JP2009072813A - Joining method and joined body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a joining method by which two base materials are joined rigidly at high dimensional accuracy and efficiently joined at low temperature partially in a partial region and a joined body which is made by joining the two base materials partially in the partial region by using such joining method. <P>SOLUTION: This joining method includes: a stage where a joining film 3a is formed in the first region 310a of a portion on a first base material 21, while a first adherend 41 is made and also a second joining film 3b is formed in a second region 310b which is set by a pattern different from the first region 310a in a portion on a second base material 22; a stage where the joining films are activated by imparting energy to each of joining films 3a, 3b and by desorbing a leaving group from the inside of each of joining films 3a, 3b; and a stage where the joined body which is made by being partially joined in the portion where respective regions 310a, 310b are overlapped by laminating two adherends 41, 42 so that the respective joining films 3a, 3b are closely adhered together. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a joining method and a joined body.

When joining (adhering) two members (base materials), conventionally, a method of using an adhesive such as an epoxy-based adhesive, a urethane-based adhesive, or a silicon-based 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 droplet discharge head (inkjet recording head) provided in an inkjet printer is assembled by bonding parts made of different materials such as a resin material, a metal material, and a silicon material using an adhesive. ing.
When the members are bonded together using the adhesive as described above, a liquid or paste adhesive is applied to the bonding surface, and the members are bonded together via the applied adhesive. Thereafter, the adhesive is cured by the action of heat or light to bond the members together.

However, such an adhesive has the following problems.
・ Low adhesion strength ・ Low dimensional accuracy ・ Long curing time required a long time for adhesion ・ Low reliability for organic solvents such as ink resistance

Further, in many cases, it is necessary to use a primer in order to increase the adhesive strength, and the cost and labor for that increase the cost and complexity of the bonding process.
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 of directly bonding members without an intermediate layer such as an adhesive (see, for example, Patent Document 1).
According to such solid bonding, since an intermediate layer such as an adhesive is not used, a bonded body with high dimensional accuracy can be obtained.

However, solid bonding has the following problems.
-There are restrictions on the materials of the members to be joined-In the joining process, heat treatment is performed at a high temperature (for example, about 700 to 800 ° C)-The atmosphere in the joining process is limited to a reduced pressure atmosphere-Select some areas Since it cannot be joined, a large stress is generated at the joining interface due to the difference in the coefficient of thermal expansion between the members, leading to peeling of the joined body. Depending on the material of the member used for joining, However, there is a need for a method for joining members to each other in a part of the region, firmly with high dimensional accuracy and efficiently at low temperatures.

JP-A-5-82404

  An object of the present invention is to provide a bonding method capable of bonding two substrates, partly in a region, firmly with high dimensional accuracy, and efficiently at low temperature, and two substrates, An object of the present invention is to provide a joined body that is partially joined in a partial region by such a joining method.

Such an object is achieved by the present invention described below.
In the bonding method of the present invention, a metal atom, an oxygen atom bonded to the metal atom, and at least one of the metal atom and the oxygen atom are bonded to a first region set on a part of the substrate. A first adherend including a first bonding film including a leaving group, and a second region set in a pattern different from the first region on a part of a substrate; Preparing a second adherend including a second bonding film having the same function as the bonding film;
Energy is imparted to each of the first bonding film and the second bonding film, and the leaving group existing near the surface of each bonding film is desorbed from at least one of the metal atom and the oxygen atom. A step of expressing adhesiveness in each of the bonding films,
By bonding the first adherend and the second adherend so that the first bonding film and the second bonding film are in close contact with each other, these are attached to the first region. And a step of obtaining a joined body partially joined at a portion where the second region overlaps with the second region.
Thereby, two base materials can be joined together with high dimensional accuracy in a partial region, and efficiently at a low temperature. Further, a space having a height corresponding to the thickness of the bonding film is formed between the two base materials in the bonded body. Therefore, by appropriately adjusting the shape of the predetermined region, it is possible to make use of this space to form a closed space or a flow path in the joined body.

In the bonding method of the present invention, a metal atom, an oxygen atom bonded to the metal atom, and at least one of the metal atom and the oxygen atom are bonded to a first region set on a part of the substrate. A first adherend including a first bonding film including a leaving group, and a second region set in a pattern different from the first region on a part of a substrate; Preparing a second adherend including a second bonding film having the same function as the bonding film;
A step of superimposing the first adherend and the second adherend to obtain a temporary joined body so that the first bonding film and the second bonding film are in close contact with each other;
Energy is applied to the first bonding film and the second bonding film, and the leaving group existing in the vicinity of the surface of each bonding film is released from at least one of the metal atom and the oxygen atom. By causing the bonding film to exhibit adhesiveness, the first adherend and the second adherend are in a portion where the first region and the second region overlap each other. And a step of obtaining a partially joined joined body.

  As a result, the two substrates can be bonded partially and partially firmly in the region with high dimensional accuracy and efficiently at a low temperature. Further, a space having a height corresponding to the thickness of the bonding film is formed between the two base materials in the bonded body. Therefore, by appropriately adjusting the shape of the predetermined region, it is possible to make use of this space to form a closed space or a flow path in the joined body. Furthermore, in the state of the temporary joined body, the first adherend and the second adherend are not joined. For this reason, a 1st to-be-adhered body and a 2nd to-be-adhered body can be shifted, and these relative positions can be adjusted. In this way, after the two adherends are superposed, their positions can be easily finely adjusted, so that the workability of the position adjustment is improved and the surface of the joined body finally obtained The dimensional accuracy in the direction can be increased.

The bonding method of the present invention includes a first bonding film including a metal atom, an oxygen atom bonded to the metal atom, and a leaving group bonded to at least one of the metal atom and the oxygen atom on a substrate. Providing a first adherend comprising: a second adherend comprising a second bonding film having the same function as the first bonding film on a substrate;
The first region set in a part of the first bonding film and the second region set in a pattern different from the first region in a part of the second bonding film, respectively. And desorbing the leaving group present in the vicinity of the surface of each bonding film from at least one of the metal atom and the oxygen atom, thereby expressing adhesiveness in each bonding film;
By bonding the first adherend and the second adherend so that the first region and the second region overlap, these are attached to the first region and the second region. And a step of obtaining a joined body partially joined at a portion where the two regions overlap.
Thereby, two base materials can be joined together with high dimensional accuracy in a partial region, and efficiently at a low temperature. Moreover, the area | region of a junction part can be easily controlled only by selecting the area | region which provides energy.

In the bonding method of the present invention, it is preferable that the leaving group is unevenly distributed near the surface of the bonding film.
Thereby, the function as a metal oxide film can be suitably exhibited in the bonding film. In other words, in addition to the function responsible for bonding, the bonding film can be advantageously provided with a function as a metal oxide film having excellent characteristics such as conductivity and translucency. In other words, it is possible to reliably prevent the leaving group from impairing the properties of the bonding film such as conductivity and translucency.
In the bonding method of the present invention, the bonding film preferably has translucency.
Thereby, the joined body of this invention is applicable to the area | region which requires translucency in an optical element etc.

In the bonding method of the present invention, the metal atom is preferably an atom of a transition metal element.
Transition metals generally have high hardness and melting point, and high electrical and thermal conductivity. Therefore, by selecting the transition metal element atoms as the metal atoms contained in the bonding film, the adhesion expressed in the bonding film is further enhanced. be able to. In addition, the conductivity of the bonding film can be further increased.
In the bonding method of the present invention, the metal atom is preferably at least one of indium, tin, zinc, titanium, and antimony.
By making the bonding film contain these metal atoms, the bonding film exhibits excellent conductivity and transparency.

In the bonding method of the present invention, the leaving group is at least one of a hydrogen atom, a carbon atom, a nitrogen atom, a phosphorus atom, a sulfur atom and a halogen atom, or an atomic group composed of each of these atoms. It is preferable.
These leaving groups are relatively excellent in binding / leaving selectivity by applying energy. For this reason, by giving energy, a leaving group that can be removed relatively easily and uniformly can be obtained, and the adhesion between the first adherend and the second adherend can be further improved. It can be advanced.

In the bonding method of the present invention, the bonding film includes indium tin oxide (ITO), indium zinc oxide (IZO), antimony tin oxide (ATO), fluorine-containing indium tin oxide (FTO), and zinc oxide (ZnO). ) Or titanium dioxide (TiO ₂ ), preferably a hydrogen atom introduced as a leaving group.
The bonding film having such a configuration itself has excellent mechanical characteristics. In addition, it exhibits particularly excellent adhesion to many materials. Therefore, such a bonding film particularly strongly adheres to the first substrate and also exhibits a particularly strong adhesion force to the second adherend, and as a result, the first adhesion The body and the second adherend can be firmly bonded.
In the bonding method of the present invention, the abundance ratio of metal atoms and oxygen atoms in the bonding film is preferably 3: 7 to 7: 3.
Thereby, the stability of the bonding film is increased, and the first adherend and the second adherend can be bonded more firmly.

The bonding method of the present invention includes a first target film including a first bonding film including a metal atom and a leaving group composed of an organic component in a first region set on a part of a substrate. A second body provided with a second bonding film having the same function as the first bonding film in a second area set in a pattern different from the first area on a part of the substrate and the first area A step of preparing an adherend;
By applying energy to each of the first bonding film and the second bonding film and detaching the leaving group existing near the surface of each bonding film from each bonding film, each bonding A step of developing adhesiveness in the membrane;
By bonding the first adherend and the second adherend so that the first bonding film and the second bonding film are in close contact with each other, these are attached to the first region. And a step of obtaining a joined body partially joined at a portion where the second region overlaps with the second region.
Thereby, two base materials can be joined together with high dimensional accuracy in a partial region, and efficiently at a low temperature. Further, a space having a height corresponding to the thickness of the bonding film is formed between the two base materials in the bonded body. Therefore, by appropriately adjusting the shape of the predetermined region, it is possible to make use of this space to form a closed space or a flow path in the joined body.

The bonding method of the present invention includes a first target film including a first bonding film including a metal atom and a leaving group composed of an organic component in a first region set on a part of a substrate. A second body provided with a second bonding film having the same function as the first bonding film in a second area set in a pattern different from the first area on a part of the substrate and the first area A step of preparing an adherend;
A step of superimposing the first adherend and the second adherend to obtain a temporary joined body so that the first bonding film and the second bonding film are in close contact with each other;
By applying energy to the first bonding film and the second bonding film and detaching the leaving group existing near the surface of each bonding film from each bonding film, Bonding in which adhesiveness is expressed in a bonding film, and the first adherend and the second adherend are partially bonded at a portion where the first region and the second region overlap each other. And obtaining a body.

  As a result, the two substrates can be bonded partially and partially firmly in the region with high dimensional accuracy and efficiently at a low temperature. Further, a space having a height corresponding to the thickness of the bonding film is formed between the two base materials in the bonded body. Therefore, by appropriately adjusting the shape of the predetermined region, it is possible to make use of this space to form a closed space or a flow path in the joined body. Furthermore, in the state of the temporary joined body, the first adherend and the second adherend are not joined. For this reason, a 1st to-be-adhered body and a 2nd to-be-adhered body can be shifted, and these relative positions can be adjusted. In this way, after the two adherends are superposed, their positions can be easily finely adjusted, so that the workability of the position adjustment is improved and the surface of the joined body finally obtained The dimensional accuracy in the direction can be increased.

The bonding method of the present invention includes a first adherend including a first bonding film including a metal atom and a leaving group composed of an organic component on a substrate, and the first adherend on the substrate. Preparing a second adherend including a second bonding film having the same function as that of the first bonding film;
The first region set in a part of the first bonding film and the second region set in a pattern different from the first region in a part of the second bonding film, respectively. And desorbing the leaving group present in the vicinity of the surface of each bonding film from each bonding film, thereby expressing adhesiveness in each bonding film;
By bonding the first adherend and the second adherend so that the first region and the second region overlap, these are attached to the first region and the second region. And a step of obtaining a joined body partially joined at a portion where the two regions overlap.
Thereby, two base materials can be joined together with high dimensional accuracy in a partial region, and efficiently at a low temperature. Moreover, the area | region of a junction part can be easily controlled only by selecting the area | region which provides energy.

In the bonding method of the present invention, the bonding film is preferably formed using an organic metal material as a raw material and using a metal organic chemical vapor deposition method.
According to such a method, a bonding film having a uniform film thickness can be formed by a relatively simple process.
In the bonding method of the present invention, the bonding film is preferably formed in a low reducing atmosphere.
Thereby, it is possible to form a film in a state in which a part of the organic substance contained in the organometallic material remains without forming a pure metal film on the substrate. That is, it is possible to form a bonding film having excellent characteristics as both the bonding film and the metal film.

In the bonding method according to the aspect of the invention, it is preferable that the leaving group is one in which a part of the organic substance contained in the organometallic material remains.
By adopting a structure in which the residue remaining in the film when the film is formed is used as the leaving group, it is not necessary to introduce the leaving group into the formed metal film, and the process is relatively simple. A bonding film can be formed.

In the bonding method of the present invention, the leaving group is composed of an atomic group containing a carbon atom as an essential component and containing at least one of a hydrogen atom, a nitrogen atom, a phosphorus atom, a sulfur atom, and a halogen atom. preferable.
These leaving groups are relatively excellent in binding / leaving selectivity by applying energy. For this reason, by giving energy, a leaving group that can be removed relatively easily and uniformly can be obtained, and the adhesion between the first adherend and the second adherend can be further improved. It can be advanced.

In the bonding method of the present invention, the leaving group is preferably an alkyl group.
Since a leaving group composed of an alkyl group has high chemical stability, a bonding film having an alkyl group as the leaving group has excellent weather resistance and chemical resistance.
In the bonding method of the present invention, the organometallic material is preferably a metal complex.
By forming the bonding film using the metal complex, it is possible to reliably form the bonding film in a state where a part of the organic substance contained in the metal complex remains.

In the bonding method of the present invention, the metal atom is preferably an atom of a transition metal element.
Transition metals generally have high hardness and melting point, and high electrical and thermal conductivity. Therefore, by selecting the transition metal element atoms as the metal atoms contained in the bonding film, the adhesion expressed in the bonding film is further enhanced. be able to. In addition, the conductivity of the bonding film can be further increased.
In the bonding method of the present invention, the metal atom is preferably at least one of copper, aluminum, zinc, and iron.
By making the bonding film contain these metal atoms, the bonding film exhibits excellent conductivity.

In the bonding method of the present invention, the abundance ratio of metal atoms to carbon atoms in the bonding film is preferably 3: 7 to 7: 3.
By setting the abundance ratio of the metal atom and the carbon atom to be within the above range, the stability of the bonding film is increased, and the first adherend and the second adherend are bonded more firmly. Will be able to. In addition, the bonding film can exhibit excellent conductivity.

In the bonding method of the present invention, the bonding film preferably has conductivity.
Thereby, in the joined body, the joining film can be applied to the wiring provided in the wiring substrate, the terminal thereof, and the like.
In the bonding method of the present invention, the bonding film preferably has an active hand after the leaving group existing at least near the surface thereof is released from the bonding film.
Thereby, adhesiveness develops on the surface of the joined body. As a result, the first adherend can be firmly and efficiently bonded to the second adherend with high dimensional accuracy.
In the bonding method of the present invention, the active hand is preferably a dangling bond or a hydroxyl group.
Accordingly, the first adherend having the bonding film can be particularly strongly bonded to the second adherend.

In the bonding method of the present invention, the average thickness of the bonding film is preferably 0.2 to 1000 nm.
Thereby, these can be joined more firmly, preventing the dimensional accuracy of the joined body which joined the 1st to-be-adhered body and the 2nd to-be-adhered body falling remarkably.
In the bonding method of the present invention, it is preferable that the bonding film is in a solid state having no fluidity.
As a result, the thickness and shape of the bonding film hardly change. For this reason, the dimensional accuracy of a joined body becomes remarkably high compared with the past. Further, since the time required for curing is not required, stronger bonding can be achieved in a shorter time than in the past.

In the joining method of the present invention, the base material preferably has a plate shape.
Thereby, since a base material becomes easy to bend and it will become a thing which can fully change along with each other's shape when two base materials are piled up, these adhesiveness becomes higher. Moreover, the stress which arises in a joining interface by bending a base material can be relieved to some extent.
In the joining method of the present invention, it is preferable that the plate-like base material has flexibility.
Thereby, the joint strength of the joined body can be further improved. Moreover, when both a base material and a 2nd to-be-adhered body have flexibility, it has flexibility as a whole and a bonded body with high functionality is obtained.

In the bonding method of the present invention, it is preferable that at least a portion of the base material on which the bonding film is formed is composed mainly of a silicon material, a metal material, or a glass material.
Thereby, sufficient bonding strength can be obtained without surface treatment.
In the bonding method of the present invention, it is preferable that the surface of the base material provided with the bonding film is previously subjected to a surface treatment for improving the adhesion with the bonding film.
Thereby, the bonding surface of the base material is cleaned and activated, and the bonding film easily acts chemically on the bonding surface. As a result, the bonding strength between the bonding surface of the base material and the bonding film can be increased.
In the bonding method of the present invention, the surface treatment is preferably plasma treatment or ultraviolet irradiation treatment.
Thereby, in order to form a joining film | membrane, the surface of a base material can be optimized especially.

In the bonding method of the present invention, it is preferable that an intermediate layer is interposed between the base material and the bonding film.
Thereby, a highly reliable joined body can be obtained.
In the bonding method of the present invention, the intermediate layer is preferably composed of an oxide-based material as a main material.
Thereby, the joint strength between the base material and the joining film can be particularly increased.

In the bonding method of the present invention, the energy is applied by at least one of a method of irradiating the bonding film with energy rays, a method of heating the bonding film, and a method of applying a compressive force to the bonding film. Is preferably carried out by
Thereby, energy can be imparted to the bonding film relatively easily and efficiently.

In the bonding method of the present invention, the energy beam is preferably ultraviolet light having a wavelength of 126 to 300 nm.
As a result, the amount of energy applied is optimized so that the leaving group can be selectively cleaved from the bonding film while preventing the molecular bonds forming the skeleton in the bonding film from being destroyed more than necessary. Can do. Thereby, adhesiveness can be reliably expressed in the bonding film while preventing the characteristics (mechanical characteristics, chemical characteristics, etc.) of the bonding film from deteriorating.

In the bonding method of the present invention, the heating temperature 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 the present invention, the compressive force is preferably 0.2 to 10 MPa.
Accordingly, it is possible to reliably increase the bonding strength of the bonded body while preventing the substrate from being damaged due to the pressure being too high.
In the bonding method of the present invention, it is preferable that the application of energy is performed 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.

The bonding method of the present invention preferably further includes a step of performing a process for increasing the bonding strength of the bonded body.
Thereby, the joint strength of the joined body can be further improved.
In the bonding method of the present invention, the step of performing the process of increasing the bonding strength includes a method of irradiating the bonded body with energy rays, a method of heating the bonded body, and a method of applying a compressive force to the bonded body. It is preferable to carry out by at least one method.
Thereby, the further improvement of the joining strength of a joined body can be aimed at easily.

The joined body of the present invention is characterized in that two base materials are joined by the joining method of the present invention.
Thereby, the joined body formed by joining two base materials partially in a partial region is obtained.
In the joined body of the present invention, the joining film preferably has a function as a functional partial joining film.
Thereby, for example, various functions can be efficiently integrated in a bonded body such as a laminated substrate, so that it is possible to further increase the functionality and thickness of electronic components.

Hereinafter, a joining method and a joined object of the present invention are explained in detail based on a suitable embodiment shown in an accompanying drawing.
The bonding method of the present invention is a method in which two base materials (first base material 21 and second base material 22) are partly joined in a part of the region through the respective joining films 3a and 3b. is there.
Each of the bonding films 3a and 3b includes a leaving group, and by applying energy, the leaving groups existing in the vicinity of the surfaces 31a and 31b of the bonding films 3a and 3b are converted into the bonding films 3a and 3b. It is desorbed from. Each of the bonding films 3a and 3b is characterized in that adhesiveness develops in a region to which surface energy has been imparted by elimination of the leaving group.
According to the bonding films 3a and 3b having such characteristics, the two base materials 21 and 22 can be bonded firmly with high dimensional accuracy and efficiently at a low temperature. According to the present invention, a highly reliable bonded body 1 in which the two base materials 21 and 22 are partially bonded firmly is obtained.

<Join method>
<< First Embodiment >>
First, the first embodiment of the bonding method of the present invention and the bonded body of the present invention will be described.
1 and 2 are diagrams (longitudinal sectional views) for explaining the first embodiment of the bonding method of the present invention, and FIG. 3 shows the state of the bonding film before energy application in the bonding method of the present invention. FIG. 4 is a partially enlarged view showing a state of the bonding film after energy application in the bonding method of the present invention. In the following description, the upper side in FIGS. 1 to 4 is referred to as “upper” and the lower side is referred to as “lower”.

  In the bonding method according to the present embodiment, a first substrate 21 and a second substrate 22 are prepared, and a first region set in a part on the bonding surface 23 of the first substrate 21. The bonding film 3a (first bonding film) is formed on 310a to produce the first adherend 41, and the bonding surface of the second base material 22 (the surface facing the first base material 21) 24. A process of forming a second adherend 42 by forming a bonding film 3b (second bonding film) in a second region 310b set in a pattern different from that of the first region 310a in a part of the upper region 310a. A step of activating each bonding film 3a, 3b by applying energy to each bonding film 3a, 3b and detaching a leaving group from each bonding film 3a, 3b; By bonding the first adherend 41 and the second adherend 42 so that the bonding film 3b and the bonding film 3b are in close contact with each other, And a step of obtaining a bonded body 1 formed by partially joined in the first region 310a and second region 310b and is overlapped portion.

Hereinafter, each process of the joining method concerning this embodiment is demonstrated one by one.
[1] First, a first base material 21 and a second base material 22 are prepared.
The constituent materials of the first base material 21 and the second base material 22 are not particularly limited, but polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), and the like. Polyolefin, 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 Polyester such as coalescence (EVOH), polyethylene terephthalate (PET), polyethylene naphthalate, polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyether ether ketone (PEEK), Polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, and other fluororesins , Styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, Various thermoplastic elastomers such as lance polyisoprene, fluororubber, chlorinated polyethylene, epoxy resin, phenol resin, urea resin, melamine resin, aramid resin, unsaturated polyester, silicone resin, polyurethane, etc. Copolymers, blends, resin materials such as polymer alloys, Fe, Ni, Co, Cr, Mn, Zn, Pt, Au, Ag, Cu, Pd, Al, W, Ti, V, Mo, Nb , Zr, Pr, Nd, Sm, or alloys containing these metals, carbon steel, stainless steel, indium tin oxide (ITO), metallic materials such as gallium arsenide, single crystal silicon, polycrystalline Silicon, silicon-based materials such as amorphous silicon, silicate glass (quartz glass), alkali silicate glass, soda lime Glass-based materials such as glass, potassium lime glass, lead (alkali) glass, barium glass, borosilicate glass, alumina, zirconia, ferrite, silicon nitride, aluminum nitride, boron nitride, titanium nitride, silicon carbide, boron carbide, carbonized Examples thereof include ceramic materials such as titanium and tungsten carbide, carbon materials such as graphite, and composite materials obtained by combining one or more of these materials.

In addition, the first base material 21 and the second base material 22 are each subjected to plating treatment such as Ni plating, passivation treatment such as chromate treatment, nitriding treatment, or the like on the surface thereof. There may be.
The constituent material of the first base material 21 and the constituent material of the second base material 22 may be the same or different.

Moreover, it is preferable that the thermal expansion coefficient of the 1st base material 21 and the thermal expansion coefficient of the 2nd base material 22 are substantially equal. If these thermal expansion coefficients are substantially equal, when the first base material 21 and the second base material 22 are joined, it is difficult for stress associated with thermal expansion to occur at the joint interface. As a result, peeling can be reliably prevented in the finally obtained bonded body 1.
In addition, although it explains in full detail later, even when the thermal expansion coefficient of the 1st base material 21 and the thermal expansion coefficient of the 2nd base material 22 mutually differ, in the process mentioned later, the 1st base material 21 and 2nd By optimizing the conditions for joining the base material 22, these can be firmly joined with high dimensional accuracy.

Moreover, it is preferable that the two base materials 21 and 22 have mutually different rigidity. Thereby, the two base materials 21 and 22 can be joined more firmly.
Moreover, it is preferable that at least one constituent material of the two base materials 21 and 22 is a resin material. The resin material can relieve stress (for example, stress accompanying thermal expansion) generated at the bonding interface when the two base materials 21 and 22 are bonded 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.
In view of the above, at least one of the two base materials 21 and 22 preferably has flexibility. Thereby, the joint strength of the joined body 1 can be further improved. Furthermore, when both the two base materials 21 and 22 have flexibility, the joined body 1 which has flexibility as a whole and high functionality can be obtained.

Moreover, the shape of each base material 21 and 22 should just be a shape which has the surface which supports each bonding film 3a, 3b, respectively, for example, plate shape (layer shape), lump shape (block shape), rod shape, etc. It is said.
In the present embodiment, as shown in FIG. 1, each of the base materials 21 and 22 has a plate shape. Thereby, each base material 21 and 22 becomes easy to bend, and when the two base materials 21 and 22 are overlap | superposed, it can fully deform | transform along a mutual shape. For this reason, the adhesiveness when the two base materials 21 and 22 are overlapped is increased, and the bonding strength in the finally obtained bonded body 1 is increased.
In addition, it is expected that the base material 21 and 22 are bent to alleviate the stress generated at the joint interface to some extent.
In this case, the average thickness of each of the base materials 21 and 22 is not particularly limited, but is preferably about 0.01 to 10 mm, and more preferably about 0.1 to 3 mm.

  Next, if necessary, a surface treatment is performed on the bonding surface 23 of the first base material 21 to improve the adhesion with the bonding film 3a. As a result, the bonding surface 23 is cleaned and activated, and the bonding film 3a easily acts on the bonding surface 23 chemically. As a result, when the bonding film 3a is formed on the bonding surface 23 in the process described later, the bonding strength between the bonding surface 23 and the bonding film 3a can be increased.

This surface treatment is not particularly limited, for example, physical treatment such as sputtering treatment, blast treatment, plasma treatment using oxygen plasma, nitrogen plasma, corona discharge treatment, etching treatment, electron beam irradiation treatment, Examples thereof include a chemical surface treatment such as ultraviolet irradiation treatment, ozone exposure treatment, or a combination thereof.
In addition, when the 1st base material 21 which performs surface treatment is comprised with the resin material (polymer material), especially a corona discharge process, a nitrogen plasma process, etc. are used suitably.

In addition, the bonding surface 23 can be further cleaned and activated by performing plasma treatment or ultraviolet irradiation treatment as the surface treatment. As a result, the bonding strength between the bonding surface 23 and the bonding film 3a can be particularly increased.
Further, depending on the constituent material of the first base material 21, there is a material in which the bonding strength with the bonding film 3a is sufficiently high without performing the surface treatment as described above. Examples of the constituent material of the first base material 21 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.

The surface of the first base material 21 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 first base material 21 covered with such an oxide film, the bonding surface 23 of the first base material 21 and the bonding film 3a are not subjected to the surface treatment as described above. Bonding strength can be increased.
In this case, the entire first base material 21 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.

Instead of the surface treatment, an intermediate layer may be formed in advance on the bonding surface 23 of the first base material 21.
This intermediate layer may have any function, and for example, a layer having a function of improving adhesion to the bonding film 3a, a cushioning function (buffer function), a function of reducing stress concentration, and the like are preferable. By forming the bonding film 3a on such an intermediate layer, a highly reliable bonded body 1 can be finally 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 formed of these materials, the intermediate layer formed of the oxide-based material can particularly increase the bonding strength between the first base material 21 and the bonding film 3a. it can.

On the other hand, as with the first base member 21, the bonding surface 24 of the second base member 22 may be subjected to a surface treatment that improves the adhesion with the bonding film 3b in advance, if necessary. Thereby, the bonding surface 24 is cleaned and activated. As a result, the bonding strength between the bonding surface 24 of the second base material 22 and the bonding film 3b 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.

  Further, as in the case of the first base material 21, depending on the constituent material of the second base material 22, the adhesiveness with the bonding film 3b is sufficiently high without performing the surface treatment as described above. There is something. 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 bonding film 3b can be obtained without performing the surface treatment as described above. Bonding strength can be increased.
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 includes the following groups and substances, the bonding surface 24 and the bonding film of the second base material 22 are not subjected to the surface treatment as described above. The bonding strength with 3b can be sufficiently increased.
Examples of such groups and substances include various functional groups such as hydroxyl group, thiol group, carboxyl group, amino group, nitro group, and imidazole group, various radicals, ring-opening molecules, double bonds, and triple bonds. At least one group or substance selected from the group consisting of a leaving intermediate molecule having an unsaturated bond, a halogen such as F, Cl, Br, and I, a peroxide, or the group is desorbed. An unterminated bond (an unbonded bond, a dangling bond) is provided.
Of these, the leaving intermediate molecule is preferably a ring-opening molecule or a hydrocarbon molecule having an unsaturated bond. Such hydrocarbon molecules act strongly on the bonding film 3b based on the remarkable reactivity of ring-opening molecules and unsaturated bonds. Therefore, the bonding surface 24 having such hydrocarbon molecules can be bonded particularly firmly to the bonding film 3b.

The functional group possessed by the bonding surface 24 is particularly preferably a hydroxyl group. Thereby, the bonding surface 24 can be bonded particularly easily and firmly to the bonding film 3b.
In addition, by appropriately selecting and performing various surface treatments as described above on the bonding surface 24 so as to have such groups and substances, a second group that can be strongly bonded to the bonding film 3b. A 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 bonding film 3b where the hydroxyl group is exposed. Thereby, finally, the first adherend 41 and the second adherend 42 can be bonded particularly 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 intermediate layer has a function of improving adhesion to the bonding film 3b, a cushioning property (buffer function), a stress. What has the function etc. which ease concentration is preferable. By forming the bonding film 3b on such an intermediate layer, the highly reliable bonded body 1 can be finally 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 FIGS. 1A to 1B, the bonding film 3 a is formed in the first region 310 a set in a part of the bonding surface 23 of the first base material 21. To do. Thereby, the 1st to-be-adhered body 41 is obtained. Further, as shown in FIGS. 1A to 1B, a part of the joining surface 24 of the second base member 22 is joined to the second region 310b set in a pattern different from the first region 310a. A film 3b is formed. Thereby, the second adherend 42 is obtained. Note that the pattern is different between the first region 310a and the second region 310b means that the planar view shape of the first region 310a is different from the planar view shape of the second region 310b. Point to.

  Each bonding film 3a, 3b is located between the 1st base material 21 and the 2nd base material 22, and bears these joining.

Each of the bonding films 3a and 3b includes a leaving group as described above. When energy is applied to the bonding films 3a and 3b, the leaving groups existing near the surfaces 31a and 31b of the bonding films 3a and 3b are released from the bonding films 3a and 3b. Each of the bonding films 3a and 3b has the same characteristic (function) that adhesiveness develops in a region to which surface energy is imparted by elimination of the leaving group.
The bonding films 3a and 3b will be described in detail later.

[3] Next, energy is applied to the bonding film 3a of the first adherend 41 and the bonding film 3b of the second adherend 42, respectively.
When energy is applied to each bonding film 3a, 3b, in each bonding film 3a, 3b, as shown in FIGS. 3 and 4, the leaving group 303 is released from each bonding film 3a, 3b, and the leaving group 303 is removed. After desorption, active hands are generated near the surfaces 31a and 31b of the bonding films 3a and 3b. Thereby, adhesiveness develops on the surfaces 31a and 31b of the bonding films 3a and 3b. 3 and 4 show the bonding film 3a as a representative.
The first adherend 41 and the second adherend 42 in such a state can be firmly bonded to each other based on chemical bonding.

Here, the energy applied to each bonding film 3a, 3b may be applied using any method. For example, the method of irradiating each bonding film 3a, 3b with energy rays, each bonding film A method of heating 3a, 3b, a method of applying compressive force (physical energy) to each bonding film 3a, 3b, a method of exposing each bonding film 3a, 3b to plasma (applying plasma energy), and each bonding film 3a And a method of exposing 3b to ozone gas (applying chemical energy). In particular, in the present embodiment, as a method for applying energy to the bonding films 3a and 3b, it is particularly preferable to use a method of irradiating the bonding films 3a and 3b with energy rays. Since this method can apply energy relatively easily and efficiently to each of the bonding films 3a and 3b, it is preferably used as a method of applying energy.
Among these, as energy rays, for example, light such as ultraviolet rays and laser light, electromagnetic waves such as X-rays and γ rays, particle beams such as electron beams and ion beams, or two types of these energy rays are used. The combination is mentioned.

Among these energy rays, it is particularly preferable to use ultraviolet rays having a wavelength of about 126 to 300 nm (see FIG. 1C). According to the ultraviolet rays within such a range, the amount of energy to be applied is optimized. The leaving group 303 can be selectively cleaved from 3a and 3b. Thereby, adhesiveness can be reliably expressed in each bonding film 3a, 3b, preventing the characteristic (mechanical characteristic, chemical characteristic, etc.) of each bonding film 3a, 3b falling.
In addition, since ultraviolet rays can be processed in a short time without unevenness, the leaving group 303 can be efficiently eliminated. Furthermore, ultraviolet rays also have the advantage that they can be generated with simple equipment such as UV lamps.
The wavelength of the ultraviolet light is more preferably about 126 to 200 nm.

When a UV lamp is used, the output varies depending on the areas of the bonding films 3a and 3b, but is preferably about 1 mW / cm ^{2 to} 1 W / cm ² , and is preferably 5 mW / cm ^{2 to} 50 mW / cm. More preferably, it is about ² . In this case, the separation distance between the UV lamp and each of the bonding films 3a and 3b is preferably about 3 to 3000 mm, and more preferably about 10 to 1000 mm.

Further, the time for irradiating the ultraviolet rays is such a time that the leaving groups 303 in the vicinity of the surfaces 31a and 31b of the bonding films 3a and 3b can be released, that is, desorption existing in the vicinity of the surfaces of the bonding films 3a and 3b. It is preferable to set the time so that the group 303 can be selectively removed. Specifically, although it varies slightly depending on the amount of ultraviolet light, the constituent materials of the bonding films 3a and 3b, etc., it is preferably about 1 second to 30 minutes, more preferably about 1 second 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 a pulsed laser (pulse laser) such as an excimer laser, a continuous wave laser such as a carbon dioxide laser, and a semiconductor laser. Among these, a pulse laser is preferably used. In the pulse laser, heat hardly accumulates with time in the portions irradiated with the laser light of the bonding films 3a and 3b, so that the deterioration and deterioration of the bonding films 3a and 3b due to the accumulated heat is surely prevented. Can do. That is, according to the pulse laser, it is possible to prevent the heat accumulated in the bonding films 3a and 3b from being affected.

  The pulse width of the pulse laser is preferably as short as possible in consideration of the influence of heat. Specifically, the pulse width is preferably 1 ps (picosecond) or less, and more preferably 500 fs (femtosecond) or less. If the pulse width is within the above range, the influence of heat generated in each of the bonding films 3a and 3b due to laser light irradiation can be accurately suppressed. A pulse laser having a pulse width as small as the above range is called a “femtosecond laser”.

The wavelength of the laser light is not particularly limited, but is preferably about 200 to 1200 nm, and more preferably about 400 to 1000 nm.
In the case of a pulse laser, the peak output of the laser light varies depending on the pulse width, but is preferably about 0.1 to 10 W, and more preferably about 1 to 5 W.
Furthermore, the repetition frequency of the pulse laser is preferably about 0.1 to 100 kHz, and more preferably about 1 to 10 kHz. By setting the frequency of the pulse laser within the above range, the temperature of the portion irradiated with the laser light is remarkably increased, and the molecular bond forming the skeleton of each bonding film 3a, 3b is prevented from being broken. The leaving group 303 can be reliably cut from the bonding films 3a and 3b.

  The various conditions of such laser light are such that the temperature of the portion irradiated with the laser light is preferably from room temperature (room temperature) to about 600 ° C., more preferably about 200 to 600 ° C., and even more preferably 300 to 400 ° C. It is preferable to adjust as appropriate. Accordingly, the temperature of the portion irradiated with the laser light is remarkably increased and the molecular bond forming the skeleton of each of the bonding films 3a and 3b is prevented from being broken, and the leaving group 303 is connected to each bonding film 3a, It can cut | disconnect reliably from 3b.

  Further, the laser light applied to each of the bonding films 3a and 3b is scanned along the respective surfaces 31a and 31b in a state where the focal point is aligned with the surfaces 31a and 31b of the bonding films 3a and 3b. It is preferable to do this. Thereby, the heat generated by the laser light irradiation is locally accumulated in the vicinity of the surfaces 31a and 31b. As a result, the leaving groups 303 present on the surfaces 31a and 31b of the bonding films 3a and 3b can be selectively removed.

Further, the irradiation of the energy beam to each of the bonding films 3a and 3b may be performed in any atmosphere. Specifically, the atmosphere, an oxidizing gas atmosphere such as oxygen, or a reducing gas atmosphere such as hydrogen. In addition, an inert gas atmosphere such as nitrogen or argon, or a reduced pressure (vacuum) atmosphere obtained by reducing the pressure of these atmospheres, is particularly preferable. Thereby, it is not necessary to spend time and cost to control the atmosphere, and irradiation of energy rays can be performed more easily.
As described above, according to the method of irradiating energy rays, energy can be easily selectively applied to the bonding films 3a and 3b. Alteration and deterioration can be prevented.

  Moreover, according to the method of irradiating energy rays, the magnitude of energy to be applied can be easily adjusted with high accuracy. For this reason, it becomes possible to adjust the desorption amount of the leaving group 303 desorbed from each bonding film 3a, 3b. In this way, by adjusting the amount of elimination of the leaving group 303, the bonding strength between the first adherend 41 and the second adherend 42 can be easily controlled.

That is, by increasing the amount of elimination of the leaving group 303, more active hands are generated on the surfaces 31a, 31b and the inside of each bonding film 3a, 3b, so that the adhesion expressed in each bonding film 3a, 3b. The sex can be increased. On the other hand, by reducing the amount of elimination of the leaving group 303, the surface 31a, 31b of each bonding film 3a, 3b and the active hands generated inside are reduced, and the adhesiveness expressed in each bonding film 3a, 3b is suppressed. be able to.
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.
Furthermore, according to the method of irradiating energy rays, a large amount of energy can be applied in a short time, so that the energy can be applied more efficiently.

  Here, each bonding film 3a, 3b before energy is applied has a leaving group 303 at least near the surfaces 31a, 31b, as shown in FIG. When energy is applied to each of the bonding films 3a and 3b, the leaving group 303 (hydrogen atom in FIG. 3) is released from the bonding films 3a and 3b. As a result, as shown in FIG. 4, active hands 304 are generated and activated on the surfaces 31a and 31b of the bonding films 3a and 3b. As a result, adhesiveness develops on the surfaces 31a and 31b of the bonding films 3a and 3b.

  Here, in this specification, the state in which each bonding film 3a, 3b is “activated” means that the surfaces 31a, 31b of each bonding film 3a, 3b and the internal leaving group 303 are removed as described above. In addition to a state in which bond bonds (hereinafter also referred to as “unbonded hands” or “dangling bonds”) that are not terminated in the bonding films 3a and 3b are generated, The bonding films 3a and 3b are referred to as “activated” states including a state terminated by an (OH group) and a state in which these states are mixed.

Therefore, the active hand 304 means an unbonded hand (dangling bond) or an unbonded hand terminated by a hydroxyl group as shown in FIG. If such active hands 304 are present, the bonding film 3a and the bonding film 3b can be particularly strongly bonded.
The latter state (state in which the dangling bond is terminated by a hydroxyl group) is obtained by, for example, irradiating the bonding films 3a and 3b with energy rays in the atmospheric air so that moisture in the air is not bonded. It is easily generated by terminating the hand.

  [4] Next, the first adherend 41 and the second adherend 42 are bonded together so that the bonding film 3a and the bonding film 3b are in close contact (see FIG. 1D). Thereby, in the said process [3], since adhesiveness has expressed to each bonding film 3a, 3b, the bonding film 3a and the bonding film 3b are couple | bonded chemically. As a result, in the portion where the first region 310a and the second region 310b overlap each other, the first adherend 41 and the second adherend 42 are partially joined, and FIG. A joined body 1 as shown is obtained. That is, the joined body 1 is joined in the first region 310a.

  The bonded body 1 thus obtained is not bonded mainly based on a physical bond such as an anchor effect, but a short time such as a covalent bond, unlike the adhesive used in the conventional bonding method. The two base materials 21 and 22 are bonded to each other based on the strong chemical bond generated in step (b). For this reason, the bonded body 1 can be formed in a short time, is extremely difficult to peel off, and is difficult to cause uneven bonding.

Moreover, according to such a joining method, unlike the conventional solid joining, since the heat treatment at a high temperature (for example, 700 ° C. or higher) is not required, the first base made of a material having low heat resistance is used. The material 21 and the second base material 22 can also be used for bonding.
Moreover, since the 1st base material 21 and the 2nd base material 22 are joined via each joining film | membrane 3a, 3b, there also exists an advantage that there is no restriction | limiting in the constituent material of each base material 21 and 22.

From the above, according to the present invention, the range of selection of each constituent material of the first base material 21 and the second base material 22 can be expanded.
In solid bonding, since there is no bonding layer, when there is a large difference in the coefficient of thermal expansion between the first base material 21 and the second base material 22, stress based on the difference is applied to the bonding interface. However, in the bonded body (bonded body of the present invention), stress concentration is reduced by the bonding films 3a and 3b, and the occurrence of peeling is accurately suppressed or prevented. be able to.

Moreover, when the thermal expansion coefficient of the 1st base material 21 and the thermal expansion coefficient of the 2nd base material 22 are mutually different, it is preferable to join 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, the temperature of the first base material 21 and the second base material 22 is 25 to 50 ° C., depending on the difference in thermal expansion coefficient between the first base material 21 and the second base material 22. It is preferable that the first adherend 41 and the second adherend 42 are bonded together under the condition of about 25 to 40 ° C., and more preferable. Within such a temperature range, even if the difference in thermal expansion coefficient between the first base material 21 and the second base material 22 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 suppress or prevent the occurrence of warpage or peeling in the bonded body 1.
In this case, when the specific difference in thermal expansion coefficient between the first base material 21 and the second base material 22 is 5 × 10 ⁻⁵ / K or more, as described above. Therefore, it is particularly recommended to perform bonding at as low a temperature as possible.

  Moreover, according to this embodiment, when joining the 1st base material 21 and the 2nd base material 22, rather than joining these joining surfaces (surfaces which mutually oppose), a part of them is joined. Only the region (the first region 310a) is selectively joined. At the time of bonding, the region to be bonded can be easily selected only by controlling the region (first region 310a) where the bonding film 3a is formed. 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.

That is, the bonding strength of the bonded body 1 can be adjusted, and at the same time, the strength (split strength) when separating the bonded body 1 can be adjusted.
From this point of view, when the bonded body 1 that can be easily separated is manufactured, the bonding strength of the bonded body 1 is preferably large enough to be easily separated by a human hand. Thereby, when isolate | separating the conjugate | zygote 1 can be performed easily, without using an apparatus etc.

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 according to the present embodiment, as shown in FIGS. 2E and 2F, in the region other than the first region 310a to be bonded, the first base material 21 and the second substrate 21 A space 3 c having a distance (height) corresponding to the thickness of the bonding film 3 a is formed between the base material 22 and the base material 22. The space 3c also has a portion having a height corresponding to the sum of the thickness of the bonding film 3a and the thickness of the bonding film 3b. In order to make use of such a space 3c, a closed space or a flow path is formed between the first base material 21 and the second base material 22 by appropriately adjusting the shape of the first region 310a. can do.

Here, a mechanism for joining the first adherend 41 and the second adherend 42 in this step will be described.
For example, a case where a hydroxyl group is exposed on the bonding surface 24 of the second adherend 42 will be described as an example. In this step, the bonding film 3a of the first adherend 41 and the second adherend 42 are used. When these are bonded so as to be in contact with the bonding film 3b, the hydroxyl group existing on the surface 31a of the bonding film 3a and the hydroxyl group existing on the surface 31b of the bonding film 3b attract each other by hydrogen bonding, An attractive force is generated between them. It is assumed that the first adherend 41 and the second adherend 42 are joined by this attractive force.

Further, the hydroxyl groups attracting each other by the hydrogen bond are cleaved from the surface with dehydration condensation depending on the temperature condition or the like. As a result, at the contact interface between the first adherend 41 and the second adherend 42, the bonds in which the hydroxyl groups are bonded are bonded. Thereby, it is guessed that the 1st to-be-adhered body 41 and the 2nd to-be-adhered body 42 are joined more firmly.
Further, bonds that are not terminated, i.e., unbonded hands (on the surface and inside of the bonding film 3a of the first adherend 41 and the surface and inside of the bonding film 3b of the second adherend 42, respectively) In the case where a dangling bond) exists, when the first adherend 41 and the second adherend 42 are bonded together, these unbonded hands 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 1st to-be-adhered body 41 and the 2nd to-be-adhered body 42 are joined especially firmly.

  Note that the active state of the surfaces of the bonding films 3a and 3b activated in the step [3] relaxes with time. For this reason, it is preferable to perform this process [4] as soon as possible after 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 such a time, the surfaces of the bonding films 3a and 3b maintain a sufficiently active state. Therefore, when the first adherend 41 and the second adherend 42 are bonded together, In this case, sufficient bonding strength can be obtained.

In other words, each of the bonding films 3a and 3b before activation is a bonding film in which a leaving group 303 is introduced into a metal skeleton, so that it is chemically relatively stable and has excellent weather resistance. . For this reason, the bonding films 3a and 3b before being activated are suitable for long-term storage. Therefore, the adherends 41 and 42 each having such bonding films 3a and 3b are manufactured or purchased in large quantities and stored, and just before the bonding in this step, the necessary number is only described. If energy is applied as described in step [3], it is effective from the viewpoint of manufacturing efficiency of the bonded body 1.
As described above, the joined body (joined body of the present invention) 1 shown in FIG. 2 (e) can be obtained.

The joined body 1 thus obtained preferably has a joining strength between the first base material 21 and the second base material 22 of 5 MPa (50 kgf / cm ² ) or more, preferably 10 MPa (100 kgf / cm ² ). ² ) or more. The bonded body 1 having such bonding strength can sufficiently prevent the peeling. As will be described later, for example, when a droplet discharge head is configured using the joined body 1, a droplet discharge head having excellent durability can be obtained. Moreover, according to the joining method of the present invention, it is possible to efficiently produce the joined body 1 in which the first base material 21 and the second base material 22 are joined with the above-described great joint strength.

  In addition, in the conventional solid bonding where the silicon substrates are directly bonded to each other, even if the surface of the substrate used for bonding is activated, the active state is an extremely short time of about several seconds to several tens of seconds in the atmosphere. It could only be maintained. For this reason, there has been a problem that it is not possible to sufficiently secure the time required for operations such as bonding the two substrates to be bonded after the surface activation.

On the other hand, according to the present invention, the active state can be maintained for a relatively long time. For this reason, the time required for the bonding operation can be sufficiently secured, and the efficiency of the bonding operation can be increased.
In addition, when obtaining the joined body 1 or after obtaining the joined body 1, the following three steps ([5A], [5B] and [5C]) are performed on the joined body 1 as necessary. At least one of these steps (step of increasing the bonding strength of the bonded body 1) may be performed. Thereby, the joint strength of the joined body 1 can be further improved easily.

[5A] As shown in FIG. 2 (f), the obtained bonded body 1 is pressurized in a direction in which the first base material 21 and the second base material 22 approach each other.
Thereby, the surfaces 31a and 31b of the bonding films 3a and 3b are closer to each other, and the bonding strength in the bonded body 1 can be further increased.
Further, by pressurizing the bonded body 1, the gap remaining at the bonded interface in the bonded body 1 can be crushed and the bonded area can be further expanded. Thereby, the joint strength in the joined body 1 can be further increased.

In addition, what is necessary is just to adjust this pressure suitably according to conditions, such as each constituent material of each of the 1st base material 21 and the 2nd base material 22, each thickness, and a joining apparatus. Specifically, it is preferably about 0.2 to 10 MPa, preferably about 1 to 5 MPa, although it varies slightly depending on the constituent materials and thicknesses of the first base material 21 and the second base material 22. It is more preferable that 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 each component material of the 1st base material 21 and the 2nd base material 22, there exists a possibility that damage etc. may arise in each base material 21 and 22. .
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 higher the bonding strength can be achieved even if the pressing time is shortened.

[5B] As shown in FIG. 2F, the obtained bonded body 1 is heated.
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. 2F, 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.

[5C] The obtained bonded body 1 is irradiated with ultraviolet rays.
Thereby, the chemical bond formed between the bonding films 3a and 3b can be increased, and the bonding strength of the bonded body 1 can be particularly increased.
The conditions of the ultraviolet rays irradiated at this time may be equivalent to the conditions of the ultraviolet rays shown in the step [3].
Moreover, when performing this process [5C], it is necessary for either one of the 1st base material 21 and the 2nd base material 22 to have translucency. Then, by irradiating ultraviolet rays from the side of the base material having translucency, each of the bonding films 3a and 3b can be reliably irradiated with ultraviolet rays.
By performing the steps as described above, it is possible to easily further improve the bonding strength in the bonded body 1.
Here, each bonding film 3a, 3b which bears joining of the 1st base material 21 and the 2nd base material 22 is explained in full detail.

  In the bonding method according to the present embodiment as described above, the bonding films 3a and 3b having the following I or II configuration are applied. If each of the bonding films 3a and 3b has a configuration of I or II, energy is applied to each of the bonding films 3a and 3b, so that the desorption existing near the surfaces 31a and 31b of the bonding films 3a and 3b. The release group 303 is detached from the bonding films 3a and 3b. The bonding films 3a and 3b exhibit adhesion on the surfaces 31a and 31b due to the elimination of the leaving group 303.

Hereinafter, each of the bonding films 3a and 3b configured as I and II will be described in detail. Since the bonding film 3a and the bonding film 3b have the same configuration, the bonding film 3a will be described as a representative here.
<I> First, the bonding film 3a having the configuration I is provided on each of the base materials 21 and 22, and is bonded to a metal atom, an oxygen atom bonded to the metal atom, and at least one of the metal atom and the oxygen atom. And a leaving group 303 (see FIG. 3). In other words, it can be said that the bonding film 3a is obtained by introducing the leaving group 303 into a metal oxide film made of a metal oxide.

  In such a bonding film 3a, when energy is applied, the leaving group 303 is detached from the bonding film 3a (at least one of a metal atom and an oxygen atom), and as shown in FIG. 4, at least the surface of the bonding film 3a. An active hand 304 is generated in the vicinity of 31a. As a result, adhesiveness is developed on the surface of the bonding film 3a. When such adhesiveness is expressed, the first adherend 41 including the bonding film 3a can be firmly and efficiently bonded to the bonding film 3b of the second adherend 42 with high dimensional accuracy. Become.

In addition, the bonding film 3a is composed of a metal atom and an oxygen atom bonded to the metal atom, that is, a bonding film 3a in which the leaving group 303 is bonded to the metal oxide. It becomes. For this reason, the bonding film 3a itself has a high dimensional accuracy, and the bonded body 1 finally obtained also has a high dimensional accuracy.
Further, the bonding film 3a is a solid that does not have fluidity. For this reason, the thickness and shape of the adhesive layer (bonding film 3a) are hardly changed compared to a liquid or viscous liquid (semi-solid) adhesive having fluidity that has been conventionally used. Therefore, the dimensional accuracy of the bonded body 1 obtained using the bonding film 3a 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.

In the present invention, it is preferable that the bonding film 3a has conductivity. Thereby, in the bonded body 1 to be described later, the bonding film 3a can be applied to wirings provided in the wiring board, terminals thereof, and the like.
Also, if the bonding film 3a has conductivity, the resistivity of the bonding film 3a, while slightly different depending on the composition of the material, but preferably not more than ^{1 × 10 -3 Ω · cm,} 1 × 10 - More preferably, it is ⁴ Ω · cm or less. If the resistivity of the bonding film 3a is sufficiently low in this way, the bonding film 3a can be sufficiently used as, for example, a wiring with little loss.
Furthermore, it is preferable that the bonding film 3a has a light transmitting property. Thereby, the joined body of this invention is applicable to the area | region which requires translucency in an optical element etc.

  The leaving group 303 only needs to be present at least near the surface 31a of the bonding film 3a, may be present almost throughout the bonding film 3a, or is unevenly distributed near the surface 31a of the bonding film 3a. May be. Note that the structure in which the leaving group 303 is unevenly distributed in the vicinity of the surface 31a can preferably cause the bonding film 3a to function as a metal oxide film. In other words, the bonding film 3a can be advantageously provided with a function as a metal oxide film excellent in characteristics such as conductivity and translucency in addition to the function responsible for bonding. In other words, it is possible to reliably prevent the leaving group 303 from impairing properties such as the conductivity and translucency of the bonding film 3a.

The metal atom is selected so that the function as the bonding film 3a as described above is suitably exhibited.
Specifically, the metal atom is not particularly limited. For example, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd , Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au, various lanthanoid elements, transition metal elements such as various actinoid elements, Li, Be, Na, Mg, Al, K, Ca, Zn, Ga , Rb, Sr, Cd, In, Sn, Sb, Cs, Ba, Tl, Pd, Bi, Po, and other typical metal elements.

Among these transition metals, the outermost electrons are located in the d orbital or f orbital, and the transition metal elements are different only in the number of outermost shell electrons, so the physical properties are similar. ing. Transition metals generally have high hardness and melting point, and high electrical conductivity and thermal conductivity. For this reason, by selecting an atom of a transition metal element as the metal atom contained in the bonding film 3a, the adhesiveness expressed in the bonding film 3a can be further enhanced. In addition, the conductivity of the bonding film 3a can be further increased.
In particular, the bonding film 3a has particularly excellent conductivity and transparency by using one or more of In, Sn, Zn, Ti and Sb as metal atoms contained in the bonding film 3a. And will demonstrate.

More specifically, examples of the metal oxide include indium tin oxide (ITO), indium zinc oxide (IZO), antimony tin oxide (ATO), fluorine-containing indium tin oxide (FTO), and zinc oxide. (ZnO) and titanium dioxide (TiO _2), and the like.
When indium tin oxide (ITO) is used as the metal oxide, the atomic ratio of indium to tin (indium / tin ratio) is preferably 99/1 to 80/20, and 97/3 More preferably, it is -85/15. Thereby, the effects as described above can be more remarkably exhibited.

The abundance ratio of metal atoms to oxygen atoms in the bonding film 3a is preferably about 3: 7 to 7: 3, and more preferably about 4: 6 to 6: 4. By setting the abundance ratio of the metal atoms and oxygen atoms to be within the above range, the stability of the bonding film 3a is increased, and the first adherend 41 and the second adherend 42 are made stronger. It becomes possible to join.
Further, as described above, the leaving group 303 behaves so as to generate an active hand in the bonding film 3a by leaving from at least one of a metal atom and an oxygen atom. Therefore, although the leaving group 303 is relatively easily and uniformly desorbed by being given energy, it is reliably bonded to the bonding film 3a so as not to be desorbed when no energy is given. Those are preferably selected.

From this viewpoint, the leaving group 303 is preferably a hydrogen atom, a carbon atom, a nitrogen atom, a phosphorus atom, a sulfur atom and a halogen atom, or at least one of atomic groups composed of these atoms. It is done. Such a leaving group 303 is relatively excellent in bond / elimination selectivity by applying energy. For this reason, such a leaving group 303 can sufficiently satisfy the above-described necessity, and has a higher degree of adhesion between the first adherend 41 and the second adherend 42. Can be.
Examples of the atomic group (group) composed of the above atoms include, for example, an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a carboxyl group, an amino group, and a sulfonic acid. Groups and the like.

Among the atoms and atomic groups as described above, the leaving group 303 is particularly preferably a hydrogen atom. Since the leaving group 303 composed of hydrogen atoms has high chemical stability, the bonding film 3a having a hydrogen atom as the leaving group 303 has excellent weather resistance and chemical resistance.
Considering the above, as the bonding film 3a, indium tin oxide (ITO), indium zinc oxide (IZO), antimony tin oxide (ATO), fluorine-containing indium tin oxide (FTO), zinc oxide ( A material in which a hydrogen atom is introduced as a leaving group 303 into a metal oxide of ZnO) or titanium dioxide (TiO ₂ ) is preferably selected.

The bonding film 3a having such a configuration itself has excellent mechanical characteristics. In addition, it exhibits particularly excellent adhesion to many materials. Therefore, such a bonding film 3a adheres particularly firmly to the first substrate 21, and also exhibits a particularly strong adhesion force to the bonding film 3b. As a result, each adherend 41, 42 can be firmly joined.
In addition, the average thickness of the bonding film 3a is preferably about 0.2 to 1000 nm, and more preferably about 2 to 800 nm. By making the average thickness of the bonding film 3a within the above range, the first adherend 41 and the second adherend 42 are more bonded while preventing the dimensional accuracy of the bonded body 1 from being significantly lowered. It can be firmly joined.
That is, when the average thickness of the bonding film 3a 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 bonding film 3a exceeds the upper limit, the dimensional accuracy of the bonded body 1 may be significantly reduced.

Furthermore, if the average thickness of the bonding film 3a is within the above range, a certain degree of shape followability is ensured for the bonding film 3a. For this reason, for example, even when unevenness exists on the bonding surface 23 (the surface on which the bonding film 3a is formed) of the first base material 21, the unevenness follows the shape of the unevenness depending on the height of the unevenness. Thus, the bonding film 3a can be deposited. As a result, the bonding film 3a can absorb the unevenness and reduce the height of the unevenness generated on the surface. And when the 1st to-be-adhered body 41 and the 2nd to-be-adhered body 42 are bonded together, the adhesiveness with respect to the 2nd to-be-adhered body 42 of the bonding film 3a can be improved.
Note that the degree of the shape followability as described above becomes more prominent as the thickness of the bonding film 3a increases. Therefore, in order to ensure sufficient shape followability, the thickness of the bonding film 3a should be as large as possible.

  In the bonding film 3a described above, when the leaving group 303 is present in almost the entire bonding film 3a, for example, A: physical atmosphere in an atmosphere containing an atomic component constituting the leaving group 303 is used. It can be formed by depositing a metal oxide material containing metal atoms and oxygen atoms by a phase film formation method. Further, in the case where the leaving group 303 is unevenly distributed near the surface 31a of the bonding film 3a, for example, after forming a metal oxide film containing B: metal atom and the oxygen atom, It can be formed by introducing a leaving group 303 into at least one of a metal atom and an oxygen atom contained in the vicinity of the surface.

Hereinafter, the case where the bonding film 3a is formed on the first substrate 21 using the methods A and B will be described in detail.
<A> In the method A, as described above, the bonding film 3a is formed of a metal atom and an oxygen by a physical vapor deposition method (PVD method) in an atmosphere containing an atomic component constituting the leaving group 303. It is formed by depositing a metal oxide material containing atoms. When the PVD method is used as described above, the leaving group 303 is introduced into at least one of the metal atom and the oxygen atom relatively easily when the metal oxide material is made to fly toward the first base material 21. can do. For this reason, the leaving group 303 can be introduced over almost the entire bonding film 3a.

  Furthermore, according to the PVD method, a dense and homogeneous bonding film 3a can be efficiently formed. Thereby, the bonding film 3a formed by the PVD method can be particularly strongly bonded to the bonding film 3b. Furthermore, the bonding film 3a formed by the PVD method is maintained for a relatively long time in a state where energy is applied and activated. For this reason, the manufacturing process of the joined body 1 can be simplified and efficient.

  Further, examples of the PVD method include a vacuum deposition method, a sputtering method, an ion plating method, a laser ablation method, and the like. Among these, the sputtering method is preferably used. According to the sputtering method, metal oxide particles can be knocked out into an atmosphere containing an atomic component constituting the leaving group 303 without breaking a bond between a metal atom and an oxygen atom. Since the metal oxide particles can be brought into contact with a gas containing an atomic component constituting the leaving group 303, the leaving group to the metal oxide (metal atom or oxygen atom) can be contacted. 303 can be introduced more smoothly.

Hereinafter, as a method for forming the bonding film 3a by the PVD method, a case where the bonding film 3a is formed by a sputtering method (ion beam sputtering method) will be described as a representative.
First, prior to describing the method of forming the bonding film 3a, the film forming apparatus 200 used when forming the bonding film 3a on the first substrate 21 by the ion beam sputtering method will be described.

FIG. 5 is a longitudinal sectional view schematically showing a film forming apparatus used in the bonding method of the present invention, and FIG. 6 is a schematic view showing a configuration of an ion source provided in the film forming apparatus shown in FIG. In the following description, the upper side in FIG. 5 is referred to as “upper” and the lower side is referred to as “lower”.
The film forming apparatus 200 shown in FIG. 5 is configured so that the bonding film 3a can be formed in a chamber (apparatus) by an ion beam sputtering method.

  Specifically, the film forming apparatus 200 includes a chamber (vacuum chamber) 211 and a substrate holder (film forming object holding) that is installed in the chamber 211 and holds the first base material 21 (film forming object). Part) 212, an ion source (ion supply part) 215 that irradiates the inside of the chamber 211 with the ion beam B, and a metal that contains metal atoms and oxygen atoms by the irradiation of the ion beam B. A target holder (target holding portion) 217 that holds a target (metal oxide material) 216 that generates oxide (for example, ITO).

The chamber 211 has a gas supply means 260 for supplying a gas containing an atomic component constituting the leaving group 303 (for example, hydrogen gas) into the chamber 211, and the chamber 211 is evacuated to control the pressure. And an evacuation unit 230 for performing the operation.
In the present embodiment, the substrate holder 212 is attached to the ceiling portion of the chamber 211. The substrate holder 212 is rotatable. Thereby, the bonding film 3a can be formed on the first base material 21 with a uniform and uniform thickness.

As shown in FIG. 6, the ion source (ion gun) 215 includes an ion generation chamber 256 in which an opening (irradiation port) 250 is formed, a filament 257 provided in the ion generation chamber 256, grids 253 and 254, And a magnet 255 installed outside the ion generation chamber 256.
Further, as shown in FIG. 5, a gas supply source 219 for supplying a gas (sputtering gas) is connected to the ion generation chamber 256.

In the ion source 215, when the filament 257 is energized and heated in a state where gas is supplied from the gas supply source 219 into the ion generation chamber 256, electrons are emitted from the filament 257, and the emitted electrons are generated by the magnetic field of the magnet 255. It moves and collides with gas molecules supplied into the ion generation chamber 256. Thereby, gas molecules are ionized. The ions I ⁺ of the gas are extracted from the ion generation chamber 256 and accelerated by a voltage gradient between the grid 253 and the grid 254 and are emitted (irradiated) from the ion source 215 as an ion beam B through the opening 250. Is done.
The ion beam B irradiated from the ion source 215 collides with the surface of the target 216, and particles (sputtered particles) are knocked out from the target 216. The target 216 is made of a metal oxide material as described above.

  In the film forming apparatus 200, the ion source 215 is fixed (installed) on the side wall of the chamber 211 so that the opening 250 is located in the chamber 211. Note that the ion source 215 can be arranged at a position separated from the chamber 211 and connected to the chamber 211 via a connection portion. 200 can be reduced in size.

The ion source 215 is installed such that the opening 250 faces in a direction different from that of the substrate holder 212, in this embodiment, the bottom side of the chamber 211.
The number of ion sources 215 installed is not limited to one, and may be plural. By installing a plurality of ion sources 215, the deposition rate of the bonding film 3a can be increased.

In addition, a first shutter 220 and a second shutter 221 that can cover the target holder 217 and the substrate holder 212 are disposed, respectively.
These shutters 220 and 221 are for preventing the target 216, the first base material 21, and the bonding film 3a from being exposed to an unnecessary atmosphere or the like, respectively.
The exhaust means 230 includes a pump 232, an exhaust line 231 that communicates the pump 232 and the chamber 211, and a valve 233 provided in the middle of the exhaust line 231. The pressure can be reduced.

  Further, the gas supply means 260 includes a gas cylinder 264 that stores a gas (for example, hydrogen gas) that includes an atomic component constituting the leaving group 303, a gas supply line 261 that guides the gas from the gas cylinder 264 to the chamber 211, and a gas A pump 262 and a valve 263 provided in the middle of the supply line 261 are configured so that a gas containing an atomic component constituting the leaving group 303 can be supplied into the chamber 211.

Using the film forming apparatus 200 configured as described above, the bonding film 3a is formed as follows.
Here, a method of forming the bonding film 3a on the first substrate 21 will be described.
First, the first base material 21 is prepared, and the first base material 21 is carried into the chamber 211 of the film forming apparatus 200 and mounted (set) on the substrate holder 212.

Next, the exhaust means 230 is operated, that is, the valve 233 is opened while the pump 232 is operated, whereby the inside of the chamber 211 is decompressed. The degree of vacuum (degree of vacuum) is not particularly limited, but is preferably about 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ Torr, preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻⁵ Torr. Is more preferable.
Further, the gas supply means 260 is operated, that is, the valve 263 is opened while the pump 262 is operated, so that the gas containing the atomic components constituting the leaving group 303 is supplied into the chamber 211. Thereby, the inside of a chamber can be made into the atmosphere containing this gas (hydrogen gas atmosphere).

The flow rate of the gas containing the atomic component constituting the leaving group 303 is preferably about 1 to 100 ccm, and more preferably about 10 to 60 ccm. Thereby, the leaving group 303 can be reliably introduced into at least one of the metal atom and the oxygen atom.
Further, the temperature in the chamber 211 may be 25 ° C. or higher, but is preferably about 25 to 100 ° C. By setting within this range, the reaction between the metal atom or oxygen atom and the gas containing the atomic component is efficiently performed, and the gas containing the atomic component is reliably introduced into the metal atom and the oxygen atom. Can do.

Next, the second shutter 221 is opened, and the first shutter 220 is further opened.
In this state, a gas is introduced into the ion generation chamber 256 of the ion source 215, and the filament 257 is energized and heated. Thereby, electrons are emitted from the filament 257, and the emitted electrons collide with gas molecules, whereby the gas molecules are ionized.

The ions I ⁺ of the gas are accelerated by the grid 253 and the grid 254, emitted from the ion source 215, and collide with a target 216 made of a cathode material. Thereby, particles of metal oxide (for example, ITO) are knocked out from the target 216. At this time, since the inside of the chamber 211 is in an atmosphere containing a gas containing an atomic component constituting the leaving group 303 (for example, in a hydrogen gas atmosphere), the metal atoms contained in the particles knocked out into the chamber 211 And a leaving group 303 is introduced into the oxygen atom. Then, the metal oxide into which the leaving group 303 is introduced is deposited on the first base material 21, whereby the bonding film 3a is formed.

In the ion beam sputtering method described in this embodiment, in the ion generation chamber 256 of the ion source 215, a discharge is performed, the electron e ^- is occurs, the electron e ^- is shielded by the grid 253, Release into the chamber 211 is prevented.
Further, since the irradiation direction of the ion beam B (the opening 250 of the ion source 215) is directed to the target 216 (a direction different from the bottom side of the chamber 211), the ultraviolet rays generated in the ion generation chamber 256 are formed. Irradiation to the bonding film 3a can be prevented more reliably, and the leaving group 303 introduced during the formation of the bonding film 3a can be reliably prevented from detaching.
As described above, the bonding film 3a in which the leaving group 303 exists almost entirely can be formed.

  <B> On the other hand, in the method B, as described above, the bonding film 3a is formed of a metal oxide film containing metal atoms and oxygen atoms, and then the metal contained in the vicinity of the surface of the metal oxide film. It is formed by introducing a leaving group 303 into at least one of an atom and an oxygen atom. According to such a method, it is possible to introduce the leaving group 303 in an unevenly distributed state near the surface of the metal oxide film in a relatively simple process, and to achieve both characteristics as a bonding film and a metal oxide film. An excellent bonding film 3a can be formed.

  Here, the metal oxide film may be formed by any method, for example, PVD method (physical vapor deposition method), CVD method (chemical vapor deposition method), plasma polymerization method, etc. The film can be formed by various vapor phase film forming methods, various liquid phase film forming methods, and the like, and it is particularly preferable to form the film by the PVD method. According to the PVD method, a dense and homogeneous metal oxide film can be efficiently formed.

  Moreover, examples of the PVD method include a vacuum deposition method, a sputtering method, an ion plating method, a laser ablation method, and the like. Among these, it is preferable to use a sputtering method. According to the sputtering method, the metal oxide particles can be knocked out into the atmosphere and supplied onto the first substrate 21 without breaking the bond between the metal atom and the oxygen atom. An excellent metal oxide film can be formed.

  Furthermore, as a method for introducing the leaving group 303 near the surface of the metal oxide film, various methods are used. For example, the metal oxide film is formed in an atmosphere containing an atomic component constituting the B1: leaving group 303. Examples of the method include heat treatment (annealing), B2: ion implantation, and the like. In particular, it is preferable to use the method B1. According to the method B1, the leaving group 303 can be selectively introduced near the surface of the metal oxide film relatively easily. Further, by appropriately setting the processing conditions such as the atmospheric temperature and the processing time when performing the heat treatment, the amount of the leaving group 303 to be introduced, and further the thickness of the metal oxide film into which the leaving group 303 is introduced. Can be accurately controlled.

Thereafter, a metal oxide film is formed by a sputtering method (ion beam sputtering method), and then the obtained metal oxide film is subjected to heat treatment (annealing) in an atmosphere containing an atomic component constituting the leaving group 303. Thus, a case where the bonding film 3a is obtained will be described as a representative.
Even when the bonding film 3a is formed using the method B, a film forming apparatus similar to the film forming apparatus 200 used when forming the bonding film 3a using the method A is used. A description of the film forming apparatus is omitted.

[I] First, the base materials 21 and 22 are prepared. Then, each of the base materials 21 and 22 is carried into the chamber 211 of the film forming apparatus 200 and mounted (set) on the substrate holder 212.
[Ii] Next, the exhaust means 230 is operated, that is, the valve 233 is opened while the pump 232 is operated, so that the inside of the chamber 211 is decompressed. The degree of vacuum (degree of vacuum) is not particularly limited, but is preferably about 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ Torr, preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻⁵ Torr. Is more preferable.
At this time, the heating means is operated to heat the chamber 211. Although the temperature in the chamber 211 should just be 25 degreeC or more, it is preferable that it is about 25-100 degreeC. By setting within this range, a metal oxide film having a high film density can be formed.

[Iii] Next, the second shutter 221 is opened, and the first shutter 220 is further opened.
In this state, a gas is introduced into the ion generation chamber 256 of the ion source 215, and the filament 257 is energized and heated. Thereby, electrons are emitted from the filament 257, and the emitted electrons collide with gas molecules, whereby the gas molecules are ionized.
The ions I ⁺ of the gas are accelerated by the grid 253 and the grid 254, emitted from the ion source 215, and collide with a target 216 made of a cathode material. As a result, metal oxide (for example, ITO) particles are knocked out of the target 216 and deposited on the first base material 21, and a metal oxide containing a metal atom and an oxygen atom bonded to the metal atom. A material film is formed.

In the ion beam sputtering method described in this embodiment, in the ion generation chamber 256 of the ion source 215, a discharge is performed, the electron e ^- is occurs, the electron e ^- is shielded by the grid 253, Release into the chamber 211 is prevented.
Further, since the irradiation direction of the ion beam B (the opening 250 of the ion source 215) is directed to the target 216 (a direction different from the bottom side of the chamber 211), the ultraviolet rays generated in the ion generation chamber 256 are formed. Irradiation to the bonding film 3a can be prevented more reliably, and the leaving group 303 introduced during the formation of the bonding film 3a can be reliably prevented from detaching.

[Iv] Next, with the second shutter 221 open, the first shutter 220 is closed.
In this state, the heating means is operated to further heat the chamber 211. The temperature in the chamber 211 is set to a temperature at which the leaving group 303 is efficiently introduced onto the surface of the metal oxide film, and is preferably about 100 to 600 ° C., more preferably about 150 to 300 ° C. preferable. By setting within this range, in the next step [v], the leaving group 303 is efficiently introduced into the surface of the metal oxide film without deteriorating / degrading the base materials 21 and 22 and the metal oxide film. can do.

[V] Next, the gas supply means 260 is operated, that is, the valve 263 is opened in a state where the pump 262 is operated, so that the gas containing the atomic component constituting the leaving group 303 is supplied into the chamber 211. Thereby, the inside of the chamber 211 can be made into the atmosphere containing this gas (under hydrogen gas atmosphere).
As described above, in the state where the inside of the chamber 211 is heated in the step [iv], the inside of the chamber 211 includes an atmosphere containing a gas containing an atomic component constituting the leaving group 303 (for example, under a hydrogen gas atmosphere). Then, the leaving group 303 is introduced into at least one of metal atoms and oxygen atoms existing near the surface of the metal oxide film, and the bonding film 3a is formed.
The flow rate of the gas containing the atomic component constituting the leaving group 303 is preferably about 1 to 100 ccm, and more preferably about 10 to 60 ccm. Thereby, the leaving group 303 can be reliably introduced into at least one of the metal atom and the oxygen atom.

  Note that, in the chamber 211, it is preferable to maintain the reduced pressure state adjusted by operating the exhaust unit 230 in the step [ii]. Thereby, the leaving group 303 can be introduced more smoothly into the vicinity of the surface of the metal oxide film. In addition, by reducing the pressure in the chamber 211 in this step while maintaining the reduced pressure state in the step [ii], it is possible to save the time for reducing the pressure again. There is also an advantage that it can be achieved.

The degree of vacuum (degree of vacuum) is not particularly limited, but is preferably about 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ Torr, preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻⁵ Torr. Is more preferable.
Moreover, it is preferable that the time which heat-processes is about 15 to 120 minutes, and it is more preferable that it is about 30 to 60 minutes.

Although depending on the type of leaving group 303 to be introduced and the like, the metal oxide film can be obtained by setting the conditions (temperature in the chamber 211, degree of vacuum, gas flow rate, treatment time) during the heat treatment within the above ranges. A leaving group 303 can be selectively introduced in the vicinity of the surface.
As described above, the bonding film 3a in which the leaving group 303 is unevenly distributed in the vicinity of the surface 31a can be formed.

<II> Next, the bonding film 3 a having the configuration II is provided on the first base material 21 and includes a leaving group 303 including a metal atom and an organic component (see FIG. 3).
When such a bonding film 3a is applied with energy, the bond of the leaving group 303 is cut and desorbed from at least the vicinity of the surface 31a of the bonding film 3a, and as shown in FIG. 4, at least the surface of the bonding film 3a. Active hands 304 are generated in the vicinity of 31a. Thereby, adhesiveness is developed on the surface 31a of the bonding film 3a. When such adhesiveness is developed, the first adherend 41 including the bonding film 3a can be firmly and efficiently bonded to the second adherend 42 with high dimensional accuracy.
Further, since the bonding film 3a includes a metal atom and a leaving group 303 composed of an organic component, that is, an organic metal film, the bonding film 3a is a strong film that is difficult to be deformed. For this reason, the bonding film 3a itself has a high dimensional accuracy, and the bonded body 1 finally obtained also has a high dimensional accuracy.

Such a bonding film 3a is a solid having no fluidity. For this reason, the thickness and shape of the adhesive layer (bonding film 3a) are hardly changed compared to a liquid or viscous liquid (semi-solid) adhesive having fluidity that has been conventionally used. Therefore, the dimensional accuracy of the bonded body 1 obtained using such a bonding film 3a 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.
In the present invention, it is preferable that the bonding film 3a has conductivity. Thereby, in the bonded body 1 to be described later, the bonding film 3a can be applied to wirings provided in the wiring board, terminals thereof, and the like.

The metal atom and the leaving group 303 are selected so that the function as the bonding film 3a as described above is suitably exhibited.
Specifically, examples of the metal atom include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Transition metal elements such as Ta, W, Re, Os, Ir, Pt, Au, various lanthanoid elements, various actinoid elements, Li, Be, Na, Mg, Al, K, Ca, Zn, Ga, Rb, Sr, Typical metal elements such as Cd, In, Sn, Sb, Cs, Ba, Tl, Pd, Bi, and Po are listed.

  Among these, as described above, the transition metals have similar physical properties because the transition metal elements are different only in the number of outermost electrons. Transition metals generally have high hardness and melting point, and high electrical conductivity and thermal conductivity. For this reason, by selecting an atom of a transition metal element as the metal atom contained in the bonding film 3a, the adhesiveness expressed in the bonding film 3a can be further enhanced. In addition, the conductivity of the bonding film 3a can be further increased.

  In particular, the bonding film 3a exhibits particularly excellent conductivity by using one or more of Cu, Al, Zn and Fe as metal atoms included in the bonding film 3a. Become. Further, when the bonding film 3a is formed using a metal organic chemical vapor deposition method, which will be described later, a bonding film having a relatively easy and uniform film thickness using a metal complex containing these metals as a raw material. 3a can be formed.

  Further, as described above, the leaving group 303 behaves so as to generate an active hand in the bonding film 3a by detaching from the bonding film 3a. Therefore, although the leaving group 303 is relatively easily and uniformly desorbed by being given energy, it is securely bonded to the bonding film 3a so as not to be desorbed when no energy is given. Those are preferably selected.

Specifically, as the leaving group 303, an atomic group containing a carbon atom as an essential component and containing at least one of a hydrogen atom, a nitrogen atom, a phosphorus atom, a sulfur atom and a halogen atom is suitably selected. Such a leaving group 303 is relatively excellent in bond / elimination selectivity by applying energy. For this reason, such a leaving group 303 can sufficiently satisfy the above-described necessity, and the adhesiveness of the first adherend 41 can be made higher.
More specifically, examples of the atomic group (group) include an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, and a carboxyl group, and the end of the alkyl group is an isocyanate group. And those terminated with a group, an amino group, a sulfonic acid group, and the like.

Among the atomic groups as described above, the leaving group 303 is particularly preferably an alkyl group. Since the leaving group 303 composed of an alkyl group has high chemical stability, the bonding film 3a having an alkyl group as the leaving group 303 has excellent weather resistance and chemical resistance.
In the bonding film 3a having such a configuration, the abundance ratio of metal atoms to oxygen atoms is preferably about 3: 7 to 7: 3, and more preferably about 4: 6 to 6: 4. By setting the abundance ratio of the metal atoms and the carbon atoms to be within the above range, the stability of the bonding film 3a is increased, and the first adherend 41 and the second adherend 42 are strengthened more firmly. It becomes possible to join. Further, the bonding film 3a can exhibit excellent conductivity.

In addition, the average thickness of the bonding film 3a is preferably about 0.2 to 1000 nm, and more preferably about 2 to 800 nm. By making the average thickness of the bonding film 3a within the above range, the first adherend 41 and the second adherend 42 are more bonded while preventing the dimensional accuracy of the bonded body 1 from being significantly lowered. It can be firmly joined.
That is, when the average thickness of the bonding film 3a 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 bonding film 3a exceeds the upper limit, the dimensional accuracy of the bonded body 1 may be significantly reduced.

Furthermore, if the average thickness of the bonding film 3a is within the above range, a certain degree of shape followability is ensured for the bonding film 3a. For this reason, for example, even when unevenness exists on the bonding surface 23 (the surface on which the bonding film 3a is formed) of the first base material 21, the unevenness follows the shape of the unevenness depending on the height of the unevenness. Thus, the bonding film 3a can be deposited. As a result, the bonding film 3a can absorb the unevenness and reduce the height of the unevenness generated on the surface. And when the 1st to-be-adhered body 41 and the 2nd to-be-adhered body 42 are bonded together, the adhesiveness with respect to the 2nd to-be-adhered body 42 of the bonding film 3a can be improved.
Note that the degree of the shape followability as described above becomes more prominent as the thickness of the bonding film 3a increases. Therefore, in order to ensure sufficient shape followability, the thickness of the bonding film 3a should be as large as possible.

  The bonding film 3a as described above may be formed by any method. For example, IIa: an organic substance containing a leaving group (organic component) 303 on a metal film composed of metal atoms, a metal film A method of forming the bonding film 3a by selectively imparting (chemical modification) to almost the entire surface or in the vicinity of the surface, IIb: an organic metal material having a metal atom and an organic substance containing a leaving group (organic component) 303 as a raw material As a method of forming the bonding film 3a using a metal organic chemical vapor deposition method (a method of laminating or forming a bonding layer made of a monoatomic layer), IIc: an organic substance containing a metal atom and a leaving group 303 Examples thereof include a method in which an organic metal material is dissolved in an appropriate solvent as a raw material and a bonding film is formed using a spin coating method or the like. Among these, it is preferable to form the bonding film 3a by the method IIb. According to this method, it is possible to form the bonding film 3a having a uniform film thickness in a relatively simple process.

Hereinafter, by the method of IIb, that is, a method of forming the bonding film 3a using a metal organic chemical vapor deposition method using an organic metal material having a metal atom and an organic substance containing a leaving group (organic component) 303 as a raw material, A case where the bonding film 3a is obtained will be described as a representative.
First, prior to describing the method of forming the bonding film 3a, the film forming apparatus 400 used when forming the bonding film 3a will be described.

FIG. 7 is a longitudinal sectional view schematically showing a film forming apparatus used in the bonding method of the present invention. In the following description, the upper side in FIG. 7 is referred to as “upper” and the lower side is referred to as “lower”.
A film forming apparatus 400 shown in FIG. 7 is configured so that the bonding film 3 a can be formed in the chamber 411 by a metal organic chemical vapor deposition method (hereinafter sometimes abbreviated as “MOCVD method”). .

  Specifically, the film forming apparatus 400 includes a chamber (vacuum chamber) 411 and a substrate holder (film forming object holding) that is installed in the chamber 411 and holds the first base material 21 (film forming object). Part) 412, organometallic material supply means 460 for supplying vaporized or atomized organometallic material into the chamber 411, and gas supply means 470 for supplying gas for making the inside of the chamber 411 under a low reducing atmosphere. And an exhaust means 430 for exhausting the chamber 411 and controlling the pressure, and a heating means (not shown) for heating the substrate holder 412.

The substrate holder 412 is attached to the bottom of the chamber 411 in this embodiment. The substrate holder 412 can be rotated by the operation of a motor. Thereby, the bonding film 3a can be formed on the first base material 21 with a uniform and uniform thickness.
Further, in the vicinity of the substrate holder 412, a shutter 421 that can cover them is provided. The shutter 421 is for preventing the first base material 21 and the bonding film 3a from being exposed to an unnecessary atmosphere or the like.

The organometallic material supply unit 460 is connected to the chamber 411. The organometallic material supply means 460 includes a storage tank 462 that stores a solid organometallic material, a gas cylinder 465 that stores a carrier gas that feeds the vaporized or atomized organometallic material into the chamber 411, and a carrier gas. And a gas supply line 461 for introducing the vaporized or atomized organometallic material into the chamber 411, and a pump 464 and a valve 463 provided in the middle of the gas supply line 461. In the organometallic material supply unit 460 having such a configuration, the storage tank 462 has a heating unit, and the operation of the heating unit can heat and vaporize the solid organometallic material. Therefore, when the pump 464 is operated with the valve 463 opened and the carrier gas is supplied from the gas cylinder 465 to the storage tank 462, the organometallic material vaporized or atomized together with the carrier gas passes through the supply line 461. Then, it is supplied into the chamber 411.
In addition, it does not specifically limit as carrier gas, For example, nitrogen gas, argon gas, helium gas, etc. are used suitably.

  In this embodiment, the gas supply unit 470 is connected to the chamber 411. The gas supply means 470 includes a gas cylinder 475 for storing a gas for making the inside of the chamber 411 under a low reducing atmosphere, a gas supply line 471 for introducing the gas for making the low reducing atmosphere into the chamber 411, A pump 474 and a valve 473 provided in the middle of the gas supply line 471 are configured. In the gas supply means 470 having such a configuration, when the pump 474 is operated with the valve 473 opened, the gas for making the low reducing atmosphere is supplied from the gas cylinder 475 through the supply line 471 to the chamber 411. It is designed to be supplied inside. When the gas supply unit 470 is configured as described above, the inside of the chamber 411 can be surely set in a low reducing atmosphere with respect to the organometallic material. As a result, when the bonding film 3a is formed using the MOCVD method using the organic metal material as a raw material, at least a part of the organic component contained in the organic metal material is left as the leaving group 303 in the bonding film 3a. Is deposited.

The gas for bringing the inside of the chamber 411 into a low reducing atmosphere is not particularly limited, and examples thereof include nitrogen gas and rare gases such as helium, argon, and xenon, nitrogen monoxide, and dinitrogen monoxide. These can be used alone or in combination of two or more.
In the case of using an organic metal material containing an oxygen atom in the molecular structure, such as 2,4-pentadionate-copper (II) or [Cu (hfac) (VTMS)] described later. In addition, it is preferable to add hydrogen gas to the gas for achieving a low reducing atmosphere. Thereby, the reducibility with respect to oxygen atoms can be improved, and the bonding film 3a can be formed without excessive oxygen atoms remaining in the bonding film 3a. As a result, the bonding film 3a has a low abundance of metal oxide in the film, and exhibits excellent conductivity.
In addition, when at least one of the nitrogen gas, argon gas and helium gas described above is used as the carrier gas, the carrier gas can also exhibit a function as a gas for providing a low reducing atmosphere. it can.
The exhaust means 430 includes a pump 432, an exhaust line 431 that communicates the pump 432 and the chamber 411, and a valve 433 provided in the middle of the exhaust line 431. The pressure can be reduced.

The bonding film 3a is formed on the first base material 21 by the MOCVD method using the film forming apparatus 400 having the above-described configuration.
[I] First, the first substrate 21 is prepared. Then, the first base material 21 is carried into the chamber 411 of the film forming apparatus 400 and mounted (set) on the substrate holder 412.
[Ii] Next, the exhaust unit 430 is operated, that is, the valve 433 is opened while the pump 432 is operated, so that the inside of the chamber 411 is decompressed. The degree of vacuum (degree of vacuum) is not particularly limited, but is preferably about 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ Torr, preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻⁵ Torr. Is more preferable.
Further, the gas supply means 470 is operated, that is, the valve 473 is opened while the pump 474 is operated, whereby the gas for making a low reducing atmosphere is supplied into the chamber 411 and the inside of the chamber 411 is supplied. Under a low reducing atmosphere. The flow rate of the gas by the gas supply means 470 is not particularly limited, but is preferably about 0.1 to 10 sccm, and more preferably about 0.5 to 5 sccm.
Further, at this time, the heating means is operated to heat the substrate holder 412. The temperature of the substrate holder 412 varies slightly depending on the type of the bonding film 3a to be formed, that is, the type of raw material used when forming the bonding film 3a, but is preferably about 80 to 600 ° C, and preferably 100 to 450 ° C. More preferably, it is about 200-300 degreeC. By setting within this range, it is possible to form the bonding film 3a having excellent adhesiveness using an organometallic material described later.

[Iii] Next, the shutter 421 is opened.
Then, by operating the heating means provided in the storage tank 462 in which the solid organic metal material is stored, the pump 464 is operated in a state where the organic metal material is vaporized, and the valve 463 is opened to vaporize. Alternatively, the atomized organometallic material is introduced into the chamber together with the carrier gas.

As described above, when the vaporized or atomized organometallic material is supplied into the chamber 411 in a state where the substrate holder 412 is heated in the step [ii], the organometallic material is heated on the first base material 21. As a result, the bonding film 3a can be formed on the first base material 21 in a state in which a part of the organic matter contained in the organometallic material remains.
That is, according to the MOCVD method, if a film containing metal atoms is formed so that a part of the organic substance contained in the organometallic material remains, a part of the organic substance exhibits a function as the leaving group 303. The film 3a can be formed on the first substrate 21.

The organometallic material used in such MOCVD method is not particularly limited. For example, 2,4-pentadionate-copper (II), tris (8-quinolinolato) aluminum (Alq ₃ ), tris (4 - methyl-8-quinolinolato) aluminum (III) (Almq _3), (8- hydroxyquinoline) zinc _(Znq 2), copper phthalocyanine, Cu (hexafluoroacetylacetonate) (vinyltrimethylsilane) [Cu (hfac) (VTMS )], Cu (hexafluoroacetylacetonate) (2-methyl-1-hexen-3-ene) [Cu (hfac) (MHY)], Cu (perfluoroacetylacetonate) (vinyltrimethylsilane) [Cu ( pfac) (VTMS)], Cu (perfluoroacetylacetonate) 2-methyl-1-hexen-3-ene) [Cu (pfac) (MHY)] and other amides, acetylacetonates, alkoxys, silicon-containing silyls, and carboxyl groups containing various transition metal elements. Examples include carbonyl-based metal complexes, alkyl metals such as trimethylgallium, trimethylaluminum, and diethylzinc, and derivatives thereof. Among these, the organometallic material is preferably a metal complex. By using the metal complex, it is possible to reliably form the bonding film 3a in a state in which a part of the organic substance contained in the metal complex remains.

Further, in this embodiment, the gas supply means 470 is operated, so that the inside of the chamber 411 is in a low reducing atmosphere. Without forming a pure metal film, it is possible to form a film in a state where a part of the organic substance contained in the organometallic material remains. That is, it is possible to form the bonding film 3a having excellent characteristics as both the bonding film and the metal film.
The flow rate of the vaporized or atomized organometallic material is preferably about 0.1 to 100 ccm, and more preferably about 0.5 to 60 ccm. Accordingly, the bonding film 3a can be formed with a uniform film thickness and with a part of the organic substance contained in the organometallic material remaining.

As described above, it is not necessary to introduce a leaving group into the formed metal film or the like by using the residue remaining in the film when forming the bonding film 3a as the leaving group 303. The bonding film 3a can be formed by a relatively simple process.
Note that part of the organic substance remaining in the bonding film 3a formed using the organometallic material may function as the leaving group 303, or part of the organic substance may be the leaving group 303. It may function as.

As described above, the bonding film 3a can be formed.
Note that, when the bonding film 3a is formed in the first region 310a set in a part of the bonding surface 23 of the first base material 21, the window portion 61a corresponding to the shape of the first region 310a. The bonding film 3a may be formed by the method described above using the mask 6a having the above.
That is, as shown in FIG. 1A, a mask 6a is provided above the bonding surface 23 of the first base material 21, and the bonding film 3a is formed on the bonding surface 23 through the mask 6a. During this film formation, the raw material constituting the bonding film 3a passes through the window 61a of the mask 6a, so that the raw material is deposited only in the first region 310a. Thereby, the bonding film 3 a is formed in the first region 310 a of the bonding surface 23 of the first base material 21.

In FIG. 1A, 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.
Similarly, when the bonding film 3b is formed in the second region 310b set in a part of the bonding surface 24 of the second base material 22, the shape of the second region 310b is also formed. The bonding film 3b may be formed by the method described above using the mask 6b having the window portion 61b corresponding to the above. Thereby, the bonding film 3 b is formed in the second region 310 b of the bonding surface 24 of the second base material 22.

<< Second Embodiment >>
Next, a second embodiment of the joining method of the present invention will be described.
8 and 9 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. 8 and 9 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, after the first adherend 41 and the second adherend 42 are overlapped before applying energy to the bonding films 3a and 3b, the temporary bonded body 5 is obtained. This is the same as the first embodiment except that energy is applied to the temporary joined body 5 to obtain the joined body 1.
That is, in the bonding method according to the present embodiment, the first base 21 and the second base 22 are prepared, and the first region set as a part of the bonding surface 23 of the first base 21. The bonding film 3a is formed on 310a to produce the first adherend 41, and a second pattern set in a pattern different from the first region 310a is formed on a part of the bonding surface 24 of the second base material 22. The first adherend 41 and the second adherend are formed so that the bonding film 3b is formed in the region 310b and the second adherend 42 is formed, and the bonding film 3a and the bonding film 3b are in close contact with each other. The process includes a step of obtaining the temporary joined body 5 by superimposing the adherend 42 and a step of obtaining the joined body 1 by applying energy to the temporary joined body 5.

Hereinafter, each process of the joining method concerning this embodiment is demonstrated one by one.
[1] First, as in the first embodiment, as shown in FIGS. 8A to 8B, a bonding film 3a is formed on the first base material 21. Similarly, the bonding film 3 b is formed on the second base material 22. Thereby, the 1st to-be-adhered body 41 and the 2nd to-be-adhered body 42 are obtained.
In this case, the constituent material of the bonding film 3a and the constituent material of the bonding film 3b may be different from each other, but are preferably the same material. Thereby, the affinity between the bonding film 3a and the bonding film 3b is improved. As a result, the bonding film 3a and the bonding film 3b can be firmly bonded through the steps described later.

[2] Next, as shown in FIG. 8C, the two adherends 41 and 42 are overlapped so that the bonding film 3a and the bonding film 3b are in close contact with each other. Thereby, the temporary joined body 5 is obtained.
In addition, in the state of this temporary joined body 5, between the 1st to-be-adhered body 41 and the 2nd to-be-adhered body 42 is not joined. For this reason, similarly to the first embodiment, the first adherend 41 and the second adherend 42 can be shifted and their relative positions can be adjusted.

[3] Next, energy is applied to each of the bonding films 3 a and 3 b in the obtained temporary bonded body 5.
Specifically, as shown in FIG. 9D, energy is applied by irradiating the temporary joined body 5 with ultraviolet rays. Thereby, in the temporary joined body 5, a part of molecular bond of each joining film 3a, 3b is cut | disconnected and activated. As a result, adhesiveness develops in each of the bonding films 3a and 3b. Then, due to this adhesiveness, in the portion where the bonding film 3a and the bonding film 3b overlap (the first region 310a and the second region 310b), that is, in the first region 310a, the first deposition is performed. The body 41 and the second adherend 42 are partially joined. Thereby, the joined body 1 shown in FIG.9 (e) is obtained.

The energy applied to the temporary bonded body 5 may be applied by any method other than the method of irradiating with ultraviolet rays, for example, by the method described in the first embodiment.
Here, as another method of applying energy to the temporary bonded body 5, a method of heating the bonding films 3a and 3b in the temporary bonded body 5 and a method of applying a compressive force to the bonding films 3a and 3b. Explained as an example.

When heating each bonding film 3a, 3b, 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, the bonding films 3a and 3b can be reliably activated while reliably preventing the first base material 21 and the second base material 22 from being altered or deteriorated by heat. Can do.
Further, the heating time may be a time that can remove the leaving group 303 of each bonding film 3a, 3b. Specifically, if the heating temperature is within the above range, the heating time is about 1 to 30 minutes. Preferably there is.

The bonding films 3a and 3b may be heated by any method. For example, the bonding films 3a and 3b can be heated by various 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 1st base material 21 or the 2nd base material 22 is comprised with the material which has a light absorptivity. Thereby, the 1st substrate 21 or the 2nd substrate 22 irradiated with infrared rays generates heat efficiently. As a result, the bonding films 3a and 3b can be efficiently heated.

Moreover, when using the method using a heater or the method of making it contact with a flame, it is preferable that the 1st base material 21 or the 2nd base material 22 is comprised with the material excellent in thermal conductivity. Thereby, heat can be efficiently transmitted to each bonding film 3a, 3b via the first base material 21 or the second base material 22, and each bonding film 3a, 3b is efficiently heated. Can do.
Further, when energy is applied to each bonding film 3a, 3b by applying a compressive force to each bonding film 3a, 3b, the first base material 21 and the second base material 22 are mutually connected. In the approaching direction, the temporary joined body 5 is preferably compressed with a pressure of about 0.2 to 10 MPa, and more preferably compressed with a pressure of about 1 to 5 MPa. As a result, it is possible to easily apply appropriate energy to the bonding films 3a and 3b by simply compressing, and the bonding film 3a and the bonding film 3b exhibit sufficient adhesion to each other. In addition, although this pressure may exceed the said upper limit, depending on each component material of the 1st base material 21 and the 2nd base material 22, there exists a possibility that damage etc. may arise in each base material 21 and 22. .
The time for applying the compressive force 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 which provides compression force according to the magnitude | size of compression force. Specifically, the time for applying the compressive force can be shortened as the compressive force increases.

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.
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 easily.

<< Third Embodiment >>
Next, a third embodiment of the joining method of the present invention will be described.
10 and 11 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. 10 and 11 is referred to as “upper” and the lower side is referred to as “lower”.
Hereinafter, the bonding method according to the third embodiment will be described, but the description will focus on differences from the first embodiment or the second embodiment, and the description of the same matters will be omitted.

  In the bonding method according to the present embodiment, the first adherend 41 having the bonding film 3a on the entire surface of the first substrate 21 and the second film having the bonding film 3b on the entire surface of the second substrate 22 are used. The adherend 42 is prepared, and energy is applied to the first region 310a set as a part of the bonding film 3a and the second region 310b set as a part of the bonding film 3b. Except for the above, it is the same as the first embodiment.

  That is, in the bonding method according to the present embodiment, the bonding films 3a and 3b are formed on the entire bonding surfaces 23 and 24 of the base materials 21 and 22, whereby the first adherend 41 and the second adhesion are formed. A step of obtaining the body 42, a first region 310a set in a part of the bonding film 3a, and a second region 310b set in a pattern different from the first region 310a in a part of the bonding film 3b. A step of applying energy, a step of bonding the first adherend 41 and the second adherend 42 so that the bonding film 3a and the bonding film 3b are in close contact with each other, and obtaining the bonded body 1. Have

Hereinafter, each process of the joining method concerning this embodiment is demonstrated one by one.
[1] First, as shown in FIGS. 10A to 10B, a bonding film 3 a is formed on the entire bonding surface 23 of the first base material 21. Thereby, the 1st to-be-adhered body 41 is obtained. Similarly, the bonding film 3 b is formed on the entire bonding surface 24 of the second base material 22. Thereby, the second adherend 42 is obtained.
The method for forming the bonding films 3a and 3b is the same as that in the first embodiment except that a mask is not used.

  [2] Next, as shown in FIG. 10 (c), the first region 310 a set in a part of the surface 31 a of the bonding film 3 a of the first adherend 41 is selectively selected. Giving energy. Similarly, energy is selectively applied to a part of the surface 31b of the bonding film 3b of the second adherend 42 with respect to the second region 310b set in a pattern different from the first region 310a. Is granted. Hereinafter, the bonding film 3a will be described as a representative.

When energy is applied, the first region 310a is partially activated in the bonding film 3a. Thereby, adhesiveness is expressed in the first region 310a of the bonding film 3a. On the other hand, this adhesiveness is hardly expressed in regions other than the first region 310a of the bonding film 3a.
According to such a method, the area | region of a junction part can be easily controlled only by selecting the area | region which provides energy.

Here, the energy applied to the bonding film 3a may be applied by any method, for example, by the method described in the first embodiment.
In the present embodiment, it is particularly preferable to use a method of irradiating the bonding film 3a with energy rays as a method for applying energy to the bonding film 3a. This method is suitable as an energy application method because energy can be applied to the bonding film 3a easily and efficiently.

  Moreover, in this embodiment, it is preferable to use an energy beam with high directivity like a laser beam and an electron beam especially as an energy beam. With such an energy beam, the first region 310a can be selectively and easily irradiated with an energy beam by irradiating it in a target direction.

Further, even if the energy beam has a low directivity, it can be irradiated so as to cover (hide) a region other than the first region 310a to be irradiated with the energy beam in the surface 31a of the bonding film 3a. The first region 310a can be selectively irradiated with energy rays.
Specifically, as shown in FIG. 10C, a mask having a window portion 61a having a shape corresponding to the shape of the first region 310a to be irradiated with energy rays above the surface 31a of the bonding film 3a. 6a may be provided, and energy rays may be irradiated through the mask 6a. In this way, it is easy to selectively irradiate the first region 310a with energy rays. Similarly, a mask 6b having a window portion 61b having a shape corresponding to the shape of the second region 310b to be irradiated with energy rays is provided above the surface 31b of the bonding film 3b. It is only necessary to irradiate the energy beam through. In this way, it is easy to selectively irradiate the second region 310b with energy rays.

[3] Next, as shown in FIG. 11D, the two adherends 41 and 42 are bonded together so that the bonding film 3a and the bonding film 3b are in close contact with each other. Thereby, in the part which the 1st area | region 310a and the 2nd area | region 310b overlapped, ie, in the 1st area | region 310a, the 1st to-be-adhered body 41 and the 2nd to-be-adhered body 42 are partially. Be joined. Thereby, the joined body 1 shown in FIG.
In the bonded body 1, a slight gap is generated in a region other than the bonded first region 310 a in the gap between the first adherend 41 and the second adherend 42 ( Remains). Therefore, by appropriately adjusting the shape of the first region 310a, a closed space, a flow path, and the like can be easily formed between the first adherend 41 and the second adherend 42. it can.

Moreover, after obtaining the joined body 1, at least one of the steps [5A], [5B] and [5C] of the first embodiment is performed on the joined body 1 as necessary. It may be.
For example, as shown in FIG. 11 (f), 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, the dehydration condensation of the hydroxyl group at the interface between the bonding film 3a and the bonding film 3b is promoted. And the further improvement of the joint strength of the joined body 1 can be aimed at easily.

At this time, as described above, in the interface between the bonding film 3a and the bonding film 3b, in the region (non-bonding region) other than the first region 310a, a slight gap is generated (remains). Therefore, when heating the bonded body 1 while applying pressure, it is preferable to perform the heating under the condition that the bonding film 3a and the bonding film 3b are not bonded in a region other than the first region 310a.
In consideration of the above, when performing at least one of the steps [5A], [5B] and [5C] of the first embodiment, these steps are performed on the first region 310a. It is preferable to perform it selectively. Thereby, it is possible to prevent the bonding film 3a and the bonding film 3b from being bonded in a region other than the first region 310a.

FIG. 12 shows another configuration example of the joined body according to the present embodiment.
In this example, as shown to Fig.12 (a), the 1st to-be-adhered body 41 was provided in the upper surface of the 1st base material 21 and the 1st base material 21 (it formed into a film). And a bonding film 3a. The second adherend 42 includes a second base material 22 and a bonding film 3 b provided (formed) on the entire lower surface of the second base material 22.

Then, a part of the surface 31a of the bonding film 3a is irradiated with ultraviolet rays to the first region 310a set in a stripe shape. Similarly, a part of the surface 31b of the bonding film 3b is irradiated with ultraviolet rays to the second region 310b set in a stripe shape orthogonal to the first region 310a. Thereby, adhesiveness is expressed in the first region 310a of the bonding film 3a and the second region 310b of the bonding film 3b.
When the first adherend 41 and the second adherend 42 are bonded so that the bonding film 3a and the bonding film 3b are in close contact with each other, the first region 310a and the second region 310b The first adherend 41 and the second adherend 42 are partially joined at the portion where the two overlap. Thereby, the joined body 1 as shown in FIG.12 (b) is obtained.

According to the method as described above, it is possible to efficiently form a plurality of island-shaped complex joints as shown in FIG. 12B only by using a mask having striped windows. it can.
Moreover, according to the above method, it is easy to control the position and shape of each joint part with high precision compared with the case where island-like joint parts are individually formed.
In such a bonded body 1, by appropriately controlling the area and shape of the bonded portion, for example, it is easy to adjust the bonding strength of the bonded body 1 or to relax the local concentration of stress generated in the bonded portion. Can be realized.

<< Fourth Embodiment >>
Next, a fourth embodiment of the joining method of the present invention will be described.
13 and 14 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. 13 and 14 is referred to as “upper” and the lower side is referred to as “lower”.

Hereinafter, the bonding method according to the fourth embodiment will be described, but the description will focus on differences from the first embodiment to the third embodiment, and description of similar matters will be omitted.
The joining method according to the present embodiment is the same as that of the first embodiment except that the configuration of the first embodiment and the configuration of the third embodiment are combined.

  That is, in the bonding method according to the present embodiment, the bonding film 3a is formed in the first region 310a set in a part of the bonding surface 23 of the first base material 21, and the first adherend 41 is manufactured. At the same time, a bonding film 3b is formed on the entire bonding surface 24 of the second base material 22 to produce the second adherend 42, the entire bonding film 3a, and a part of the bonding film 3b. The step of applying energy to the second region 310b set in a different pattern from the first region 310a and the bonding film 3a and the second region 310b of the bonding film 3b are in close contact with each other. And bonding the first adherend 41 and the second adherend 42 to obtain the joined body 1.

Hereinafter, each process of the joining method concerning this embodiment is demonstrated one by one.
[1] First, in the same manner as in the first embodiment, as shown in FIGS. 13A to 13B, the first region 310a set in a part on the first base member 21 is joined. A film 3a is formed. Thereby, the 1st to-be-adhered body 41 is obtained. Similarly to the third embodiment, as shown in FIGS. 13A to 13B, the bonding film 3b is formed on the entire bonding surface 24 of the second base member 22. Thereby, the second adherend 42 is obtained.

  [2] Next, as shown in FIG. 13C, energy is applied to the entire surface of the bonding film 3 a of the first adherend 41. On the other hand, a part of the bonding film 3b of the second adherend 42 is selectively given energy to the second region 310b set in a pattern different from that of the first region 310a. As a result, adhesiveness develops on the entire surface of the bonding film 3a and the second region 310b of the bonding film 3b.

  [3] Next, as shown in FIG. 14 (d), the first adherend 41 and the second adherend are adhered so that the bonding film 3a and the second region 310b of the bonding film 3b are in close contact with each other. The body 42 is bonded together. Thereby, in the part which the 1st area | region 310a and the 2nd area | region 310b overlapped, ie, in the 1st area | region 310a, the 1st to-be-adhered body 41 and the 2nd to-be-adhered body 42 are partially. Be joined. Thereby, the joined body 1 shown in FIG.

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. , Photoelectric conversion elements such as solar cells, semiconductor substrates and semiconductor elements mounted thereon, insulating substrates and wiring or electrodes, inkjet recording heads, microreactors, microelectromechanical system (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.

  Moreover, the joined body obtained by the joining method according to each of the above embodiments can impart conductivity to the joining film by selecting a constituent material. As a result, the bonding film in the bonded body is used as a “functional partial bonding film” having various functions of wiring and comb-like electrodes (antenna, filter, etc.) in addition to the function of partially bonding members together. Can do. As a result, for example, various functions as described above can be efficiently integrated in a bonded body such as a laminated substrate, so that it is possible to further increase the functionality and thickness of electronic components.

<Droplet ejection head>
Here, an embodiment in which the joined body of the present invention is applied to an ink jet recording head will be described.
FIG. 15 is an exploded perspective view showing an ink jet recording head (droplet discharge head) obtained by applying the joined body of the present invention, and FIG. 16 shows the configuration of the main part of the ink jet recording head shown in FIG. FIG. 17 is a schematic view showing an embodiment of an ink jet printer including the ink jet recording head shown in FIG. In addition, FIG. 15 is shown upside down from the state normally used.
The ink jet recording head 10 shown in FIG. 15 is mounted on an ink jet printer 9 as shown in FIG.

The ink jet printer 9 shown in FIG. 17 includes an apparatus main body 92, a tray 921 in which the recording paper P is installed at the upper rear, a paper discharge port 922 for discharging the recording paper P in the lower front, and an operation panel on the upper surface. 97.
The operation panel 97 includes, for example, a liquid crystal display, an organic EL display, an LED lamp, and the like, and a display unit (not shown) for displaying an error message and the like, and an operation unit (not shown) configured with various switches and the like. And.
Further, inside the apparatus main body 92, mainly a printing apparatus (printing means) 94 provided with a reciprocating head unit 93 and a paper feeding apparatus (paper feeding means) for feeding recording paper P to the printing apparatus 94 one by one. 95 and a control unit (control means) 96 for controlling the printing device 94 and the paper feeding device 95.

  Under the control of the control unit 96, the paper feeding device 95 intermittently feeds the recording paper P one by one. The recording paper P passes near the lower part of the head unit 93. At this time, the head unit 93 reciprocates in a direction substantially orthogonal to the feeding direction of the recording paper P, and printing on the recording paper P is performed. That is, the reciprocating motion of the head unit 93 and the intermittent feeding of the recording paper P are the main scanning and sub-scanning in printing, and ink jet printing is performed.

The printing apparatus 94 includes a head unit 93, a carriage motor 941 that is a drive source of the head unit 93, and a reciprocating mechanism 942 that reciprocates the head unit 93 in response to the rotation of the carriage motor 941.
The head unit 93 includes an ink jet recording head 10 (hereinafter simply referred to as “head 10”) having a large number of nozzle holes 111 at a lower portion thereof, an ink cartridge 931 that supplies ink to the head 10, the head 10 and And a carriage 932 on which the ink cartridge 931 is mounted.
Ink cartridge 931 is filled with four color inks of yellow, cyan, magenta, and black (black), thereby enabling full color printing.

The reciprocating mechanism 942 includes a carriage guide shaft 943 whose both ends are supported by a frame (not shown), and a timing belt 944 extending in parallel with the carriage guide shaft 943.
The carriage 932 is supported by the carriage guide shaft 943 so as to be able to reciprocate and is fixed to a part of the timing belt 944.
When the timing belt 944 travels forward and backward via a pulley by the operation of the carriage motor 941, the head unit 93 reciprocates as guided by the carriage guide shaft 943. During this reciprocation, ink is appropriately discharged from the head 10 and printing on the recording paper P is performed.

The sheet feeding device 95 includes a sheet feeding motor 951 serving as a driving source thereof, and a sheet feeding roller 952 that is rotated by the operation of the sheet feeding motor 951.
The paper feed roller 952 includes a driven roller 952a and a drive roller 952b that are vertically opposed to each other with a recording paper P feeding path (recording paper P) interposed therebetween. The drive roller 952b is connected to the paper feed motor 951. As a result, the paper feed roller 952 can feed a large number of recording sheets P set on the tray 921 one by one toward the printing apparatus 94. Instead of the tray 921, a configuration in which a paper feed cassette that stores the recording paper P can be detachably mounted may be employed.

The control unit 96 performs printing by controlling the printing device 94, the paper feeding device 95, and the like based on print data input from a host computer such as a personal computer or a digital camera.
Although not shown, the control unit 96 mainly includes a memory that stores a control program for controlling each unit, a piezoelectric element driving circuit that drives the piezoelectric element (vibration source) 14 to control the ink ejection timing, A driving circuit for driving the printing device 94 (carriage motor 941), a driving circuit for driving the paper feeding device 95 (paper feeding motor 951), a communication circuit for obtaining print data from the host computer, and these electrically And a CPU that is connected and performs various controls in each unit.
Further, for example, various sensors that can detect the remaining ink amount of the ink cartridge 931, the position of the head unit 93, and the like are electrically connected to the CPU.

  The control unit 96 obtains print data via the communication circuit and stores it in the memory. The CPU processes the print data and outputs a drive signal to each drive circuit based on the process data and input data from various sensors. The piezoelectric element 14, the printing device 94, and the paper feeding device 95 are each activated by this drive signal. As a result, printing is performed on the recording paper P.

Hereinafter, the head 10 will be described in detail with reference to FIGS. 15 and 16.
The head 10 includes a head main body 17 including a nozzle plate 11, an ink chamber substrate 12, a vibration plate 13, and a piezoelectric element (vibration source) 14 bonded to the vibration plate 13, and a base body that houses the head main body 17. 16. The head 10 constitutes an on-demand piezo jet head.

The nozzle plate 11 is made of, for example, a silicon-based material such as SiO ₂ , SiN, or quartz glass, a metal-based material such as Al, Fe, Ni, Cu, or an alloy containing these, or an oxide-based material such as alumina or iron oxide. The material is composed of carbon-based materials such as carbon black and graphite.
A number of nozzle holes 111 for discharging ink droplets are formed in the nozzle plate 11. The pitch between these nozzle holes 111 is appropriately set according to the printing accuracy.

An ink chamber substrate 12 is fixed (fixed) to the nozzle plate 11.
The ink chamber substrate 12 includes a plurality of ink chambers (cavities, pressure chambers) 121 and a reservoir chamber that stores ink supplied from the ink cartridge 931 by the nozzle plate 11, side walls (partition walls) 122, and a vibration plate 13 described later. 123 and a supply port 124 for supplying ink from the reservoir chamber 123 to each ink chamber 121 are partitioned.

Each ink chamber 121 is formed in a strip shape (cuboid shape), and is disposed corresponding to each nozzle hole 111. Each ink chamber 121 has a variable volume due to vibration of a diaphragm 13 described later, and is configured to eject ink by this volume change.
As a base material for obtaining the ink chamber substrate 12, for example, a silicon single crystal substrate, various glass substrates, various resin substrates and the like can be used. Since these substrates are general-purpose substrates, the manufacturing cost of the head 10 can be reduced by using these substrates.

On the other hand, a vibration plate 13 is bonded to the ink chamber substrate 12 on the side opposite to the nozzle plate 11, and a plurality of piezoelectric elements 14 are provided on the vibration plate 13 on the side opposite to the ink chamber substrate 12.
A communication hole 131 is formed at a predetermined position of the diaphragm 13 so as to penetrate in the thickness direction of the diaphragm 13. Ink can be supplied from the ink cartridge 931 to the reservoir chamber 123 through the communication hole 131.

Each piezoelectric element 14 has a piezoelectric layer 143 interposed between the lower electrode 142 and the upper electrode 141, and is disposed corresponding to the substantially central portion of each ink chamber 121. Each piezoelectric element 14 is electrically connected to a piezoelectric element drive circuit and is configured to operate (vibrate, deform) based on a signal from the piezoelectric element drive circuit.
Each piezoelectric element 14 functions as a vibration source, and the diaphragm 13 vibrates due to vibration of the piezoelectric element 14 and functions to instantaneously increase the internal pressure of the ink chamber 121.
The base body 16 is made of, for example, various resin materials, various metal materials, and the like, and the nozzle plate 11 is fixed and supported on the base body 16. That is, the edge of the nozzle plate 11 is supported by the step 162 formed on the outer periphery of the recess 161 in a state where the head body 17 is housed in the recess 161 provided in the base body 16.

When the nozzle plate 11 and the ink chamber substrate 12 are bonded as described above, the ink chamber substrate 12 and the vibration plate 13 are bonded, and the nozzle plate 11 and the substrate 16 are bonded, at least one place of the present invention is used. A joining method is applied.
In other words, the present invention is provided in at least one place among the joined body of the nozzle plate 11 and the ink chamber substrate 12, the joined body of the ink chamber substrate 12 and the vibration plate 13, and the joined body of the nozzle plate 11 and the substrate 16. The joined body is applied.

Such a head 10 has high bonding strength and chemical resistance at the bonding interface of the bonding portion, and thereby has high durability and liquid tightness with respect to the ink stored in each ink chamber 121. As a result, the head 10 becomes highly reliable.
In addition, since highly reliable bonding can be performed at a very low temperature, it is advantageous in that a large-area head can be formed even with materials having different linear expansion coefficients.

  Such a head 10 is in a state where a predetermined ejection signal is not input via the piezoelectric element driving circuit, that is, in a state where no voltage is applied between the lower electrode 142 and the upper electrode 141 of the piezoelectric element 14. The piezoelectric layer 143 is not deformed. For this reason, the vibration plate 13 is not deformed, and the volume of the ink chamber 121 is not changed. Therefore, no ink droplet is ejected from the nozzle hole 111.

  On the other hand, in a state where a predetermined ejection signal is input via the piezoelectric element driving circuit, that is, in a state where a constant voltage is applied between the lower electrode 142 and the upper electrode 141 of the piezoelectric element 14, the piezoelectric layer 143 is applied. Deformation occurs. As a result, the diaphragm 13 is greatly deflected, and the volume of the ink chamber 121 is changed. At this time, the pressure in the ink chamber 121 increases instantaneously, and ink droplets are ejected from the nozzle holes 111.

  When the ejection of one ink is completed, the piezoelectric element driving circuit stops applying the voltage between the lower electrode 142 and the upper electrode 141. As a result, the piezoelectric element 14 returns almost to its original shape, and the volume of the ink chamber 121 increases. At this time, a pressure (pressure in the positive direction) from the ink cartridge 931 toward the nozzle hole 111 acts on the ink. Therefore, air is prevented from entering the ink chamber 121 from the nozzle hole 111, and an amount of ink corresponding to the amount of ink discharged is supplied from the ink cartridge 931 (reservoir chamber 123) to the ink chamber 121.

In this manner, in the head 10, arbitrary (desired) characters and figures can be printed by sequentially inputting ejection signals to the piezoelectric elements 14 at the positions to be printed via the piezoelectric element driving circuit. it can.
The head 10 may have an electrothermal conversion element instead of the piezoelectric element 14. That is, the head 10 may have a configuration (so-called “bubble jet method” (“bubble jet” is a registered trademark)) that ejects ink using thermal expansion of a material by an electrothermal transducer.

  In the head 10 having such a configuration, the nozzle plate 11 is provided with a coating 114 formed for the purpose of imparting liquid repellency. Thus, when ink droplets are ejected from the nozzle holes 111, it is possible to reliably prevent ink droplets from remaining around the nozzle holes 111. As a result, the ink droplets ejected from the nozzle hole 111 can be reliably landed on the target area.

<Wiring board>
Furthermore, an embodiment when the joined body of the present invention is applied to a wiring board will be described.
FIG. 18 is a perspective view showing a wiring board obtained by applying the joined body of the present invention.
18 includes an insulating substrate 513, an electrode 512 provided on the insulating substrate 513, a lead 514, and an electrode 515 provided at one end of the lead 514 so as to face the electrode 512. Have

  A bonding film (not shown) similar to the bonding film 3b described above is formed on a part of the upper surface of the electrode 512, while the bonding film 3a described above is also formed on a part of the lower surface of the electrode 515. A similar bonding film (not shown) is formed. That is, the electrode 512 and the electrode 515 are bonded together by bonding by the above-described bonding method of the present invention. As a result, the electrodes 512 and 515 are firmly bonded by the bonding film. As a result, delamination between the electrodes 512 and 515 and the like can be reliably prevented, and a highly reliable wiring board 510 can be obtained.

The bonding film also has a function of conducting between the electrodes 512 and 515 by selecting a conductive metal oxide contained in the bonding film. Even if the bonding film is very thin, it exhibits a sufficient bonding force. For this reason, the separation distance between the electrodes 512 and 515 can be further reduced, and the electrical resistance component (contact resistance) between the electrodes 512 and 515 can be reduced. As a result, the conductivity between the electrodes 512 and 515 can be further increased.
Further, as described above, the thickness of the bonding film can be easily controlled with high accuracy. As a result, the wiring board 510 has higher dimensional accuracy, and the conductivity between the electrodes 512 and 515 can be easily controlled.

As mentioned above, although the joining method and joined body of this invention were demonstrated based on embodiment of illustration, this invention is not limited to these.
For example, the joining method of the present invention may be any one or a combination of two or more of the above embodiments.
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 substrates, the first substrate and the second substrate, has been described. However, when three or more substrates are joined, the present invention is described. The joining method may be used.

Next, specific examples of the present invention will be described.
1. Manufacture of 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.

Next, the single crystal silicon substrate and the glass substrate were accommodated in the chamber 211 of the film formation apparatus 200 illustrated in FIG. 5 and subjected to surface treatment with oxygen plasma.
Next, a bonding film (average thickness: 100 nm) in which hydrogen atoms were introduced into ITO was formed on the entire surface of each substrate subjected to surface treatment by ion beam sputtering. The film forming conditions are as shown below.

<Ion beam sputtering deposition conditions>
・ Target: ITO
・ Vacuum ultimate vacuum: 2 × 10 ⁻⁶ Torr
-Pressure in the chamber during film formation: 1 × 10 ⁻³ Torr
・ Hydrogen gas flow rate: 60 sccm
・ Temperature in chamber: 20 ℃
・ Ion beam acceleration voltage: 600V
Voltage applied to the grid on the ion generation chamber side: + 400V
Applied voltage to grid on chamber side: -200V
・ Ion beam current: 200 mA
-Gas species supplied to the ion generation chamber: Kr gas-Processing time: 20 minutes The bonding film formed in this manner is composed of ITO with hydrogen atoms introduced, and metal atoms (indium and Tin), an oxygen atom bonded to the metal atom, and a leaving group (hydrogen atom) bonded to at least one of the metal atom and the oxygen atom.

Next, the obtained bonding film was irradiated with ultraviolet rays under the following conditions. In addition, ultraviolet rays are a frame-shaped area | region with a width of 3 mm in a peripheral part among ITO films (bonding film) formed on a single crystal silicon substrate, and a width of 5 mm at a peripheral part among ITO films formed on a glass substrate. The frame-shaped region was irradiated.
<Ultraviolet irradiation conditions>
・ Atmosphere gas composition: Nitrogen gas ・ Atmosphere gas temperature: 20 ° C.
・ Atmospheric gas pressure: Atmospheric pressure (100 kPa)
UV wavelength: 172 nm
-Irradiation time of ultraviolet rays: 5 minutes Next, a single crystal silicon substrate and a glass substrate were overlapped so that the bonding films were in contact with each other one minute after the irradiation with ultraviolet rays. Thereby, the joined body was obtained.
Next, the resulting joined body was heated at 80 ° C. while being pressurized at 3 MPa, and maintained for 15 minutes. Thereby, the joint strength of the joined body was improved.

(Example 2)
A joined body was obtained in the same manner as in Example 1 except that the heating temperature for heating the joined body was changed from 80 ° C to 25 ° C.
(Examples 3 to 13)
A joined body 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.

(Example 14)
When the ITO film (bonding film) was formed on the single crystal silicon substrate, the film was formed only on the frame-like region having a width of 3 mm at the periphery of the silicon substrate. In addition, when the ITO film (bonding film) is formed on the glass substrate, the film is formed only in the frame-like region having a width of 5 mm at the peripheral portion of the glass substrate, and the same as in the first embodiment. To obtain a joined body. The ultraviolet rays were irradiated to the entire ITO film.

(Example 15)
First, in the same manner as in Example 14, an ITO film (bonding film) was formed on a frame-like region having a width of 3 mm at the peripheral edge of the single crystal silicon substrate. On the other hand, in the same manner as in Example 14, an ITO film (bonding film) was formed in a frame-like region having a width of 5 mm at the peripheral edge of the glass substrate.
Next, the single crystal silicon substrate and the glass substrate were overlapped so that the bonding films were in contact with each other. Thereby, a temporary joined body was obtained.
And the ultraviolet-ray was irradiated with respect to the temporary joining body on the conditions shown below.

<Ultraviolet irradiation conditions>
・ Atmosphere gas composition: Nitrogen gas ・ Atmosphere gas temperature: 20 ° C.
・ Atmospheric gas pressure: Atmospheric pressure (100 kPa)
UV wavelength: 172 nm
-UV irradiation time: 5 minutes Thereby, each board | substrate was joined and the joined body was obtained.
Subsequently, the obtained bonded body was heated at 80 ° C. while being pressurized at 3 MPa, and maintained for 15 minutes. Thereby, the joint strength of the joined body was improved.

(Example 16)
Next, in the same manner as in Example 1 except that ATO was used instead of ITO as a target, a bonding film in which hydrogen atoms were introduced into ATO was applied to the surface of the silicon substrate and the glass substrate that were subjected to surface treatment. Each was formed into a film. This will be described in detail below.
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.

Next, both of these base materials were accommodated in the chamber 211 of the film forming apparatus 200 shown in FIG. 5 and subjected to surface treatment with oxygen plasma.
Next, a bonding film (average thickness: 100 nm) in which hydrogen atoms were introduced into ATO was formed on each surface of each substrate subjected to surface treatment using an ion beam sputtering method. The film forming conditions are as shown below.

<Ion beam sputtering deposition conditions>
・ Target: ATO
・ Vacuum ultimate vacuum: 2 × 10 ⁻⁶ Torr
-Pressure in the chamber during film formation: 1 × 10 ⁻³ Torr
・ Hydrogen gas flow rate: 60 sccm
・ Temperature in chamber: 20 ℃
・ Ion beam acceleration voltage: 600V
Voltage applied to the grid on the ion generation chamber side: + 400V
Applied voltage to grid on chamber side: -200V
・ Ion beam current: 200 mA
-Gas type supplied to ion generation chamber: Kr gas-Processing time: 20 minutes Next, the obtained bonding film was irradiated with ultraviolet rays under the following conditions. In addition, ultraviolet rays have a frame-shaped region having a width of 3 mm in the peripheral portion of the ATO film (bonding film) formed on the single crystal silicon substrate and a width of 5 mm in the peripheral portion of the ATO film formed on the glass substrate. The frame-shaped region was irradiated.

<Ultraviolet irradiation conditions>
・ Atmosphere gas composition: Nitrogen gas ・ Atmosphere gas temperature: 20 ° C.
・ Atmospheric gas pressure: Atmospheric pressure (100 kPa)
UV wavelength: 172 nm
-Irradiation time of ultraviolet rays: 5 minutes Subsequently, each substrate was superposed so that the bonding films were in contact with each other one minute after the ultraviolet rays were irradiated. Thereby, the joined body was obtained.
Next, the resulting joined body was heated at 80 ° C. while being pressurized at 3 MPa, and maintained for 15 minutes. Thereby, the joint strength of the joined body was improved.

(Example 17)
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.
Next, the single crystal silicon substrate and the glass substrate were accommodated in the chamber 211 of the film formation apparatus 200 illustrated in FIG. 5 and subjected to surface treatment with oxygen plasma.

Next, an ITO film having an average thickness of 100 nm was formed as a metal oxide film on the surface of each substrate that was subjected to surface treatment, using an ion beam sputtering method. The film forming conditions are as shown below.
<Ion beam sputtering deposition conditions>
・ Target: ITO
・ Vacuum ultimate vacuum: 2 × 10 ⁻⁶ Torr
-Pressure in the chamber during film formation: 1 × 10 ⁻³ Torr
・ Temperature in chamber: 20 ℃
・ Ion beam acceleration voltage: 600V
Voltage applied to the grid on the ion generation chamber side: + 400V
Applied voltage to grid on chamber side: -200V
・ Ion beam current: 200 mA
・ Gas type supplied to the ion generation chamber: Kr gas ・ Processing time: 20 minutes

Next, the obtained metal oxide film was subjected to heat treatment under the following conditions, and hydrogen atoms were introduced near the surface of the metal oxide film (ITO film) to form a bonding film. The conditions for the heat treatment are as shown below.
<Conditions for heat treatment>
-Pressure in chamber during heat treatment: 1 × 10 ⁻³ Torr
・ Hydrogen gas flow rate: 60 sccm
-Temperature in the chamber: 150 ° C
Processing time: 60 minutes The bonding film formed as described above is composed of hydrogen atoms introduced near the surface of the ITO film, and metal atoms (indium and tin) and the metal atoms And an oxygen atom bonded to at least one of the metal atom and the oxygen atom (hydrogen atom).

Next, the obtained bonding film was irradiated with ultraviolet rays under the following conditions. In addition, ultraviolet rays are a frame-shaped area | region with a width of 3 mm in a peripheral part among ITO films (bonding film) formed on a single crystal silicon substrate, and a width of 5 mm at a peripheral part among ITO films formed on a glass substrate. The frame-shaped region was irradiated.
<Ultraviolet irradiation conditions>
・ Atmosphere gas composition: Nitrogen gas ・ Atmosphere gas temperature: 20 ° C.
・ Atmospheric gas pressure: Atmospheric pressure (100 kPa)
UV wavelength: 172 nm
-Irradiation time of ultraviolet rays: 5 minutes Next, a single crystal silicon substrate and a glass substrate were overlapped so that the bonding films were in contact with each other one minute after the irradiation with ultraviolet rays. Thereby, the joined body was obtained.
Next, the resulting joined body was heated at 80 ° C. while being pressurized at 3 MPa, and maintained for 15 minutes. Thereby, the joint strength of the joined body was improved.

(Example 18)
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.
Next, the single crystal silicon substrate and the glass substrate were housed in a chamber 411 of the film formation apparatus 400 illustrated in FIG. 7, and surface treatment with oxygen plasma was performed.

Next, a bonding film having an average thickness of 100 nm was formed on the surface of each substrate subjected to the surface treatment using a raw material of 2,4-pentadionate-copper (II) and MOCVD. The film forming conditions are as shown below.
<Film formation conditions>
・ Atmosphere in the chamber: Nitrogen gas + Hydrogen gas ・ Organic metal material (raw material): 2,4-pentadionate-copper (II)
・ Flow rate of organometallic material: 1 sccm
・ Carrier gas: Nitrogen gas ・ Hydrogen gas flow rate: 0.2 sccm
・ Vacuum ultimate vacuum: 2 × 10 ⁻⁶ Torr
-Pressure in the chamber during film formation: 1 × 10 ⁻³ Torr
-Temperature of substrate holder: 275 ° C
・ Processing time: 10 minutes

The bonding film formed as described above contains a copper atom as a metal atom, and a part of an organic substance (alkyl group) contained in 2,4-pentadionate-copper (II) as a leaving group. It is what remains.
Next, the obtained bonding film was irradiated with ultraviolet rays under the following conditions. Note that the ultraviolet ray has a frame-shaped region with a width of 3 mm in the peripheral portion of the bonding film formed on the single crystal silicon substrate and a frame-shaped region with a width of 5 mm in the peripheral portion of the bonding film formed on the glass substrate. Irradiated to the area.

<Ultraviolet irradiation conditions>
・ Atmosphere gas composition: Nitrogen gas ・ Atmosphere gas temperature: 20 ° C.
・ Atmospheric gas pressure: Atmospheric pressure (100 kPa)
UV wavelength: 172 nm
-Irradiation time of ultraviolet rays: 5 minutes Next, a single crystal silicon substrate and a glass substrate were overlapped so that the bonding films were in contact with each other one minute after the irradiation with ultraviolet rays. Thereby, the joined body was obtained.
Next, the resulting joined body was heated at 120 ° C. while being pressurized at 10 MPa, and maintained for 15 minutes. Thereby, the joint strength of the joined body was improved.

(Comparative Examples 1-3)
The constituent material of the first base material and the constituent material of the second base material are the materials shown in Table 1, respectively, and a frame-like region having a width of 3 mm between the base materials is bonded with an epoxy adhesive. Except for the above, a joined body was obtained in the same manner as in Example 1.

(Comparative Examples 4-6)
The constituent material of the first base material and the constituent material of the second base material are the materials shown in Table 1, respectively, except that a frame-like region having a width of 3 mm between the base materials is bonded with Ag paste. In the same manner as in Example 1, a joined body was obtained.
(Reference Examples 1-3)
The constituent material of the first base material and the constituent material of the second base material are the materials shown in Table 1, respectively, and when each bonding film is irradiated with ultraviolet rays, the entire surface of each bonding film is irradiated. Except for the above, a joined body was obtained in the same manner as in Example 1. The joined body thus obtained is obtained by joining the first base material and the second base material over the entire surface.

2. 2. Evaluation of Bonded Body 2.1 Evaluation of Bonding Strength (Split Strength) The bonding strength was measured for each of the bonded bodies obtained in each Example, each Comparative Example, and each Reference Example.
The measurement of the bonding strength was performed by measuring the strength (load) immediately before peeling off each substrate. Then, the bonding strength was evaluated according to the following criteria.

As a result, the joint strength of the joined body obtained in each example was lower than the joint strength of the joined body obtained in each reference example. From this, it is possible to adjust the bonding strength (the magnitude of the load) by selecting whether the bonding area is part or all of the bonding surface, that is, by changing the area of the bonding part. It became clear that.
Moreover, the joint strength of the joined body obtained in each Example was larger than the joint strength of the joined body obtained in each Comparative Example.

2.2 Evaluation of dimensional accuracy The dimensional accuracy in the thickness direction was measured for each of the joined bodies obtained in each Example, each Comparative Example, and each Reference Example.
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 chemical resistance The joined bodies obtained in each Example, each Comparative Example and each Reference Example were applied to an ink for an ink jet printer (“HQ4” manufactured by Epson Corporation) maintained at 80 ° C. under the following conditions. Soaked for 3 weeks. Thereafter, each base material was peeled off, and it was confirmed whether or not ink entered the bonding interface. The results were evaluated according to the following criteria.

<Evaluation criteria for chemical resistance>
◎: Not penetrated at all ○: Slightly penetrated into the corner △: Infiltrated along the edge ×: Intruded inside

2.4 Evaluation of Resistivity For each of the bonded bodies obtained in Examples 12 and 13 and Comparative Example 6, the resistivity of each bonded portion was measured. The measured resistivity was evaluated according to the following criteria.
<Evaluation criteria for resistivity>
○: Less than 1 × 10 ⁻³ Ω · cm ×: 1 × 10 ⁻³ Ω · cm or more

2.5 Evaluation of Shape Change About the joined body obtained in each Example, each comparative example, and each reference example, the shape change before and after joining of each joined body was measured.
Specifically, the warpage amount of the joined body was measured before and after joining and evaluated according to the following criteria.

<Evaluation criteria for warpage>
◎: The amount of warpage hardly changed before and after joining. ○: The amount of warpage slightly changed before and after joining. △: The amount of warpage slightly changed before and after joining. Table 1 shows the evaluation results of 2.2 to 2.5.

As is clear from Table 1, the joined bodies obtained in each Example exhibited excellent characteristics in all items of dimensional accuracy, chemical resistance, change in warpage, and resistivity.
Moreover, the joined body obtained in each example had a smaller change in warpage than the joined body obtained in each reference example.
On the other hand, the joined body obtained in each comparative example was not sufficient in chemical resistance. Also, it was recognized that the dimensional accuracy was particularly low. Furthermore, the result that the resistivity of the bonding film was high was obtained.

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. In the joining method of this invention, it is the elements on larger scale which show the state of the joining film | membrane before energy provision. In the joining method of this invention, it is the elements on larger scale which show the state of the joining film | membrane after energy provision. It is a longitudinal cross-sectional view which shows typically the film-forming apparatus used for the joining method of this invention. It is a schematic diagram which shows the structure of the ion source with which the film-forming apparatus shown in FIG. 5 is provided. It is a longitudinal cross-sectional view which shows typically the film-forming apparatus used for 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 (perspective view) which shows the other structural example of the conjugate | zygote concerning 3rd Embodiment. 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 disassembled perspective view which shows the inkjet recording head (droplet discharge head) obtained by applying the conjugate | zygote of this invention. FIG. 16 is a cross-sectional view illustrating a configuration of a main part of the ink jet recording head illustrated in FIG. 15. It is the schematic which shows embodiment of an inkjet printer provided with the inkjet recording head shown in FIG. 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 ... Bonded body 21 ... 1st base material 22 ... 2nd base material 23, 24 ... Bonding surface 3a, 3b ... Bonding film 303 ... Leaving group 304 ... Active hand 3c ... Space 31a, 31b ... surface 310a ... first region 310b ... second region 41 ... first adherend 42 ... second adherend 5 ... temporary joined body 6a, 6b ... mask 61a, 61b ... Window 200 ... Deposition device 211 ... Chamber 212 ... Substrate holder 215 ... Ion source 216 ... Target 217 ... Target holder 219 ... Gas supply source 220 ... First shutter 221 ... Second shutter 230 ... Exhaust means 231 ... Exhaust line 232 ... Pump 233 ... Valve 250 ... Opening 253 ... Grid 254 ... Grid 255 ... Magnetic Stone 256 ... Ion generation chamber 257 ... Filament 260 ... Gas supply means 261 ... Gas supply line 262 ... Pump 263 ... Valve 264 ... Gas cylinder 400 ... Deposition device 411 ... Chamber 412 ... Substrate holder 421 …… Shutter 430 …… Exhaust means 431 …… Exhaust line 432 …… Pump 433 …… Valve 460 …… Organic metal material supply means 461 …… Gas supply line 462 …… Storage tank 463 …… Valve 464 …… Pump 465 Gas cylinder 470 Gas supply means 471 Gas supply line 473 Valve 474 Pump 475 Gas cylinder 10 Inkjet recording head 11 Nozzle plate 111 Nozzle hole 114 coating 12 ... Ink chamber substrate 121 ... ... Ink chamber 122 ... Side wall 123 ... Reservoir chamber 124 ... Supply port 13 ... Diaphragm 131 ... Communication hole 14 ... Piezoelectric element 141 ... Upper electrode 142 ... Lower electrode 143 ... Piezoelectric layer 16 ... ... Base 161 ... Concave 162 ... Step 17 ... Head body 9 ... Inkjet printer 92 ... Device body 921 ... Tray 922 ... Paper discharge port 93 ... Head unit 931 ... Ink cartridge 932 ... Carriage 94 …… Printer 941 …… Carriage motor 942 …… Reciprocating mechanism 943 …… Carriage guide shaft 944 …… Timing belt 95 …… Feeding device 951 …… Feeding motor 952 …… Feeding roller 952a …… Following roller 952b …… Drive roller 96 …… Control unit 97 …… Operation panel P …… Record Paper 510 ...... wiring board 512 ...... electrode 513 ...... insulating substrate 514 ...... lead 515 ...... electrode

Claims (43)

A first region set in a part on the substrate includes a metal atom, an oxygen atom bonded to the metal atom, and a leaving group bonded to at least one of the metal atom and the oxygen atom. 1st adherend provided with 1 bonding film, and the same function as the 1st bonding film in the 2nd field set up in a pattern different from the 1st field in a part on a substrate Preparing a second adherend comprising a second bonding film;
Energy is imparted to each of the first bonding film and the second bonding film, and the leaving group existing near the surface of each bonding film is desorbed from at least one of the metal atom and the oxygen atom. A step of expressing adhesiveness in each of the bonding films,
By bonding the first adherend and the second adherend so that the first bonding film and the second bonding film are in intimate contact with each other, these are the first region. And a step of obtaining a joined body partially joined at a portion where the second region overlaps with the second region. A first region set in a part on the substrate includes a metal atom, an oxygen atom bonded to the metal atom, and a leaving group bonded to at least one of the metal atom and the oxygen atom. 1st adherend provided with 1 bonding film, and the same function as the 1st bonding film in the 2nd field set up in a pattern different from the 1st field in a part on a substrate Preparing a second adherend comprising a second bonding film;
A step of superimposing the first adherend and the second adherend to obtain a temporary joined body so that the first bonding film and the second bonding film are in close contact with each other;
Energy is applied to the first bonding film and the second bonding film, and the leaving group existing in the vicinity of the surface of each bonding film is released from at least one of the metal atom and the oxygen atom. By causing the bonding film to exhibit adhesiveness, the first adherend and the second adherend are in a portion where the first region and the second region overlap each other. And a step of obtaining a partially joined joined body. A first deposition comprising a first bonding film comprising a metal atom, an oxygen atom bonded to the metal atom, and a leaving group bonded to at least one of the metal atom and the oxygen atom on a substrate. Preparing a body and a second adherend including a second bonding film having the same function as the first bonding film on the substrate;
The first region set in a part of the first bonding film and the second region set in a pattern different from the first region in a part of the second bonding film, respectively. And desorbing the leaving group present in the vicinity of the surface of each bonding film from at least one of the metal atom and the oxygen atom, thereby expressing adhesiveness in each bonding film;
By bonding the first adherend and the second adherend so that the first region and the second region overlap, these are attached to the first region and the second region. And a step of obtaining a joined body partially joined at a portion where the two regions overlap.   The bonding method according to claim 1, wherein the leaving group is unevenly distributed near the surface of the bonding film.   The bonding method according to claim 1, wherein the bonding film has translucency.   The bonding method according to claim 1, wherein the metal atom is an atom of a transition metal element.   The bonding method according to claim 1, wherein the metal atom is at least one of indium, tin, zinc, titanium, and antimony.   The said leaving group is a hydrogen atom, a carbon atom, a nitrogen atom, a phosphorus atom, a sulfur atom and a halogen atom, or at least one of atomic groups composed of these atoms. The joining method according to the above. The bonding film includes indium tin oxide (ITO), indium zinc oxide (IZO), antimony tin oxide (ATO), fluorine-containing indium tin oxide (FTO), zinc oxide (ZnO), or titanium dioxide (TiO _2). The bonding method according to claim 1, wherein a hydrogen atom is introduced as a leaving group.   The bonding method according to any one of claims 1 to 9, wherein an abundance ratio of metal atoms to oxygen atoms in the bonding film is 3: 7 to 7: 3. A first adherend including a first bonding film including a metal atom and a leaving group composed of an organic component in a first region set in a part of the substrate; A second adherend including a second bonding film having the same function as that of the first bonding film is prepared in a second region set in a pattern different from that of the first region. Process,
By applying energy to each of the first bonding film and the second bonding film and detaching the leaving group existing near the surface of each bonding film from each bonding film, each bonding A step of developing adhesiveness in the membrane;
By bonding the first adherend and the second adherend so that the first bonding film and the second bonding film are in intimate contact with each other, these are the first region. And a step of obtaining a joined body partially joined at a portion where the second region overlaps with the second region. A first adherend including a first bonding film including a metal atom and a leaving group composed of an organic component in a first region set in a part of the substrate; A second adherend including a second bonding film having the same function as that of the first bonding film is prepared in a second region set in a pattern different from that of the first region. Process,
A step of superimposing the first adherend and the second adherend to obtain a temporary joined body so that the first bonding film and the second bonding film are in close contact with each other;
By applying energy to the first bonding film and the second bonding film and detaching the leaving group existing near the surface of each bonding film from each bonding film, Bonding in which adhesiveness is expressed in a bonding film, and the first adherend and the second adherend are partially bonded at a portion where the first region and the second region overlap each other. And a step of obtaining a body. A first adherend including a first bonding film including a metal atom and a leaving group composed of an organic component on a base material, and the same function as the first bonding film on the base material Preparing a second adherend comprising a second bonding film having:
The first region set in a part of the first bonding film and the second region set in a pattern different from the first region in a part of the second bonding film, respectively. And desorbing the leaving group present in the vicinity of the surface of each bonding film from each bonding film, thereby expressing adhesiveness in each bonding film;
By bonding the first adherend and the second adherend so that the first region and the second region overlap, these are attached to the first region and the second region. And a step of obtaining a joined body partially joined at a portion where the two regions overlap.   The bonding method according to claim 11, wherein the bonding film is formed using an organic metal material as a raw material and using a metal organic chemical vapor deposition method.   The bonding method according to claim 14, wherein the bonding film is formed in a low reducing atmosphere.   The bonding method according to claim 14 or 15, wherein the leaving group is a residue of a part of an organic substance contained in the organometallic material.   The said leaving group is a carbon atom as an essential component, and is comprised by the atomic group containing at least 1 sort (s) of a hydrogen atom, a nitrogen atom, a phosphorus atom, a sulfur atom, and a halogen atom. The joining method described.   The bonding method according to claim 17, wherein the leaving group is an alkyl group.   The bonding method according to claim 14, wherein the organometallic material is a metal complex.   The bonding method according to claim 11, wherein the metal atom is an atom of a transition metal element.   The joining method according to claim 11, wherein the metal atom is at least one of copper, aluminum, zinc, and iron.   The bonding method according to any one of claims 11 to 21, wherein an abundance ratio of metal atoms to carbon atoms in the bonding film is 3: 7 to 7: 3.   The bonding method according to claim 1, wherein the bonding film has conductivity.   The bonding method according to claim 1, wherein an active hand is generated after the leaving group present at least near the surface of the bonding film is released from the bonding film.   The joining method according to claim 24, wherein the active hand is a dangling hand or a hydroxyl group.   The bonding method according to claim 1, wherein an average thickness of the bonding film is 0.2 to 1000 nm.   The joining method according to any one of claims 1 to 26, wherein the joining film is in a solid state having no fluidity.   The joining method according to claim 1, wherein the base material has a plate shape.   The joining method according to claim 28, wherein the plate-like base material has flexibility.   30. The joining method according to any one of claims 1 to 29, wherein at least a portion of the base material on which the joining film is formed is composed mainly of a silicon material, a metal material, or a glass material.   The bonding method according to any one of claims 1 to 30, wherein a surface of the base material provided with the bonding film is previously subjected to a surface treatment for improving adhesion with the bonding film.   32. The bonding method according to claim 31, wherein the surface treatment is a plasma treatment or an ultraviolet irradiation treatment.   The joining method according to any one of claims 1 to 32, wherein an intermediate layer is interposed between the base material and the joining film.   The joining method according to claim 33, wherein the intermediate layer is formed using an oxide-based material as a main material.   The energy is applied by at least one of a method of irradiating the bonding film with energy rays, a method of heating the bonding film, and a method of applying a compressive force to the bonding film. 34. The joining method according to any one of 34.   36. The bonding method according to claim 35, wherein the energy ray is ultraviolet light having a wavelength of 126 to 300 nm.   The joining method according to claim 35 or 36, wherein the heating temperature is 25 to 100 ° C.   The joining method according to any one of claims 35 to 37, wherein the compressive force is 0.2 to 10 MPa.   39. The joining method according to claim 35, wherein the application of energy is performed in an air atmosphere.   The joining method according to any one of claims 1 to 39, further comprising a step of performing a process of increasing the joining strength of the joined body.   The step of increasing the bonding strength is performed by at least one of a method of irradiating the bonded body with energy rays, a method of heating the bonded body, and a method of applying a compressive force to the bonded body. The bonding method according to claim 40.   42. A joined body comprising two substrates joined by the joining method according to claim 1.   43. The joined body according to claim 42, wherein the joining film has a function as a functional partial joining film.

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