JP2011129591A - Bonding method and method of manufacturing sealed type device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bonding method capable of achieving easy bonding while controlling a bonding region of a member to which a bonding film has been transferred, so that the bonding film in a desired shape can be easily transferred to a surface of the member; and to provide a method of manufacturing a sealed type device in which the sealed type device with high reliability can be efficiently manufactured. <P>SOLUTION: Two bonding film transfer sheets have a base material and a first bonding film 31 formed thereon, and a base material and a second bonding film 32 formed thereon, respectively. The former has a part of the first bonding film 31 transferred corresponding to an energy-imparted region of a case 2, and the latter has a part of the second bonding film 32 transferred corresponding to an energy-imparted region of a cover body 4. The bonding films 31 and 32 each includes an atomic structure including a siloxane bond, and a leaving group bonded to the siloxane bond, and the case 2 and cover body 4 are bonded together through the transferred parts to constitute a quartz oscillator 1. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a bonding method and a manufacturing method of a sealed device.

When joining (adhering) two members, conventionally, a method of using an adhesive such as an epoxy-based adhesive, a urethane-based adhesive, or a silicone-based adhesive is often used.
Thus, when bonding a member using an adhesive agent, a liquid or paste-like adhesive agent is apply | coated to an adhesive surface, and members are bonded together through the apply | coated adhesive agent. Thereafter, the bonding is completed by curing the adhesive by the action of heat or light.

However, when applying an adhesive to the bonding surface of the member, it is necessary to use a complicated method such as a printing method. For example, when an adhesive is selectively applied to a partial region of the adhesive surface, it is extremely difficult to strictly control the position accuracy and thickness of the application.
Also, since the curing time of the adhesive becomes very long, it takes a long time to bond, and the positions of the members are shifted during curing, or between members having a difference in thermal expansion coefficient due to heating during curing Thermal stress remains at the bonding interface, which may cause deformation and damage of the bonded body.

Further, depending on the constituent material of the member, it is necessary to use a primer in order to increase the bonding strength, and the cost and labor for that purpose complicate the bonding process.
As described above, an adhesive made of an organic material is generally used as described above. However, since such an adhesive itself has air permeability, a place where airtightness is required. Is difficult to bond.

On the other hand, solid bonding such as anodic bonding is known as a bonding method that does not use an adhesive. Anodic bonding is a method in which a glass member and a silicon member are overlapped and heated, and when a voltage is applied to both of them, a covalent bond is formed at the contact interface and the members are directly bonded.
Patent Document 1 discloses a crystal resonator (sealed device) that is hermetically sealed by housing a crystal resonator element inside and anodic bonding a base substrate and a lid. ing.

However, in anodic bonding, the materials that can be bonded are limited due to the bonding principle. Specifically, it is necessary to contain ions that move in a member such as alkali metal ions at the time of joining, and the two members used for joining are limited to members that can be covalently bonded. For this reason, the material that can be joined is limited to a combination of glass material and silicon material.
Moreover, in solid joining, since the whole surface which mutually contacts is joined among each joining surface of two members, it is difficult to selectively join a part. For this reason, when members made of different materials are joined together, a large stress is generated at the joining interface with a difference in coefficient of thermal expansion between the members, which may cause problems such as warpage, peeling, and hermetic failure.

Therefore, Patent Document 2 proposes a method of bonding members using a bonding film formed by a plasma polymerization method.
Since such a bonding film is formed by a vapor deposition method, it is easier to strictly control the film quality and thickness of the bonding film than in the past. However, when patterning the bonding film formed by the plasma polymerization method, it is necessary to remove unnecessary portions by using a photolithography technique and an etching technique, and the manufacturing process is complicated and expensive. Furthermore, when photolithography is used, it is necessary to use an alkaline solution in the development step. However, the plasma polymerized film is weak in resistance to the alkaline solution, and the characteristics of the bonding film are deteriorated during etching. For this reason, there exists a possibility that the airtightness of film | membrane itself may be impaired, and it is unsuitable for the junction part which requires airtightness.
Further, in Patent Document 2, since it is necessary to form a bonding film on the surface of a member used for bonding, the film forming apparatus and the member are inseparable, and a member must be prepared where the film forming apparatus is located. Don't be. However, since the film forming apparatus is large in size, heavy in weight, and extremely low in portability, it is inevitable that the product manufacturing process involves geographical restrictions on the flow lines of the members.

  Patent Document 3 discloses a bonding film in which a first structure and a second structure that form a closed space therein include a siloxane (Si—O) skeleton and a leaving group that bonds to the siloxane skeleton. In this case, a bonding film is formed on the entire surface of the first structure serving as a lid of the closed space. However, if a bonding film is formed on the entire surface of the lid in the closed space, the bonding film missing from the lid may adhere to the electronic device housed in the closed space, which may adversely affect the element characteristics. is there.

JP 2008-252805 A JP 2008-307873 A JP 2009-131911 A

  An object of the present invention is that a bonding film having a desired shape can be easily transferred onto the surface of a member, thereby enabling a simple bonding while controlling the bonding region of the member to which the bonding film is transferred. Another object of the present invention is to provide a method for manufacturing a sealed device that can efficiently manufacture a highly reliable sealed device.

The above object is achieved by the present invention described below.
The bonding method of the present invention includes a base material, an atomic structure including a siloxane (Si-O) bond provided on one surface side of the base material, and a leaving group formed of an organic group bonded to the siloxane bond. A preparation step of preparing a base member with a bonding film having a bonding film including a first member and a second member to be bonded so that their bonding surfaces face each other;
The first member and the bonding film are provided such that energy is applied to a partial region of the bonding surface of the first member to activate the region, and the region and the bonding film are in close contact with each other. A temporary bonding step of laminating a base material with a base to obtain a first temporary bonded body;
A transfer step of peeling the base material from the first temporary bonded body, partially transferring the bonding film corresponding to the region to the first member, and obtaining a second temporary bonded body;
Energy is applied to the peeling surface of the bonding film transferred to the second temporary bonded body, the leaving group is released from the siloxane bond, and adhesiveness is exhibited, and the bonding surfaces face each other. As described above, the present invention includes a main joining step in which the second temporary joined body and the second member are stacked to obtain a joined body.
As a result, the bonding film having a desired shape can be easily transferred onto the surface of the member, thereby enabling easy bonding while controlling the bonding region between the member to which the bonding film has been transferred and the other member. .

In the joining method of this invention, it is preferable to provide energy to the said joining film of the said base material with a joining film in the said temporary joining process.
Thereby, a stronger bonded state can be obtained.
In the bonding method of the present invention, it is preferable that the bonding film includes a Si—H bond.
Si-H bonds are thought to inhibit the regular formation of siloxane bonds. For this reason, the siloxane bond is formed so as to avoid the Si—H bond, and the regularity of the atomic structure including the siloxane bond is lowered. Thus, an atomic structure with a low degree of crystallinity can be efficiently formed by including Si—H bonds in the bonding film.

In the bonding method of the present invention, the bonding film is preferably a plasma polymerization film.
Thereby, a dense and homogeneous bonding film can be efficiently produced. In addition, in the bonding film manufactured by the plasma polymerization method, the activated state is imparted with energy and is maintained for a relatively long time. For this reason, the manufacturing process of the joined body can be simplified and improved in efficiency.

In the bonding method of the present invention, it is preferable that the base material has a release layer that is provided on a surface thereof and has a peelability from the bonding film.
Thereby, a base material will have peelability with respect to a joining film | membrane irrespective of a composition of a base material.
In the bonding method of the present invention, it is preferable that the energy is applied to the region by at least one of a method of exposing the region to plasma and a method of irradiating the region with energy rays.
Thereby, while cleaning the said area | region, a part of coupling | bonding of the surface vicinity can be cut | disconnected and the surface can be activated.

In the bonding method of the present invention, it is preferable that energy is applied to the bonding film by at least one of a method of exposing the bonding film to plasma and a method of irradiating the bonding film with energy rays.
Thereby, the bonding film can be activated efficiently. In addition, since the bonds in the bonding film are not cut more than necessary, it is possible to avoid deterioration of the characteristics of each bonding film.
In the bonding method of the present invention, after the main bonding step, at least a step of heating the bonded body and a step of pressurizing the bonded body so that the first member and the second member approach each other It is preferable to have one.
Thereby, the joint strength in the joined body can be further increased.

In the bonding method of the present invention, in the preparation step, a substrate with a first bonding film and a substrate with a second bonding film similar to the substrate with a bonding film are prepared,
In the temporary bonding step, the first member is configured such that energy is applied to a first region of a part of the bonding surface of the first member so that the first region and the bonding film are in close contact with each other. And the first substrate with the bonding film are laminated, and energy is applied to a second region of a part of the bonding surface of the second member, and the second region and the bonding film are Laminating the second member and the second substrate with a bonding film so as to closely adhere to obtain two first temporary bonded bodies,
In the transfer step, the base material is peeled off from the two first temporary joined bodies, the bonding film corresponding to the first region is partially transferred to the first member, and the first Partially transferring the bonding film corresponding to the region of 2 to the second member to obtain two second temporary bonded bodies,
In the main bonding step, energy is applied to the separation surfaces of the bonding films of the two second temporary bonded bodies, and the two second temporary bonded bodies are arranged so that the bonded surfaces face each other. Is preferably laminated to obtain a joined body.
This makes it possible to easily form a bonding film having a complicated shape.

The method for producing a sealed device of the present invention includes a base material, an atomic structure provided on one surface side of the base material, including a siloxane (Si-O) bond, and an organic group bonded to the siloxane bond A first member capable of forming a closed space therein and a second member by superimposing the substrate with a bonding film having a bonding film including a leaving group and a bonding film including the bonding group so as to face each other. A first step of preparing a member;
A second step of placing the device in a position that can be the closed space;
The first member and the bonding film are provided such that energy is applied to a partial region of the bonding surface of the first member to activate the region, and the region and the bonding film are in close contact with each other. A third step of laminating a substrate with a substrate to obtain a first temporary joined body;
A fourth step of peeling the base material from the first temporary bonded body, partially transferring the bonding film corresponding to the region to the first member, and obtaining a second temporary bonded body; ,
Energy is applied to the peeling surface of the bonding film transferred to the second temporary bonded body, the leaving group is released from the siloxane bond, and adhesiveness is exhibited, and the bonding surfaces face each other. And a fifth step of stacking the second temporary joined body and the second member, hermetically sealing the closed space in which the device is housed, and obtaining a sealed device. It is characterized by that.
Thereby, a highly reliable sealed device can be efficiently manufactured.
In the sealed device manufacturing method of the present invention, in the third step, the region where energy is applied to the bonding surface of the first member is a frame shape surrounding the periphery of the region corresponding to the closed space. It is preferable to set so that it becomes the area | region of this.
Accordingly, the closed space can be reliably hermetically sealed by the bonding film.

In the manufacturing method of the encapsulated device of the present invention, in the first step, a first substrate with a bonding film and a second substrate with a bonding film similar to the substrate with a bonding film are prepared,
In the third step, energy is applied to a first region of a part of the bonding surface of the first member so that the first region and the bonding film are in close contact with each other. While laminating a member and the first substrate with a bonding film, energy is applied to a second region of a part of the bonding surface of the second member, and the second region and the bonding film The second member and the base material with the second bonding film are laminated so that the two first temporary bonded bodies are obtained.
In the fourth step, the base material is peeled from the two first temporary joined bodies, and the first film and the bonding film corresponding to the first area and the second area are separated from the first member and the second area. Partially transferred to the second member to obtain two second temporary joined bodies,
In the fifth step, the two second temporary joined bodies are provided such that energy is applied to the separation surfaces of the bonding films of the two second temporary joined bodies, and the joined surfaces face each other. It is preferable to laminate them to obtain a sealed device.
Thereby, a complex-shaped bonding film can be easily formed, and a highly reliable sealed device can be efficiently manufactured.

In the sealed device manufacturing method of the present invention, the first region and the second region are:
When the two second temporary joined bodies are laminated in the fifth step, the area obtained by combining these areas is set to be a frame-like area surrounding the area corresponding to the closed space. It is preferable.
Thereby, the closed space can be reliably hermetically sealed by the bonding film, and a highly reliable sealed device can be efficiently manufactured.
In the manufacturing method of the sealed device of the present invention, in the third step, before the member and the substrate with the bonding film are stacked, energy is applied to the bonding film of the substrate with the bonding film. Is preferred.
Thereby, a sealed device having a stronger bonding state can be manufactured.

It is the top view and sectional drawing which show the structure of the crystal oscillator which is an example of the sealing type device manufactured by the manufacturing method (sealing method of this invention) of the sealing type device of this invention. FIG. 2 is an exploded perspective view of the crystal unit shown in FIG. 1. It is a figure (longitudinal sectional view) for demonstrating embodiment of the manufacturing method (sealing method of this invention) of the sealing type device of this invention. It is a top view which shows the structure of a mask. It is a figure (longitudinal sectional view) for demonstrating embodiment of the manufacturing method (sealing method of this invention) of the sealing type device of this invention. It is a figure (longitudinal sectional view) for demonstrating embodiment of the manufacturing method (sealing method of this invention) of the sealing type device of this invention. It is the elements on larger scale which show the state before energy provision of the bonding film transcribe | transferred to the 1st member. It is the elements on larger scale which show the state after the energy provision of the bonding film transcribe | transferred to the 1st member. It is a longitudinal cross-sectional view which shows typically the plasma polymerization apparatus used for the joining method of this invention. It is sectional drawing which shows the other structural example 1 of the manufacturing method (joining method of this invention) of the sealing type device of this invention. It is sectional drawing which shows the other structural example 2 of the manufacturing method (joining method of this invention) of the sealing type device of this invention.

Hereinafter, the joining method and the manufacturing method of a sealing type device of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
FIG. 1 is a plan view and a cross-sectional view showing a configuration of a crystal resonator which is an example of a sealed device manufactured by a manufacturing method of a sealed device of the present invention (a bonding method of the present invention), and FIG. 1 is an exploded perspective view of the crystal unit shown in FIG. 1, and FIGS. 3, 5, and 6 are diagrams (longitudinal sectional views) for explaining an embodiment of a method for manufacturing a sealed device of the present invention (joining method of the present invention). 4 is a plan view showing the structure of the mask, FIG. 7 is a partially enlarged view showing a state before energy application of the bonding film transferred to the first member, and FIG. 8 is transferred to the first member. It is the elements on larger scale which show the state after energy provision of the made bonding film. In the following description, the upper side in FIGS. 2, 3, and 5 to 8 is referred to as “upper”, and the lower side is referred to as “lower”.
Hereinafter, as an example of the bonding method of the present invention, a method of manufacturing the crystal unit 1 shown in FIG. 1 (a manufacturing method of the sealed device of the present invention) will be described.

(Sealed device)
A crystal resonator (sealed device) 1 shown in FIG. 1 has a bottomed box shape, and has a case (first member) 2 having a recess 22 inside, a case 2 provided above the case 2, The lid (second member) 4 that closes the recess 22 by covering the opening, and the crystal vibrating piece 5 provided in the recess 22 are provided. The case 2 and the lid 4 are joined by a joining film 3. Thereby, between the case 2 and the cover body 4 is airtightly sealed, and the recessed part 22 becomes a closed space.

Here, the crystal vibrating piece 5 is provided with an electric wiring (not shown), and this electric wiring is electrically connected to an electrode pad (not shown) provided on the outer surface of the case 2. Thereby, a voltage can be applied to the crystal vibrating piece 5 from the outside of the case 2.
When a voltage is applied to the crystal vibrating piece 5, the crystal vibrating piece 5 can be vibrated at a certain frequency (resonance frequency) due to the inverse piezoelectric effect of the crystal. Further, when the crystal vibrating piece 5 vibrates, a voltage fluctuation is generated at the electrode pad at a certain frequency this time due to the piezoelectric effect of the crystal. Utilizing these properties, the crystal unit 1 is used as an electronic component that generates an electrical signal that vibrates at a resonance frequency.

  By the way, the inside of the recess 22 of the crystal unit 1 is normally maintained under reduced pressure or in an inert gas atmosphere. This is to reduce the vibration resistance of the crystal vibrating piece 5 and to prevent deterioration and deterioration of the crystal vibrating piece 5 and the electrical wiring provided in the recess 22. Therefore, the joint between the case 2 and the lid body 4 is required to have a high degree of airtightness (or liquid tightness) for maintaining a reduced pressure state or an inert gas filling state for a long time.

In the crystal unit 1 shown in FIG. 1, the airtightness of such a joint is ensured by the bonding film 3.
Hereinafter, each part of the crystal unit 1 shown in FIG. 1 will be described in detail.
As shown in FIG. 1A, the case 2 has a rectangular shape in plan view, and has a concave portion 22 that has a rectangular shape in plan view. As shown in FIG. 1B, the case 2 includes a side wall 23 provided so as to surround the side surface of the concave portion 22 and a bottom portion 24 provided below the concave portion 22.

Of the upper surface of the bottom portion 24, the vicinity of the left end is partially raised and serves as a support portion 21 that supports the crystal vibrating piece 5.
Such a case 2 is made of an insulating material. Examples of the material include various glass materials, various ceramic materials, various silicon materials, and various resin materials. In addition, when the case 2 does not need insulation, various metal materials, various carbon materials, etc. may be sufficient.

The quartz crystal vibrating piece 5 has a flat plate shape, and its left end is fixed on the support portion 21. The crystal vibrating piece 5 is fixed only by this fixing portion, and the other portions are held in a state of floating in the space of the recess 22. The constituent material of the quartz crystal vibrating piece 5 is not limited to quartz but may be a piezoelectric material. Examples of the piezoelectric material include crystal, lithium tantalate, lithium niobate, lithium borate, and barium titanate.
A space between the crystal vibrating piece 5 and the support portion 21 is fixed by a mount material 6. Examples of the constituent material of the mount material 6 include various adhesives such as epoxy and silicone, various solders, various brazing materials, and the like.

As a constituent material of the lid 4 provided on the side wall 23 of the case 2, any material can be used, and the same materials as the case 2, various metal materials, and the like can be mentioned.
The case 2 and the lid 4 are joined between the joint surface 231 that is the upper surface of the side wall 23 of the case 2 and the joint surface 401 that is the edge of the lower surface of the lid 4. In addition, the bonding film 3 having a rectangular frame shape in plan view is responsible for bonding. As shown in the exploded perspective view of FIG. 2, the bonding film 3 is formed on the first bonding film 31 formed on the bonding surface 231 of the side wall 23 of the case 2 and the bonding surface 401 of the lid 4. The second bonding film 32 is formed by integrating them.
The bonding film 3 includes an atomic structure including a siloxane (Si—O) bond and a leaving group bonded to the siloxane bond. Such a bonding film 3 itself has a high density and low air permeability, and is firmly adhered to the case 2 and the lid body 4, and therefore can maintain extremely high airtightness.

(Method for manufacturing sealed device)
The method for manufacturing the crystal unit 1 shown in FIG. 1 includes a first bonding film transfer sheet (base material with a bonding film) 10 having a base material 20 and a first bonding film 31 formed thereon. And a second bonding film transfer sheet (base material with bonding film) 10 having a base material 20 and a second bonding film 32 formed thereon, and a case 2 and a lid 4 are prepared. The first step (preparation step) to be performed, the second step of housing the crystal vibrating piece 5 in the recess 22, the partial region 232 of the bonding surface 231 of the case 2, and the bonding surface 401 of the lid 4 The case 2 and the lid 4 so that energy is applied to each of the partial regions 402 and the region 232 and the first bonding film 31 and the region 402 and the second bonding film 32 are in close contact with each other. Each of the bonding film transfer sheets 10 is laminated to obtain two first temporary bonded bodies 7 In step (temporary bonding step), the base material 20 is peeled off from each first temporary bonding body 7, and a portion corresponding to the region 232 in the first bonding film 31 is transferred to the bonding surface 231, Of the two bonding films 32, a portion corresponding to the region 402 is transferred to the bonding surface 401 to obtain two second temporary bonded bodies 8 (transfer process), and each transferred bonding film 31. , 32 by applying energy to the release surfaces of the bonding films 31 and 32, respectively, so that the release surfaces of the bonding films 31 and 32 exhibit adhesiveness, and the bonding surfaces 231 and the bonding surfaces 401 face each other. By stacking the temporary bonded bodies 8 together, the concave portion 22 is hermetically sealed, and a fifth step (main bonding step) for obtaining the crystal unit 1 is included.
The crystal resonator 1 obtained in this way has excellent airtightness and high reliability. Further, according to the bonding method of the present invention and the manufacturing method of the sealed device of the present invention, such a crystal unit 1 can be efficiently manufactured even at a low temperature.

Hereinafter, each process will be described sequentially.
[1] First, two bonding film transfer sheets 10, a case 2 and a lid 4 are prepared (first step).
(Bonding film transfer sheet)
Hereinafter, the two bonding film transfer sheets 10 will be described.

  The two bonding film transfer sheets 10 shown in FIG. 3A include a base material 20 and a first bonding film 31 formed on the base material 20 (first bonding film transfer sheet). The substrate 20 and the second bonding film 32 formed on the substrate 20 (second bonding film transfer sheet). The former is used to transfer the first bonding film 31 to the case 2, and the latter is used to transfer the second bonding film 32 to the lid 4.

The first bonding film 31 and the second bonding film 32 include a Si skeleton having an atomic structure including a siloxane (Si—O) bond and a leaving group bonded to the Si skeleton. Further, the base material 20 preferably has peelability from the bonding films 31 and 32.
Each of the bonding films 31 and 32 is characterized in that, by applying energy, the leaving group present in each bonding film 31 and 32 is released from the Si skeleton, and adhesiveness develops in the region to which energy is applied. Have

Hereinafter, the configuration of each part of the bonding film transfer sheet 10 will be described in detail. Here, the bonding film transfer sheet 10 having the base material 20 and the first bonding film 31 will be described as a representative, but the bonding film transfer sheet 10 having the base material 20 and the second bonding film 32 is also the same. It is.
The base material 20 supports the first bonding film 31, and preferably has peelability with respect to the first bonding film 31. Moreover, the base material 20 shown in FIG. 3 is a board | substrate form (sheet form) whose both surfaces are flat surfaces, and the thickness is uniform as a whole.

  Examples of the constituent material of the base material 20 include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, Polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer Copolymer (AS resin), butadiene-styrene copolymer, polyoxymethylene, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PE ), Polyester such as polyethylene naphthalate, polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyether imide, polyacetal (POM), Polyphenylene oxide, modified polyphenylene oxide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluororesins, styrene, polyolefin, polychlorination Vinyl, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluoro rubber, chlorinated polyester Various thermoplastic elastomers such as len, epoxy resins, phenol resins, urea resins, melamine resins, aramid resins, unsaturated polyesters, silicone resins, polyurethanes, etc., or copolymers, blends, polymer alloys mainly containing these And fluorine-based inorganic materials such as potassium fluoride titanate, potassium silicofluoride, potassium fluorozirconate, and silicic hydrofluoric acid.

  Of these, the substrate 20 is preferably flexible. Thereby, when the bonding film transfer sheet 10 is laminated with the case 2, the adhesion at the lamination interface can be improved. This is because, since the base material 20 has flexibility, even if the surface of the case 2 has unevenness, the bonding film transfer sheet 10 can be deformed along the uneven shape, so that the adhesion between the two is close. This is because the property is improved. Therefore, when the base material 20 has flexibility, in the first temporary joined body 7, uneven lamination between the bonding film transfer sheet 10 and the case 2 is suppressed, and the first bonding film 31 is reliably transferred. be able to.

Further, when the base material 20 is peeled from the bonding film transfer sheet 10 laminated on the case 2, the base material 20 can be easily bent. For this reason, the peeling work is facilitated, and problems such as the base material 20 damaging the first bonding film 31 at the time of peeling are prevented.
Furthermore, since the base material 20 has flexibility, the bonding film transfer sheet 10 itself also has flexibility. Since such a bonding film transfer sheet 10 can be wound up in a roll shape, space saving can be achieved during storage and transportation. Further, the bonding film transfer sheet 10 wound up in a roll shape can be easily supplied in a necessary length by being sequentially fed out. For this reason, when performing the manufacturing method of the sealing type device of the present invention and the bonding method of the present invention using, for example, a bonding apparatus, the bonding film transfer sheet 10 is excellent in affinity with the apparatus and suitable for mass production.

  In addition, the base material 20 is preferably a resin-based material as a main material, and the resin-based material is more preferably any one of fluorine-based resin, polyolefin, polyester, and polyimide. Such a base material 20 is not only excellent in flexibility, but also has excellent peelability with respect to the first bonding film 31, and thus the above-described effects become more remarkable. In particular, even when the base material 20 is bent with a small radius of curvature, the peeling process described above can be performed easily and reliably because the base material 20 is less likely to break. Specific examples of the fluororesin include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), perfluoroethylene- Examples include propene copolymer (FEP) and ethylene-chlorotrifluoroethylene copolymer (ECTFE).

Furthermore, since the resin-based material is lightweight, even if a large amount of the bonding film transfer sheet 10 is wound up in a roll shape, the roll is relatively lightweight and excellent in portability, so that handling is easy. .
The average thickness of the base material 20 is appropriately set according to the constituent material and the desired flexibility, but as an example, it is preferably about 0.001 mm to 10 mm, preferably 0.01 mm to 1 mm. More preferably, it is about the following.

  The base material 20 preferably has a surface energy (surface free energy) smaller than the surface energy of the case 2. As a result, the case 2 exhibits relatively high adhesion to the first bonding film 31 and is firmly bonded to the first bonding film 31, while the base material 20 is bonded to the first bonding film 31. Relatively low adhesion is exhibited. That is, the interface between the case 2 and the first bonding film 31 is bonded relatively firmly, while the bonding strength at the interface between the base material 20 and the first bonding film 31 is relatively low. Thus, when the bonding film transfer sheet 10 and the case 2 are laminated and the base material 20 is peeled from the obtained first temporary bonded body 7, the interface between the case 2 and the first bonding film 31 is used. It is possible to reliably cause peeling at the interface between the base material 20 and the first bonding film 31 without causing peeling. As a result, the first bonding film 31 can be reliably transferred to the case 2.

  The specific surface energy of the substrate 20 is preferably 5 mN / m or more and 200 mN / m or less, and more preferably 10 mN / m or more and 100 mN / m or less. When the surface energy of the base material 20 is within the above range, the base material 20 is peeled off at the interface between the base material 20 and the first bonding film 31 when not intended when manufactured and distributed as the bonding film transfer sheet 10. In addition, when transferring the first bonding film 31 to the case 2, it is easy and easy at the interface between the base material 20 and the first bonding film 31 by applying an appropriate peeling force. It can be surely peeled off.

  On the other hand, the surface energy of the case 2 may be higher than the surface energy of the substrate 20, but is preferably 1.1 times or more, more preferably 1.5 times or more, and further preferably 2 times or more. The If there is such a difference, the variation in the surface energy of the base material 20 and the case 2 is sufficiently absorbed, so that it is possible to prevent the magnitude relationship between the adhesion strengths of the two from being partially reversed.

As a constituent material of the case 2 having such a large surface energy, an inorganic material is preferably used as will be described in detail later.
Further, the surface energy of the substrate 20 is preferably smaller than the surface energy of the case 2 as described above, but the bonding strength between the case 2 and the first bonding film 31 is forcibly increased by some surface treatment or the like. In such a case, the size is not necessarily small. Examples of the surface treatment include physical surface treatment such as sputtering treatment and blast treatment, plasma treatment using oxygen plasma, nitrogen plasma, etc., corona discharge treatment, etching treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, ozone Examples include chemical surface treatment such as exposure treatment, or a combination of these. By performing such treatment, the surface of the case 2 can be cleaned and activated. As a result, the adhesion strength between the case 2 and the first bonding film 31 can be reliably increased.

Further, in the physical surface treatment, by increasing the surface roughness of the surface of the case 2, an anchor effect is generated at the interface between the case 2 and the first bonding film 31, and the adhesion strength can be improved.
In addition, the base material 20 may be configured by a base material and a release layer that is provided on the surface of the base material and has a peelability with respect to the first bonding film 31. Thereby, the base material 20 has peelability with respect to the first bonding film 31 regardless of the composition of the base material. In this case, the release layer preferably has the same characteristics as the base material 20 described above. That is, the constituent material of the release layer includes the constituent material of the base material 20 described above, and the surface energy of the release layer is preferably the same as the surface energy of the base material 20 described above.

For example, the release layer may be formed by applying or printing a liquid material to obtain a liquid film, followed by drying to form a film by various liquid phase film formation methods, CVD methods, vacuum deposition methods, sputtering methods, plasma polymerization methods, etc. The film is formed by various vapor deposition methods, various plating methods such as electroplating and electroless plating.
The release layer can also be formed by supplying a coupling agent having a functional group having a low affinity for the first bonding film 31 to the upper surface of the substrate 20. According to such a coupling agent, it is possible to form an extremely thin release layer of about one molecule or several molecules. For this reason, the adhesiveness of the peeling layer with respect to the base material 20 improves, and when the base material 20 is curved, the peeling layer is hardly peeled off from the base material 20.
In addition, in the release layer formed using the coupling agent, the density of functional groups having low affinity for the first bonding film 31 described above increases. For this reason, the functional groups are arranged without gaps on the surface of the release layer, and the bonding strength at the interface between the release layer and the first bonding film 31 can be suppressed evenly.

  Examples of the functional group having low affinity for the first bonding film 31 (showing peelability) include a fluorine atom, a fluoroalkyl group, a fluoroalkenyl group, a fluoroalkynyl group, a fluoroaryl group, a fluoroalkoxy group, and a fluoro group. Fluoro group such as aryloxy group, fluoroalkylthio group, fluoroarylthio group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group And alkyl groups such as dodecyl group.

  Examples of the coupling agent containing a fluoro group include tridecafluoro-1,1,2,2 tetrahydrooctyltriethoxysilane, tridecafluoro-1,1,2,2 tetrahydrooctyltrimethoxysilane, Examples include decafluoro-1,1,2,2 tetrahydrooctyltrichlorosilane, trifluoropropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

The average thickness of the release layer is not particularly limited, but is preferably about 1 nm to 1000 μm, more preferably about 1 nm to 500 μm. Thereby, the adhesiveness of the peeling layer with respect to the base material 20 and the peelability of the peeling layer with respect to the first bonding film 31 are improved. Further, when the thickness of the release layer is within the above range, the smoothness of the surface of the release layer can be relatively enhanced even when the surface smoothness of the substrate 20 is low. As a result, a gap generated at the interface between the release layer and the first bonding film 31 is suppressed. When the bonding film transfer sheet 10 and the case 2 are stacked and further compressed, the bonding film transfer sheet 10 and The case 2 can be adhered to the case without unevenness. As a result, the first bonding film 31 can be reliably transferred to the case 2.
The first bonding film 31 is provided on the upper surface of the substrate 20 as described above. As described above, the first bonding film 31 has a characteristic that adhesiveness is developed by applying energy.

FIG. 7 is a partially enlarged view showing a state before energy application of the first bonding film 31 transferred to the case 2, and FIG. 8 shows a state after energy application of the first bonding film 31 transferred to the case 2. It is the elements on larger scale which show a state.
As shown in FIG. 7, the first bonding film 31 has a skeleton (Si—O) bond 302 and a Si skeleton 301 having a random (or low crystallinity) atomic structure (amorphous structure). And a leaving group 303 bonded to the Si skeleton 301. Such a first bonding film 31 is a strong film that is difficult to be deformed due to the influence of the Si skeleton 301 including the siloxane bond 302 and having a random atomic structure. This is presumably because the crystallinity of the Si skeleton 301 becomes low (becomes amorphous), so that defects such as dislocations and misalignments at the crystal grain boundaries hardly occur. For this reason, the bonding film 3 itself has high bonding strength, chemical resistance, light resistance and dimensional accuracy, and the finally obtained crystal resonator 1 also has bonding strength, chemical resistance, light resistance and dimensional accuracy. A high one is obtained.

  When energy is applied to the first bonding film 31, the leaving group 303 is released from the Si skeleton 301, and as shown in FIG. 8, the active hands 304 are formed on the surface 35 and the inside of the first bonding film 31. Arise. As a result, adhesiveness develops on the surface of the first bonding film 31. When such adhesiveness is expressed, the first bonding film 31 can be firmly and efficiently bonded to the lid 4.

  Note that the bond energy between the leaving group 303 and the Si skeleton 301 is often smaller than the bond energy of the siloxane bond 302 in the Si skeleton 301. This is because the bond energy of the siloxane bond 302 is about 430 kJ / mol, which is considerably larger than other bond types. Therefore, when energy is applied to the first bonding film 31, Without causing breakage, the bond between the leaving group 303 and the Si skeleton 301 can be selectively broken to remove the leaving group 303.

  In addition, since the first bonding film 31 has a structure that is relatively close to an inorganic material, the first bonding film 31 is a solid that does not have fluidity. For this reason, the thickness and shape of the adhesive layer (first bonding film 31) hardly change compared to conventional liquid or viscous liquid adhesives. Thereby, the dimensional accuracy of the crystal unit 1 is remarkably higher than the conventional one. Furthermore, since the time required for curing the adhesive is not required, bonding in a short time is possible.

Further, when the bonding film transfer sheet 10 is circulated, since the first bonding film 31 is in a solid state, problems such as the first bonding film 31 flowing out during distribution or storage are prevented.
In the first bonding film 31, among the atoms obtained by removing H atoms from all atoms constituting the first bonding film 31, the total of the Si atom content and the O atom content is 10 atoms. % Or more and about 90 atom% or less is preferable, and about 20 atom% or more and 80 atom% or less is more preferable. If Si atoms and O atoms are contained in the above-mentioned range, the first bonding film 31 forms a strong network of Si atoms and O atoms, and the film itself becomes strong. Such a first bonding film 31 exhibits a particularly high bonding strength with respect to the case 2.

The abundance ratio of Si atoms and O atoms in the first bonding film 31 is preferably about 3: 7 to 7: 3, more preferably about 4: 6 to 6: 4. . By setting the abundance ratio of Si atoms and O atoms to be in the above range, the stability of the first bonding film 31 is increased, and the lid 4 can be more firmly bonded. .
Further, the crystallinity of the Si skeleton 301 in the first bonding film 31 is preferably 45% or less, and more preferably 40% or less. As a result, the Si skeleton 301 includes a sufficiently random atomic structure and exhibits more amorphous characteristics. For this reason, the characteristics of the Si skeleton 301 described above become obvious, and the dimensional accuracy and adhesiveness of the first bonding film 31 become more excellent. Moreover, since the mechanical strength and density of the film itself are also improved, the air permeability can be further reduced. Thereby, the airtightness by the first bonding film 31 is further enhanced.

Note that the crystallinity of the Si skeleton 301 can be measured by a general crystallinity measurement method, and specifically, a method of measuring based on the intensity of scattered X-rays in a crystal portion (X-ray method). , The method of obtaining from the intensity of the crystallization band of infrared absorption (infrared method), the method of obtaining based on the area under the differential curve of nuclear magnetic resonance absorption (nuclear magnetic resonance absorption method), It can be measured by a chemical method utilizing the difficulty.
Among these, the X-ray method is preferably used from the viewpoint of convenience and the like.

  Further, when the crystallinity of the Si skeleton 301 is measured, the above-described measurement method may be applied to the first bonding film 31, but the first bonding film 31 is pretreated beforehand. Is preferred. Examples of the pretreatment include a process for applying energy to the first bonding film 31 described later (for example, an ultraviolet irradiation process). By applying energy, the leaving group in the first bonding film 31 is released, and the crystallinity of the Si skeleton 301 can be measured more accurately.

  Further, the first bonding film 31 preferably includes Si—H bonds in the structure. This Si—H bond is considered to be generated in a polymer when a silane undergoes a polymerization reaction by, for example, a plasma polymerization method, and inhibits regular formation of siloxane bonds. For this reason, the siloxane bond is formed so as to avoid the Si—H bond, and the regularity of the atomic structure of the Si skeleton 301 is lowered. Thus, according to the plasma polymerization method, the Si skeleton 301 having a low crystallinity can be efficiently formed.

  On the other hand, the greater the Si—H bond content in the first bonding film 31, the lower the crystallinity. Specifically, in the infrared light absorption spectrum of the first bonding film 31, when the intensity of the peak attributed to the siloxane bond is 1, the intensity of the peak attributed to the Si—H bond is 0.001 or more and 0. It is preferably about 2 or less, more preferably about 0.002 or more and 0.05 or less, and further preferably about 0.005 or more and 0.02 or less. When the ratio of the Si—H bond to the siloxane bond is within the above range, the atomic structure in the first bonding film 31 is relatively most random. For this reason, when the peak intensity of the Si—H bond is within the above range with respect to the peak intensity of the siloxane bond, the first bonding film 31 is particularly excellent in bonding strength, chemical resistance, and dimensional accuracy. .

  Such a first bonding film 31 may be produced by any method, such as a plasma polymerization method, a CVD method (particularly a plasma CVD method), various gas phase film forming methods such as a PVD method, It can be produced by various liquid phase film forming methods. Among these, according to the plasma polymerization method, the dense and homogeneous first bonding film 31 can be efficiently produced. In addition, in the first bonding film 31 manufactured by the plasma polymerization method, the state where the energy is applied and activated is maintained for a relatively long time. For this reason, simplification and efficiency improvement of the manufacturing process of the crystal unit 1 can be achieved.

By the way, the leaving group 303 bonded to the Si skeleton 301 behaves so as to generate an active hand in the first bonding film 31 by detaching from the Si skeleton 301 as described above. Therefore, although the leaving group 303 is relatively easily and uniformly desorbed by being given energy, it is securely bonded to the Si skeleton 301 so as not to be desorbed when no energy is given. It is preferable.
In the film formation by the plasma polymerization method, the component of the source gas is polymerized to generate a Si skeleton 301 containing a siloxane bond and a residue bonded thereto. For example, this residue is a leaving group. 303. Also in other film forming methods, the residue of the siloxane bond contained in the raw material can be the leaving group 303.

  The leaving group 303 is not particularly limited as long as it is an atomic group that can be bonded to and desorbed from the Si skeleton 301, but an H atom, B atom, C atom, N atom, O atom, P atom, S atom And those containing at least one selected from the group consisting of atomic groups including halogen atoms or each of these atoms, each of which is arranged so that each of these atoms is bonded to the Si skeleton 301 are preferably used. Such a leaving group 303 is relatively excellent in bond / elimination selectivity by energy application. For this reason, such a leaving group 303 can sufficiently satisfy the above-described necessity, and the adhesiveness of the first bonding film 31 can be made higher.

  Examples of the atomic group (group) arranged so that each atom as described above is bonded to the Si skeleton 301 include, for example, an alkyl group such as a methyl group and an ethyl group, and an alkenyl group such as a vinyl group and an allyl group. Aldehyde group, ketone group, carboxyl group, amino group, amide group, nitro group, halogenated alkyl group, mercapto group, sulfonic acid group, cyano group, isocyanate group and the like.

Among these groups, the leaving group 303 is particularly preferably an organic group, and more preferably an alkyl group. Since the organic group and the alkyl group have high chemical stability, the first bonding film 31 including the organic group and the alkyl group has excellent weather resistance and chemical resistance.
Here, when the leaving group 303 is a methyl group (—CH ₃ ) in particular, the preferred content is defined as follows from the peak intensity in the infrared light absorption spectrum.

  That is, in the infrared light absorption spectrum of the first bonding film 31, when the intensity of the peak attributed to the siloxane bond is 1, the intensity of the peak attributed to the methyl group is about 0.05 to 0.45. It is preferably about 0.1 or more and 0.4 or less, and more preferably about 0.2 or more and 0.3 or less. Since the ratio of the peak intensity of the methyl group to the peak intensity of the siloxane bond is within the above range, it is necessary in the first bonding film 31 while preventing the methyl group from inhibiting the generation of the siloxane bond more than necessary. In addition, since a sufficient number of active hands are generated, sufficient adhesiveness is generated in the first bonding film 31. Further, the first bonding film 31 exhibits sufficient weather resistance and chemical resistance due to the methyl group.

Examples of the constituent material of the first bonding film 31 having such characteristics include a polymer containing a siloxane bond such as polyorganosiloxane and an organic group capable of forming a leaving group 303 bonded thereto.
The first bonding film 31 made of polyorganosiloxane itself has excellent mechanical properties. In addition, it exhibits particularly excellent adhesion to many materials. Therefore, the first bonding film 31 made of polyorganosiloxane adheres particularly firmly to the case 2 and also exhibits a particularly strong adherence to the lid 4. As a result, the case 2 And the lid 4 can be firmly joined.

Polyorganosiloxane usually exhibits water repellency (non-adhesiveness), but when given energy, it can easily desorb organic groups, changes to hydrophilicity, and exhibits adhesiveness. However, there is an advantage that the non-adhesiveness and the adhesiveness can be controlled easily and reliably.
This water repellency (non-adhesiveness) is mainly an effect of organic groups (for example, alkyl groups) contained in the polyorganosiloxane. Therefore, the first bonding film 31 made of polyorganosiloxane exhibits an adhesive property on the surface 35 when energy is applied thereto, and in the portion other than the surface 35, the action by the organic group described above is performed. There is also an advantage that an effect is obtained. Therefore, such a first bonding film 31 has excellent weather resistance and chemical resistance. For example, a crystal resonator, an optical element, a droplet discharge head, etc. that are exposed to chemicals for a long time. This is particularly effective when assembling.

  Further, among polyorganosiloxanes, those mainly composed of a polymer of octamethyltrisiloxane are preferred. The first bonding film 31 mainly composed of a polymer of octamethyltrisiloxane is particularly excellent in adhesiveness. Moreover, since the raw material which has octamethyltrisiloxane as a main component is liquid at normal temperature and has an appropriate viscosity, there is also an advantage that it is easy to handle.

The average thickness of the first bonding film 31 is preferably about 1 nm to 1000 nm, and more preferably about 2 nm to 800 nm. By making the average thickness of the first bonding film 31 within the above range, the case 2 and the lid 4 are bonded more firmly while preventing the dimensional accuracy of the crystal unit 1 from being significantly reduced. Can do.
If the average thickness of the first bonding film 31 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 first bonding film 31 exceeds the upper limit, the dimensional accuracy of the crystal unit 1 may be reduced.

Furthermore, if the average thickness of the first bonding film 31 is within the above range, the first bonding film 31 has a certain degree of shape followability. For this reason, for example, even when unevenness is present on the bonding surface of the case 2 (surface adjacent to the first bonding film 31), it follows the shape of the unevenness depending on the height of the unevenness. The first bonding film 31 can be deposited. As a result, the first bonding film 31 can absorb the unevenness and reduce the height of the unevenness generated on the surface. Then, when the bonding film transfer sheet 10 and the case 2 are bonded together, the adhesion between them can be improved.
Note that the degree of the shape followability as described above becomes more prominent as the thickness of the first bonding film 31 increases. Therefore, the thickness of the first bonding film 31 may be increased as much as possible in order to sufficiently ensure the shape followability.

  The bonding film transfer sheet 10 as described above may be provided with a cover sheet provided so as to cover the upper surface of the first bonding film 31 as necessary. Such a cover sheet protects the upper surface of the first bonding film 31 and prevents adhesion of foreign matters, damage to the first bonding film 31, and the like. As a result, the bonding film transfer sheet 10 has excellent durability and is suitable for long-term storage and distribution.

This cover sheet is peeled off before using the bonding film transfer sheet 10. At this time, since it is necessary to surely peel off at the interface between the first bonding film 31 and the cover sheet, the adhesion strength at this interface is smaller than the adhesion strength between the substrate 20 and the first bonding film 31. It is preferable.
From this point of view, the cover sheet preferably has a surface energy smaller than that of the substrate 20. As a result, the base material 20 exhibits relatively high adhesion to the first bonding film 31 and adheres relatively strongly to the first bonding film 31, while the cover sheet is attached to the first bonding film 31. On the other hand, relatively low adhesion will be exhibited. As a result, even if energy is given to the bonding film transfer sheet 10 unintentionally, the cover sheet and the first bonding film 31 are prevented from being bonded, and the first bonding film 31 and A cover sheet that can be reliably peeled off at the interface is obtained.

Specifically, the surface energy of the cover sheet is preferably about 0.3 to 0.95 times the surface energy of the substrate 20, and is about 0.4 to 0.9 times. Is more preferable.
Examples of the constituent material of the cover sheet include the same constituent materials as those of the base material 20 described above.
Further, since the bonding film transfer sheet 10 may be stored or distributed in a state of being wound in a roll shape, a flexible cover sheet is preferably used as the base sheet 20.

Hereinafter, a method for producing the first bonding film 31 will be described.
The first bonding film 31 can be formed by any manufacturing method as described above, but here, as an example, a method of manufacturing the first bonding film 31 by a plasma polymerization method will be described. Hereinafter, prior to the description of the manufacturing method, a plasma polymerization apparatus used when manufacturing the first bonding film 31 by the plasma polymerization method will be described.

FIG. 9 is a longitudinal sectional view schematically showing a plasma polymerization apparatus used in the bonding method of the present invention. In the following description, the upper side in FIG. 9 is referred to as “upper” and the lower side is referred to as “lower”.
The plasma polymerization apparatus 100 shown in FIG. 9 includes a chamber 101, a first electrode 130 that supports the substrate 20, a second electrode 140, and a power supply circuit 180 that applies a high-frequency voltage between the electrodes 130 and 140. A gas supply unit 190 that supplies gas into the chamber 101 and a pump 170 that exhausts the gas in the chamber 101 are provided. Among these parts, the first electrode 130 and the second electrode 140 are provided in the chamber 101. Hereinafter, each part will be described in detail.

The chamber 101 is a container that can keep the inside airtight, and is used with the inside being in a reduced pressure (vacuum) state. Therefore, the chamber 101 has pressure resistance that can withstand a pressure difference between the inside and the outside.
The chamber 101 shown in FIG. 9 has a substantially cylindrical chamber body whose axis is arranged along the horizontal direction, a circular side wall that seals the left opening of the chamber body, and a circle that seals the right opening. And side walls.

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

The first electrode 130 has a plate shape and supports the base material 20.
The first electrode 130 is provided on the inner wall surface of the side wall of the chamber 101 along the vertical direction, whereby the first electrode 130 is electrically grounded via the chamber 101. The first electrode 130 is provided concentrically with the chamber body as shown in FIG.

An electrostatic chuck (suction mechanism) 139 is provided on the surface of the first electrode 130 that supports the base material 20.
The electrostatic chuck 139 can support the base material 20 along the vertical direction as shown in FIG. Further, even if the base material 20 has a slight warp, the base material 20 can be subjected to plasma treatment in a state where the warp is corrected by adsorbing the base material 20 to the electrostatic chuck 139.

The second electrode 140 is provided to face the first electrode 130 with the base material 20 interposed therebetween. Note that the second electrode 140 is provided in a state of being separated (insulated) from the inner wall surface of the side wall of the chamber 101.
A high frequency power source 182 is connected to the second electrode 140 via a wiring 184. A matching box (matching unit) 183 is provided in the middle of the wiring 184. The wiring 184, the high-frequency power source 182 and the matching box 183 constitute a power circuit 180.

According to such a power supply circuit 180, since the first electrode 130 is grounded, a high frequency voltage is applied between the first electrode 130 and the second electrode 140. As a result, an electric field whose direction is reversed at a high frequency is induced in the gap between the first electrode 130 and the second electrode 140.
The gas supply unit 190 supplies a predetermined gas into the chamber 101.

  A gas supply unit 190 shown in FIG. 9 stores a liquid storage unit 191 that stores a liquid film material (raw material liquid), a vaporizer 192 that vaporizes the liquid film material to change it into a gaseous state, and stores a carrier gas. And a gas cylinder 193. Each of these parts and the supply port 103 of the chamber 101 are connected by a pipe 194, and a mixed gas of a gaseous film material (raw material gas) and a carrier gas is supplied from the supply port 103 into the chamber 101. It is configured to supply.

The liquid film material stored in the liquid storage unit 191 is a raw material that is polymerized by the plasma polymerization apparatus 100 to form a polymer film on the surface of the substrate 20.
Such a liquid film material is vaporized by the vaporizer 192 and is supplied into the chamber 101 as a gaseous film material (raw material gas). The source gas will be described in detail later.

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

The diffusion plate 195 has a function of promoting the diffusion of the mixed gas supplied into the chamber 101. Thereby, the mixed gas can be dispersed in the chamber 101 with a substantially uniform concentration.
The pump 170 exhausts the inside of the chamber 101, and is composed of, for example, an oil rotary pump or a turbo molecular pump. Thus, by exhausting the chamber 101 and reducing the pressure, the gas can be easily converted into plasma. In addition, contamination and oxidation of the base material 20 due to contact with the air atmosphere can be prevented, and reaction products resulting from the plasma treatment can be effectively removed from the chamber 101.
The exhaust port 104 is provided with a pressure control mechanism 171 that adjusts the pressure in the chamber 101. Thereby, the pressure in the chamber 101 is appropriately set according to the operation state of the gas supply unit 190.

Next, a method for producing the first bonding film 31 on the substrate 20 using the plasma polymerization apparatus 100 will be described.
The first bonding film 31 is obtained by supplying a mixed gas of a source gas and a carrier gas in a strong electric field to polymerize molecules in the source gas and deposit a polymer on the substrate 20. be able to. This will be described in detail below.

First, the base material 20 is prepared.
Next, the base material 20 is accommodated in the chamber 101 of the plasma polymerization apparatus 100.
Next, the gas supply unit 190 is operated to supply a mixed gas of the source gas and the carrier gas into the chamber 101. The supplied mixed gas is filled in the chamber 101.
Here, the ratio (mixing ratio) of the source gas in the mixed gas is slightly different depending on the type of the source gas and the carrier gas, the target film forming speed, and the like. For example, the ratio of the source gas in the mixed gas is 20 It is preferable to set it to about volume% or more and 70 volume% or less, and it is more preferable to set to about 30 volume% or more and 60 volume% or less. As a result, it is possible to optimize the conditions for formation (film formation) of the polymer film.

Further, the flow rate of the gas to be supplied is appropriately determined depending on the type of gas, the target film formation rate, the film thickness, etc., and is not particularly limited, but usually the flow rates of the source gas and the carrier gas are respectively It is preferably set to about 1 ccm or more and 100 ccm or less, and more preferably set to about 10 ccm or more and 60 ccm or less.
Next, the power supply circuit 180 is activated, and a high frequency voltage is applied between the pair of electrodes 130 and 140. As a result, gas molecules existing between the pair of electrodes 130 and 140 are ionized to generate plasma. Molecules in the raw material gas are polymerized by the energy of the plasma, and the polymer is adhered and deposited on the substrate 20. Thereby, the first bonding film 31 made of a plasma polymerization film is formed. Thereby, the first bonding film 31 made of a plasma polymerization film is formed.

Moreover, the surface of the base material 20 is activated and cleaned by the action of plasma. For this reason, the polymer of the source gas is easily deposited on the surface of the base material 20, and the first bonding film 31 can be stably formed. Thus, according to the plasma polymerization method, the first bonding film 31 can be reliably formed on the base material 20 regardless of the constituent material of the base material 20.
Examples of the source gas include organosiloxanes such as methylsiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, and methylphenylsiloxane.

The plasma polymerized film obtained using such a raw material gas is composed of a polymer obtained by polymerizing these raw materials, that is, a polyorganosiloxane.
In the plasma polymerization, the frequency of the high frequency applied between the pair of electrodes 130 and 140 is not particularly limited, but is preferably about 1 kHz to 100 MHz, and more preferably about 10 MHz to 60 MHz.

The high frequency output density is not particularly limited, but is preferably about 0.01 W / cm ² or more and 100 W / cm ² or less, more preferably about 0.05 W / cm ² or more and 50 W / cm ² or less. Preferably, it is about 0.05 W / cm ² or more and about 1 W / cm ² or less. By setting the high-frequency power density within the above range, the Si skeleton 301 having a random atomic structure can be reliably secured while preventing the plasma gas from being added to the source gas more than necessary because the high-frequency power density is too high. Can be formed. That is, when the high-frequency power density is lower than the lower limit value, there is a possibility that the polymerization reaction cannot be caused in the molecules in the raw material gas and the first bonding film 31 cannot be formed. On the other hand, when the high-frequency output density exceeds the upper limit, the structure that can become the leaving group 303 is separated from the Si skeleton 301 due to decomposition of the raw material gas or the like, and in the obtained first bonding film 31. There is a possibility that the content of the leaving group 303 is lowered, or the randomness of the Si skeleton 301 is lowered (regularity is increased).

The pressure in the chamber 101 at the time of film formation is preferably about 133.3 × 10 ⁻⁵ Pa to 1333 Pa (1 × 10 ⁻⁵ Torr to 10 Torr), preferably 133.3 × 10 ⁻⁴ Pa. More preferably, it is about 133.3 Pa or less (1 × 10 ⁻⁴ Torr or more and 1 Torr or less).
The raw material gas flow rate is preferably about 0.5 sccm to 200 sccm, more preferably about 1 sccm to 100 sccm. On the other hand, the carrier gas flow rate is preferably about 5 sccm or more and 750 sccm or less, and more preferably about 10 sccm or more and 500 sccm or less.

The treatment time is preferably about 1 minute to 30 minutes, and more preferably about 1 minute to 15 minutes.
Moreover, it is preferable that the temperature of a base material is 25 degreeC or more, and it is more preferable that it is about 25 degreeC or more and 100 degrees C or less.
As described above, the first bonding film 31 shown in FIG. 3A is obtained. Similarly, the second bonding film 32 is obtained.

  Note that the first bonding film 31 and the second bonding film 32 have relatively high translucency depending on the thickness thereof. Then, by appropriately setting conditions for forming the first bonding film 31 and the second bonding film 32 (conditions for plasma polymerization, composition of raw material gas, etc.), the first bonding film 31 and the second bonding film The refractive index of the film 32 can be adjusted. Specifically, the refractive index of the first bonding film 31 and the second bonding film 32 can be increased by increasing the power density of the high frequency during the plasma polymerization, and conversely, the high frequency during the plasma polymerization. By reducing the output density, the refractive index of the first bonding film 31 and the second bonding film 32 can be lowered.

  Specifically, according to the plasma polymerization method using a silane-based gas as a raw material, the first bonding film 31 and the second bonding film 32 having a refractive index range of about 1.35 to 1.6 are obtained. . Since the refractive index of the first bonding film 31 and the second bonding film 32 is close to the refractive index of quartz or quartz glass, for example, the first bonding film 31 and the second bonding film 32 pass through the optical path. It is preferably used when manufacturing an optical component having a structure in which a through hole penetrates. In addition, since the refractive indexes of the first bonding film 31 and the second bonding film 32 can be adjusted, the first bonding film 31 and the second bonding film 32 having a desired refractive index can be manufactured. .

[2] Next, the crystal vibrating piece 5 is housed in the recess 22 of the case 2 (second step). Then, the crystal vibrating piece 5 and the support portion 21 of the case 2 are fixed by the mount material 6.
[3] Next, as shown in FIG. 3B, energy is applied to a part of the bonding surface 231 of the case 2 through a mask 36. Thereby, a partial region 232 of the bonding surface 231 is activated (see FIG. 3C). Thereafter, the case 2 and the bonding film transfer sheet 10 are laminated so that the region to which the energy of the bonding surface 231 is applied and the first bonding film 31 are in close contact with each other. Thereby, the 1st temporary joining body 7 shown in FIG.3 (d) is obtained.

  Similarly, as shown in FIG. 3B, energy is applied to a part of the bonding surface 401 of the lid body 4 through a mask 37. As a result, a partial region 402 of the bonding surface 401 is activated (see FIG. 3C). Thereafter, the lid 4 and the bonding film transfer sheet 10 are laminated so that the energy-applied region of the bonding surface 401 and the second bonding film 32 are in close contact with each other. Thereby, another first temporary joined body 7 shown in FIG. 3D is obtained (third step).

Any method may be used to apply energy to each of the bonding surfaces 231 and 401. For example, a method of irradiating energy rays, a method of exposing to plasma (applying plasma energy), or exposure to ozone gas (chemical) And the like). By applying energy in this way, even when the activity of each of the bonding surfaces 231 and 401 is extremely low, it can be partially activated.
Among these, it is preferable that the method of applying energy to the bonding surfaces 231 and 401 is at least one of a method of exposing to plasma and a method of irradiating energy rays. According to such a method, the bonding surfaces 231 and 401 are activated efficiently.

  For the method of exposure to plasma, atmospheric pressure plasma is preferably used. According to atmospheric pressure plasma, plasma treatment can be easily performed without using expensive equipment such as decompression means. In addition to the direct plasma method in which plasma is generated in the vicinity of each of the bonding surfaces 231 and 401, a remote plasma method or a downflow plasma method in which the object to be processed and the plasma generation unit are separated is also preferable for this plasma treatment. Used. According to the direct plasma method, plasma is generated in the vicinity of each of the bonding surfaces 231 and 401, so that plasma processing can be performed efficiently and uniformly. In addition, when the object to be processed and the plasma generating part are separated as in the remote plasma method or the downflow plasma method, the object to be processed and the plasma generating part do not interfere with each other. 401) can be avoided from ion damage.

On the other hand, examples of energy rays include light such as ultraviolet light and laser light, electron beams, and particle beams.
Among these, it is preferable to use ultraviolet rays (for example, a wavelength of about 126 nm to about 300 nm) for the energy rays. According to such ultraviolet rays, a wide range can be processed in a shorter time without unevenness while preventing the characteristics of the bonding surfaces 231 and 401 from being significantly deteriorated. For this reason, activation of each joint surface 231 and 401 can be performed more efficiently. In addition, ultraviolet rays also have an advantage that they can be generated with simple equipment such as an ultraviolet lamp.

The wavelength of the ultraviolet light is more preferably about 160 nm to 200 nm.
Further, the time for irradiating with ultraviolet rays is not particularly limited as long as the chemical bond near the surfaces of the bonding surfaces 231 and 401 can be cut, but it is about 0.5 minutes to 30 minutes. Is preferable, and it is more preferably about 1 minute or more and 10 minutes or less.

  The bond surfaces 231 and 401 that are energized and activated in this manner have bond bonds that are not terminated (dangling bonds) and hydroxyl groups formed by contacting the bond hands with surrounding moisture ( OH group) is exposed. In addition, the above-mentioned “activate” means a state in which the bond near the surface of each of the bonding surfaces 231 and 401 and in the interior is cut, and an unterminated bond is generated, or a hydroxyl group is bonded to the bond. It means one of these states, or a state in which these states are mixed.

  On the other hand, the surfaces of the first bonding film 31 and the second bonding film 32 of the bonding film transfer sheet 10 also have unterminated bonds and hydroxyl groups (OH groups) formed by contacting the bonding hands with surrounding moisture. ) Are preferably bonded. In such a state, the bonding strength between the bonding surfaces 231 and 401 and the bonding films 31 and 32 is improved, and the airtightness of the crystal unit 1 is further increased. This effect is presumed to be due to the following phenomenon.

When the first bonding film 31 and the bonding surface 231 are brought into contact with each other, or when the second bonding film 32 and the bonding surface 401 are brought into contact with each other, the hydroxyl groups present on the respective bonding surfaces 231 and 401 and the respective bonding The hydroxyl groups present in the films 31 and 32 attract each other by hydrogen bonding, and an attractive force is generated between the hydroxyl groups.
Further, the hydroxyl groups attracting each other by this hydrogen bond are dehydrated and condensed depending on the temperature condition or the like. As a result, at the contact interfaces between the bonding films 31 and 32 and the bonding surfaces 231 and 401, the bonds in which the detached OH groups are bonded are bonded through oxygen atoms. Thereby, each bonding film 31 and 32 and each bonding surface 231 and 401 are joined more firmly.
In order to form a state in which hydroxyl groups are bonded to the bonding films 31 and 32, the energy application method as described above may be applied to the bonding films 31 and 32.

  In addition, each of the bonding surfaces 231 and 401 to which energy is applied may include an active bond that is not terminated (dangling bond). Furthermore, the bonding surfaces 231 and 401 may be in a state where hydroxyl groups and dangling bonds are mixed. When dangling bonds are included in the respective bonding surfaces 231 and 401, the dangling bonds exposed to the surfaces of the respective bonding films 31 and 32 are stronger than those derived from the covalent bond constructed in a network shape. Joining is done. As a result, the case 2 and the lid 4 can be joined more firmly.

  It should be noted that the activated bonding surfaces 231 and 401 to which energy is applied have their active states relaxed over time. For this reason, it is preferable that the bonding surfaces 231 and 401 are laminated with the bonding films 31 and 32 as soon as possible after energy is applied. Specifically, it is preferable to laminate within 60 minutes after application of energy, and more preferably within 5 minutes. Within such a time, since the surfaces of the bonding surfaces 231 and 401 maintain a sufficiently active state, a sufficient bonding strength can be obtained when they are bonded.

  By the way, in the conventional solid bonding such as silicon direct bonding and optical contact, even if the surface is activated, the active state is maintained only for a very short time of several seconds to several tens of seconds in the atmosphere. For this reason, after the surface was activated, there was a problem that it was not possible to ensure sufficient time for performing operations such as bonding the two members to be joined together.

On the other hand, according to the present invention, the active state can be maintained for a relatively long time of several minutes or more even after energy is applied. For this reason, the time required for the work can be sufficiently secured, and the efficiency of the joining work can be improved.
In the two first temporary joined bodies 7 thus obtained, the bonding strength between the bonding film transfer sheet 10 and each of the bonding surfaces 231 and 401 is preferably 5 MPa (50 kgf / cm ² ) or more. More preferably (100 kgf / cm ² ) or more. The first temporary bonded body 7 having such bonding strength peels off at the interface between the bonding films 31 and 32 and the bonding surfaces 231 and 401 when the substrate 20 is peeled off in a process described later. Can be surely prevented.
For laminating the bonding film transfer sheet 10 and the bonding surfaces 231 and 401, various laminating apparatuses and various pressing apparatuses are used.

Here, in order to apply energy to a partial region 232 of the bonding surface 231, a mask 36 is disposed above the bonding surface 231 as shown in FIG. The mask 36 has a window portion 361 having a planar view shape corresponding to the region 232.
Similarly, in order to apply energy to a partial region 402 of the bonding surface 401, a mask 37 is disposed above the bonding surface 401 as shown in FIG. The mask 37 has a window portion 371 having a shape in plan view corresponding to the region 402.

  And each area | region 232,401 can be selectively activated by irradiating an energy beam, for example through such a mask 36,37. That is, by appropriately setting the planar view shapes of the window portions 361 and 371, the regions 232 and 402 to be activated on the bonding surfaces 231 and 401 can be easily selected (patterned). As a result, in the steps to be described later, only the regions of the bonding films 31 and 32 that are in contact with the regions 232 and 402 are partially transferred to the bonding surfaces 231 and 401. In this way, the bonding area is optimized by appropriately selecting the shape (pattern) of each of the regions 232 and 402, rather than bonding all over the bonding surfaces 231 and 401, and the bonding interface after bonding is achieved. It is possible to reduce the stress concentration generated in

  Here, FIG. 3C shows a plan view shape of a part of the region 232 of the joint surface 231 and a plan view shape of a part of the region 402 of the joint surface 401. As shown below, the plan view shape of the region 232 is a pattern having a frame shape with four corners missing, while the plan view shape of the region 402 is arranged corresponding to the location where the region 232 is missing. In addition, it is a triangular island pattern.

The planar view shape of the region 232 and the planar view shape of the region 402 are reflected in the planar view shape of the first bonding film 31 and the planar view shape of the second bonding film 32 transferred to the case 2 and the lid body 4. However, these shapes are configured such that when the second temporary joined bodies 8 are overlapped with each other, the non-deposition regions are complemented with each other. As a result, the combined pattern of the transfer pattern of the first bonding film 31 and the transfer pattern of the second bonding film 32 is a pattern that forms a completely closed frame shape. As a result, the bonding film 3 formed by integrating the first bonding film 31 and the second bonding film 32 surrounds the periphery of the recess 22 without any gap, and the recess 22 can be hermetically sealed.
From this point of view, the shape of the window portion 361 of the mask 36 that defines the region 232 and the shape of the window portion 371 of the mask 37 that defines the region 402 are also set to satisfy the above relationship.

FIG. 4 is a plan view showing the configuration of the mask 36 and the mask 37.
The mask 36 shown in FIG. 4A has a quadrangular shape in plan view, and a first shielding portion 362 that shields the concave portion 22 of the case 2 is disposed at the center thereof. In addition, a second shielding part 363 that shields a region outside the joint surface 231 via the window part 361 is disposed outside the first shielding part 362. In addition, the 1st shielding part 362 has comprised the substantially square shape in planar view, and the 2nd shielding part 363 has comprised the square frame shape. The first shielding part 362 and the second shielding part 363 are connected via four connecting parts 364 provided corresponding to the four corners of the quadrangle. Such a mask 36 makes it possible to apply energy to a part of the region 232 in the bonding surface 231.

  On the other hand, the mask 37 shown in FIG. 4B also has a quadrangular shape in plan view, and four window portions 371 each having a triangular shape are arranged in the vicinity of the four corners. The arrangement of the four window portions 371 corresponds to the arrangement of the four connecting portions 364 described above, and is configured to include the four connecting portions 364. Thereby, the region 402 can surely complement the non-energy application region in the region 232. As a result, the first bonding film 31 and the second bonding film 32 that are partially transferred to these regions 232 and 402 can complement the non-film-forming regions of these regions. Since the bonding film 3 formed by integrating 31 and 32 becomes a completely closed frame-shaped film, the concave portion 22 can be surely hermetically sealed.

By integrating the bonding films 31 and 32 in this way, the bonding film 3 having a complicated plan view shape can be easily formed.
Further, the planar view shape of the region 232 and the planar view shape of the region 402 are not particularly limited, but preferably overlap at least in the vicinity of the connection portion. As a result, the positions of the mask 36 and the mask 37 are shifted or the case 2 to which the first bonding film 31 is transferred and the lid 4 to which the second bonding film 32 is transferred are overlapped. Even if it shifts, it is possible to absorb the displacement in the overlapping portion and prevent the airtightness of the recess 22 from being impaired. That is, since the tolerance of various variations in the manufacturing process can be expanded, manufacturing efficiency can be increased.

In addition, when irradiating an energy beam to a part of the regions 232 and 402 instead of the entire surfaces of the bonding surfaces 231 and 401, if the energy beam to be used has high directivity such as a laser beam or an electron beam Irradiation can be performed without using the masks 36 and 37.
Further, energy may be applied to the bonding films 31 and 32 as necessary. In this case, the various energy applying methods described above can be applied.

  [4] Next, as shown by an arrow in FIG. 5 (e), the base material 20 is peeled from each first temporary joined body 7. This peeling is performed by peeling the base material 20 from each first temporary joined body 7 (fourth step). As a result, a portion of the first bonding film 31 corresponding to the region 232 is transferred to the bonding surface 231 of the case 2, and the region 402 of the second bonding film 32 is the region 402. A second temporary joined body 8 obtained by transferring a part corresponding to the above to the joining surface 401 of the lid body 4 is obtained (see FIG. 5F).

  Note that the upper surfaces of the bonding films 31 and 32 transferred to the two obtained second temporary bonded bodies 8 are peeled surfaces separated from the base material 20, respectively. Further, as shown in the plan view on the upper side of FIG. 5F, the film formation pattern of the transferred bonding films 31 and 32 is the same as the plan view shape of the regions 232 and 402 to which energy is applied. . The shape in plan view is the same, but the direction of the shape is reversed by transfer.

[5] Next, energy is applied to the upper surfaces (peeling surfaces) of the bonding films 31 and 32 of the second temporary bonding bodies 8 (see FIG. 6G).
Examples of the method for applying energy to the bonding films 31 and 32 include the same method as the method for applying energy described above. In particular, at least one of a method of exposing to plasma and a method of irradiating energy rays is preferably used. It is done. These methods can activate the bonding films 31 and 32 efficiently.

Among these, atmospheric pressure plasma is preferably used in the method of exposing to plasma.
When energy is applied, adhesiveness develops in the first bonding film 31 and the second bonding film 32.
Next, as shown in FIG. 6H, the two second temporary joined bodies 8 are overlapped so that the joining surface 231 and the joining surface 401 face each other. Thereby, the first bonding film 31 and the second bonding film 32 are integrated to obtain the bonding film 3, and the case 2 and the lid body 4 are bonded by the bonding film 3. As a result, the concave portion 22 is hermetically sealed, and the crystal resonator 1 shown in FIG. 6I is obtained (fifth step).

Here, the recess 22 is hermetically sealed to form a closed space. At this time, the surrounding environment is confined in the closed space. In the sealed device such as the crystal unit 1, the surrounding environment in this process is important because the environment of the closed space greatly affects the reliability of the device as described above.
Specifically, the ambient environment in this step is preferably a reduced pressure atmosphere or an inert gas atmosphere. As a result, the closed space becomes an inert environment, and the device can be prevented from being deteriorated or deteriorated over a long period of time. When the pressure is further reduced, resistance in the operation of the movable device such as the crystal vibrating piece 5 is suppressed, so that the movable accuracy is improved. As a result, the crystal resonator 1 having excellent characteristics can be obtained.
In addition, after obtaining the crystal unit 1, one or both of the following two steps [6A] and [6B] may be performed as necessary.

[6A] The obtained crystal resonator 1 is pressurized in a direction in which the case 2 and the lid 4 approach each other. Thereby, the bonding films 31 and 32 are closer to the bonding surfaces 231 and 401, and the bonding strength of the crystal unit 1 can be further increased.
At this time, the pressure at the time of pressurizing the crystal unit 1 is preferably as high as possible. Thereby, the joint strength in the crystal unit 1 can be increased according to this pressure.

In addition, what is necessary is just to adjust this pressure suitably according to conditions, such as a constituent material and thickness of case 2 and the cover body 4, and a joining apparatus. Specifically, it is preferably about 1 MPa or more and 10 MPa or less, and more preferably about 1 MPa or more and 5 MPa or less.
The time for pressurization is not particularly limited, but is preferably about 10 seconds to 30 minutes.

[6B] The obtained crystal unit 1 is heated. Thereby, the joint strength in the crystal unit 1 can be further increased.
At this time, the temperature at which the crystal unit 1 is heated is not particularly limited as long as it is higher than room temperature and lower than the heat-resistant temperature of the crystal unit 1, but is preferably about 25 ° C. or more and 100 ° C. or less, and more preferably. Is about 50 ° C. or more and 100 ° C. or less. Heating at a temperature in such a range can reliably increase the bonding strength while preventing the quartz resonator 1 from being altered or deteriorated by heat.

Moreover, although heating time is not specifically limited, It is preferable that it is about 1 minute or more and 30 minutes or less.
Moreover, when performing both said process [6A] and [6B], it is preferable to perform these simultaneously. That is, it is preferable to heat the crystal unit 1 while applying pressure. Thereby, the effect by pressurization and the effect by heating are exhibited synergistically, and the bonding strength of the crystal unit 1 can be particularly increased.

When the thermal expansion coefficients of the case 2 and the lid 4 are substantially equal, it is preferable to heat the crystal unit 1 as described above, but the thermal expansion coefficients of the two adherends are greatly different. In some cases, it is preferable to perform bonding at as low a temperature as possible. By performing the bonding at a low temperature, it is possible to further reduce the thermal stress generated at the bonding interface.
Specifically, although it depends on the difference in thermal expansion coefficient, it is preferable to heat at about 25 ° C. or more and 50 ° C. or less, and more preferably about 25 ° C. or more and 40 ° C. or less. In such a temperature range, even if the difference in thermal expansion coefficient is large to some extent (for example, 5 × 10 ⁻⁵ / K or more), the thermal stress generated at the bonding interface can be sufficiently reduced. As a result, it is possible to reliably prevent the crystal resonator 1 from being warped or peeled off.

By performing the steps [6A] and [6B] as described above, the bonding strength in the crystal unit 1 can be further improved.
The crystal resonator 1 manufactured in this way has such characteristics because the bonding films 31 and 32 are excellent in bonding strength, chemical resistance and dimensional accuracy.
In particular, the quartz resonator 1 is not a bond based on a physical bond such as an anchor effect like an adhesive used in a conventional bonding method, but a strong chemical that occurs in a short time like a covalent bond. Bonding is based on bonding. For this reason, the crystal unit 1 is extremely difficult to peel off, and uneven bonding or the like hardly occurs.

In addition, unlike conventional solid bonding, heat treatment at a high temperature (about 700 ° C. or more and about 800 ° C. or less) is not required, so that an adherend made of a material having low heat resistance can also be used for bonding. it can. Thereby, the restriction of the constituent materials of the case 2 and the lid 4 is eliminated, and the range of material selection can be expanded.
As described in [5] above, each of the bonding films 31 and 32 has a characteristic of developing adhesiveness when energy is applied thereto. In order to define the transfer region of 32, energy is not given to a predetermined region of each of the bonding films 31, 32, but the case 2 and the lid 4 which are bonding partners of the bonding films 31, 32 in [3]. Energy is applied to a predetermined region of the bonding surface. Thereby, the surface energy of the area | region where the energy of the joining surfaces 231 and 401 of case 2 and the cover body 4 was provided can be made relatively large with respect to the area | region where energy is not provided. Thereby, in the part corresponding to the area | region to which energy was provided, while each joining film 31 and 32 is transcribed, since the total amount of energy given to each joining film 31 and 32 can be minimized, Deterioration and deterioration of the bonding films 31 and 32 due to energy application can be minimized, and a highly reliable bonding can be realized.

Moreover, energy may be applied to the bonding films 31 and 32 to develop adhesiveness. In this case, a stronger bonded state can be obtained, but adhesiveness also appears in the regions where the energy of the bonding surfaces 231 and 401 of the case 2 and the lid 4 is not applied. Therefore, in order to transfer the bonding film only to the region to which the energy of the bonding surfaces 231 and 401 is applied,
(Surface energy of regions where energy is not applied to bonding surfaces 231 and 401) <(Surface energy of base material 20 of bonding film transfer sheet 10) <(Surface energy of regions where energy is applied to bonding surfaces 231 and 401)
The surface energy may be controlled by selecting the material of the base material 20 of the bonding film transfer sheet 10 so as to satisfy this relationship or by adjusting the energy application conditions.

  In addition, by using the masks 36 and 37, regions (regions 232 and 402) for applying energy to the bonding surfaces 231 and 401 are selected, and the bonding films 31 and 32 transferred to the case 2 and the lid 4 are selected. The pattern can be freely controlled. Therefore, by optimizing the shape and area of each bonding film 31 and 32 to be transferred, local concentration of stress generated in the bonding portion can be reduced. Thereby, the thermal expansion difference which arises in the joining interface of the crystal oscillator 1 can be relieved.

Further, the bonding film transfer sheet 10 used for the production of the quartz crystal resonator 1 has a sheet-like form that is easy to handle and suitable for distribution and storage, and simply applies physical or chemical energy. Strong adhesiveness can be freely expressed. For this reason, the bonding film transfer sheet 10 has excellent affinity for mass production processes of various products.
Specifically, since the bonding film included in the bonding film transfer sheet 10 has conventionally been required to be directly formed on the surface of the member to be bonded, a member is prepared where the film forming apparatus is installed. There was a need to do. This is because the film forming apparatus is large and heavy, and cannot be moved easily. However, when there is a geographical restriction that the film forming apparatus and the member are inseparable as described above, there is a problem that the flow line of the member is limited, and the degree of freedom of the manufacturing process of the product is lowered. .

  On the other hand, according to the present invention, the process of forming the bonding film and the process of bonding the members can be performed at different locations. For this reason, if a large amount of the bonding film transfer sheet 10 is manufactured, the bonding film transfer sheet 10 can be transported to a desired location and the members can be bonded at the desired location. As a result, the degree of freedom in the manufacturing process of the crystal unit 1 is dramatically increased, and the mass production efficiency can be improved.

  Further, according to the present invention, when the two second temporary bonded bodies 8 are bonded to each other, the peeling surfaces of the bonding films 31 and 32 become the bonding interface. Since this peeling surface is in contact with the base material 20 just before peeling and is protected from adhesion or damage of foreign matter, it is in a state suitable for good bonding. Furthermore, even if energy is applied to the bonding films 31 and 32 as necessary in the third step, the leaving group is difficult to be removed in the vicinity of the release surface, so that the state immediately after the film formation is easily maintained, and adhesion is achieved. There is also an advantage that sex can be sufficiently latent. Therefore, by applying energy to the peeling surface, the peeling surface is firmly bonded to the bonding surfaces 231 and 401. If the bonding film transfer sheet 10 is used in this manner, the bonding films 31 and 32 whose expression of adhesiveness can be freely controlled by applying energy can be handled like a double-sided tape. Can be easily and firmly joined.

  Furthermore, according to the present invention, the bonding film is formed by transfer, and it is not necessary to form the bonding film directly on the surface of the member to be bonded. There is no need to expose to harsh environments. Further, there is no possibility that the bonding film is formed in a region where it is not desired to adhere. For this reason, for example, it is possible to prevent the bonding film from adhering to the upper side of the quartz crystal vibrating piece 5 and dropping to change the characteristics of the quartz crystal vibrating piece 5. As a result, the quartz resonator 1 having high airtightness and high reliability can be manufactured.

Further, the bonding interface in the obtained crystal unit 1 is excellent in both airtightness and liquid tightness. This is because each of the bonding films 31 and 32 has a high density and low air permeability, and the bonding mechanism is based on the chemical bond as described above, so that the passage of small molecules is restricted. . Therefore, when the crystal resonator 1 as shown in FIG. 1 is manufactured, the airtightness of the obtained closed space is 1 × 10 ⁻⁹ Pa · m ^{3 //} in terms of the leak amount (leak rate) using helium gas. It can be expected to be less than sec. With such a leak amount, the hermeticity of the closed space can be maintained over a long period of time. Therefore, when the quartz resonator 1 in which the closed space is maintained in a reduced pressure state or replaced with a predetermined gas is manufactured. In addition, the present invention is effectively used.
Further, the bonding strength between the case 2 and the lid 4 in the crystal unit 1 is preferably 5 MPa (50 kgf / cm ² ) or more, and more preferably 10 MPa (100 kgf / cm ² ) or more. With such a bonding strength, peeling of the bonding interface and hermetic failure can be reliably prevented, and the crystal resonator 1 with high reliability can be obtained.

(Other configuration example 1)
FIG. 10: is sectional drawing which shows the other structural example 1 of the manufacturing method (joining method of this invention) of the sealing type device of this invention.
Hereinafter, another configuration example 1 of the method of manufacturing the crystal unit 1 will be described with reference to FIG. In FIG. 10, the same components as those in FIG. 3 are denoted by the same reference numerals as those in FIG. 3, and detailed description thereof is omitted.

In this configuration example, in the first step, only one bonding film transfer sheet 10 is prepared, and energy is applied to a closed frame-shaped region set on the bonding surface 401 of the lid 4, and bonding is performed to this region. Except for the partial transfer of the film, it is the same as the above configuration example.
That is, in the first step, the bonding film transfer sheet (base material with bonding film) 10 having the base material 20 and the second bonding film 32 formed thereon, the case 2 and the lid 4 Prepare.

Next, the crystal vibrating piece 5 is housed in the recess 22 in the same manner as in the above configuration example.
Next, a mask 38 shown in FIG. 10 is prepared.
The mask 38 has a quadrangular shape in plan view, and is provided in the vicinity of the edge thereof. Have.
Next, as shown in FIG. 10A, the mask 38 is disposed above the bonding surface 401 of the lid 4. Then, energy is applied to the lid body 4 through the mask 38. As a result, the L-shaped region 403 corresponding to the window 381 of the mask 38 in the lid 4 is activated.

Subsequently, as shown in FIG. 10B, the mask 38 is horizontally rotated by 180 ° from the arrangement of FIG. Then, energy is applied to the lid 4 again through the mask 38. Thereby, the area | region 404 which rotated the area | region 403 180 degrees among the cover bodies 4 is activated. As a result, the region formed by combining the region 403 and the region 404 is a rectangular closed frame region. Thus, the closed frame-like regions 403 and 404 are activated, and the second bonding film 32 is partially transferred to these regions 403 and 404 in the fourth step.
Thereafter, in the same manner as in the above configuration example, the concave portion 22 is hermetically sealed, and the crystal resonator 1 is obtained.

In the above configuration example, the same operation and effect as in the above configuration example can be obtained, and since only one bonding film transfer sheet 10 and one mask 38 are used, the manufacturing cost can be reduced and the manufacturing method can be reduced. Simplification can be achieved.
In the above description, the bonding film is transferred only to the lid 4. However, the bonding film may be transferred only to the case 2.

(Other configuration example 2)
FIG. 11: is sectional drawing which shows the other structural example 2 of the manufacturing method (joining method of this invention) of the sealing type device of this invention.
Hereinafter, another configuration example 2 of the method of manufacturing the crystal unit 1 will be described with reference to FIG. In FIG. 11, the same components as those in FIG. 6 are denoted by the same reference numerals as those in FIG. 6, and detailed description thereof is omitted.

This configuration example is the same as the configuration example described above except that the case 2 and the lid body 4 are overlapped before energy is applied and energy is applied thereafter.
In this configuration example, two second temporary joined bodies 8 shown in FIG. 5F are prepared.
Next, without applying energy to the first bonding film 31 and the second bonding film 32, as shown in FIG. 11A, the two first films 231 and the bonding surface 401 face each other. Two temporary joined bodies 8 are overlapped. Thereby, the 3rd temporary joined body 9 shown in FIG.11 (b) is obtained. Since the adhesive films 31 and 32 in the third temporary bonded body 9 do not exhibit adhesiveness at this stage, the positions of the two second temporary bonded bodies 8 in the third temporary bonded body 9 are determined. The relative position can be finely adjusted by shifting.

Next, as shown by an arrow in FIG. 11C, energy is applied to the third temporary joined body 9. Thereby, adhesiveness develops in each bonding film 31 and 32, and these bonding films are integrated and the bonding film 3 is formed. Further, the concave portion 22 is hermetically sealed by the bonding film 3, and the crystal resonator 1 shown in FIG. 11D is obtained (fifth step).
As a method for applying energy to the third temporary joined body 9, a method similar to the above-described energy applying method is used, but here, a method for applying compressive force will be described.

  The compressive force applied to the third temporary joined body 9 is preferably about 0.2 MPa or more and 10 MPa or less, and more preferably about 1 MPa or more and 5 MPa or less. Thereby, in each bonding film 31 and 32, the adhesiveness can be expressed sufficiently and necessary. Although this pressure may exceed the upper limit, damage or the like may occur depending on the constituent materials of the case 2 and the lid 4.

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 when the third temporary joined body 9 is pressed, the more sufficient adhesiveness can be expressed even if the pressing time is shortened.
Note that the compression of the third provisional bonded body 9 may be performed in any atmosphere when airtight sealing is not required, but is preferably performed in an air atmosphere. Thereby, it is not necessary to spend time and cost to control the atmosphere, and the activation process can be performed more easily. When hermetic sealing is required, it is preferably performed in a reduced pressure atmosphere or an inert gas atmosphere. As a result, the closed space becomes an inert environment, and the device can be prevented from being deteriorated or deteriorated over a long period of time. When the pressure is further reduced, resistance in the operation of the movable device such as the crystal vibrating piece 5 is suppressed, so that the movable accuracy is improved. As a result, the crystal resonator 1 having excellent characteristics can be obtained.
In the configuration example as described above, the same operation and effect as the configuration example described above can be obtained.

As mentioned above, although the joining method of this invention and the manufacturing method of the sealing type device of this invention were demonstrated based on embodiment of illustration, this invention is not limited to these.
For example, an arbitrary layer may be added between the case and the bonding film and between the lid and the bonding film in the crystal resonator. Examples of such a layer include an intermediate layer that increases adhesion strength between layers, an intermediate layer that increases cushioning properties between layers, and an intermediate layer that has a function of relaxing stress concentration.

  Moreover, in the manufacturing method of the sealing type device of this invention, it is not limited to the structure of the said embodiment, The process for arbitrary objectives may be added 1 or 2 or more. Further, the order of each step is not limited to the configuration of the above-described embodiment. For example, in the first configuration example and the other configuration example 1, the device is accommodated after transfer of the bonding film or after application of energy. In another configuration example 2, the device may be accommodated after the bonding film is transferred.

  In the above-described embodiment, the crystal resonator is described as an example of the sealed device. However, the present invention can be applied to any other sealed device. The sealed device is a device having a joint that requires hermetic sealing. For example, piezoelectric devices such as piezoelectric actuators, piezoelectric vibrators, surface acoustic wave elements (SAW devices), fluorescent lamps, discharge lamps, Light emitting diodes, light emitting elements such as semiconductor lasers, light receiving elements such as photodiodes, liquid crystal display elements, organic EL elements, inorganic EL elements, display elements such as plasma displays and electrophoretic display elements, charge coupled devices (CCD) Image sensors such as complementary metal oxide semiconductors (CMOS), acceleration sensors, angular velocity sensors, various sensors such as pressure sensors, tunable filters, MEMS (Micro Electro Mechanical Systems) such as biosensors, optical connectors, Optical communication devices such as optical modulators, semiconductor elements such as IC packages, ID Grayed, a recording medium such as an IC card, wristwatch, and a medical instrument or the like to enclose any gas or liquid as the accommodated article.

Furthermore, the joining method of the present invention can be applied to joining any member or the like that does not require hermetic sealing in addition to the above-described manufacturing of the sealed device.
Specifically, semiconductor elements such as transistors, diodes, memories, reflectors, optical lenses, diffraction gratings, optical elements such as optical filters, photoelectric conversion elements such as solar cells, semiconductor substrates and semiconductors mounted on them Elements, insulating substrates and wiring or electrodes, inkjet recording heads, microreactors, MEMS (Micro Electro Mechanical Systems) parts such as micromirrors, package parts for semiconductor elements and electronic parts, magnetic recording media, magneto-optical recording media, When joining a recording medium such as an optical recording medium, fuel cell components, etc., the joining method of the present invention is applicable.

Next, specific examples of the present invention will be described.
1. Production of crystal unit (sealed device) (Example 1)
<1> First, two polyethylene films each having a width of 50 mm, a length of 100 mm, and an average thickness of 100 μm were prepared as substrates. The surface energy of polyethylene is 31 mN / m.
As a first member, an alumina case, an OA10 glass lid, and a quartz crystal vibrating piece as shown in FIG. 2 were prepared. The surface energy of alumina is 840 mN / m, and the surface energy of OA10 glass is 300 mN / m.

<2> Next, a plasma polymerization film having an average thickness of 200 nm was formed on the two substrates by the plasma polymerization apparatus 100 shown in FIG. The film forming conditions are as shown below.
<Film formation conditions>
-Source gas composition: Octamethyltrisiloxane-Source gas flow rate: 30 sccm
Carrier gas composition: Argon Carrier gas flow rate: 30 sccm
・ High-frequency power output: 250W
・ High frequency output density: 0.5 W / cm ²
-Chamber pressure: 5 Pa (low vacuum)
・ Processing time: 3 minutes ・ Substrate temperature: 60 ° C.
Thereby, a plasma polymerization film was formed on the substrate. And the joining film transfer sheet which consists of two layers of a base material and a plasma polymerization film | membrane was obtained.

  The plasma polymerized film thus formed is composed of a polymer of octamethyltrisiloxane (raw material gas), and includes a Si skeleton including a siloxane bond and a random atomic structure, and an alkyl group (desorbed). Group). Further, in order to measure the crystallinity of the Si skeleton, a part of the plasma polymerized film was irradiated with ultraviolet rays having a wavelength of 405 nm for 600 seconds, and then the crystallinity was measured by X-ray diffraction. As a result, the crystallinity of the plasma polymerized film was 30% or less.

<3> Next, the prepared case and lid were subjected to plasma treatment under the following conditions.
<Plasma treatment conditions>
・ Plasma treatment method: Direct plasma method ・ Process gas composition: Helium gas ・ Atmospheric pressure: Atmospheric pressure (100 kPa)
・ Distance between electrodes: 1mm
・ Applied voltage: 1 kVp-p
-Voltage frequency: 40 MHz
The plasma treatment for the case and the lid was performed through the mask shown in FIG. Thus, the plasma treatment was performed only on the region corresponding to the shape of the window portion of each mask in the joint surface of the case and the joint surface of the lid.

<4> Next, one minute after the plasma treatment was performed, the bonding film transfer sheet, the case, and the lid were laminated so that the plasma polymerization film and the case, and the plasma polymerization film and the lid were in contact with each other. The obtained laminate was compressed at 5 MPa. As a result, two first temporary joined bodies were obtained.
<5> Next, the base material was peeled off from the first temporary joined body. As a result, a bonding film having a shape corresponding to the shape of the window portion of the mask was transferred to the case and the lid. As a result, two second temporary joined bodies were obtained.

<6> Next, plasma treatment was performed on the plasma polymerization film of the second temporary joined body in the same manner as in <3>.
<7> Next, one minute after the plasma treatment was performed, the two second temporary joined bodies were overlapped with each other so that the joint surfaces face each other. Thus, the two second temporary joined bodies were joined to obtain a crystal resonator. This superposition operation was performed in a reduced pressure atmosphere.
Next, the obtained crystal resonator was compressed at 5 MPa.

(Example 2)
First, a mask was placed on the lid as shown in FIG. 10A and plasma treatment was performed.
Next, the arrangement of the mask was changed as shown in FIG. 10B, and plasma treatment was performed again.
Thereafter, one minute after the plasma treatment was performed, the bonding film transfer sheet and the lid were laminated so that the plasma polymerized film and the lid were in contact with each other. The obtained laminate was compressed at 5 MPa. As a result, a first temporary joined body was obtained.

Next, the base material was peeled off from the first temporary joined body. Thereby, a quadrangular closed frame-shaped bonding film corresponding to the composition of the shape of the window portion of the mask when the plasma treatment was performed twice on the lid was transferred. As a result, a second temporary joined body was obtained.
Next, the plasma treatment was performed on the plasma polymerization film of the second temporary joined body in the same manner as described above.
Next, one minute after the plasma treatment was performed, the second temporary joined body and the case were overlapped so that the joint surfaces face each other. As a result, the second temporary joined body and the case were joined to obtain a crystal resonator. This superposition operation was performed in a reduced pressure atmosphere.
Next, the obtained crystal resonator was compressed at 5 MPa.

(Example 3)
A crystal resonator was obtained in the same manner as in Example 1 except that the step of applying energy and the step of overlapping the case and the lid were replaced.
Example 4
A crystal resonator was obtained in the same manner as in Example 1 except that the base material was changed to a polyethylene terephthalate (PET) film having a width of 50 mm, a length of 100 mm, and an average thickness of 100 μm. The surface energy of polyethylene terephthalate is 43 mN / m.

(Example 5)
A crystal resonator was obtained in the same manner as in Example 1 except that the base material was changed to a polytetrafluoroethylene (PTFE) film having a width of 50 mm, a length of 100 mm, and an average thickness of 100 μm. The surface energy of polytetrafluoroethylene is 18 mN / m.
(Example 6)
A crystal resonator was obtained in the same manner as in Example 1 except that the substrate was changed to a polyimide film having a width of 50 mm, a length of 100 mm, and an average thickness of 50 μm. The surface energy of polyimide is 50 mN / m.

(Comparative Example 1)
A crystal resonator was obtained in the same manner as in Example 1 except that the case and the lid were bonded with an epoxy adhesive. The average thickness of the epoxy adhesive was 200 μm.
(Comparative Example 2)
First, a crystal case and a glass lid were prepared. Then, a crystal resonator was obtained in the same manner as in Example 1 except that the case and the lid were joined by anodic bonding.

2. 2. Evaluation of Quartz Crystal Resonator (Encapsulated Device) 2.1 Evaluation of Bond Strength Bond strength was measured for each of the crystal resonators obtained in the examples and comparative examples.
The measurement of the bonding strength was performed by measuring the pulling force immediately before the case and the lid were peeled off in each bonded body. Further, the measurement of the bonding strength was performed immediately after the bonding and after the temperature cycle from −40 ° C. to 125 ° C. was repeated 50 times after the bonding.
As a result, the crystal resonators obtained in each example had sufficient bonding strength (10 MPa or more) immediately after bonding and after temperature cycling.
On the other hand, for the crystal resonators obtained in each comparative example, the bonding strength was very small and could not be measured.

2.2 Evaluation of Leakage Amount of leakage was measured for the crystal resonators obtained in the examples and comparative examples.
The leak amount was measured by a vacuum method using a leak detector. Helium gas was used as the probe gas.

Further, the amount of leakage was measured immediately after bonding and after the temperature cycle of 2.1.
As a result, in the crystal resonators obtained in each example, the leak amount was less than 1 × 10 ⁻⁹ Pa · m ³ / sec immediately after bonding and after the temperature cycle.
On the other hand, the crystal resonators obtained in the respective comparative examples had too much leakage and could not be measured.
From the above evaluation results, it has been clarified that the crystal resonators obtained in the respective examples have excellent bonding strength and airtightness even after a temperature cycle.

2.3 Evaluation of Oscillation Characteristics With respect to the crystal resonators obtained in the examples and the comparative examples, the oscillation characteristics after each 2.1 temperature cycle were evaluated.
As a result, the characteristics of the crystal resonators obtained in each example were all within the characteristic range assumed at the time of design.
On the other hand, the characteristics of the crystal resonators obtained in the comparative examples were all out of the characteristic range assumed at the time of design.

  DESCRIPTION OF SYMBOLS 1 ... Quartz crystal vibrator 10 ... Bonding film transfer sheet 20 ... Base material 2 ... Case 21 ... Supporting part 22 ... Recessed part 23 ... Side wall 231 ... Joining surface 232 ... Area 24 ... Bottom part 3 ... ... bonding film 31 ... first bonding film 32 ... second bonding film 301 ... Si skeleton 302 ... siloxane bond 303 ... leaving group 304 ... active hand 35 ... surface 36, 37, 38 ... ... Masks 361, 371, 381 ... Window part 362 ... First shielding part 363 ... Second shielding part 364 ... Connecting part 4 ... Lid 401 ... Bonding surface 402, 403, 404 ... Area 5 ....... Crystal vibrating piece 6... Mount material 7... First temporary joined body 8... Second temporary joined body 9... Third temporary joined body 100. ... Grounding wire 103 ... Port 104 ... Exhaust port 130 ... First electrode 139 ... Electrostatic chuck 140 ... Second electrode 170 ... Pump 171 ... Pressure control mechanism 180 ... Power supply circuit 182 ... High frequency power supply 183 ... Matching Box 184 ... Wiring 190 ... Gas supply part 191 ... Liquid storage part 192 ... Vaporizer 193 ... Gas cylinder 194 ... Piping 195 ... Diffusion plate

Claims (14)

A bonding film including a base material, an atomic structure provided on one surface side of the base material and including a siloxane (Si-O) bond, and a leaving group bonded to the siloxane bond and including an organic group. A preparation step of preparing a substrate with a bonding film and a first member and a second member to be bonded so that the bonding surfaces thereof face each other;
The first member and the bonding film are provided such that energy is applied to a partial region of the bonding surface of the first member to activate the region, and the region and the bonding film are in close contact with each other. A temporary bonding step of laminating a base material with a base to obtain a first temporary bonded body;
A transfer step of peeling the base material from the first temporary bonded body, partially transferring the bonding film corresponding to the region to the first member, and obtaining a second temporary bonded body;
Energy is applied to the peeling surface of the bonding film transferred to the second temporary bonded body, the leaving group is released from the siloxane bond, and adhesiveness is exhibited, and the bonding surfaces face each other. Thus, a joining method comprising: a main joining step of stacking the second temporary joined body and the second member to obtain a joined body.   The bonding method according to claim 1, wherein in the temporary bonding step, energy is applied to the bonding film of the base material with the bonding film.   The bonding method according to claim 1, wherein the bonding film includes a Si—H bond.   The bonding method according to claim 1, wherein the bonding film is a plasma polymerization film.   The bonding method according to claim 1, wherein the base material has a release layer that is provided on a surface thereof and has a peelability for the bonding film.   6. The bonding method according to claim 1, wherein the energy is applied to the region by at least one of a method of exposing the region to plasma and a method of irradiating the region with energy rays.   The bonding method according to claim 1, wherein the energy is applied to the bonding film by at least one of a method of exposing the bonding film to plasma and a method of irradiating the bonding film with energy rays.   2. The method according to claim 1, comprising at least one of a step of heating the joined body and a step of pressurizing the joined body so that the first member and the second member approach each other after the main joining step. 8. The joining method according to any one of 7 above. In the preparation step, a first base material with a bonding film and a second base material with a bonding film similar to the base material with a bonding film are prepared,
In the temporary bonding step, the first member is configured such that energy is applied to a first region of a part of the bonding surface of the first member so that the first region and the bonding film are in close contact with each other. And the first substrate with the bonding film are laminated, and energy is applied to a second region of a part of the bonding surface of the second member, and the second region and the bonding film are Laminating the second member and the second substrate with a bonding film so as to closely adhere to obtain two first temporary bonded bodies,
In the transfer step, the base material is peeled off from the two first temporary joined bodies, the bonding film corresponding to the first region is partially transferred to the first member, and the first Partially transferring the bonding film corresponding to the region of 2 to the second member to obtain two second temporary bonded bodies,
In the main bonding step, energy is applied to the separation surfaces of the bonding films of the two second temporary bonded bodies, and the two second temporary bonded bodies are arranged so that the bonded surfaces face each other. The bonding method according to any one of claims 1 to 8, wherein a bonded body is obtained by laminating layers. A bonding film including a base material, an atomic structure including a siloxane (Si-O) bond provided on one surface side of the base material, and a leaving group formed of an organic group bonded to the siloxane bond; A first step of preparing a base member with a bonding film and a first member and a second member that can form a closed space inside by superimposing them so that their bonding surfaces face each other;
A second step of placing the device in a position that can be the closed space;
The first member and the bonding film are provided such that energy is applied to a partial region of the bonding surface of the first member to activate the region, and the region and the bonding film are in close contact with each other. A third step of laminating a substrate with a substrate to obtain a first temporary joined body;
A fourth step of peeling the base material from the first temporary bonded body, partially transferring the bonding film corresponding to the region to the first member, and obtaining a second temporary bonded body; ,
Energy is applied to the peeling surface of the bonding film transferred to the second temporary bonded body, the leaving group is released from the siloxane bond, and adhesiveness is exhibited, and the bonding surfaces face each other. The second temporary joined body and the second member are stacked, and the closed space in which the device is housed is hermetically sealed to obtain a sealed device. The manufacturing method of the sealing type device characterized by the above-mentioned.   The region where energy is applied to the joint surface of the first member in the third step is set to be a frame-like region surrounding the periphery of the region corresponding to the closed space. The manufacturing method of the sealing type device of description. In the first step, a base material with a first bonding film and a base material with a second bonding film similar to the base material with a bonding film are prepared,
In the third step, energy is applied to a first region of a part of the bonding surface of the first member so that the first region and the bonding film are in close contact with each other. While laminating a member and the first substrate with a bonding film, energy is applied to a second region of a part of the bonding surface of the second member, and the second region and the bonding film The second member and the base material with the second bonding film are laminated so that the two first temporary bonded bodies are obtained.
In the fourth step, the base material is peeled from the two first temporary joined bodies, and the first film and the bonding film corresponding to the first area and the second area are separated from the first member and the second area. Partially transferred to the second member to obtain two second temporary joined bodies,
In the fifth step, the two second temporary joined bodies are provided such that energy is applied to the separation surfaces of the joining films of the two second temporary joined bodies, and the joined surfaces face each other. The manufacturing method of the sealing type device of Claim 10 which laminates | stacks each and obtains a sealing type device. The first region and the second region are:
When the two second temporary joined bodies are laminated in the fifth step, a region obtained by combining these regions is set to be a frame-like region surrounding the region corresponding to the closed space. The manufacturing method of the sealing type device of Claim 12.   The sealing according to any one of claims 10 to 13, wherein, in the third step, energy is applied to the bonding film of the substrate with a bonding film before the member and the substrate with the bonding film are laminated. Type device manufacturing method.

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