JP2009027120A - Joining method, joining body, and wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a joining method capable of efficiently and tightly joining two members each other at high dimensional accuracy and forming a conductivity layer between the two members, to provide a joining body obtained by tightly joining the two members each other at high dimensional accuracy and provided with a layer having conductivity between the two members, and to provide a wiring board provided with the joining body and having high reliability. <P>SOLUTION: The joining method includes a process (first process) for forming plasma polymerization films 3 including a conductive component on respective surfaces of two base materials 2, a process (second process) for irradiating the surfaces of the plasma polymerization films 3 with ultraviolet light to activate the surfaces and generate conductivity on respective plasma polymerization films 3, a process (third process) for sticking the two base materials 2 to each other so that the activated surfaces are stuck to each other to obtain a joining body 1, and a process for pressing the joining body 1 while heating the joining body 1. The plasma polymerization film 3 is preferably composed of an organic metal polymer as a main material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a bonding method, a bonded body, and a wiring board.

When joining (adhering) two members (base materials), conventionally, a method of using an adhesive such as an epoxy adhesive, a urethane adhesive, or a silicone adhesive is often used.
The adhesive can exhibit adhesiveness regardless of the material of the member. For this reason, members composed of various materials can be bonded in various combinations.
For example, a flexible wiring board such as an FPC is configured by sandwiching a copper foil between two resin sheets and bonding them using an adhesive.

When the members are bonded together using an adhesive as described above, a liquid or paste-like adhesive is applied to the bonding surface with a thickness of several μm or more, and the members are pasted via the applied adhesive. Match. Thereafter, when the adhesive is cured by the action of heat or light, the members are bonded to each other based on the anchor effect.
In addition, when the electrodes are bonded while being electrically bonded, a conductive paste such as an Ag paste is used.

  However, when applying an adhesive or conductive paste to the bonding surface of the member, it is necessary to use a complicated method such as a printing method. In addition, the thickness of the applied adhesive or conductive paste is affected by many parameters such as viscosity, temperature, humidity, and printing device conditions, so it is extremely difficult to control precisely. . For this reason, it has the problem that the dimensional accuracy of a joined body cannot fully be raised.

In addition, since the curing time of the adhesive and Ag paste becomes very long, there is a problem that a long time is required for bonding. Further, in many cases, it is necessary to use a primer for increasing the adhesive strength of the adhesive, and the cost and labor for that purpose complicate the bonding process.
Moreover, since Ag paste requires heat treatment at a high temperature, there is a problem that only a base material having high heat resistance can be bonded.

On the other hand, there is a solid bonding method as a bonding method that does not use an adhesive.
Solid bonding is a method for directly bonding members without a bonding film (intermediate layer) such as an adhesive (for example, see Patent Document 1).
According to such solid bonding, since a bonding film such as an adhesive is not used, a bonded body with high dimensional accuracy can be obtained.

On the other hand, there is a problem that the material of the member is limited. Specifically, in general, solid bonding can only be performed between the same kind of materials. In addition, materials that can be joined are limited to silicon-based materials and some metal materials.
Furthermore, there are problems in the bonding process, such as the fact that the atmosphere in which solid bonding is performed is limited to a reduced-pressure atmosphere and that high-temperature (about 700 to 800 ° C.) heat treatment is required.
In response to such problems, a method for joining two members firmly and efficiently with high dimensional accuracy is required.

JP-A-5-82404

  An object of the present invention is to join two members firmly and efficiently with high dimensional accuracy, and to form a conductive layer between the two members. An object of the present invention is to provide a bonded body that is firmly bonded with dimensional accuracy and includes a conductive layer between two members, and a highly reliable wiring board including the bonded body.

Such an object is achieved by the present invention described below.
The bonding method of the present invention includes a substrate, a first adherend including a plasma polymerization film including a conductive component provided in at least a part of the substrate, and a second adherend. A first step of preparing
A second step of applying energy to at least a part of the plasma polymerized film to activate the plasma polymerized film and exhibiting conductivity in the plasma polymerized film;
A third step of bonding the first adherend and the second adherend to obtain a joined body so that the plasma polymerized film and the second adherend are brought into close contact with each other; It is characterized by that.
Accordingly, the two members can be bonded firmly and efficiently with high dimensional accuracy, and a conductive layer can be formed between the two members.

In the bonding method of the present invention, the first adherend includes the base material and a plasma polymerized film including a conductive component provided in the entire region on the base material,
In the second step, the plasma polymerization film located in the predetermined area is partially activated by applying energy to a predetermined area of the plasma polymerization film, and the predetermined process is performed. It is preferable that the plasma polymerization film located in the region is partially made conductive.
Thereby, for example, wiring can be formed in a part of the plasma polymerization film.

In the bonding method of the present invention, a hydroxyl group is present on the surface of the second adherend that is in close contact with the plasma polymerization film of the first adherend,
In the third step, the first adherend and the second adherend are adhered so that the plasma polymerized film and the surface of the second adherend on which the hydroxyl group exists are in close contact with each other. Are preferably bonded together.
As a result, an attractive force based on a hydrogen bond is generated between the hydroxyl group present in the plasma polymerized film and the hydroxyl group present in the second adherend, and the gap between the plasma polymerized film and the second adherend is strong. To be joined.

In the bonding method of the present invention, at least a surface of the second adherend that is in close contact with the plasma polymerization film is covered with an oxide film,
In the third step, the first adherend and the second adherend are adhered so that the plasma polymerized film and the surface of the second adherend covered with the oxide film are in close contact with each other. It is preferable to bond the body together.
Since the hydroxyl group is bonded to the surface of the oxide film, the hydroxyl group and the hydroxyl group present in the plasma polymerized film attract each other by hydrogen bonding, and the plasma polymerized film and the second adherend are firmly bonded. Is done.

The bonding method of the present invention includes a first step of preparing a first adherend and a second adherend each having a plasma polymerized film containing a conductive component on a substrate,
Energy is applied to the surface of each plasma polymerized film of the first adherend and the second adherend to activate the surface of each plasma polymerized film, and the plasma polymerized film is electrically conductive. A second step of expressing sex;
A third step of bonding the first adherend and the second adherend to obtain a joined body so that the surfaces of the activated plasma polymerization films are brought into close contact with each other; It is characterized by.
Thereby, two base materials can be joined firmly and efficiently with high dimensional accuracy, and a conductive layer can be formed between the two base materials.

In the bonding method of the present invention, each of the first adherend and the second adherend is subjected to a ground treatment with plasma on each of the substrates in advance, and then is applied to the region subjected to the ground treatment. It is preferable to form the plasma polymerized film.
Thereby, when the joining surface of a base material is cleaned and activated and a plasma polymerization film | membrane is formed on a joining surface, the joining strength of a joining surface and a plasma polymerization film | membrane can be raised.

In the bonding method of the present invention, it is preferable that the base material provided in the first adherend and the base material provided in the second adherend have different rigidity.
Thereby, two base materials can be joined more firmly.
In the bonding method of the present invention, the plasma polymerized film containing the conductive component is preferably composed of an organometallic polymer as a main material.
Thereby, it is possible to obtain a joined body that has a layer that is particularly excellent in conductivity and can be used as a highly reliable wiring that can reliably prevent peeling and the like.

In the bonding method of the present invention, it is preferable that the organometallic polymer is mainly composed of a polymer of trimethylgallium or trimethylaluminum.
As a result, the joined body is particularly strongly joined between the two base materials and has a particularly high conductivity.
In the bonding method of the present invention, the average thickness of the plasma polymerized film is preferably 1 to 1000 nm.
Thereby, while preventing the dimensional accuracy of a joined body falling significantly, two base materials can be joined more firmly and sufficient electroconductivity is obtained for a plasma polymerization film. This also ensures a certain degree of shape following in the plasma polymerized film, so that the unevenness present on the bonding surface of the base material can be absorbed to reduce the height of the irregularities generated on the surface of the plasma polymerized film. it can.

In the bonding method of the present invention, it is preferable that the application of the energy in the second step is performed by a method of heating the plasma polymerization film.
Thereby, energy can be imparted to the plasma polymerization film relatively easily and efficiently.
In the bonding method of the present invention, the heating temperature is preferably 25 to 100 ° C.
Thereby, the plasma polymerized film can be reliably activated and adhesiveness can be expressed in the plasma polymerized film while reliably preventing the base material from being altered or deteriorated by heat.

In the bonding method of the present invention, it is preferable that the application of the energy in the second step is performed by a method of irradiating the plasma polymerization film with energy rays.
Thereby, the surface of a plasma polymerization film | membrane can be activated efficiently. Further, since the molecular structure in the plasma polymerized film is not cut more than necessary, it is possible to avoid deterioration of the characteristics of the plasma polymerized film.

In the bonding method of the present invention, the energy beam is preferably ultraviolet light having a wavelength of 150 to 300 nm.
Thereby, it is possible to process a wide range in a shorter time without unevenness while preventing a remarkable deterioration of the characteristics of the plasma polymerized film. For this reason, activation of the surface of a plasma polymerization film | membrane can be performed more efficiently.

In the bonding method of the present invention, it is preferable that the second step is performed in an air atmosphere.
Thereby, it is not necessary to spend time and cost to control the atmosphere, and the activation process can be performed more easily.
In the joining method of this invention, it is preferable to have the process of heat-processing the said joined body after the said 3rd process.
Thereby, the joint strength in the joined body can be further increased.

In the bonding method of the present invention, the temperature of the heat treatment is preferably 25 to 100 ° C.
Thereby, it is possible to reliably increase the bonding strength while reliably preventing the bonded body from being deteriorated and deteriorated by heat.
In the joining method of this invention, it is preferable to have the process of pressurizing the said joined body after the said 3rd process.
Thereby, the integration of the two plasma polymerized films further proceeds, and the bonding strength in the bonded body can be further increased.

In the bonding method of the present invention, it is preferable that the pressure applied to the bonded body is 0.2 to 10 MPa.
Thereby, the joining strength of the joined body can be reliably increased without causing damage to the substrate.
In the joining method of the present invention, it is preferable to start the third step within 60 minutes after the end of the second step.
Thereby, the surface of a plasma polymerization film | membrane can be maintained in a sufficient active state, and sufficient bonding strength can be obtained when it bonds together.

The joined body of the present invention is characterized in that two substrates are joined by the joining method of the present invention.
As a result, a joined body is obtained in which the two base materials are joined firmly and efficiently with high dimensional accuracy, and a conductive layer is provided between the two base materials.

The joined body of the present invention comprises two substrates,
Having a plasma polymerized film having conductivity,
The two base materials are bonded to each other through the plasma polymerization film.
As a result, a bonded body is obtained in which the two substrates are bonded to each other firmly and efficiently with high dimensional accuracy, and a bonding film having conductivity is provided between the two substrates.

In the joined body of the present invention, the conductive plasma polymerized film is formed by applying energy to each of the plasma polymerized films each including a conductive component previously formed on the two base materials. It is preferable that the plasma polymerized film containing the components exhibit conductivity and the plasma polymerized films are bonded to each other.
As a result, it is possible to obtain a joined body in which the two base materials are joined particularly strongly and efficiently with high dimensional accuracy, and a joining film having conductivity is provided between the two base materials.

In the joined body of the present invention, the joining strength between the two base materials is preferably 5 MPa or more.
Thereby, the joined body can sufficiently prevent the peeling.
In the joined body of the present invention, the resistivity of the plasma polymerized film exhibiting the conductivity in the joined body is preferably 1 × 10 ⁻³ Ω · cm or less.
As a result, the plasma polymerized film can be sufficiently utilized as a wiring with little loss.
The wiring board of the present invention is characterized by having the joined body of the present invention.
Thereby, a highly reliable wiring board is obtained.

Hereinafter, the joining method, joined body and wiring board of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
<Join method>
The bonding method of the present invention is a method of bonding a first base material 21 and a second base material 22 using a plasma polymerization film 3 containing a conductive component, and plasma polymerization containing this conductive component. By applying energy to the film 3, the plasma polymerization film 3 containing a conductive component is made to exhibit conductivity, and the two base materials 21 and 22 are joined.

According to the joining method of the present invention, the two base materials 21 and 22 can be joined firmly with high dimensional accuracy and efficiently at a low temperature. Moreover, the joined body 1 obtained by this joining has a conductive layer between two base materials.
Specifically, the plasma polymerization film 3 is formed on the first substrate 21 by patterning in advance in a linear shape. Then, by applying energy to the plasma polymerized film 3 patterned in a linear shape, the plasma polymerized film 3 becomes conductive and functions as a wiring. Thereby, the obtained joined body 1 can be utilized as a wiring board, for example.

Further, by imparting energy to a part of the plasma polymerized film 3 containing a conductive component, conductivity can be selectively expressed in a part of the plasma polymerized film 3. Thereby, for example, a wiring can be formed in a part of the plasma polymerization film 3.
Here, prior to describing the bonding method of the present invention, first, a plasma polymerization apparatus used to form a plasma polymerization film containing the above-described conductive component will be described.

FIG. 1 is a longitudinal sectional view schematically showing a plasma polymerization apparatus used in the bonding method of the present invention. In the following description, the upper side in FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.
The plasma polymerization apparatus 100 shown in FIG. 1 includes a chamber 101, a first electrode 130 that supports the substrate 2, a second electrode 140, and a power supply circuit 180 that applies a high-frequency voltage between the electrodes 130 and 140. A gas supply unit 190 that supplies gas into the chamber 101 and an exhaust pump 170 that exhausts the gas in the chamber 101 are provided. Among these parts, the first electrode 130 and the second electrode 140 are provided in the chamber 101. Hereinafter, each part will be described in detail.

The chamber 101 is a container that can keep the inside airtight, and is used with the inside being in a reduced pressure (vacuum) state. Therefore, the chamber 101 has pressure resistance that can withstand a pressure difference between the inside and the outside.
A chamber 101 shown in FIG. 1 has a substantially cylindrical chamber body whose axis is arranged in the horizontal direction, a circular side wall that seals the left-side opening of the chamber body, and a circle that seals the right-side opening. And side walls.

A supply port 103 is provided above the chamber 101, and an exhaust port 104 is provided below the chamber 101. A gas supply unit 190 is connected to the supply port 103, and an exhaust pump 170 is connected to the exhaust port 104.
In this embodiment, the chamber 101 is made of a highly conductive metal material and is electrically grounded via the ground wire 102.

The first electrode 130 has a plate shape and supports the substrate 2.
The first electrode 130 is provided on the inner wall surface of the side wall of the chamber 101 along the vertical direction, whereby the first electrode 130 is electrically grounded via the chamber 101. The first electrode 130 is provided concentrically with the chamber body as shown in FIG.

An electrostatic chuck (suction mechanism) 139 is provided on the surface of the first electrode 130 that supports the substrate 2.
As shown in FIG. 1, the electrostatic chuck 139 can support the substrate 2 along the vertical direction. Moreover, even if the base material 2 has some warpage, the base material 2 can be subjected to plasma treatment in a state in which the warpage is corrected by being attracted to the electrostatic chuck 139.

The second electrode 140 is provided to face the first electrode 130 with the base material 2 interposed therebetween. Note that the second electrode 140 is provided in a state of being separated (insulated) from the inner wall surface of the side wall of the chamber 101.
A high frequency power source 182 is connected to the second electrode 140 via a wiring 184. A matching box (matching unit) 183 is provided in the middle of the wiring 184. The wiring 184, the high-frequency power source 182 and the matching box 183 constitute a power circuit 180.
According to such a power supply circuit 180, since the first electrode 130 is grounded, a high frequency voltage is applied between the first electrode 130 and the second electrode 140. As a result, an electric field whose direction is reversed at a high frequency is induced in the gap between the first electrode 130 and the second electrode 140.

The gas supply unit 190 supplies a predetermined gas into the chamber 101.
A gas supply unit 190 shown in FIG. 1 stores a liquid storage unit 191 that stores a liquid film material (raw material liquid), a vaporizer 192 that vaporizes the liquid film material to change it into a gaseous state, and stores a carrier gas. And a gas cylinder 193. Each of these parts and the supply port 103 of the chamber 101 are connected by a pipe 194, and a mixed gas of a gaseous film material (raw material gas) and a carrier gas is supplied from the supply port 103 into the chamber 101. It is configured to supply.

The liquid film material stored in the liquid storage unit 191 is a raw material that is polymerized by the plasma polymerization apparatus 100 to form a polymer film on the surface of the substrate 2.
Such a liquid film material is vaporized by the vaporizer 192 and is supplied into the chamber 101 as a gaseous film material (raw material gas). The source gas will be described in detail later.

The carrier gas stored in the gas cylinder 193 is a gas that is discharged due to the action of an electric field and introduced to maintain this discharge. Examples of such a carrier gas include Ar gas and He gas.
A diffusion plate 195 is provided near the supply port 103 in the chamber 101.

The diffusion plate 195 has a function of promoting the diffusion of the mixed gas supplied into the chamber 101. Thereby, the mixed gas can be dispersed in the chamber 101 with a substantially uniform concentration.
The exhaust pump 170 exhausts the inside of the chamber 101, and includes, for example, an oil rotary pump, a turbo molecular pump, or the like. Thus, by exhausting the chamber 101 and reducing the pressure, the gas can be easily converted into plasma. In addition, contamination and oxidation of the base material 2 due to contact with the air atmosphere can be prevented, and reaction products resulting from the plasma treatment can be effectively removed from the chamber 101.
The exhaust port 104 is provided with a pressure control mechanism 171 that adjusts the pressure in the chamber 101. Thereby, the pressure in the chamber 101 is appropriately set according to the operation state of the gas supply unit 190.

<< First Embodiment >>
Next, the first embodiment of the bonding method of the present invention will be described by taking the case of using the plasma polymerization apparatus 100 as an example.
2 and 3 are views (longitudinal sectional views) for explaining the first embodiment of the joining method of the present invention. In the following description, the upper side in FIGS. 2 and 3 is referred to as “upper” and the lower side is referred to as “lower”.

  The bonding method according to this embodiment is a method of bonding two substrates 2 to each other using a plasma polymerization film 3 containing a conductive component, and imparting energy to the plasma polymerization film 3 containing this conductive component. In this way, the plasma polymerized film 3 containing the conductive component is made to exhibit conductivity, and the two base materials 2 are bonded to each other. According to such a method, the two base materials 2 can be firmly and efficiently joined with high dimensional accuracy, and the obtained joined body includes a conductive layer between the two base materials 2. It will be. That is, since this layer functions as, for example, wiring, the obtained bonded body can be used as a wiring board.

  The bonding method according to the present embodiment includes a step (first step) of forming plasma polymerized films 3 each containing a conductive component on the surfaces of two substrates 2, and energy on the surfaces of the plasma polymerized films 3. The two substrates 2 are applied so that the surface is activated and the plasma polymerized film 3 is made electrically conductive (second step) and the activated surfaces are in contact with each other. Are bonded together to obtain a joined body (third step), and the joined body is heated and pressurized. Hereinafter, each process will be described sequentially.

[1] First, two base materials 2 are prepared. In FIG. 2, one of the two base materials 2 is omitted.
Although the constituent material of such a base material 2 is not specifically limited, Fe, Ni, Co, Cr, Mn, Zn, Pt, Au, Ag, Cu, Pd, Al, W, Ti, Ta, V, Mo, Metals such as Nb, Zr, Pr, Nd, Sm, or alloys containing these metals, metal materials such as carbon steel, stainless steel, indium tin oxide (ITO), fluorine doped tin oxide (FTO), etc. Metal thin film deposition materials, single-crystal silicon, polycrystalline silicon, silicon-based semiconductor materials such as amorphous silicon, compound-based semiconductor materials such as gallium arsenide (GaAs) and gallium phosphide (GaP), graphite Examples thereof include carbon-based materials such as these, conductive polymer materials such as polyacetylene, and composite materials obtained by combining one or more of these materials. Since these materials are all conductive, conduction between the two base materials 2 can be achieved.

  In addition, the constituent material of the base material 2 does not necessarily need to be a conductive material. That is, the constituent material of the base material 2 is polyolefin such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene. , Polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), butadiene-styrene copolymer, polyoxymethylene, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), Polyester such as reethylene naphthalate, polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyether imide, polyacetal (POM), polyphenylene oxide , Modified polyphenylene oxide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluororesins, styrene, polyolefin, polyvinyl chloride , Polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluoro rubber, chlorinated polyethylene Various thermoplastic elastomers such as epoxy resin, phenol resin, urea resin, melamine resin, aramid resin, unsaturated polyester, silicone resin, polyurethane, etc., or copolymers, blends, polymer alloys, etc. mainly comprising these Resin materials, silicate glass (quartz glass), alkali silicate glass, soda lime glass, potash lime glass, lead (alkali) glass, barium glass, borosilicate glass glass materials such as alumina, zirconia, ferrite, Ceramic materials such as silicon nitride, aluminum nitride, boron nitride, titanium nitride, silicon carbide, boron carbide, titanium carbide, tungsten carbide, or composite materials combining one or more of these materials. May be.

In addition, each substrate 2 may have a surface subjected to plating treatment such as Ni plating, passivation treatment such as chromate treatment, or nitriding treatment.
Further, the constituent materials of the two base materials 2 may be the same or different.
Further, the thermal expansion coefficients of the two base materials 2 are preferably substantially equal, but may be different from each other. If the thermal expansion coefficient of each base material 2 is substantially equal, when the two base materials 2 are joined together, it becomes difficult to generate stress accompanying thermal expansion at the joint interface. As a result, peeling can be reliably prevented in the finally obtained bonded body 1. In addition, as will be described in detail later, even when the thermal expansion coefficients of the respective base materials 2 are different from each other, the two base materials 2 are optimized by optimizing the conditions for bonding the two base materials 2 to each other in the process described later. The two can be firmly bonded with high dimensional accuracy.

Moreover, it is preferable that the two base materials 2 have mutually different rigidity. Thereby, two base materials 2 can be joined more firmly.
Moreover, it is preferable that at least one of the two base materials 2 is made of a resin material. The resin material can relieve stress (for example, stress accompanying thermal expansion, etc.) generated at the bonding interface when the two base materials 2 are bonded to each other due to its flexibility. For this reason, it becomes difficult to destroy the bonding interface, and as a result, the bonded body 1 having high bonding strength can be obtained.

Moreover, the shape of each base material 2 should just be a shape which has the surface which supports the plasma polymerization film | membrane 3, respectively, For example, it is set as plate shape (layer shape), lump shape (block shape), rod shape, etc.
In the present embodiment, as shown in FIG. 2A, each base material 2 has a plate shape. Thereby, each base material 2 becomes easy to bend, and when the two base materials 2 are overlapped, they can be sufficiently deformed along each other. For this reason, the adhesiveness when the two base materials 2 are overlapped increases, and the bonding strength in the finally obtained bonded body 1 increases.
Moreover, the effect | action which relieves to some extent the stress which arises in a joining interface because each base material 2 bends can be anticipated.
In this case, the average thickness of each substrate 2 is not particularly limited, but is preferably about 0.01 to 10 mm, and more preferably about 0.1 to 3 mm.

Next, a base treatment (surface treatment) is performed on the bonding surface 23 of the substrate 2 as necessary. Thereby, the bonding surface 23 is cleaned and activated. As a result, when the plasma polymerization film 3 is formed on the bonding surface 23 in a process described later, the bonding strength between the bonding surface 23 and the plasma polymerization film 3 can be increased.
The base treatment is not particularly limited, but for example, physical surface treatment such as sputtering treatment, blast treatment, oxygen plasma treatment, plasma treatment using nitrogen plasma, corona discharge treatment, etching treatment, electron beam irradiation treatment. , Ultraviolet light irradiation treatment, chemical surface treatment such as ozone exposure treatment, or a combination thereof.

In addition, especially when the base material 2 which performs a base treatment is comprised with the resin material (polymer material), a corona discharge process, a nitrogen plasma process, etc. are used suitably.
In addition, the surface 23 can be cleaned and activated more particularly by performing plasma treatment. As a result, the bonding strength between the bonding surface 23 and the plasma polymerization film 3 can be particularly increased.

Further, depending on the constituent material of the base material 2, there is a material in which the bonding strength with the plasma polymerization film 3 is sufficiently high without performing the surface treatment as described above. Examples of the constituent material of the base material 2 that can obtain such an effect include those mainly composed of various metal-based materials, various silicon-based materials, various glass-based materials and the like as described above.
The surface of the substrate 2 made of such a material is covered with an oxide film, and a hydroxyl group is bonded to the surface of the oxide film. Therefore, by using the base material 2 covered with such an oxide film, the bonding strength between the base material 2 and the plasma polymerized film 3 can be increased without performing the surface treatment as described above.

In this case, the entire base material 2 may not be made of the material as described above, and at least the vicinity of the bonding surface 23 may be made of the material as described above.
Further, instead of the surface treatment, an intermediate layer may be formed in advance on the bonding surface 23 of the substrate 2.
This intermediate layer may have any function, and for example, a layer having a function of improving adhesion to the plasma polymerized film 3, a cushioning function (buffer function), a function of reducing stress concentration, and the like are preferable. The base material 2 and the plasma polymerized film 3 are joined via such an intermediate layer, and the highly reliable joined body 1 can be obtained.

Examples of the constituent material of the intermediate layer include metal materials such as aluminum and titanium, metal oxides, oxide materials such as silicon oxide, metal nitrides, and nitride materials such as silicon nitride. Carbon materials such as graphite and diamond-like carbon, silane coupling agents, thiol compounds, metal alkoxides, self-assembled film materials such as metal-halogen compounds, resin adhesives, resin films, resin coating materials, Various rubber materials, resin materials such as various elastomers, and the like can be used, and one or more of these can be used in combination.
Further, among the intermediate layers made of these materials, the intermediate layer made of an oxide-based material can particularly increase the bonding strength between the substrate 2 and the plasma polymerized film 3.

[2] Next, as shown in FIGS. 2A to 2C, plasma polymerized films 3 each including a conductive component are formed on the two base materials 2 (one surface of the base material 2). (First step). Thereby, two adherends (the first adherend 41 and the second adherend 42) provided with the plasma polymerization film 3 containing the conductive component on the substrate 2 are obtained.
The plasma polymerized film 3 can be obtained by polymerizing molecules in the source gas by supplying a mixed gas of the source gas and the carrier gas in a strong electric field.
Specifically, first, the base material 2 is accommodated in the chamber 101 to be in a sealed state, and then the inside of the chamber 101 is depressurized by the operation of the exhaust pump 170.

Next, the gas supply unit 190 is operated to supply a mixed gas of the source gas and the carrier gas into the chamber 101. The supplied mixed gas is filled into the chamber 101 (see FIG. 2A).
The ratio (mixing ratio) of the raw material gas in the mixed gas is slightly different depending on the kind of the raw material gas and the carrier gas, the target film forming speed, and the like. For example, the proportion of the raw material gas in the mixed gas is 20 to 70%. It is preferable to set it to a degree, and it is more preferable to set it to about 30 to 60%. As a result, it is possible to optimize the conditions for formation (film formation) of the polymer film.
Further, the flow rate of the gas to be supplied is appropriately determined depending on the type of gas, the target film formation rate, the film thickness, etc., and is not particularly limited, but usually the flow rates of the source gas and the carrier gas are respectively , Preferably about 1 to 100 ccm, more preferably about 10 to 60 ccm.

  Next, the power supply circuit 180 is activated, and a high frequency voltage is applied between the pair of electrodes 130 and 140. As a result, gas molecules existing between the pair of electrodes 130 and 140 are ionized to generate plasma. Due to the energy of the plasma, molecules in the raw material gas are polymerized, and the polymer is deposited and deposited on the substrate 2 as shown in FIG. Thereby, the plasma polymerization film | membrane 3 is formed on the base material 2 (refer FIG.2 (c)).

Examples of the source gas include organometallic compounds such as trimethylgallium, triethylgallium, trimethylaluminum, triethylaluminum, triisobutylaluminum, trimethylindium, triethylindium, trimethylzinc, and triethylzinc, and π-electron organic materials such as acetylene and thiophene. Compounds and the like.
The plasma polymerized film 3 obtained using such a raw material gas is composed of a material obtained by polymerizing these raw materials (polymer), that is, an organic metal polymer, a π-electron organic polymer, or the like. Each of these polymers contains a conductive component (metal element, π-electron organic compound, etc.) as a constituent component.

  Of these, the plasma polymerized film 3 is preferably composed of an organometallic polymer as a main material. The organometallic polymer exhibits an excellent electrical conductivity through the activation treatment, and can more firmly join the two substrates 2 to each other. Therefore, the plasma polymerized film 3 made of an organometallic polymer constitutes a bonded body 1 that can be used as a highly reliable wiring that can reliably prevent peeling and the like through an activation process described later. It will be possible.

Further, among the organometallic polymers, those mainly composed of a polymer of trimethylgallium or trimethylaluminum are preferable. Among these organometallic polymers, these components are capable of expressing excellent conductivity by joining the two substrates 2 particularly firmly and through an activation treatment.
In the plasma polymerization, the frequency of the high frequency applied between the pair of electrodes 130 and 140 is not particularly limited, but is preferably about 1 kHz to 100 MHz, and more preferably about 10 to 60 MHz.

Further, the power density of the high frequency is not particularly limited, and is preferably about 0.01 to 10 / cm ^2, more preferably about 0.1 to 1 W / cm ^2.
Further, the pressure in the chamber 101 during film formation is preferably about 133.3 × 10 ^{−5 to} 1333 Pa (1 × 10 ^{−5 to} 10 Torr), and 133.3 × 10 ^{−4 to} 133.3 Pa ( More preferably, it is about 1 × 10 ^{−4 to} 1 Torr).

The raw material gas flow rate is preferably about 0.5 to 200 sccm, and more preferably about 1 to 100 sccm. On the other hand, the carrier gas flow rate is preferably about 5 to 750 sccm, and more preferably about 10 to 500 sccm.
The treatment time is preferably about 1 to 10 minutes, more preferably about 4 to 7 minutes.

Moreover, it is preferable that the temperature of the base material 2 is 25 degreeC or more, and it is more preferable that it is about 25-100 degreeC.
By appropriately setting such conditions, the dense plasma polymerized film 3 can be formed without unevenness.
In this embodiment, the procedure for forming a plasma polymerized film on the substrate 2 using a plasma polymerization apparatus is described. However, a substrate (adhered body) provided with a plasma polymerized film is prepared in advance. In addition, the adherend may be used.

Moreover, it is preferable that the average thickness of the plasma polymerization film | membrane 3 is about 1-1000 nm, and it is more preferable that it is about 2-800 nm. By making the average thickness of the plasma polymerized film 3 within the above range, it is possible to bond more firmly while preventing the dimensional accuracy of the joined body obtained by joining the two base materials 2 from being significantly lowered, And sufficient electroconductivity is obtained for the plasma polymerization film 3 through the activation treatment.
That is, when the average thickness of the plasma polymerized film 3 is less than the lower limit value, there is a possibility that sufficient bonding strength cannot be obtained. On the other hand, when the average thickness of the plasma polymerized film 3 exceeds the upper limit, the dimensional accuracy of the joined body may be significantly reduced.

Furthermore, if the average thickness of the plasma polymerized film 3 is within the above range, a certain degree of shape followability is ensured for the plasma polymerized film 3. For this reason, for example, even when unevenness is present on the bonding surface of the substrate 2 (surface adjacent to the plasma polymerization film 3), the plasma follows the shape of the unevenness depending on the height of the unevenness. The polymer film 3 can be deposited. As a result, the plasma polymerized film 3 can absorb the unevenness and reduce the height of the unevenness generated on the surface.
In addition, the degree of the shape followability as described above becomes more prominent as the thickness of the plasma polymerization film 3 increases. Therefore, in order to ensure sufficient shape followability, the thickness of the plasma polymerization film 3 should be as thick as possible.

[3] Next, energy is applied to the surface 31 of the obtained plasma polymerization film 3. Thereby, a part of the molecular bond in the vicinity of the surface 31 is cut, the surface 31 is activated, and conductivity is expressed in each plasma polymerized film 3 (second step).
As a method for applying energy to the surface 31 of the plasma polymerized film 3, any method may be used as long as it can activate the surface 31. For example, a method of irradiating energy rays, heating the plasma polymerized film 3 or the like. A method of exposing the plasma polymerized film 3 to plasma (applying plasma energy), a method of exposing it to ozone gas (applying chemical energy), etc., and a method of irradiating energy rays is particularly preferable. According to the energy beam, the surface 31 of the plasma polymerization film 3 is activated efficiently. Further, according to this method, the molecular structure in the plasma polymerized film 3 is not cut more than necessary (for example, until reaching the interface of the base material 2), so that the characteristics of the plasma polymerized film 3 are prevented from deteriorating. be able to. Examples of energy rays include light such as ultraviolet light and laser light, electromagnetic waves such as X-rays and γ rays, electron beams, and particle beams.

In addition, it is preferable to use a method of irradiating ultraviolet rays having a wavelength of about 150 to 300 nm as energy rays, as shown in FIG. According to such ultraviolet light, a wide range can be processed in a shorter time without unevenness while preventing a significant deterioration in the characteristics of the plasma polymerized film 3. For this reason, activation of the surface 31 of the plasma polymerized film 3 can be performed more efficiently. In addition, ultraviolet light has an advantage that it can be generated by simple equipment such as an ultraviolet (UV) lamp.
The wavelength of the ultraviolet light is more preferably about 160 to 200 nm.

In the case of using the UV lamp, the output may vary depending on the area of the plasma polymerization film 3 is preferably from ^1mW / cm ^{2 ~1W} / cm 2 ^{approximately, 5mW / cm 2 ~50mW / cm} 2 of about It is more preferable that In this case, the separation distance between the UV lamp and the plasma polymerization film 3 is preferably about 3 to 3000 mm, and more preferably about 10 to 1000 mm.

Further, the time of irradiation with ultraviolet light is not particularly limited as long as the molecular bond near the surface 31 of the plasma polymerized film 3 can be cut, but is preferably about 0.5 to 30 minutes. More preferably, it is about 1 to 10 minutes.
Moreover, although an ultraviolet-ray may be irradiated continuously in time, you may irradiate intermittently (pulse form).

On the other hand, examples of the laser light include an excimer laser (femtosecond laser), an Nd-YAG laser, an Ar laser, a CO ₂ laser, and a He—Ne laser.
As described above, according to the method of irradiating the energy beam, it is possible to easily apply energy selectively to the plasma polymerized film 3, and thus, for example, preventing deterioration and deterioration of the base material 2 due to energy application. can do.

In addition, according to the method of irradiating energy rays, a large amount of energy can be applied in a short time, so that energy can be applied more efficiently.
Furthermore, according to the method of irradiating energy rays, the magnitude of energy to be applied can be adjusted easily and accurately. Thereby, the degree of adhesiveness developed in the plasma polymerized film 3 can be easily controlled.

That is, by increasing the energy to be applied, the adhesiveness expressed in the plasma polymerized film 3 can be further increased. On the other hand, the adhesiveness expressed in the plasma polymerization film 3 can be suppressed by reducing the applied energy. Thereby, the joining strength of the joined body 1 finally obtained can be adjusted.
In addition, in order to adjust the magnitude | size of the energy to provide, what is necessary is just to adjust conditions, such as the kind of energy beam, the output of an energy beam, the irradiation time of an energy beam.

  Moreover, it is preferable to irradiate such energy rays so that the energy is concentrated on the surface 31 of the plasma polymerization film 3 so as to be focused. In this way, molecular bonds near the surface 31 of the plasma polymerized film 3 can be selectively cut. Thereby, it can prevent more reliably that an energy ray cut | disconnects the molecular structure in the plasma polymerization film | membrane 3 more than necessary. As a result, it can be avoided more reliably that the characteristics of the plasma polymerized film 3 are significantly deteriorated.

The above-mentioned “activate” means a state in which the molecular bond in the vicinity of and inside the surface 31 is broken, and an unterminated bond is generated, or a hydroxyl group is bonded to the broken bond. Or a state in which these states are mixed.
When energy is applied to the plasma polymerized film 3, molecular bonds near and inside the surface 31 of the plasma polymerized film 3 are broken, and atomic groups (leaving groups) are desorbed from the plasma polymerized film 3. As a result, the bond to which the leaving group is bonded becomes an unterminated bond (unbonded bond).

Further, when moisture is contained in the surrounding atmosphere, the moisture acts on the dangling bonds, so that the dangling hands are terminated with a hydroxyl group.
Here, the leaving group is, for example, selected from the group consisting of an H atom, a B atom, a C atom, an N atom, an O atom, a P atom, an S atom and a halogen atom, or an atomic group containing each of these atoms. Those composed of at least one selected from the above are preferably used. Such a leaving group is relatively excellent in bond / elimination selectivity by energy application. For this reason, such a leaving group can highly control the adhesiveness developed in the plasma polymerized film 3.

Specific examples of leaving groups include, for example, alkyl groups such as methyl and ethyl groups, alkenyl groups such as vinyl and allyl groups, aldehyde groups, ketone groups, carboxyl groups, amino groups, amide groups, nitro groups, and the like. Group, halogenated alkyl group, mercapto group, sulfonic acid group, cyano group, isocyanate group and the like.
Among these groups, the leaving group is particularly preferably an alkyl group. Since the alkyl group has high chemical stability, the plasma polymerized film 3 containing the alkyl group has excellent weather resistance and chemical resistance.

Further, when energy is applied to the plasma polymerization film 3, the organic component is removed from the plasma polymerization film 3, and the conductive component becomes dominant. As a result, the plasma polymerized film 3 exhibits conductivity.
Depending on the type of the organometallic polymer, some may have conductivity even if energy is not applied. Such an organometallic polymer has conductivity immediately after being formed.

A method of applying energy to the plasma polymerized film 3 by heating the plasma polymerized film 3 as follows is also preferably used.
When the plasma polymerization film 3 is heated, the heating temperature is preferably set to about 25 to 100 ° C, more preferably about 50 to 100 ° C. By heating at a temperature in such a range, it is possible to reliably activate the plasma polymerization film 3 while reliably preventing the base material 2 from being altered or deteriorated by heat.

The heating time may be a time that can break the molecular bond in the vicinity of the surface 31 of the plasma polymerized film 3. Specifically, if the heating temperature is within the above range, the heating time is about 1 to 30 minutes. Preferably there is.
The plasma polymerized film 3 may be heated by any method, but can be heated by various heating methods such as a method using a heater, a method of irradiating infrared rays, and a method of contacting with a flame.
In addition, when using the method of irradiating infrared rays, it is preferable that the base material 2 is comprised with the material which has light absorptivity (infrared absorptivity) like a silicon-type material. The base material 2 made of such a material efficiently generates heat by absorbing infrared rays. For this reason, the plasma polymerization film | membrane 3 can be efficiently heated by irradiating the base material 2 with infrared rays.

  Moreover, when using the method using a heater or the method of making it contact with a flame, it is preferable that the base material 2 is comprised with the material excellent in thermal conductivity like a metal type material. Thereby, the heat energy of a heater or a flame can be efficiently transmitted with respect to the plasma polymerization film | membrane 3 through the base material 2 comprised with such a material. As a result, the plasma polymerization film 3 can be efficiently heated.

In addition, when the thermal expansion coefficients of the two base materials 2 and 2 are substantially equal, it is preferable to heat under the above conditions, but the thermal expansion coefficients of the two base materials 2 and 2 are different from each other. For this, it is preferable to perform bonding at as low a temperature as possible. By performing the bonding at a low temperature, it is possible to further reduce the thermal stress generated at the bonding interface.
Specifically, although it depends on the difference in thermal expansion coefficient between the two base materials 2 and 2, it is preferable to perform the bonding at a temperature of about 25 to 50 ° C, and it is preferable to perform the bonding at a temperature of about 25 to 40 ° C. More preferred. In such a temperature range, even if the difference in thermal expansion coefficient between the two substrates 2 and 2 is large to some extent, the thermal stress generated at the bonding interface can be sufficiently reduced. As a result, it is possible to reliably prevent warpage, peeling, and the like in the joined body 1.

In this case, when the difference in thermal expansion coefficient between the two substrates 2 and 2 is 5 × 10 ⁻⁵ / K or more, it is strongly recommended that the bonding be performed at the lowest possible temperature as described above. Is done.
The application of energy to the plasma polymerization film 3 may be performed in any atmosphere, and specifically, the atmosphere, an oxidizing gas atmosphere such as oxygen, a reducing gas atmosphere such as hydrogen, nitrogen, An inert gas atmosphere such as argon, a reduced pressure (vacuum) atmosphere obtained by reducing these atmospheres, and the like can be given, and it is particularly preferable to perform in an air atmosphere. Thereby, it is not necessary to spend time and cost to control the atmosphere, and energy can be applied more easily.

[4] Next, the two base materials 2 are bonded together so that the activated surfaces are in contact with each other (see FIG. 3E). Thereby, the two plasma polymerization films 3 are integrated with each other, and the two base materials 2 are bonded to each other.
Here, this joining is presumed to be based on both or one of the following two mechanisms (i) and (ii).

(I) When two base materials 2 are bonded together, OH groups existing on the surface of each plasma polymerization film 3 are adjacent to each other. The adjacent OH groups attract each other by hydrogen bonding, and an attractive force is generated between the OH groups.
In addition, OH groups that are attracted to each other by this hydrogen bond are desorbed from the surface with dehydration condensation depending on temperature conditions and the like. As a result, at the contact interface between the two plasma polymerized films 3, the bonds in which the detached OH groups are bonded are bonded. That is, the respective base materials constituting each plasma polymerized film 3 are directly coupled and integrated to form one plasma polymerized film 30.

  (Ii) When the two base materials 2 are bonded to each other, unterminated bonds generated on the surface 31 and inside of each plasma polymerized film 3 are recombined. Since this recombination occurs in a complicated manner so as to overlap (entangle) with each other, a network-like bond is formed at the bonding interface. Thereby, the respective base materials constituting each plasma polymerized film 3 are directly joined and integrated to form one plasma polymerized film 30.

  Here, the irradiation of energy rays to the plasma polymerized film 3 in the step [3] and the bonding operation in this step may be performed in any atmosphere, but in an inert gas atmosphere or a reduced pressure atmosphere. It is preferably carried out in the medium. In such an atmosphere, since moisture is hardly contained, it is possible to prevent a hydroxyl group from being bonded to an unterminated bond. As a result, a state in which unterminated bonds are generated in the vicinity of and inside the surface 31 of the plasma polymerization film 3 is dominant. In other words, a state in which a hydroxyl group is bonded to an unterminated bond is relatively less likely to occur.

  Thus, when the state in which the unterminated bond is generated becomes dominant, when the two base materials 2 are bonded to each other, these bonds are rebonded. That is, the joining by the mechanism (ii) described above becomes dominant. In the joining by the mechanism (ii), since the hydroxyl group is not involved in the joining and the conductive component in the plasma polymerized film 3 is directly involved in the joining, the conductivity at the joining interface is improved.

In other words, when bonding by mechanism (i) becomes dominant, hydroxyl groups are involved in the bonding. This hydroxyl group promotes the formation of a metal oxide in the plasma polymerized film 3 and acts as an electrical resistance component. For this reason, although the electroconductivity in a joining interface is obtained, there exists a possibility that electroconductivity may fall a little.
From the above, the conductivity at the bonding interface can be further increased by performing the irradiation of energy rays on the plasma polymerized film 3 and the above-described bonding operation in an inert gas atmosphere or a reduced pressure atmosphere. .

With the above mechanism, the joined body 1 is obtained as shown in FIG. 3 (f) (third step).
Note that the active state of the surface of the plasma polymerized film 3 activated in the step [3] relaxes with time. For this reason, this process [4] is performed as soon as possible after the completion of the process [3]. Specifically, after the completion of the step [3], the step [4] is preferably performed within 60 minutes, and more preferably within 5 minutes. Within this time, the surface of the plasma polymerized film 3 maintains a sufficiently active state, so that a sufficient bonding strength can be obtained when bonded.

  In other words, the plasma polymerization film 3 before activation is chemically stable and excellent in weather resistance. For this reason, the plasma polymerized film 3 at the time when the step [2] is completed is suitable for long-term storage. Therefore, a large amount of the base material 2 (adhered body) provided with such a plasma polymerized film 3 is manufactured or purchased and stored, and just before the bonding in this step [4], only the necessary number is performed. If the step [3] is performed, it is effective from the viewpoint of the manufacturing efficiency of the joined body.

In the conventional solid bonding such as silicon direct bonding, even if the surface is activated, the active state is maintained for only a very short time of several seconds to several tens of seconds in the atmosphere. For this reason, after the surface was activated, there was a problem that it was not possible to ensure sufficient time for performing operations such as bonding the two members to be joined together.
On the other hand, according to the present invention, the active state can be maintained for a relatively long time of several minutes or more by the action of the plasma polymerized film. For this reason, the time required for the work can be sufficiently secured, and the efficiency of the joining work can be increased.

In the bonded body 1 obtained in this manner, the bonding occurs in a short time like a covalent bond, not an adhesive based on a physical bond such as an anchor effect, like an adhesive used in a conventional bonding method. Based on a strong chemical bond, the two substrates 2 are joined together. For this reason, the joined body 1 is extremely difficult to be peeled off, and joining unevenness or the like hardly occurs.
Further, according to the bonding method of the present invention, unlike the conventional solid bonding, a heat treatment at a high temperature (about 700 to 800 ° C.) is not required. Can be used for joining.
Moreover, since the two base materials 2 and 2 are joined together via the plasma polymerization film 3, there is also an advantage that there is no restriction in the material of the base material as in the conventional solid joining.

From the above, according to the present invention, the range of selection of the constituent materials of the base materials 2 and 2 can be expanded.
Furthermore, since conventional solid bonding is not bonding via a bonding layer, when there is a large difference in the coefficient of thermal expansion between two substrates, when these are bonded, a large stress based on the difference is bonded. Concentration at the interface may cause problems such as peeling, but according to the present invention, stress concentration is mitigated through the plasma polymerized film 3, and peeling in the bonded body 1 can be reliably prevented. it can.

  Moreover, the plasma polymerization film | membrane 3 becomes a solid thing which does not have fluidity | liquidity. For this reason, by using the plasma polymerized film 3 as a bonding layer, the thickness and shape of the bonding layer (plasma polymerized film 3) hardly change compared to a conventional liquid or viscous liquid adhesive. Thereby, the dimensional accuracy of the joined body 1 obtained using the plasma polymerized film 3 is remarkably higher than the conventional one. Furthermore, since the time required for curing the adhesive is not required, strong bonding can be achieved in a short time.

The joined body (joined body of the present invention) 1 can be obtained as described above.
The bonded body 1 thus obtained preferably has a bonding strength between the substrates 2 of 5 MPa (50 kgf / cm ² ) or more, more preferably 10 MPa (100 kgf / cm ² ) or more. The bonded body 1 having such bonding strength can sufficiently prevent the peeling. Moreover, according to the joining method of the present invention, the joined body 1 in which the two base materials 2 are joined with such a large joining strength can be efficiently produced.

In addition, the plasma polymerized film 30 in the joined body 1 has conductivity, but its resistivity is preferably 1 × 10 ⁻³ Ω · cm or less, although it varies slightly depending on the composition of the constituent materials. More preferably, it is 10 ⁻⁴ Ω · cm or less. If the resistivity of the plasma polymerized film 30 is sufficiently low in this way, the plasma polymerized film 30 can be sufficiently utilized as a wiring with little loss.
In addition, after obtaining the joined body 1, you may make it perform either one or both of the following two processes [5A] and [5B] with respect to this joined body 1 as needed. Thereby, the joint strength of the joined body 1 can be further improved. At the same time, it is possible to further improve the conductivity developed in the plasma polymerized film 3.

[5A] As shown in FIG. 3G, the obtained bonded body 1 is pressurized in a direction in which the base materials 2 approach each other.
Thereby, the surfaces of the respective plasma polymerization films 3 are closer to each other. As a result, dehydration condensation and recombination of binding activity in the step [4] are promoted. Then, the integration of the two plasma polymerized films 3 further proceeds, and the bonding strength in the bonded body 1 can be further increased.
At this time, the pressure when pressurizing the bonded body 1 is preferably as high as possible. Thereby, the joint strength in the joined body 1 can be increased in proportion to the pressure.

In addition, what is necessary is just to adjust this pressure suitably according to conditions, such as a constituent material and thickness of the base material 2, and a joining apparatus. Specifically, although it varies slightly depending on the constituent material and thickness of the substrate 2, it is preferably about 0.2 to 10 MPa, more preferably about 1 to 5 MPa. Thereby, the joining strength of the joined body 1 can be reliably increased. In addition, although this pressure may exceed the said upper limit, depending on the constituent material of the base material 2, there exists a possibility that damage etc. may arise in the base material 2. FIG.
The time for pressurization is not particularly limited, but is preferably about 10 seconds to 30 minutes. In addition, what is necessary is just to change suitably the time to pressurize according to the pressure at the time of pressurizing. Specifically, the higher the pressure at which the bonded body 1 is pressed, the shorter the pressing time.

[5B] As shown in FIG. 3G, the obtained bonded body 1 is heated.
Thereby, dehydration condensation of OH groups further proceeds at the interface of each plasma polymerized film 3. Thereby, the joint strength in the joined body 1 can be further increased.
At this time, the temperature at the time of heating the bonded body 1 is not particularly limited as long as it is higher than room temperature and lower than the heat resistance temperature of the bonded body 1, but is preferably about 25 to 100 ° C., more preferably 50 to 100 ° C. About ℃. By heating at a temperature in such a range, it is possible to reliably increase the bonding strength while reliably preventing the bonded body 1 from being altered or deteriorated by heat.

The heating time is not particularly limited, but is preferably about 1 to 30 minutes.
Moreover, when performing both said process [5A] and [5B], it is preferable to perform these simultaneously. That is, as shown in FIG. 3G, it is preferable to heat the bonded body 1 while applying pressure. Thereby, the effect by pressurization and the effect by heating are exhibited synergistically, and the joint strength of the joined body 1 can be particularly increased.

In addition, when the thermal expansion coefficients of two base materials 2 are substantially equal, it is preferable to heat the joined body 1 as described above, but when the thermal expansion coefficients of the two base materials 2 are different from each other. Is preferably performed at as low a temperature as possible. By performing the bonding at a low temperature, it is possible to further reduce the thermal stress generated at the bonding interface.
Specifically, although it depends on the difference in thermal expansion coefficient between the two base materials 2, it is preferable to perform the bonding at a temperature of about 25 to 50 ° C, and it is more preferable to perform the bonding at a temperature of about 25 to 40 ° C. . Within such a temperature range, even if the difference in thermal expansion coefficient between the two base materials 2 is large to some extent, the thermal stress generated at the bonding interface can be sufficiently reduced. As a result, it is possible to reliably prevent warpage, peeling, and the like in the joined body 1.

In this case, when the difference in thermal expansion coefficient between the two base materials 2 is 5 × 10 ⁻⁵ / K or more, it is strongly recommended that the bonding be performed at the lowest possible temperature as described above. .
By performing the steps as described above, the two plasma polymer films 3 are almost completely integrated into one plasma polymer film 30. As a result, as shown in FIG. 3 (h), a joined body 1 ′ with higher joint strength is obtained.

<< Second Embodiment >>
Next, a second embodiment of the joining method of the present invention will be described.
4 and 5 are views (longitudinal sectional views) for explaining a second embodiment of the joining method of the present invention. In the following description, the upper side in FIGS. 4 and 5 is referred to as “upper” and the lower side is referred to as “lower”.

Hereinafter, although 2nd Embodiment of the joining method is described, it demonstrates centering around difference with the joining method concerning the said 1st Embodiment, and the description is abbreviate | omitted about the same matter.
In the bonding method according to the present embodiment, the first adherend 41 having the plasma polymerized film 3 on the first base 21 and the second adherend 42 having the second base 22 are joined. Except for the above, it is the same as the first embodiment.

  That is, in the bonding method according to the present embodiment, the plasma polymerized film 3 is formed on the first base material 21 to produce the first adherend 41 (first process), and the plasma polymerized film 3. Two steps are performed so that the plasma polymerized film 3 and the second base material 22 are in contact with each other, applying energy to the material and activating the plasma polymerized film 3 so that the plasma polymerized film 3 exhibits conductivity (second process). The adherends 41 and 42 are bonded together to obtain a joined body (third step). Hereinafter, each process will be described sequentially.

[1] First, the first base material 21 and the second base material 22 (second adherend 42) are prepared. Then, in the same manner as in the first embodiment, as shown in FIGS. 4A to 4C, the plasma polymerized film 3 containing a conductive component is formed on the first base material 21. Thereby, the 1st to-be-adhered body 41 is obtained. (First step).
Note that, as in the case of the first base material 21, the second base material 22 is also provided with a plasma polymerized film in advance on the bonding surface 24 (the surface that is in close contact with the plasma polymerized film 3 in the process described later). 3 may be subjected to a surface treatment for improving the adhesion to the surface. Thereby, the bonding surface 24 is cleaned and activated. As a result, when the bonding surface 24 and the plasma polymerized film 3 are brought into close contact with each other in the process described later, the bonding strength between the bonding surface 24 and the plasma polymerized film 3 can be increased.

Although it does not specifically limit as this surface treatment, The process similar to the surface treatment with respect to the joint surface 23 of the above-mentioned 1st base material 21 can be used.
Similarly to the case of the first base material 21, depending on the constituent material of the second base material 22, the adhesion to the plasma polymerized film 3 is sufficiently high even without performing the surface treatment as described above. There is something to be. Examples of the constituent material of the second base material 22 that can obtain such an effect include materials mainly composed of various metal-based materials, various silicon-based materials, various glass-based materials and the like as described above.

That is, the surface of the second substrate 22 made of such a material is covered with an oxide film, and hydroxyl groups are bonded to the surface of the oxide film. Therefore, by using the second base material 22 covered with such an oxide film, the bonding surface 24 of the second base material 22 and the plasma polymerization film 3 can be obtained without performing the surface treatment as described above. It is possible to increase the bonding strength.
In this case, the entire second base material 22 may not be made of the material as described above, and at least the vicinity of the bonding surface 24 may be made of the material as described above.

Further, when the bonding surface 24 of the second base material 22 has the following groups or substances, the bonding surface 24 of the second base material 22 and the plasma polymerization can be performed without performing the surface treatment as described above. The bonding strength with the film 3 can be sufficiently increased.
Examples of such groups and substances include functional groups such as hydroxyl groups, thiol groups, carboxyl groups, amino groups, nitro groups, and imidazole groups, radicals, ring-opened molecules, double bonds, and triple bonds. At least one group or substance selected from the group consisting of saturated bonds, halogens such as F, Cl, Br and I, and peroxides, or unterminated bonds formed by elimination of these groups ( (Unbonded hand, dangling bond).

Moreover, the second surface capable of being strongly bonded to the plasma polymerized film 3 by appropriately selecting and performing various surface treatments as described above on the bonding surface 24 so as to have such groups and substances The base material 22 is obtained.
Among these, it is preferable that the bonding surface 24 of the second base material 22 has a hydroxyl group. A large attractive force based on the hydrogen bond is generated between the bonding surface 24 and the plasma polymerization film 3 where the hydroxyl group is exposed. Thereby, the 1st to-be-adhered body 41 and the 2nd to-be-adhered body 42 can be joined especially firmly.

Further, instead of the surface treatment, an intermediate layer may be formed in advance on the bonding surface 24 of the second base material 22.
This intermediate layer may have any function. For example, as in the case of the first base material 21, the function of improving the adhesion with the plasma polymerization film 3, the cushioning property (buffer function), What has the function etc. which relieve stress concentration is preferable. By bonding the second base material 22 and the plasma polymerized film 3 through such an intermediate layer, a highly reliable bonded body 1 can be obtained.
As the constituent material of the intermediate layer, for example, the same material as the constituent material of the intermediate layer formed on the bonding surface 23 of the first base member 21 can be used.
The surface treatment and the formation of the intermediate layer as described above may be performed as necessary, and can be omitted when a high bonding strength is not particularly required.

[2] Next, as shown in FIG. 4 (d), energy is applied to the surface 31 of the obtained plasma polymerization film 3. Thereby, a part of molecular bond of the plasma polymerized film 3 is cut, and the plasma polymerized film 3 is activated. At the same time, conductivity is developed in the plasma polymerization film 3 (second step).
[3] Next, as shown in FIG. 5 (e), the two adherends 41 and 42 are bonded together so that the plasma polymerization film 3 and the bonding surface 24 of the second base material 22 are in close contact with each other. Thereby, the 1st to-be-adhered body 41 and the 2nd to-be-adhered body 42 are joined, and the conjugate | zygote 1 shown in FIG.5 (f) is obtained (3rd process).

In the joining method according to the present embodiment, the same actions and effects as the joining method according to the first embodiment can be obtained.
Further, in the present embodiment, of the two adherends 41 and 42, the first adherend 41 has the plasma polymerized film 3, but the second adherend 42 has the plasma polymerized film. Not done. Therefore, when the plasma polymerized film 3 is manufactured, the first base material 21 is exposed to plasma for a relatively long time, but the second base material 22 is not exposed to plasma. For this reason, even if the 2nd base material 22 is comprised with the material with low durability with respect to a plasma, there is no possibility that the 2nd base material 22 may change and deteriorate. Therefore, the constituent material of the second base material 22 has an advantage that it can be selected from a wide range of materials without considering durability against plasma.

After obtaining the joined body 1, at least one of the three steps ([5A], [5B] and [5C]) in the first embodiment is performed on the joined body 1 as necessary. One process may be performed.
For example, as shown in FIG. 5G, the base materials 21 and 22 of the joined body 1 are brought closer to each other by heating the joined body 1 while applying pressure. Thereby, dehydration condensation of hydroxyl groups at the interface of the plasma polymerized film 3 is promoted. The plasma polymerization film 3 and the second base material 22 are almost completely integrated to form a single layer of plasma polymerization film. As a result, the joint strength of the joined body 1 can be further improved.

<< Third Embodiment >>
Next, a third embodiment of the joining method of the present invention will be described.
6 and 7 are views (longitudinal sectional views) for explaining a third embodiment of the joining method of the present invention. In the following description, the upper side in FIGS. 6 and 7 is referred to as “upper” and the lower side is referred to as “lower”.

Hereinafter, the third embodiment of the bonding method will be described. However, the difference from the bonding method according to the first embodiment and the second embodiment will be mainly described, and description of similar matters will be omitted. .
In the bonding method according to the present embodiment, in the second step, a plasma polymerization film is formed by applying energy to a predetermined region (hereinafter referred to as “first region 311”) of a part of the plasma polymerization film 3. 3 is the same as that of the second embodiment except that the first region 311 is partially activated and the plasma polymerization film 3 located in the first region 311 is made to exhibit conductivity. .

  That is, the bonding method according to the present embodiment prepares the first base material 21 and the second base material 22 (second adherend 42), and on the bonding surface 23 of the first base material 21. In addition, the plasma polymerized film 3 is formed and the first adherend 41 is produced (first process), and energy is applied to the first region 311 of the plasma polymerized film 3 to activate it. Two adherends so that the plasma polymerized film 3 located in the first region 311 exhibits conductivity (second process) and the plasma polymerized film 3 and the second base material 22 are in contact with each other. 41 and 42 are bonded together to obtain a joined body (third step). Hereinafter, each process will be described sequentially.

[1] First, as in the second embodiment, as shown in FIGS. 6A to 6C, a plasma polymerization film 3 containing a conductive component is formed on the first substrate 21. . In addition, a second base material 21 (second adherend 42) similar to the first embodiment is prepared. Thereby, the 1st to-be-adhered body 41 is obtained (1st process).
[2] Next, as shown in FIG. 6 (d), energy is selectively applied to the first region 311 of the surface 31 of the plasma polymerization film 3. Thereby, a part of the molecular bond of the plasma polymerization film 3 located in the first region 311 is cut, and the plasma polymerization film 3 is activated.

In addition, when irradiating an energy ray with respect to the 1st area | region 311 among the plasma polymerization films | membranes 3, if it is an energy ray with high directivity like a laser beam and an electron beam, it will irradiate toward the target direction. As a result, the first region 311 can be selectively and easily irradiated with energy rays.
Even if the energy beam has low directivity, the energy beam is selectively applied to the first region 311 if it is irradiated so as to cover the region other than the first region 311 in the plasma polymerization film 3. Can be irradiated.

Specifically, for example, as shown in FIG. 6 (d), a mask 6 having a window portion 61 having a shape corresponding to the shape of the first region 311 to be irradiated with ultraviolet rays of the plasma polymerization film 3 is provided. What is necessary is just to irradiate an ultraviolet-ray through this mask 6. In this way, it is possible to selectively irradiate the first region 311 shown in FIG. 6D in the plasma polymerization film 3 with ultraviolet rays.
When energy is applied as described above, adhesiveness develops in the first region 311 of the plasma polymerization film 3. At the same time, conductivity is developed in the first region 311 of the plasma polymerization film 3 (second step).

[3] Next, as shown in FIG. 7 (e), the two adherends 41 and 42 are bonded together so that the plasma polymerization film 3 and the bonding surface 24 of the second base material 22 are in close contact with each other. Thereby, the first adherend 41 and the second adherend 42 are partially joined in the first region 311. As a result, a joined body 1 as shown in FIG.
In the joining method according to the present embodiment, the same operations and effects as those of the joining method according to the first embodiment or the second embodiment can be obtained.

Further, according to the present embodiment, conductivity is developed in the plasma polymerization film 3 located in the first region 311 in the joined body 1. For this reason, for example, if the first region 311 is set to a linear region, the plasma polymerization film 3 located in the linear region can be given a function as a wiring.
On the other hand, the plasma polymerized film 3 located in a region other than the first region 311 (hereinafter referred to as “second region 312”) is non-conductive and therefore has a function as an insulator. .

Therefore, the plasma polymerized film 3 according to the present embodiment includes the first region 311 having conductivity and the second region 312 having non-conductivity.
Accordingly, in the joined body 1 illustrated in FIG. 7F, the first region 311 having a function as a wiring is replaced with the second region 312 having a function as an insulator, the first base material 21, and the second base material 21. The substrate 22 can be covered.
As a result, the plasma polymerization film 3 located in the first region 311 can be electrically insulated by configuring the base materials 21 and 22 with a non-conductive material.

Further, by forming each of the base materials 21 and 22 from a conductive material, the base materials 21 and 22 can be partially connected to each other via the plasma polymerization film 3 located in the first region 311. it can.
Since such a joined body 1 has a layer having both a function as a wiring and a function as an insulator between the base materials 21 and 22, it can be applied to a highly reliable wiring board.

  Furthermore, according to the present embodiment, when the first base material 21 and the second base material 22 are joined, the first joint 21 (the face facing each other) is not joined, but the first base 21 and the second base 22 are joined. Only the region 311 is selectively joined. At the time of bonding, the region to be bonded can be easily selected only by controlling the region to which energy is applied to the plasma polymerized film 3. Thereby, since the area and shape of the junction part of the 1st base material 21 and the 2nd base material 22 can be controlled, for example, the joint strength of the joined body 1 can be adjusted easily. As a result, for example, the joined body 1 is obtained in which the joined portion can be easily separated.

Further, by controlling the area and shape of the joint portion between the first base material 21 and the second base material 22, local concentration of stress generated in the joint portion can be reduced. Thereby, for example, even when the difference in thermal expansion coefficient between the first base material 21 and the second base material 22 is large, the base materials 21 and 22 can be reliably bonded.
Furthermore, according to the bonding method of the present invention, in the second region 312 of the plasma polymerized film 3 included in the first base material 21, there is a slight amount between the plasma polymerized film 3 and the second base material 22. A gap is created. In order to make use of this gap, a closed space or a flow path may be formed between the first base material 21 and the second base material 22 by appropriately adjusting the shape of the first region 311. it can.

After obtaining the joined body 1, at least one of the three steps ([5A], [5B] and [5C]) in the first embodiment is performed on the joined body 1 as necessary. One process may be performed.
For example, as illustrated in FIG. 7G, the base materials 21 and 22 of the joined body 1 are brought closer to each other by heating the joined body 1 while applying pressure. Thereby, dehydration condensation of hydroxyl groups at the interface of the plasma polymerized film 3 is promoted. The plasma polymerized film 3 and the second base material 22 are almost completely integrated into a one-layer plasma polymerized film in the first region 311. As a result, the joint strength of the joined body 1 can be further improved.

<< Fourth Embodiment >>
Next, a fourth embodiment of the joining method of the present invention will be described.
8 and 9 are views (longitudinal sectional views) for explaining a fourth embodiment of the joining method of the present invention. In the following description, the upper side in FIGS. 8 and 9 is referred to as “upper” and the lower side is referred to as “lower”.

Hereinafter, the fourth embodiment of the bonding method will be described. However, the difference from the bonding method according to the first to third embodiments will be mainly described, and description of similar matters will be omitted. .
In the bonding method according to the present embodiment, a first adherend 41 having a plasma polymerized film 301 on the first substrate 21 and a second substrate having a plasma polymerized film 302 on the second substrate 22 are used. Except for preparing the adhering body 42 and selectively applying energy to a predetermined region (hereinafter referred to as “first region 311”) of each of the plasma polymerized films 301 and 302. The same as in the first embodiment.

  That is, in the bonding method according to the present embodiment, the plasma polymerized film 301 is formed on the first substrate 21 to produce the first adherend 41, and the plasma polymerized film is formed on the second substrate 22. 302, forming the second adherend 42 (first step), applying energy to the respective first regions 311 of the plasma polymerized films 301 and 302 and activating them, The two adherends 41 and 42 are bonded together so that the first region 311 exhibits conductivity (second step) and the plasma polymerized film 301 and the plasma polymerized film 302 are in close contact with each other. (Step 3). Hereinafter, each process will be described sequentially.

[1] First, as in the first embodiment, as shown in FIGS. 8A to 8C, a plasma polymerization film 301 containing a conductive component is formed on the first substrate 21. . Similarly, a plasma polymerization film 302 containing a conductive component is formed on the second substrate 22. Thereby, the 1st to-be-adhered body 41 and the 2nd to-be-adhered body 42 are obtained (1st process).
[2] Next, as shown in FIG. 8D, energy is selectively applied to the first region 311 of the surface 303 of the plasma polymerization film 301. As a result, a part of the molecular bond of the plasma polymer film 301 located in the first region 311 is cut, and the plasma polymer film 301 is activated. Similarly, energy is selectively given to the first region 311 of the surface 304 of the plasma polymerization film 302. As a result, a part of the molecular bond of the plasma polymer film 302 located in the first region 311 is cut, and the plasma polymer film 302 is activated.
When energy is applied as described above, adhesiveness develops in the first regions 311 of the respective plasma polymerization films 301 and 302. At the same time, the first region 311 of each of the plasma polymer films 301 and 302 develops conductivity (second step).

[3] Next, as shown in FIG. 9E, the two adherends 41 and 42 are bonded together so that the plasma polymerized film 301 and the plasma polymerized film 302 are in close contact with each other. Thereby, the first adherend 41 and the second adherend 42 are partially joined in the first region 311. As a result, the joined body 1 as shown in FIG. 9F is obtained (third step).
In the joining method according to the present embodiment, the same operations and effects as the joining methods according to the first to third embodiments can be obtained.

After obtaining the joined body 1, at least one of the three steps ([5A], [5B] and [5C]) in the first embodiment is performed on the joined body 1 as necessary. One process may be performed.
For example, as shown in FIG. 9G, the base materials 21 and 22 of the joined body 1 are brought closer to each other by heating the joined body 1 while applying pressure. This promotes dehydration condensation of hydroxyl groups and recombination of dangling bonds at the interfaces of the plasma polymerized films 301 and 302. The plasma polymer films 301 and 302 are almost completely integrated into a single plasma polymer film in the first region 311. As a result, the joint strength of the joined body 1 can be further improved.

FIG. 10 shows another configuration example of the joined body according to the present embodiment.
In this embodiment, the planar view shape of the predetermined area | region 313 of the surface 303 of the plasma polymerization film | membrane 301 has comprised stripe shape as shown to Fig.10 (a). Similarly, the planar view shape of the predetermined region 314 on the surface 304 of the plasma polymerization film 302 has a stripe shape as shown in FIG.

  That is, in this embodiment, the predetermined region 313 is selectively activated by applying energy to the stripe-shaped predetermined region 313 in the plasma polymerization film 301. Similarly, the predetermined region 314 is selectively activated by applying energy to the stripe-shaped predetermined region 314 in the plasma polymerization film 302.

Note that the stripe-shaped predetermined region 313 and the stripe-shaped predetermined region 314 intersect each other.
When the first adherend 41 and the second adherend 42 are bonded to each other, a portion where the predetermined region 313 and the predetermined region 314 overlap (hereinafter referred to as “common portion 315”). The first adherend 41 and the second adherend 42 are partially joined. Thereby, the joined body 1 as shown in FIG.10 (b) is obtained.

In such a bonded body 1, by appropriately controlling the area and shape of each of the predetermined regions 313 and 314, for example, the bonding strength of the bonded body 1 can be adjusted, or the local concentration of stress generated at the bonded interface can be reduced. can do.
In addition, by applying energy, the plasma polymerized film 301 located in the predetermined region 313 and the plasma polymerized film 302 located in the predetermined region 314 each exhibit conductivity, but each of these plasma polymerized films 301 and 302 is Conduction can occur at the common portion 315.
In addition, the shape of each predetermined area | region 313,314 is not specifically limited, Shapes, such as circular, an ellipse, and a polygon, may be sufficient.

«Fifth embodiment»
Next, a fifth embodiment of the joining method of the present invention will be described.
11 and 12 are views (longitudinal sectional views) for explaining a fifth embodiment of the joining method of the present invention. In the following description, the upper side in FIGS. 11 and 12 is referred to as “upper” and the lower side is referred to as “lower”.

Hereinafter, the fifth embodiment of the bonding method will be described, but the description will focus on differences from the bonding method according to the first to fourth embodiments, and description of similar matters will be omitted. .
In the bonding method according to the present embodiment, a plasma polymerization film containing a conductive component in a predetermined region (hereinafter referred to as “first region 311”) of the bonding surface 23 of the first base material 21. 3a is formed, and a plasma polymerization film 3b that does not contain a conductive component is formed in a region other than the first region 311 (hereinafter referred to as “second region 312”) of the bonding surface 23. The first adherend 41 including the first base material 21 and each of the plasma polymerized films 3a and 3b is produced, and the first adherend 41 and the second adherend 42 are joined together. Except for the above, it is the same as the first embodiment.

  That is, in the bonding method according to the present embodiment, the first base material 21 and the second base material 22 (second adherend 42) are prepared, and the bonding surface 23 of the first base material 21 is formed. A plasma polymerized film 3 a is formed in a part of the first region 311, and a plasma polymerized film 3 b is formed in the second region 312 of the bonding surface 23 of the first base material 21, thereby providing a first adherend. 41 (first step), a step of applying energy to each plasma polymerized film 3a, 3b and activating the plasma polymerized film 3a (second step), There is a step (third step) of bonding the two adherends 41 and 42 so that the plasma polymer films 3a and 3b and the second base material 22 are in close contact with each other to obtain a joined body. Hereinafter, each process will be described sequentially.

[1] First, the first base material 21 and the second base material 22 (second adherend 42) are prepared. Each of the base materials 21 and 22 has the same configuration as that of the first embodiment.
Next, as shown in FIG. 11A, a mask 6 a having a window portion 61 a having a shape corresponding to the shape of the first region 311 is provided above the bonding surface 23 of the first base material 21.
Next, a plasma polymerization film 3a containing a conductive component is formed on the bonding surface 23 of the first base material 21 through the mask 6a. The polymer produced by the plasma polymerization method is deposited on the bonding surface 23 of the first base material 21. At this time, the polymer passes through the window portion 61a of the mask 6a, so that the first region 311 is filled. Only polymer is deposited. As a result, the plasma polymerized film 3a is formed in a part of the first region 311 of the bonding surface 23 of the first base material 21 (see FIG. 11B).

In FIG. 11A, the mask 6 a and the first base material 21 are separated from each other, but the mask 6 a may be provided so as to be in contact with the bonding surface 23 of the first base material 21.
Next, as shown in FIG. 11C, a mask 6 b having a window portion 61 b having a shape corresponding to the shape of the second region 312 is provided above the bonding surface 23 of the first base material 21. Then, a plasma polymerization film 3b not containing a conductive component is formed in the second region 312 of the bonding surface 23 of the first base material 21 through the mask 6b.

As described above, as shown in FIG. 11 (d), the first base material 21, the plasma polymerization film 3 a provided in the first region 311 of the bonding surface 23 of the first base material 21, A first adherend 41 including a plasma polymerization film 3b provided in the second region 312 of the bonding surface 23 of the first base material 21 is produced (first step).
Here, it is preferable that the plasma polymerized film 3b containing no conductive component is composed mainly of polyorganosiloxane. Thereby, the plasma polymerization film | membrane 3b can join the 1st base material 21 and the 2nd base material 22 more firmly. Moreover, since polyorganosiloxane does not contain a conductive component and has excellent insulating properties, the plasma polymerized film 3b can be provided with an excellent function as an insulator.

Polyorganosiloxane usually exhibits water repellency (non-adhesiveness), but when given energy, it can easily desorb organic groups, changes to hydrophilicity, and exhibits adhesiveness. To do.
That is, even when the plasma polymerized film 3b composed of polyorganosiloxane exhibiting water repellency is brought into contact with the second base material 22 in the process described later, adhesion is inhibited by the organic groups on the surface of the plasma polymerized film 3b. It will be extremely difficult to bond. On the other hand, when the plasma polymerized film 3b made of polyorganosiloxane having hydrophilicity is brought into contact with the second base material 22, both can be bonded. That is, the advantage that the water repellency and the hydrophilicity can be easily controlled leads to the advantage that the adhesiveness can be easily controlled.

Therefore, the plasma polymerized film 3b exhibits an adhesive property relatively easily and uniformly by applying energy, but exhibits non-adhesiveness when energy is not applied and can prevent unintended adhesion. It will be a thing.
In addition, since polyorganosiloxane is relatively flexible, for example, even when the constituent materials of the first base material 21 and the second base material 22 are different from each other, the space between the base materials 21 and 22 is different. It is possible to relieve the stress accompanying thermal expansion that occurs in Thereby, peeling can be reliably prevented in the bonded body 1 finally obtained.

  Furthermore, since polyorganosiloxane is excellent in chemical resistance, it can be effectively used for joining members that are exposed to chemicals for a long time. Specifically, for example, when manufacturing a droplet discharge head of an industrial inkjet printer in which an organic ink that easily erodes a resin material is used, by using the plasma polymerized film 3 mainly composed of polyorganosiloxane. , Its durability can be improved.

  Such a polyorganosiloxane has a random atomic structure including a siloxane (Si—O) bond. By having such a structure, the polyorganosiloxane becomes a strong film that is hardly deformed. For this reason, the plasma polymerized film 3b exhibits particularly excellent adhesion, and the plasma polymerized film 3b itself has high dimensional accuracy. For this reason, finally, the bonded body 1 having excellent bonding strength and high dimensional accuracy is obtained.

  The crystallinity of such a polyorganosiloxane is not particularly limited, but is preferably 45% or less, and more preferably 40% or less. As a result, the polyorganosiloxane contains a sufficiently random atomic structure. For this reason, the characteristics exhibited by the polyorganosiloxane described above become obvious, and the dimensional accuracy and adhesiveness of the plasma polymerized film 3b become more excellent.

  Further, when the plasma polymerized film 3b is composed of polyorganosiloxane, the sum of the Si atom content and the O atom content of all the atoms constituting the plasma polymerized film 3b excluding H atoms. However, it is preferable that it is about 10-90 atomic%, and it is more preferable that it is about 20-80 atomic%. If Si atoms and O atoms are contained in the above-mentioned range, the plasma polymerization film 3b forms a strong network of Si atoms and O atoms, and the plasma polymerization film 3b itself is strong. Become. In addition, the plasma polymerized film 3 b exhibits particularly high bonding strength with respect to the first base material 21 and the second base material 22.

The abundance ratio of Si atoms and O atoms in the plasma polymerized film 3b is preferably about 3: 7 to 7: 3, and more preferably about 4: 6 to 6: 4. By setting the abundance ratio of Si atoms and O atoms to be within the above range, the stability of the plasma polymerized film 3b is increased, and the adherends 41 and 42 can be bonded more firmly. .
Further, among polyorganosiloxanes, those mainly composed of a polymer of octamethyltrisiloxane are preferred. The plasma polymerized film 3b mainly composed of a polymer of octamethyltrisiloxane is particularly suitable for use in the present embodiment because it is particularly excellent in adhesiveness. Moreover, since the raw material which has octamethyltrisiloxane as a main component is liquid at normal temperature and has an appropriate viscosity, there is also an advantage that it is easy to handle.

[2] Next, as shown in FIG. 12E, energy is applied to each of the plasma polymerization films 3a and 3b. Thereby, a part of molecular bond of each plasma polymerization film | membrane 3a, 3b is cut | disconnected and activated.
Specifically, as shown in FIG. 12E, energy is applied by irradiating ultraviolet rays. As a result, each plasma polymerized film 3a, 3b exhibits adhesiveness. And by this adhesiveness, each plasma polymerization film | membrane 3a, 3b and the 2nd base material 22 are joined. At the same time, the plasma polymerized film 3a exhibits conductivity (second step).

[3] Next, as shown in FIG. 12 (f), the two adherends 41 and 42 are placed so that the plasma polymer films 3 a and 3 b and the bonding surface 24 of the second base material 22 are in close contact with each other. to paste together. Thereby, the joined body 1 as shown in FIG. 12G is obtained (third step).
In the joining method according to the present embodiment, the same operations and effects as those of the joining method according to the first to fourth embodiments can be obtained.
After obtaining the joined body 1, at least one of the three steps ([5A], [5B] and [5C]) in the first embodiment is performed on the joined body 1 as necessary. One process may be performed. Thereby, the joint strength of the joined body 1 can be further improved.

<< Sixth Embodiment >>
Next, a sixth embodiment of the joining method of the present invention will be described.
13 and 14 are views (longitudinal sectional views) for explaining a sixth embodiment of the joining method of the present invention. In the following description, the upper side in FIGS. 13 and 14 is referred to as “upper” and the lower side is referred to as “lower”.

Hereinafter, the sixth embodiment of the bonding method will be described. However, the difference from the bonding method according to the first to fifth embodiments will be mainly described, and description of similar matters will be omitted. .
In the bonding method according to the present embodiment, the second adherend 42 including the second base material 22 and the plasma polymerization film 3c provided on the entire surface of the bonding surface 24 of the second base material 22 is used. Except for the above, it is the same as the fifth embodiment.

  That is, in the bonding method according to the present embodiment, the first base material 21 and the second base material 22 are prepared, and the first region 311 and the second base material 21 of the bonding surface 23 of the first base material 21 are prepared. A plasma polymerized film 3a and a plasma polymerized film 3b are respectively formed in the region 312 to produce the first adherend 41, and the plasma polymerized film 3c is formed on the entire bonding surface 24 of the second base material 22. Forming the second adherend 42 (first step), applying energy to each plasma polymerized film 3a, 3b, 3c and activating the plasma polymerized film 3a; And the step (second step) of bonding the two adherends 41 and 42 so that the plasma polymerized films 3a and 3b and the plasma polymerized film 3c are in close contact with each other (second process). 3 steps). Hereinafter, each process will be described sequentially.

[1] First, as shown in FIGS. 13A to 13D, a first adherend 41 is produced in the same manner as in the fifth embodiment.
On the other hand, as shown in FIGS. 13A to 13B, the plasma polymerization film containing no conductive component on the entire surface of the bonding surface 24 of the second substrate 22 by the same method as in the first embodiment. 3c is formed. Thereby, the 2nd to-be-adhered body 42 provided with the 2nd base material 22 and the plasma polymerization film | membrane 3c is obtained (1st process).
Here, the plasma polymerization film 3c not containing a conductive component has the same configuration as the plasma polymerization film 3b in the fifth embodiment. That is, the plasma polymerized film 3c is preferably composed of polyorganosiloxane as a main material. Thereby, the outstanding function as an insulator can be provided to the plasma polymerization film 3c.

[2] Next, as shown in FIG. 14E, energy is applied to each of the plasma polymerization films 3a, 3b, and 3c. Thereby, a part of molecular bond of each plasma polymerization film | membrane 3a, 3b, 3c is cut | disconnected and activated.
Specifically, as shown in FIG. 14E, energy is applied by irradiating ultraviolet rays. As a result, each plasma polymerized film 3a, 3b, 3c exhibits adhesiveness. And by this adhesiveness, each plasma polymerization film | membrane 3a, 3b and the plasma polymerization film | membrane 3c are joined. At the same time, the plasma polymerized film 3a exhibits conductivity (second step).

[3] Next, as shown in FIG. 14 (f), the two adherends 41 and 42 are bonded together so that the plasma polymer films 3 a and 3 b and the plasma polymer film 3 c are in close contact with each other. Thereby, the joined body 1 as shown in FIG. 14G is obtained (third step).
In the joining method according to the present embodiment, the same operations and effects as the joining methods according to the first to fifth embodiments can be obtained.
After obtaining the joined body 1, at least one of the three steps ([5A], [5B] and [5C]) in the first embodiment is performed on the joined body 1 as necessary. One process may be performed. Thereby, the joint strength of the joined body 1 can be further improved.

<< Seventh Embodiment >>
Next, a seventh embodiment of the joining method of the present invention will be described.
15 and 16 are views (longitudinal sectional views) for explaining a seventh embodiment of the joining method of the present invention. In the following description, the upper side in FIGS. 15 and 16 is referred to as “upper” and the lower side is referred to as “lower”.

Hereinafter, the seventh embodiment of the bonding method will be described. However, the difference from the bonding method according to the first to sixth embodiments will be mainly described, and description of similar matters will be omitted. .
In the joining method according to the present embodiment, the second base material 22 and a part of the joining surface 24 of the second base material 22 (hereinafter, referred to as “first region 311”). A plasma polymerized film 3 a containing a conductive component is formed, and a plasma containing no conductive component in a region other than the first region 311 (hereinafter referred to as “second region 312”) of the bonding surface 24. By forming the polymerized film 3b, a second adherend 42 including the second base material 22 and the respective plasma polymerized films 3a and 3b is produced, and the second adherend 42 and the first adherend are formed. Except for joining the body 41, it is the same as the fifth embodiment.

  That is, in the bonding method according to the present embodiment, the first base material 21 and the second base material 22 are prepared, and the first region 311 and the second base material 21 of the bonding surface 23 of the first base material 21 are prepared. A plasma polymerized film 3a and a plasma polymerized film 3b are respectively formed in the region 312 to produce the first adherend 41, and the first region 311 and the first region of the bonding surface 24 of the second base material 22 are formed. 2, the plasma polymerized film 3 a and the plasma polymerized film 3 b are respectively formed in the region 312, and the second adherend 42 is manufactured (first process). The plasma polymerized films 3a and 3b and the plasma polymerized films 3a and 3b of the second adherend 42 are activated by applying energy to the plasma polymerized films 3a and 3b of the first adherend 41, respectively. Conductivity is expressed in the plasma polymerization film 3a of the second adherend 42. And a step (third step) of bonding the two adherends 41 and 42 to obtain a joined body so that the plasma polymer films 3a and 3b are in close contact with each other. . Hereinafter, each process will be described sequentially.

[1] First, as shown in FIGS. 15A to 15D, a first adherend 41 is produced in the same manner as in the fifth embodiment.
On the other hand, as shown in FIGS. 15 (a) to 15 (d), the second base material 22 and the joint surface of the second base material 22 are formed in the same manner as the method of manufacturing the first adherend 41. The second adherend 42 including the plasma polymerized film 3a and the plasma polymerized film 3b provided in the 24 first region 311 and the second region 312 is produced (first step).

[2] Next, as shown in FIG. 16 (e), for each plasma polymerized film 3 a, 3 b of the first adherend 41 and each plasma polymerized film 3 a, 3 b of the second adherend 42. And give energy to each. Thereby, a part of molecular bond of each plasma polymerization film | membrane 3a, 3b is cut | disconnected and activated.
Specifically, as shown in FIG. 16E, energy is applied by irradiating ultraviolet rays. As a result, each plasma polymerized film 3a, 3b exhibits adhesiveness. And by this adhesiveness, each plasma polymerization film | membrane 3a, 3b of the 1st to-be-adhered body 41 and each plasma polymerization film | membrane 3a, 3b of the 2nd to-be-adhered body 42 are joined. At the same time, the plasma polymerized film 3a of the first adherend 41 and the plasma polymerized film 3a of the second adherend 42 develop conductivity.

[3] Next, as shown in FIG. 16 (f), each plasma polymerized film 3 a, 3 b of the first adherend 41 and each plasma polymerized film 3 a, 3 b of the second adherend 42 are formed. The two adherends 41 and 42 are bonded together so that they are in close contact with each other. Thereby, the joined body 1 as shown in FIG.16 (g) is obtained.
In the joining method according to the present embodiment, the same operations and effects as the joining methods according to the first to sixth embodiments can be obtained.

After obtaining the joined body 1, at least one of the three steps ([5A], [5B] and [5C]) in the first embodiment is performed on the joined body 1 as necessary. One process may be performed. Thereby, the joint strength of the joined body 1 can be further improved.
In addition, the planar view shape of the plasma polymerized film 3a included in the first adherend 41 (planar shape of the first region 311) and the planar view shape of the plasma polymerized film 3a included in the second adherend 42 ( The shape of the first region 311 in plan view) may be the same, but may be different from each other.

The joining method according to each of the embodiments as described above can be used to join various members.
Examples of members used for such bonding include semiconductor elements such as transistors, diodes, and memories, piezoelectric elements such as crystal oscillators, optical elements such as reflectors, optical lenses, diffraction gratings, and optical filters. , Optical conversion elements such as solar cells, semiconductor substrates and semiconductor elements mounted on them, insulating substrates and wiring or electrodes, inkjet recording heads, microreactors, microelectromechanical systems (MEMS) components such as micromirrors, pressure Sensor parts such as sensors, acceleration sensors, package parts for semiconductor elements and electronic parts, magnetic recording media, magneto-optical recording media, recording media such as optical recording media, liquid crystal display elements, organic EL elements, electrophoretic display elements Such display element parts, fuel cell parts, and the like.

<Wiring board>
Here, an embodiment when the joined body of the present invention is applied to a wiring board will be described.
FIG. 17 is a perspective view showing a wiring board obtained by applying the joined body of the present invention.
The wiring board 10 shown in FIG. 17 includes an insulating substrate 13, an electrode 12 disposed on the insulating substrate 13, a lead 14, and an electrode 15 provided at one end of the lead 14 so as to face the electrode 12. Have

  A plasma polymerization film is formed on each of the upper surface of the electrode 12 and the lower surface of the electrode 15. These plasma-polymerized films are bonded together by bonding by the above-described bonding method of the present invention. As a result, the electrodes 12 and 15 are firmly bonded to each other by the one-layer plasma polymerized film 11, and delamination between the electrodes 12 and 15 is reliably prevented, and highly reliable wiring is achieved. A substrate 10 is obtained.

  The plasma polymerized film 11 also has a function of conducting between the electrodes 12 and 15. Even if the plasma polymerization film 11 is very thin, it exhibits a sufficient bonding force. For this reason, the gap between the electrodes 12 and 15 can be further reduced, and the electrical resistance component (contact resistance) between the electrodes 12 and 15 can be reduced. As a result, the conductivity between the electrodes 12 and 15 can be further increased.

Further, as described above, the thickness of the plasma polymerized film 11 can be easily controlled with high accuracy. Thereby, the wiring board 10 becomes a thing with higher dimensional accuracy, and the electroconductivity between each electrode 12 and 15 can also be controlled easily.
As described above, the bonding method, the bonded body, and the wiring board of the present invention have been described based on the illustrated embodiments, but the present invention is not limited to these.

For example, the bonding method of the present invention can be suitably applied to a material that should be firmly bonded while suppressing the electrical resistance component at the bonding interface, such as bonding between electrodes. That is, the contact resistance of the bonding interface bonded by the bonding method of the present invention is small.
Moreover, in the joining method of this invention, you may add the process of 1 or more arbitrary objectives as needed.
In each of the above embodiments, the method of joining two adherends (the first adherend and the second adherend) has been described, but when joining three or more adherends, You may apply the joining method of this invention.

Next, specific examples of the present invention will be described.
1. Production of laminated body (joined body) (Example 1)
First, a single crystal silicon substrate having a length of 20 mm × width of 20 mm × an average thickness of 1 mm is prepared as the first base material, and a glass substrate of length 20 mm × width 20 mm × average thickness of 1 mm is prepared as the second base material. did.
Subsequently, these base materials were accommodated in the chamber 101 of the plasma polymerization apparatus 100 shown in FIG. 1, and the base treatment by oxygen plasma was performed.
Next, a plasma polymerization film having an average thickness of 200 nm was formed on the surface subjected to the base treatment. The film forming conditions are as shown below.

<Film formation conditions>
-Source gas composition: Trimethylgallium-Source gas flow rate: 50 sccm
Carrier gas composition: Argon Carrier gas flow rate: 100 sccm
・ High frequency power output: 100W
-Chamber pressure: 1 Pa (low vacuum)
・ Processing time: 15 minutes ・ Substrate temperature: 20 ° C.

Next, the obtained plasma polymerization film was irradiated with ultraviolet rays under the following conditions.
<Ultraviolet irradiation conditions>
-Atmospheric gas composition: Air (air)
・ Atmospheric gas temperature: 20 ℃
・ Atmospheric gas pressure: Atmospheric pressure (100 kPa)
UV wavelength: 172 nm
-Irradiation time of ultraviolet rays: 5 minutes Subsequently, one minute after the irradiation of ultraviolet rays, the respective substrates were superposed so that the surfaces irradiated with the ultraviolet rays contacted each other.
And each base material was heated at 80 degreeC, pressurizing at 3 Mpa, and maintained for 15 minutes. Thereby, each base material was joined and the laminated body (joined body) was obtained.

(Example 2)
A laminate was obtained in the same manner as in Example 1 except that the heating temperature was changed from 80 ° C to 25 ° C.
(Examples 3 to 12)
A laminate was obtained in the same manner as in Example 1 except that the constituent material of the first base material and the constituent material of the second base material were changed to the materials shown in Table 1, respectively.

(Examples 13 to 15)
Example 1 except that the constituent material of the first substrate was changed as shown in Table 1, the source gas was changed to a gas having the composition shown in Table 1, and the composition of the plasma polymerization film was changed. A laminate was obtained in the same manner as in 3 and 4.
(Example 16)
In Example 15, a laminate was obtained in the same manner as in Example 15 except that only half of the plasma polymerized film was irradiated with ultraviolet rays.
(Comparative Examples 1-3)
The constituent materials of the first base material were the materials shown in Table 1, respectively, and a laminate was obtained in the same manner as in Examples 1, 3, and 4 except that the base materials were bonded with Ag paste.

2. 2. Evaluation of Laminate (Joint) 2.1 Evaluation of Bond Strength (Split Strength) For the laminates obtained in each Example and each Comparative Example, the bond strength was measured.
The measurement of the bonding strength was performed by measuring the strength immediately before each substrate was peeled off. Then, the bonding strength was evaluated according to the following criteria.

<Evaluation criteria for bonding strength>
◎: 10 MPa (100 kgf / cm ² ) or more ○: 5 MPa (50 kgf / cm ² ) or more, less than 10 MPa (100 kgf / cm ² ) Δ: 1 MPa (10 kgf / cm ² ) or more, less than 5 MPa (50 kgf / cm ² ) ×: Less than 1 MPa (10 kgf / cm ² )

2.2 Evaluation of dimensional accuracy The dimensional accuracy in the thickness direction was measured for each joined body obtained in each of the examples and the comparative examples.
The measurement of the dimensional accuracy was performed by measuring the thickness of each corner of the square joined body and calculating the difference between the maximum value and the minimum value of the thicknesses at the four locations. This difference was evaluated according to the following criteria.
<Evaluation criteria for dimensional accuracy>
○: Less than 10 μm ×: 10 μm or more

2.3 Evaluation of Resistivity For the laminates obtained in Example 12, Example 15, Example 16, and Comparative Example 3, the resistivity of the joint portion was measured. The measured resistivity was evaluated according to the following criteria.
In the measurement of the resistivity of the laminate obtained in Example 16, along the boundary line between the region (irradiation region) where the plasma polymerization film was irradiated with ultraviolet rays and the region where the plasma polymerization film was not irradiated (non-irradiation region). The laminate was cut and the resistivity was measured individually for the laminate in the irradiated region and the laminate in the non-irradiated region.
<Evaluation criteria for resistivity>
○: Less than 1 × 10 ⁻³ Ω · cm ×: 1 × 10 ⁻³ Ω · cm or more Table 1 shows the evaluation results of 2.1 to 2.3.

As is clear from Table 1, the laminates obtained in each Example exhibited high joint strength and dimensional accuracy, and had a sufficiently low resistivity.
Moreover, in the laminated body obtained in Example 16, a difference in resistivity was observed between the irradiated region and the non-irradiated region. This is presumed to be due to the fact that the plasma polymerized film exhibited conductivity in the irradiated region and did not exhibit conductivity in the non-irradiated region.
On the other hand, the laminates obtained in the respective comparative examples had low bonding strength and dimensional accuracy and high resistivity.

It is a longitudinal cross-sectional view which shows typically the plasma polymerization apparatus used for the joining method of this invention. It is a figure (longitudinal sectional view) for demonstrating 1st Embodiment of the joining method of this invention. It is a figure (longitudinal sectional view) for demonstrating 1st Embodiment of the joining method of this invention. It is a figure (longitudinal sectional view) for demonstrating 2nd Embodiment of the joining method of this invention. It is a figure (longitudinal sectional view) for demonstrating 2nd Embodiment of the joining method of this invention. It is a figure (longitudinal section) for explaining a 3rd embodiment of the joining method of the present invention. It is a figure (longitudinal section) for explaining a 3rd embodiment of the joining method of the present invention. It is a figure (longitudinal sectional view) for demonstrating 4th Embodiment of the joining method of this invention. It is a figure (longitudinal sectional view) for demonstrating 4th Embodiment of the joining method of this invention. It is a figure which shows the other structural example of the conjugate | zygote concerning 4th Embodiment. It is a figure (longitudinal sectional view) for demonstrating 5th Embodiment of the joining method of this invention. It is a figure (longitudinal sectional view) for demonstrating 5th Embodiment of the joining method of this invention. It is a figure (longitudinal sectional view) for demonstrating 6th Embodiment of the joining method of this invention. It is a figure (longitudinal sectional view) for demonstrating 6th Embodiment of the joining method of this invention. It is a figure (longitudinal sectional view) for demonstrating 7th Embodiment of the joining method of this invention. It is a figure (longitudinal sectional view) for demonstrating 7th Embodiment of the joining method of this invention. It is a perspective view which shows the wiring board obtained by applying the conjugate | zygote of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1, 1 '... Assembly 2 ... Base material 21 ... 1st base material 22 ... 2nd base material 23, 24 ... Joining surface 3, 30, 301, 302, 3a, 3b, 3c ... ... Plasma polymerized films 31, 303, 304 ... Surface 313, 314 ... Predetermined region 315 ... Common part 311 ... First region 312 ... Second region 41 ... First adherend 42 ... Second adherend 6, 6a, 6b ... Mask 61, 61a, 61b ... Window 100 ... Plasma polymerization apparatus 101 ... Chamber 102 ... Ground wire 103 ... Supply port 104 ... Exhaust port 130 ... ... First electrode 139 ... Electrostatic chuck 140 ... Second electrode 170 ... Pump 171 ... Pressure control mechanism 180 ... Power supply circuit 182 ... High frequency power supply 183 ... Matching box 184 ... Wiring 190 …… Gas supply unit 191 …… Liquid storage unit 192 …… Vaporizer 193 …… Gas cylinder 194 …… Piping 195 …… Diffusion plate 10 …… Wiring substrate 11 …… Plasma polymerized film 12 …… Electrode 13 …… Insulating substrate 14 …… Lead 15 …… Electrodes

Claims (26)

A first step of preparing a substrate, a first adherend including a plasma polymerization film including a conductive component provided in at least a part of the substrate, and a second adherend When,
A second step of applying energy to at least a part of the plasma polymerized film to activate the plasma polymerized film and exhibiting conductivity in the plasma polymerized film;
A third step of bonding the first adherend and the second adherend to obtain a joined body so that the plasma polymerized film and the second adherend are brought into close contact with each other; The joining method characterized by the above-mentioned. The first adherend includes the base material, and a plasma polymerization film including a conductive component provided in the entire region on the base material,
In the second step, the plasma polymerization film located in the predetermined area is partially activated by applying energy to a predetermined area of the plasma polymerization film, and the predetermined process is performed. The bonding method according to claim 1, wherein the plasma polymerization film located in the region is partially made to exhibit conductivity. Of the second adherend, a surface in close contact with the plasma polymerized film of the first adherend has a hydroxyl group,
In the third step, the first adherend and the second adherend are adhered so that the plasma polymerized film and the surface of the second adherend on which the hydroxyl group exists are in close contact with each other. The bonding method according to claim 1 or 2, wherein the two are bonded together. At least the surface of the second adherend that is in close contact with the plasma polymerization film is covered with an oxide film,
In the third step, the first adherend and the second adherend are adhered so that the plasma polymerized film and the surface of the second adherend covered with the oxide film are in close contact with each other. The joining method according to any one of claims 1 to 3, wherein the body is bonded. A first step of preparing a first adherend and a second adherend each provided with a plasma polymerized film containing a conductive component on the substrate;
Energy is applied to the surface of each plasma polymerized film of the first adherend and the second adherend to activate the surface of each plasma polymerized film, and the plasma polymerized film is electrically conductive. A second step of expressing sex;
A third step of bonding the first adherend and the second adherend to obtain a joined body so that the surfaces of the activated plasma polymerization films are brought into close contact with each other; The joining method characterized by this.   Each of the first adherend and the second adherend is preliminarily subjected to a base treatment with plasma on each of the substrates, and then the plasma polymerized film is formed in the region subjected to the base treatment. The joining method according to claim 5, wherein   The joining method according to claim 5 or 6, wherein a rigidity of a base material provided in the first adherend and a base material provided in the second adherend are different from each other.   The joining method according to any one of claims 1 to 7, wherein the plasma polymerized film containing the conductive component is composed of an organometallic polymer as a main material.   The bonding method according to claim 8, wherein the organometallic polymer is mainly composed of a polymer of trimethylgallium or trimethylaluminum.   The bonding method according to claim 1, wherein the plasma polymer film has an average thickness of 1 to 1000 nm.   The bonding method according to claim 1, wherein the application of energy in the second step is performed by a method of heating the plasma polymerization film.   The joining method according to claim 11, wherein the heating temperature is 25 to 100 ° C.   The bonding method according to claim 1, wherein the application of the energy in the second step is performed by a method of irradiating the plasma polymerization film with an energy ray.   The bonding method according to claim 13, wherein the energy ray is ultraviolet light having a wavelength of 150 to 300 nm.   The joining method according to claim 1, wherein the second step is performed in an air atmosphere.   The joining method according to claim 1, further comprising a step of performing a heat treatment on the joined body after the third step.   The bonding method according to claim 16, wherein a temperature of the heat treatment is 25 to 100 ° C.   The joining method according to any one of claims 1 to 17, further comprising a step of pressurizing the joined body after the third step.   The joining method according to claim 18, wherein a pressure applied to the joined body is 0.2 to 10 MPa.   The joining method according to any one of claims 1 to 19, wherein the third step is started within 60 minutes after the end of the second step.   Two joined substrates are joined by the joining method according to any one of claims 1 to 20. Two substrates,
Having a plasma polymerized film having conductivity,
The two substrates are bonded to each other through the plasma polymerization film.   The plasma polymerized film having conductivity is applied to the plasma polymerized film containing the conductive component by applying energy to the plasma polymerized film containing the conductive component formed in advance on the two base materials, respectively. 23. The joined body according to claim 22, wherein the joined body is formed by joining the plasma polymerized films while exhibiting electrical conductivity.   The joined body according to any one of claims 21 to 23, wherein a joining strength between the two base materials is 5 MPa or more. The joined body according to any one of claims 21 to 24, wherein the plasma polymerized film exhibiting conductivity in the joined body has a resistivity of 1 × 10 ^-3 Ω · cm or less.   A wiring board comprising the joined body according to claim 21.

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