 to 12, and preferably about 6 to 10.
In addition, the temperature of the plating solution 11 during the plating process is preferably about 30 to 90 ° C, more preferably about 40 to 80 ° C.
Furthermore, the treatment time of the substrate 5 in the plating solution 11 is preferably about 10 seconds to 5 minutes, and more preferably about 20 seconds to 3 minutes.

By setting the pH and temperature of the plating solution 11 and the treatment time with the plating solution 11 within the above ranges, the film forming speed becomes particularly appropriate, and the film 8 having a uniform film thickness can be formed with high accuracy. .
It is formed by setting the plating conditions such as the working temperature (the temperature of the plating solution 11), the working time (plating time), the amount of the plating solution 11, the pH of the plating solution 11, the number of times of plating (the number of turns). The thickness of the film 8 can be adjusted.

Further, for example, additives such as a complexing agent and a stabilizing agent may be appropriately added to the plating solution 11.
Examples of complexing agents include carboxylic acids such as ethylenediaminetetraacetic acid and acetic acid, oxycarboxylic acids such as tartaric acid and citric acid, aminocarboxylic acids such as glycine, amines such as triethanolamine, glycerin and sorbitol. And polyhydric alcohols.

Examples of the stabilizer include 2,2′-bipyridyl, cyanide, ferrocyan compound, phenanthroline, thiourea, mercaptobenzothiazole, thioglycolic acid, and the like.
In this way, the base material 5 on which the film 8 is formed in the portion corresponding to the film forming region 9 is washed using, for example, pure water (ultra pure water), ion exchange water, distilled water, RO water, or the like. .

[3b] Film formation step by CVD method When the CVD method is used to form a metal film, the precursor gas (gaseous metal) is set in a state where the base material 5 on which the catalyst layer 6 is formed is set (set) in the chamber. A precursor of the constituent material of the film 12, a carrier gas, and a gas for generating a metal element from the precursor gas 12, if necessary, and apply energy such as heat and laser light, for example. (See FIG. 2 (f ′)). As a result, the catalyst present in the catalyst layer 6 in the film formation region 9 serves as a nucleus, and a chemical reaction proceeds to deposit a metal element, thereby forming a metal film (film 8) (see FIG. 2 (g ′)). ).

Examples of the precursor gas 12 include metal halide compounds and organometallic compounds such as alkylated metals, and one or more of these can be used in combination.
Examples of the carrier gas include inert gases such as He, Ne, Ar, Kr, and Xe, and one or more of these can be used in combination.

The supply flow rate of the gas is preferably about 100 to 700 sccm, and more preferably about 300 to 500 sccm.
The pressure in the chamber is preferably about 0.5 to 5 Torr, and more preferably about 1 to 3 Torr.
The temperature in the chamber is preferably about 50 to 200 ° C, more preferably about 100 to 150 ° C.

The energy may be applied to one or both of the gas supplied into the chamber and the catalyst layer 6.
Through the steps as described above, a metal film (film 8 of the present invention) is obtained.
According to the present invention, it is not necessary to form a mask (resist layer) directly on the substrate, and the film 8 can be formed with high deposition accuracy.
In addition, according to the present invention, since a resist layer is not used, a complicated process for forming a resist layer and a process for removing a resist layer that has become unnecessary can be omitted.
For this reason, according to the present invention, the film 8 can be obtained more easily and inexpensively with high film forming accuracy.

<Electronic parts>
Such a film | membrane 8 is applicable to various electronic components, such as a switching element (thin film transistor), a wiring board, a semiconductor component, a display panel, a light emitting element, for example.
Below, the case where the electronic component of this invention is applied to a thin-film transistor (especially organic thin-film transistor) is demonstrated as a representative.

FIG. 3A is a longitudinal sectional view showing an embodiment of a thin film transistor to which the electronic component of the present invention is applied. In the following description, the upper side in FIG. 3 will be described as “upper” and the lower side as “lower”.
A thin film transistor 100 illustrated in FIG. 3A is provided on a substrate 20 (base material 5), and includes a source electrode 30 and a drain electrode 40, an organic semiconductor layer (organic layer) 50, a gate insulating layer 60, The gate electrode 70 is laminated in this order from the substrate 20 side.

  Specifically, in the thin film transistor 100, the source electrode 30 and the drain electrode 40 are provided separately on the substrate 20, and the organic semiconductor layer 50 is provided so as to cover the electrodes 30 and 40. Further, a gate insulating layer 60 is provided on the organic semiconductor layer 50, and a gate electrode 70 is further provided thereon so as to overlap at least a region between the source electrode 30 and the drain electrode 40.

In the thin film transistor 100, a region between the source electrode 30 and the drain electrode 40 in the organic semiconductor layer 50 is a channel region 510 in which carriers move. Hereinafter, in this channel region 510, the length in the direction of carrier movement, that is, the distance between the source electrode 30 and the drain electrode 40 is the channel length L, and the length perpendicular to the channel length L direction is the channel width W. say.
Such a thin film transistor 100 is a thin film transistor having a structure in which the source electrode 30 and the drain electrode 40 are provided closer to the substrate 20 than the gate electrode 70 with the gate insulating layer 60 interposed therebetween, that is, a thin film transistor having a top gate structure.

Hereinafter, each part which comprises the thin-film transistor 100 is demonstrated sequentially.
The substrate 20 supports each layer (each part) constituting the thin film transistor 100. Examples of the substrate 20 include a plastic substrate (resin substrate) made of, for example, a glass substrate, polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), aromatic polyester (liquid crystal polymer), and the like. A quartz substrate, a silicon substrate, a gallium arsenide substrate, or the like can be used. When the thin film transistor 100 is provided with flexibility, a resin substrate is selected as the substrate 20.

An underlayer may be provided on the substrate 20. The underlayer is provided, for example, for the purpose of preventing diffusion of ions from the surface of the substrate 20 or for the purpose of improving the adhesion (bondability) between the source electrode 30 and the drain electrode 40 and the substrate 20.
The constituent material of the underlayer is not particularly limited, but when a glass substrate is used as the substrate 20, silicon oxide (SiO ₂ ), silicon nitride (SiN), or the like is preferably used.

On the substrate 20, a source electrode 30 and a drain electrode 40 are juxtaposed at a predetermined distance along the channel length L direction.
The film 8 of the present invention can be applied to the source electrode 30, the drain electrode 40, and the gate electrode 70 described later.
The thickness (average) of the source electrode 30 and the drain electrode 40 is not particularly limited, but is preferably about 30 to 300 nm, and more preferably about 50 to 150 nm. According to the film forming method of the present invention, an electrode having such a thin film thickness can be formed with high dimensional accuracy.

  The distance (separation distance) between the source electrode 30 and the drain electrode 40, that is, the channel length L is preferably about 2 to 30 μm, and more preferably about 5 to 20 μm. If the channel length L is smaller than the lower limit value, an error occurs in the channel length between the obtained thin film transistors 100, and the characteristics (transistor characteristics) may vary. On the other hand, when the channel length L is larger than the upper limit value, the absolute value of the threshold voltage is increased, the drain current value is decreased, and the characteristics of the thin film transistor 100 may be insufficient.

  The channel width W is preferably about 0.1 to 5 mm, and more preferably about 0.5 to 3 mm. When the channel width W is made smaller than the lower limit value, the drain current value becomes small, and the characteristics of the thin film transistor 100 may be insufficient. On the other hand, when the channel width W is larger than the upper limit value, the thin film transistor 100 is increased in size, and there is a possibility that parasitic capacitance increases and leakage current to the gate electrode 70 via the gate insulating layer 60 increases.

An organic semiconductor layer 50 is provided on the substrate 20 so as to cover the source electrode 30 and the drain electrode 40.
The organic semiconductor layer 50 is composed mainly of an organic semiconductor material (an organic material that exhibits semiconducting electrical conduction).
The organic semiconductor layer 50 is preferably oriented so as to be substantially parallel to the channel length L direction at least in the channel region 510. As a result, the carrier mobility in the channel region 51 is high, and as a result, the thin film transistor 100 has a higher operating speed.

  Examples of the organic semiconductor material include naphthalene, anthracene, tetracene, pentacene, hexacene, phthalocyanine, perylene, hydrazone, triphenylmethane, diphenylmethane, stilbene, arylvinyl, pyrazoline, triphenylamine, triarylamine, oligothiophene, phthalocyanine or Low molecular organic semiconductor materials such as these derivatives, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polythiophene, polyhexylthiophene, poly (p-phenylenevinylene), polytinylenevinylene, polyarylamine, Pyreneformaldehyde resin, ethylcarbazole formaldehyde resin, fluorene-bithiophene copolymer, fluorene-arylamine copolymer or Examples thereof include polymeric organic semiconductor materials (conjugated polymer materials) such as derivatives, and one or more of these can be used in combination. It is preferable to use a material mainly composed of (conjugated polymer material). The conjugated polymer material has a particularly high carrier mobility due to its unique electron cloud spread.

  A polymer organic semiconductor material can be formed by a simple method and can be oriented relatively easily. Of these, fluorene-bithiophene copolymers, polyarylamines or these are used as high molecular organic semiconductor materials (conjugated polymer materials) because they are difficult to oxidize in air and are stable. It is particularly preferable to use a derivative containing at least one of the derivatives as a main component.

In addition, the organic semiconductor layer 50 composed mainly of a polymer organic semiconductor material can be reduced in thickness and weight, and has excellent flexibility. Therefore, the thin film transistor can be used as a switching element of a flexible display. Suitable for applications.
The thickness (average) of the organic semiconductor layer 50 is preferably about 0.1 to 1000 nm, more preferably about 1 to 500 nm, and further preferably about 10 to 100 nm.

Note that the organic semiconductor layer 50 is not limited to a structure provided so as to cover the source electrode 30 and the drain electrode 40, and is provided at least in a region (channel region 510) between the source electrode 30 and the drain electrode 40. It only has to be.
A gate insulating layer 60 is provided on the organic semiconductor layer 50.
The gate insulating layer 60 insulates the gate electrode 70 from the source electrode 30 and the drain electrode 40.

The gate insulating layer 60 is preferably mainly composed of an organic material (particularly an organic polymer material). The gate insulating layer 60 containing an organic polymer material as a main material can be easily formed and can improve the adhesion to the organic semiconductor layer 50.
Examples of such organic polymer materials include polystyrene, polyimide, polyamideimide, polyvinylphenylene, polycarbonate (PC), acrylic resin such as polymethyl methacrylate (PMMA), and polytetrafluoroethylene (PTFE). Fluorine resin, phenolic resin such as polyvinylphenol or novolac resin, and olefinic resins such as polyethylene, polypropylene, polyisobutylene, polybutene, etc. are used, and one or more of these may be used in combination. it can.

  The thickness (average) of the gate insulating layer 60 is not particularly limited, but is preferably about 10 to 5000 nm, and more preferably about 100 to 1000 nm. By setting the thickness of the gate insulating layer 60 within the above range, the thin film transistor 100 is increased in size while the source electrode 30 and the drain electrode 40 are reliably insulated from the gate electrode 70 (in particular, the thickness is increased). ) Can be prevented.

Note that the gate insulating layer 60 is not limited to a single-layer structure, and may have a multilayer structure.
In addition, as a constituent material of the gate insulating layer 60, for example, an inorganic insulating material such as SiO ₂ can be used. By applying a solution such as polysilicate, polysiloxane, or polysilazane and heating the coating film in the presence of oxygen or water vapor, SiO ₂ can be obtained from the solution material. In addition, after applying a metal alkoxide solution, an inorganic insulating material can be obtained (known as a sol-gel method) by heating it in an oxygen atmosphere.

A gate electrode 70 is provided on the gate insulating layer 60.
The thickness (average) of the gate electrode 70 is not particularly limited, but is preferably about 0.1 to 5000 nm, more preferably about 1 to 5000 nm, and still more preferably about 10 to 5000 nm.
In the thin film transistor 100 as described above, the amount of current flowing between the source electrode 30 and the drain electrode 40 is controlled by changing the voltage applied to the gate electrode 70.

  That is, in the OFF state in which no voltage is applied to the gate electrode 70, even if a voltage is applied between the source electrode 30 and the drain electrode 40, almost no carriers are present in the organic semiconductor layer 50, so that a very small current Only flows. On the other hand, in the ON state in which a voltage is applied to the gate electrode 70, charges are induced in the portion of the organic semiconductor layer 50 facing the gate insulating layer 60, and a carrier flow path is formed in the channel region 510. When a voltage is applied between the source electrode 30 and the drain electrode 40 in this state, a current flows through the channel region 510.

<Electronic equipment>
The electronic component of the present invention can be used for various electronic devices.
FIG. 4 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which the electronic apparatus of the present invention is applied.
In this figure, a personal computer 1100 includes a main body 1104 provided with a keyboard 1102 and a display unit 1106 provided with a display. The display unit 1106 is rotatable with respect to the main body 1104 via a hinge structure. It is supported by.

The electronic component of the present invention is incorporated as, for example, a switching element for switching each pixel of the display portion, a flexible wiring board for connecting the main body portion 1104 and the display unit 1106, or the like.
FIG. 5 is a perspective view showing a configuration of a mobile phone (including PHS) to which the electronic apparatus of the present invention is applied.

In this figure, a cellular phone 1200 includes a plurality of operation buttons 1202, an earpiece 1204 and a mouthpiece 1206, and a display unit.
The electronic component of the present invention is incorporated as, for example, a switching element for switching each pixel of the display unit, a semiconductor component (various memories) for storing data, a circuit board, and the like.
FIG. 6 is a perspective view showing the configuration of a digital still camera to which the electronic apparatus of the present invention is applied. In this figure, connection with an external device is also simply shown.

Here, an ordinary camera sensitizes a silver halide photographic film with a light image of a subject, whereas a digital still camera 1300 photoelectrically converts a light image of a subject with an imaging device such as a CCD (Charge Coupled Device). An imaging signal (image signal) is generated.
A display unit is provided on the back of a case (body) 1302 in the digital still camera 1300, and is configured to display based on an imaging signal from the CCD, and functions as a finder that displays an object as an electronic image.

A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.
A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).
When the photographer confirms the subject image displayed on the display unit and presses the shutter button 1306, the CCD image pickup signal at that time is transferred and stored in the memory of the circuit board 1308.

  In the digital still camera 1300, a video signal output terminal 1312 and an input / output terminal 1314 for data communication are provided on the side surface of the case 1302. As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer 1440 is connected to the data communication input / output terminal 1314 as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

The electronic component of the present invention is incorporated as, for example, a switching element for switching each pixel of the display unit, a semiconductor component (various memories) for storing a CCD imaging signal, a circuit board 1308, and the like.
In addition to the personal computer (mobile personal computer) in FIG. 4, the mobile phone in FIG. 5, and the digital still camera in FIG. 6, the electronic apparatus of the present invention includes, for example, a television, a video camera, a viewfinder type, Monitor direct-view video tape recorder, laptop personal computer, car navigation system, pager, electronic notebook (including communication function), electronic dictionary, calculator, electronic game device, word processor, workstation, video phone, security TV Monitors, electronic binoculars, POS terminals, devices equipped with touch panels (for example, cash dispensers and automatic ticket vending machines for financial institutions), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiographs, ultrasound diagnostic devices, internal Endoscope display device), fish finder, various measuring instruments, Vessels such (e.g., gages for vehicles, aircraft, and ships), a flight simulator, various monitors, and a projection display such as a projector.
The film forming method, film, electronic component, and electronic device of the present invention have been described based on the illustrated embodiments, but the present invention is not limited to these.

It is sectional drawing which shows suitable embodiment of the film-forming method of this invention. It is sectional drawing which shows suitable embodiment of the film-forming method of this invention. It is a figure which shows embodiment of the thin-film transistor to which the electronic component of this invention is applied, (a) is a longitudinal cross-sectional view, (b) is a top view. 1 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which an electronic apparatus of the present invention is applied. It is a perspective view which shows the structure of the mobile telephone (PHS is also included) to which the electronic device of this invention is applied. It is a perspective view which shows the structure of the digital still camera to which the electronic device of this invention is applied.

Explanation of symbols

  2 ... Active energy ray 5 ... Base material 6 ... Catalyst layer 7 ... Photomask 8 ... Film 9 ... Film formation region 9 '... Non-film formation region 10 ... Catalyst solution 11 ... Plating solution 12 ...... Precursor gas 100 ... Thin film transistor 20 ... Substrate 30 ... Source electrode 40 ... Drain electrode 50 ... Organic semiconductor layer 510 ... Channel region 60 ... Gate insulating layer 70 ... Gate electrode 1100 ... Personal computer 1102 …… Keyboard 1104 …… Main body 1106 …… Display unit 1200 …… Mobile phone 1202 …… Operation buttons 1204 …… Earpiece 1206 …… Speaker 1300… Digital still camera 1302 …… Case (body) 1304 Light receiving unit 1306 Shutter button 1308 Circuit board 1 12 ‥‥ video signal output terminal 1314 ‥‥ input and output data communication terminal 1430 ‥‥ television monitor 1440 ‥‥ personal computer

Claims (12)

A film forming method for forming a film with a predetermined pattern on a substrate,
A film forming region for forming the film of the substrate having liquid repellency at least on a surface on which the film is formed is subjected to a predetermined treatment, and the liquid repellency of the film forming region is set so that the film is not formed. A first step of lowering the liquid repellency of the film forming region;
A liquid containing catalyst is supplied to the surface of the base material, and a catalyst layer is selectively formed in the film formation region by utilizing the difference in liquid repellency between the film formation region and the non-film formation region. A second step of:
And a third step of forming the film on the catalyst layer using the catalytic function of the catalyst layer.   The film forming method according to claim 1, wherein the predetermined process in the first step is performed by irradiating an active energy ray to the film forming region of the base material.   The film forming method according to claim 2, wherein the active energy ray is at least one of ultraviolet rays, electron beams, and ion beams.   In the first step, when the contact angle of pure water with respect to the non-film formation region is A [°] and the contact angle of pure water with respect to the film formation region is B [°], A−B ≧ 15. The film forming method according to claim 1, wherein the film forming method satisfies the relationship.   The film forming method according to claim 1, wherein a content of the catalyst in the catalyst layer is 50 wt% or more.   The film forming method according to claim 1, wherein the catalyst is mainly composed of at least one of Pd, Ni, Cu, Co, Pt, and an alloy containing these.   The film forming method according to claim 1, wherein the film is a metal film mainly composed of a metal material.   The film forming method according to claim 7, wherein in the third step, the metal film is formed by an electroless plating method or a CVD method.   2. The substrate is obtained by irradiating fluorine plasma to the surface of a base material mainly composed of a resin material at least in the vicinity of the surface on which the film is formed. The film forming method according to any one of 8.   A film formed by the film forming method according to claim 1.   An electronic component comprising the film according to claim 10. An electronic device comprising the electronic component according to claim 11.

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