WO2022131028A1 - Glass body for joining and joined body - Google Patents

Glass body for joining and joined body Download PDF

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Publication number
WO2022131028A1
WO2022131028A1 PCT/JP2021/044500 JP2021044500W WO2022131028A1 WO 2022131028 A1 WO2022131028 A1 WO 2022131028A1 JP 2021044500 W JP2021044500 W JP 2021044500W WO 2022131028 A1 WO2022131028 A1 WO 2022131028A1
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Prior art keywords
glass
glass layer
molar concentration
layer
target object
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PCT/JP2021/044500
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French (fr)
Japanese (ja)
Inventor
太郎 山下
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Ａｇｃ株式会社
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Publication of WO2022131028A1 publication Critical patent/WO2022131028A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing

Definitions

  • This disclosure relates to a glass body for joining and a joining body.
  • Patent Document 1 discloses a joining method for joining two substrates by an atomic diffusion method.
  • the bonding method includes forming a bonding film and a protective film on the smooth surface of each of the two substrates in this order, and superimposing the two substrates so that the protective films are in contact with each other.
  • the protective film is made of Au or Au alloy.
  • the bonding film is made of a single metal other than Au or an alloy other than Au alloy. The atoms of the bonding membrane are rearranged by the atomic diffusion of Au in the protective film.
  • Patent Document 2 discloses a joining method for joining two substrates by a surface activation method.
  • the joining method includes hydrophilizing at least one of the joining surfaces of the two substrates to be joined to each other, and joining the two substrates after hydrophilization.
  • Hydrophilization includes reactive ion etching using oxygen gas, reactive ion etching using nitrogen gas, and irradiation with nitrogen radicals.
  • Patent Document 3 discloses a joining method for joining two substrates by a surface activation method.
  • the joining method is to form a thin film of metal oxide on the joining surface of both or one of the pair of substrates, and to bring the joining surfaces of the substrates into contact with each other through the thin film and bond them together.
  • the substrate is glass containing SiO 2 , tempered glass, or the like.
  • One aspect of the present disclosure provides a technique for improving the bonding strength of a glass containing SiO 2 and a component other than SiO 2 .
  • the joining glass body according to one aspect of the present disclosure is to be joined to the target object.
  • the glass body for joining includes a first glass layer and a second glass layer.
  • the first glass layer has a Si molar concentration higher than the molar concentration of an element other than oxygen and is constant.
  • the second glass layer is formed on a surface of the first glass layer facing the target object, and the Si molar concentration changes in a direction orthogonal to the facing surface.
  • the thickness of the first glass layer is 1 ⁇ m or more.
  • the thickness of the second glass layer is 5 nm to 300 nm.
  • the Si molar concentration on the surface of the second glass layer facing the target object is higher than the Si molar concentration of the first glass layer.
  • the bonding strength of the glass can be improved by locally bringing the Si molar concentration of the glass containing SiO 2 and a component other than SiO 2 closer to the Si molar concentration of the quartz glass.
  • FIG. 1 (A) is a diagram showing a glass body for joining according to an embodiment
  • FIG. 1 (B) is a diagram showing an example of a Si molar concentration distribution
  • FIG. 1 (C) is a diagram showing a C molar concentration. It is a figure which shows an example of a distribution.
  • FIG. 2A is a diagram showing a bonding glass body according to the first modification
  • FIG. 2B is a diagram showing a bonding glass body according to the second modification
  • FIG. 2C is a diagram showing the bonding glass body. It is a figure which shows the glass body for joining which concerns on the 3rd modification.
  • FIG. 3A is a diagram showing a bonded body according to an embodiment
  • FIG. 3B is a diagram showing a bonded body according to a first modification
  • FIG. 3C is a diagram showing a second modification. It is a figure which shows the said joint body
  • FIG. 3 (D) is a figure which shows the joint body which concerns on the 3rd modification.
  • FIG. 4 (A) is a diagram showing a bonded body according to a fourth modified example
  • FIG. 4 (B) is a diagram showing a bonded body according to a fifth modified example
  • FIG. 4 (C) is a diagram showing a sixth modified example
  • 4 (D) is a diagram showing a bonded body according to the seventh modification.
  • FIG. 5 is a cross-sectional view showing an example of a method for measuring the joint strength.
  • the bonding glass body 10 is bonded to the target object 20.
  • the bonding glass body 10 is also simply referred to as a glass body 10.
  • the glass body 10 includes the first glass layer 11.
  • the first glass layer 11 is a so-called multi-component glass, which is a silicate glass containing SiO 2 as a main component.
  • the silicate glass is soda lime glass, non-alkali glass, borosilicate glass and the like.
  • the glass composition is general.
  • SiO 2 is 58.4% to 66.0%
  • Al 2 O 3 is 15.3% to 22.0%
  • B 2 O 3 is 5.0. % To 12.0%, MgO 0.0% to 6.5%, CaO 0.0% to 7.0%, SrO 4.0% to 12.5%, BaO 0.0% to It contains 2.0% and contains 9.0% to 18.0% of alkaline earth metal oxides (MgO + CaO + SrO + BaO).
  • SiO 2 is 50% to 70%
  • Al 2 O 3 is 2% to 8%
  • B 2 O 3 is 0% to 5%
  • MgO is 0% to 0%. It may contain 5%, CaO 0% to 6%, SrO 4% to 20%, BaO 14% to 35%, and alkaline earth metal oxide (MgO + CaO + SrO + BaO) 25% to 40%.
  • the glass composition of the first glass layer 11 is selected according to the use of the glass body 10. This is because the required physical properties differ depending on the application of the glass body 10, such as mechanical properties such as Young's modulus, thermal properties such as thermal expansion coefficient, and optical properties such as light transmittance.
  • the first glass layer 11 may have a Si molar concentration higher than the molar concentration of an element other than oxygen and may be constant.
  • the Si molar concentration of the first glass layer 11 is, for example, 16% or more.
  • the SiO 2 molar concentration corresponding to the Si molar concentration of 16% is 48%.
  • the Si molar concentration of the first glass layer 11 is preferably 20% or more. Further, the Si molar concentration of the first glass layer 11 is less than 33%.
  • the variation in the Si molar concentration of the first glass layer 11 is within ⁇ 1%.
  • the first glass layer 11 has, as constituent elements, for example, B, C, Si, P, V, Ge, As, Se, Zr, Sb, Al, Ti, Sn, Te, Tl, Pb, Bi, Li, Be. , Na, Mg, K, Ca, Sc, Cu, Zn, Ga, Rb, Sr, Y, Ag, Cd, In, Cs, Ba, La, Au, Hg.
  • Oxides of B, C, Si, P, V, Ge, As, Se, Zr, and Sb are called network formers and form a three-dimensional network structure without periodicity.
  • the network structure becomes the skeleton of glass.
  • the oxides of Li, Be, Na, Mg, K, Ca, Sc, Cu, Zn, Ga, Rb, Sr, Y, Ag, Cd, In, Cs, Ba, La, Au, and Hg are networks. It is called a modifier and exists in the network structure.
  • Oxides of Al, Ti, Sn, Te, Tl, Pb, and Bi are called intermediate oxides and have intermediate properties between network formers and network modifiers.
  • the thickness of the first glass layer 11 is 1 ⁇ m or more. When the thickness of the first glass layer 11 is 1 ⁇ m or more, physical properties suitable for the use of the glass body 10 can be obtained.
  • the thickness of the first glass layer 11 is preferably 30 ⁇ m or more.
  • the thickness of the first glass layer 11 is preferably 30 mm or less.
  • the glass body 10 includes a second glass layer 12 in order to improve the bonding strength with the target object 20.
  • the second glass layer 12 is formed on the facing surface 11a of the first glass layer 11 with the target object 20, and the Si molar concentration changes in the direction orthogonal to the facing surface 11a. For example, as the distance from the first glass layer 11 increases, the Si molar concentration of the second glass layer 12 increases (see FIG. 1 (B)).
  • the change in the Si molar concentration in the middle of the second glass layer 12 is not particularly limited, and M2, which will be described later, may be higher than M1.
  • the second glass layer 12 is formed by, for example, leaching to supply an acid to the surface 11a facing the target object 20 in the first glass layer 11 and elute a desired element other than Si from the glass to the acid. Therefore, the Si molar concentration of the second glass layer 12 changes in the direction orthogonal to the surface 11a facing the target object 20 in the first glass layer 11.
  • the acid in the case of leaching treatment by supplying an acid, the acid may be supplied as an acidic aqueous solution, may be supplied as an acidic vapor, or may be a plasma, radical or ion of a gas to which the acidic vapor is added. ..
  • the acidic aqueous solution contains, for example, sulfuric acid, hydrochloric acid, oxalic acid, maleic acid, phosphoric acid, citric acid, or mixed acid.
  • the mixed acid may be sulfuric acid, hydrochloric acid, a mixed acid of oxalic acid and hydrofluoric acid, or a mixed acid of hydrochloric acid and nitric acid.
  • the acidic vapor contains hydrogen sulfide or sulfurous acid.
  • the acid elutes, for example, the network modifier of glass.
  • the glass network former remains.
  • the leaching solution used in the leaching process is a neutral or alkaline solution that can be selected according to the composition of the glass to be leached, and can selectively leave the network former of the glass in addition to the acidic solution. May be good.
  • the leaching process using an acid is also referred to as an acid leaching process.
  • the Si molar concentration M2 on the surface of the second glass layer 12 facing the target object 20 is higher than the Si molar concentration M1 of the first glass layer 11, for example, 17% to 33%, preferably 25% to 33. %.
  • the second glass layer 12 may be formed by a method other than the leaching process, and is formed by, for example, a CVD (Chemical Vapor Deposition) method, an ALD (Atomic Layer Deposition) method, or a PVD (Physical Vapor Deposition) method. You may.
  • the second glass layer 12 formed by these methods may be heat-treated in order to promote mutual diffusion at the interface with the first glass layer 11.
  • the Si molar concentration can be continuously changed by solid diffusion of atoms near the bonding interface.
  • the heat treatment is carried out at a temperature higher than 25 ° C, preferably 100 ° C or higher and 500 ° C or lower.
  • the heat treatment time is adjusted as appropriate. According to the leaching process, the Si molar concentration of the second glass layer 12 can be continuously changed.
  • a hydroxide of an alkaline earth metal may be formed on the second glass layer 12.
  • the hydroxide reacts with carbon dioxide in the atmosphere to produce carbonate.
  • C may be incorporated into the second glass layer 12.
  • the C molar concentration of the second glass layer 12 can be adjusted by a washing, rinsing and drying treatment performed after the leaching treatment. Washing treats the surface of the second glass layer 12 with a chemical solution, rinsing flushes the reaction product between the chemical solution and the second glass layer 12, and drying dries the surface.
  • the second glass layer 12 contains C
  • the bond between Si and O is reduced and the mechanical strength is lowered as compared with the case where C is not contained.
  • the carbonate CaCO 3 has a lower density and lower mechanical strength than the network modifier CaO. Therefore, after the glass body 10 and the target object 20 are joined, the second glass layer 12 can be selectively destroyed when the first glass layer 11 and the target object 20 are separated from each other, and the first glass layer 11 and the target object 20 can be selectively destroyed. 20 can be prevented from being destroyed.
  • the maximum value Cmax of the C molar concentration of the second glass layer 12 is, for example, 0.1% to 20%.
  • Cmax is 0.1% or more, the second glass layer 12 can be selectively destroyed when the first glass layer 11 and the target object 20 are separated from each other. Further, when Cmax is 20% or less, unintended peeling can be prevented.
  • Cmax is preferably 3% to 20%.
  • the second glass layer 12 may not substantially contain C.
  • the fact that the second glass layer 12 does not substantially contain C means that the maximum value Cmax of the C molar concentration of the second glass layer 12 is less than 0.1%. When Cmax is less than 0.1%, high bonding strength can be obtained.
  • the thickness of the second glass layer 12 is, for example, 5 nm to 300 nm, preferably 25 nm to 150 nm.
  • the glass body 10 may further include a crystalline or non-crystalline (amorphous) metal oxide layer 13 formed on the surface 12a of the second glass layer 12 facing the target object 20.
  • the metal oxide layer 13 is, for example, SiO 2 .
  • the metal oxide layer 13 may be SiO 2 doped with an element other than Si.
  • the metal oxide layer 13 is formed by a CVD method, an ALD method, a PVD method, or the like. Further, the metal oxide layer 13 may be formed by a leaching treatment of the glass body 10. In the leaching process, it is possible to increase the Si molar concentration by utilizing the fact that the elution rate differs for each element.
  • the facing surface 13a of the metal oxide layer 13 with the target object 20 is the joining surface of the glass body 10.
  • the surface roughness Ra of the joint surface is, for example, greater than 0.1 nm and less than 10 nm. Ra is preferably 0.2 nm to 1.0 nm. Ra is the "arithmetic mean roughness" described in Japanese Industrial Standards JIS B0601: 1994.
  • the Si molar concentration M3 of the metal oxide layer 13 is equal to or higher than the Si molar concentration M2 on the surface 12a facing the target object 20 of the second glass layer 12, and is constant.
  • the metal oxide layer 13 improves the bonding strength between the glass body 10 and the target object 20, and also suppresses the diffusion of metals other than Si from the first glass layer 11 to the target object 20.
  • M3 is, for example, 17% to 33%, preferably 30% to 33%, and more preferably 33%.
  • M3 is 33%, and high bonding strength can be obtained.
  • the variation in the Si molar concentration of the metal oxide layer 13 is within ⁇ 1%.
  • the thickness of the metal oxide layer 13 is, for example, 0.1 nm to 500 ⁇ m, preferably 10 nm to 1 ⁇ m.
  • the distribution of the Si molar concentration in the glass body 10 is measured by an X-ray photoelectric spectroscopic analyzer (XPS: X-ray Photoelectron Spectroscopic) / ESCA (Electron Spectroscopic for Chemical Analysis).
  • XPS X-ray Photoelectron Spectroscopic
  • ESCA Electron Spectroscopic for Chemical Analysis.
  • the interval between measurement points is, for example, 10 nm or less, preferably 5 nm or less.
  • the distribution of Si molar concentration may be measured by using a transmission electron microscope (TEM: Transmission Electron Microscope) in addition to the X-ray photoelectric spectroscopic analyzer.
  • TEM Transmission Electron Microscope
  • the boundary between the first glass layer 11 and the second glass layer 12 is determined using the result of the analysis of the Si molar concentration.
  • the regression line is obtained by the method of least squares. a1 is set within the range of ⁇ 0.0350 (% / nm).
  • the Si molar concentration in the second glass layer 12 is represented by an approximate curve.
  • the approximate curve is obtained by the least squares method and approximated by a polynomial.
  • the approximate curve may be a straight line connecting two adjacent measurement points.
  • the data at each measurement point may be moving average data rather than raw data.
  • ⁇ 1 is the standard deviation of the Si molar concentration in the first glass layer 11.
  • the boundary between the second glass layer 12 and the metal oxide layer 13 is determined using the result of the analysis of the Si molar concentration.
  • the regression line is obtained by the method of least squares. a2 is set within the range of ⁇ 0.0350 (% / nm).
  • the Si molar concentration in the second glass layer 12 is represented by an approximate curve.
  • the approximate curve is obtained by the least squares method and approximated by a polynomial.
  • the approximate curve may be a straight line connecting two adjacent measurement points. The data at each measurement point may be moving average data rather than raw data.
  • ⁇ 2 is the standard deviation of the Si molar concentration in the metal oxide layer 13.
  • the bonding glass body 10 includes the first glass layer 11 and the second glass layer 12, and may not include the metal oxide layer 13.
  • the surface 12a facing the target object 20 in the second glass layer 12 is the joint surface of the glass body 10.
  • the bonding glass body 10 may include the second glass layer 12 on both sides of the first glass layer 11.
  • the target object 20 can be joined to both sides of the first glass layer 11.
  • the bonding glass body 10 may include the metal oxide layers 13 on both sides of the first glass layer 11.
  • the bonded body 30 includes a glass body 10 and a target object 20 bonded to the glass body 10.
  • the target object 20 may include a first glass layer 21, a second glass layer 22, and a metal oxide layer 23, similarly to the glass body 10.
  • the first glass layer 21 is formed in the same manner as the first glass layer 11
  • the second glass layer 22 is formed in the same manner as the second glass layer 12
  • the metal oxide layer 23 is formed in the same manner as the metal oxide layer 13.
  • the glass The bonding strength between multi-component glasses can be improved.
  • the target object 20 is in direct contact with the glass body 10.
  • the joint surface 13a of the glass body 10 and the joint surface 23a of the target object 20 are activated in advance by the surface activation method.
  • the surface activation method includes, for example, the technique described in Patent Document 1, the so-called sequential plasma method.
  • the sequential plasma method includes, for example, reactive ion etching using oxygen gas, reactive ion etching using nitrogen gas, and irradiation with nitrogen radicals.
  • the sequential plasma method activates the joint surface of glass or the like.
  • OH groups which are hydrophilic groups, are generated on the joint surface.
  • hydrogen bonds between OH groups are generated at the time of bonding, and high bonding strength is obtained.
  • annealing may be performed. By the annealing treatment, the hydrogen bond is changed to a covalent bond, and higher bond strength is obtained.
  • the surface activation method is not limited to the sequential plasma method.
  • the surface activation method may include, for example, only reactive ion etching using oxygen gas.
  • an OH group which is a hydrophilic group, is generated on the joint surface. After that, hydrogen bonds between OH groups are generated at the time of bonding, and covalent bonds are generated by the dehydration condensation reaction of the hydrogen bonds, so that high bonding strength can be obtained.
  • the glass body 10 and the target object 20 may be joined via an intermediate layer 40 of an inorganic substance.
  • the intermediate layer 40 includes a joint layer 41 previously formed on the joint surface of the glass body 10 and a joint layer 42 previously formed on the joint surface of the target object 20.
  • the bonding layers 41 and 42 are formed of a metal containing, for example, one or more elements of Al, Si, Ti, V, Cr, Mn, Fe, Y, Zr, Hf, and Ta. Metals include alloys.
  • the glass body 10 and the target object 20 can be joined by utilizing the atomic diffusion of the metal.
  • the bonding layers 41 and 42 may each include a plurality of metal layers.
  • the bonding layers 41 and 42 may be formed of a metal oxide containing one or more elements of Al, Si, Ti, V, Cr, Mn, Fe, Y, Zr, Hf, and Ta. ..
  • the metal oxide is formed by a film forming method such as a sputtering method, a reactive sputtering method, or an ALD method.
  • the sputtering method uses a metal oxide target and an inert gas.
  • the reactive sputtering method uses a metal target and a mixed gas of an inert gas such as a rare gas and a reactive gas (for example, oxygen gas).
  • the bonding layers 41 and 42 are metal oxides
  • the surface activity of the metal oxide developed in the process of forming the metal oxide is utilized, and the bonding is performed in an atmosphere such as vacuum, atmosphere, or an inert gas.
  • the surface of the bonding layers 41 and 42 may be activated by the above-mentioned surface activation method, and then the bonding may be performed.
  • the bonding surface activated by the above surface activation method comes into contact with water vapor, water, or the like, OH groups, which are hydrophilic groups, are generated on the bonding surface. After that, hydrogen bonds between OH groups are generated at the time of bonding, and further, a covalent bond is generated by the dehydration condensation reaction of the hydrogen bonds, so that high bonding strength can be obtained.
  • the bonding layers 41 and 42 When the bonding layers 41 and 42 are made of metal, the bonding layers 41 and 42 may be bonded by an atomic diffusion method, and then the bonding layers 41 and 42 may be oxidized with oxygen contained in the glass body 10. The bonded body 30 may be heat-treated to promote oxidation. By oxidizing the bonding layers 41 and 42, physical properties such as light transmittance, electric conductivity, thermal conductivity, and coefficient of thermal expansion can be changed.
  • the target object 20 does not have to be a glass plate, and is, for example, a semiconductor substrate such as Si, GaN, SiC, or Ga 2 O 3 , LiTaO 3 . It may be a piezoelectric substrate such as LiNbO 3 or AlN, an oxide substrate such as Al 2 O 3 , or a nitride substrate such as SiN.
  • the glass body 10 and the target object 20 may be in direct contact with each other as shown in FIG. 3C, or may be joined via an intermediate layer 40 as shown in FIG. 3D.
  • the target object 20 includes the first glass layer 21 and the second glass layer 22 and the metal oxide layer 23, similarly to the glass body 10. And may not be included.
  • the glass body 10 and the target object 20 may be in direct contact with each other as shown in FIG. 4 (A), or may be joined via an intermediate layer 40 as shown in FIG. 4 (B).
  • the target object 20 does not have to be a glass plate, and is, for example, a semiconductor substrate such as Si, GaN, SiC, or Ga 2 O 3 , LiTaO 3 . It may be a piezoelectric substrate such as LiNbO 3 or AlN, an oxide substrate such as Al 2 O 3 , or a nitride substrate such as SiN.
  • the glass body 10 and the target object 20 may be in direct contact with each other as shown in FIG. 4 (C), or may be joined via an intermediate layer 40 as shown in FIG. 4 (D).
  • the glass body 10 or the target object 20 may have a recess or a through hole in the joint surface thereof.
  • the joint strength of the joint 30 is measured by the crack opening method shown in FIG.
  • a blade BL like a razor blade is inserted from the outside at the bonding interface between the glass body 10 and the target object 20 bonded to each other, and the peeling length L is measured. The shorter the peeling length L, the higher the bonding strength. If the bonding strength is sufficiently high, the glass body 10 or the target object 20 may be destroyed by the insertion of the blade BL.
  • E1 is the Young's modulus of the glass body 10
  • E2 is the Young's modulus of the target object 20
  • t1 is the thickness of the glass body 10
  • t2 is the thickness of the target object 20
  • t0 is the thickness of the blade BL.
  • the bonding strength ⁇ is obtained as the surface energy of the bonding interface, and the unit of the bonding strength ⁇ is J / m 2 .
  • Table 1 shows the compositions of the two types of glasses A to B used in the experiment.
  • the glass A is a non-alkali glass, and more specifically, an aluminum noborosilicate glass.
  • Glass B is also non-alkali glass, more specifically aluminosilicate glass.
  • Each of the glasses A to B has a SiO 2 content of 70 mol% or less.
  • quartz glass having a SiO 2 content of 100 mol% was also prepared.
  • Examples 1 to 9 below the glasses shown in Table 1 were joined together.
  • the joining conditions and evaluation results are shown in Tables 2 to 3.
  • Examples 2 to 5 and 7 to 9 below are examples, and examples 1 and 6 below are reference examples.
  • the adhesion When the adhesion is "A”, it means that the bonding strength is 2.0J / m 2 or more or exceeds the measurement limit, and when the adhesion is "B", the bonding strength is 0.8J. It means that it is more than / m 2 and less than 2.0 J / m 2 , and that the adhesion is "C” means that the bonding strength is less than 0.8 J / m 2 .
  • the joint strength is 0.8 J / m 2 or more, good results can be obtained in the die shear strength test of the cut joint according to the industrial standard such as MIL-STD-883 standard.
  • the peelability is "A”
  • the bonding strength is less than 0.3 J / m 2
  • the peeling property is "B”
  • the bonding strength is 0.3 J / m 2 or more 1 It means that it is less than 0.0 J / m 2
  • the peelability is "C” means that the bonding strength is 1.0 J / m 2 or more. If the bonding strength is less than 1.0 J / m 2 , the glasses can be separated from each other by inserting a blade into the bonding interface.
  • the blade BL used in the experiment had a thickness t0 of 0.1 mm.
  • Example 1 two quartz glasses were joined. Quartz glass had a glass body thickness of 0.5 mm and did not have a second glass layer and a metal oxide. Prior to joining, the opposing surfaces of the two quartz glasses were activated only by reactive ion etching using oxygen gas and exposed to water vapor. The processing time for reactive ion etching using oxygen gas was 120 seconds. Then, two quartz glasses were joined in the atmosphere. The bonding strength was 1.5 J / m 2 or more, the evaluation of adhesion was "B", and the evaluation of peelability was "C”.
  • Example 2 two glasses A were joined.
  • the thickness of the glass body was 0.5 mm, and the thickness of the second glass layer was 45 nm.
  • the joining surfaces of the two glasses A facing each other were subjected to acid leaching treatment. Each joint surface was washed so that no carbon remained after the acid leaching treatment. Then, each joint surface was activated only by reactive ion etching using oxygen gas, and then each joint surface was subsequently exposed to water vapor. The processing time for reactive ion etching using oxygen gas was 120 seconds. Then, the two glasses A were joined in the atmosphere.
  • the bonding strength was 0.9 J / m 2 , the evaluation of adhesion was "B", and the evaluation of peelability was "B".
  • Example 3 two glasses B were joined.
  • the thickness of the glass body was 0.5 mm, and the thickness of the second glass layer was 60 nm.
  • the joining surfaces of the two glasses B facing each other were subjected to acid leaching treatment. Each joint surface was washed so that no carbon remained after the acid leaching treatment. Then, each joint surface was activated only by reactive ion etching using oxygen gas, and then each joint surface was subsequently exposed to water vapor. The processing time for reactive ion etching using oxygen gas was 120 seconds. Then, the two glasses B were joined in the atmosphere.
  • the bonding strength was 0.2 J / m 2 , the evaluation of adhesion was "C”, and the evaluation of peelability was "A".
  • Example 4 two glasses A were joined.
  • the thickness of the glass body was 0.5 mm
  • the thickness of the second glass layer was 45 nm
  • the thickness of the metal oxide layer was 15 nm.
  • the joining surfaces of the two glasses A facing each other were subjected to acid leaching treatment. Carbon remained after the acid leaching treatment.
  • a metal oxide layer which is a non-crystalline SiO 2 film, is formed on each joint surface by a sputtering method using a SiO 2 target, and the surface of each SiO 2 film is obtained only by reactive ion etching using oxygen gas. Was activated, and subsequently the surface of each SiO 2 film was exposed to steam.
  • the processing time for reactive ion etching using oxygen gas was 120 seconds. Then, in the atmosphere, two glasses A were joined via two SiO 2 films. The bonding strength was 0.9 J / m 2 , the evaluation of adhesion was "B”, and the evaluation of peelability was "B".
  • Example 5 the acid leaching treatment is not performed on the two glasses A, the two glasses A are etched with an alkaline solution having a pH of 11, and then the glass surface is leached with a neutral solution to obtain a Cmax of 20 mol.
  • a metal oxide layer which is a non-crystalline SiO 2 film was formed by a sputtering method using a SiO 2 target. The surface of each SiO 2 film was activated only by reactive ion etching using oxygen gas, and then the surface of each SiO 2 film was exposed to steam. The processing time for reactive ion etching using oxygen gas was 120 seconds. Then, in the atmosphere, two glasses A were joined via two SiO 2 films.
  • the thickness of the glass body was 0.5 mm
  • the thickness of the second glass layer was 25 nm
  • the thickness of the metal oxide layer was 15 nm.
  • the peeling was caused by the fracture of the second glass layer, the bonding strength thereof was 0.1 J / m 2 , the evaluation of the adhesion was “C”, and the evaluation of the peelability was “A”.
  • Example 6 two quartz glasses were joined. Quartz glass had a glass body thickness of 0.5 mm and did not have a second glass layer and a metal oxide. Before joining, a Ti film having a thickness of 2 nm and an Au film having a thickness of 50 nm were formed on the bonding surfaces of the two quartz glasses facing each other by a sputtering method in this order. Then, two quartz glasses were joined in the atmosphere. The joint strength exceeded the measurement limit, and when the blade was inserted into the joint interface, the joint body broke and could not be measured. The evaluation of adhesion was "A”, and the evaluation of peelability was "C".
  • Example 7 two glasses A were joined.
  • the thickness of the glass body was 0.5 mm, and the thickness of the second glass layer was 45 nm.
  • the joining surfaces of the two glasses A facing each other were subjected to acid leaching treatment. Each joint surface was washed so that no carbon remained after the acid leaching treatment. Then, a Ti film having a thickness of 2 nm and an Au film having a thickness of 50 nm were formed on each joint surface in this order by a sputtering method. Then, the two glasses A were joined in the atmosphere.
  • the bonding strength was 2.0 J / m 2 , the evaluation of adhesion was "A”, and the evaluation of peelability was "C”.
  • Example 8 two glasses A were joined.
  • the thickness of the glass body was 0.5 mm
  • the thickness of the second glass layer was 45 nm
  • the thickness of the metal oxide layer was 15 nm.
  • the joining surfaces of the two glasses A facing each other were subjected to acid leaching treatment. Carbon remained after the acid leaching treatment.
  • a metal oxide layer which is a non-crystalline SiO 2 film is formed on each joint surface by a sputtering method using a SiO 2 target, and then a Ti film having a thickness of 2 nm and an Au film having a thickness of 50 nm are formed. In this order, a film was formed by a sputtering method.
  • the two glasses A were joined in the atmosphere.
  • the bonding strength was 0.9 J / m 2
  • the evaluation of adhesion was "B”
  • the evaluation of peelability was "B".
  • Example 9 the two glasses A are not subjected to the acid leaching treatment, the two glasses A are etched with an alkaline solution having a pH of 11, and then the glass surface is leached with a neutral solution to obtain a Cmax of 20 mol.
  • a metal oxide layer which is a non-crystalline SiO 2 film is formed by a sputtering method using a SiO 2 target, and then a Ti film having a thickness of 2 nm and an Au film having a thickness of 50 nm are formed in this order. Then, a film was formed by the sputtering method. Then, the two glasses A were joined in the atmosphere.
  • the thickness of the glass body was 0.5 mm
  • the thickness of the second glass layer was 25 nm
  • the thickness of the metal oxide layer was 15 nm. Peeling occurs at the interface between the second glass layer of glass A and the Ti film formed on the second glass layer, the bonding strength thereof is 0.1 J / m 2 , and the evaluation of adhesion is "C”. The evaluation of peelability was "A”.

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Abstract

This glass body for joining is joined with a target object. The glass body for joining includes a first glass layer and a second glass layer. The Si molar concentration of the first glass layer is higher than the molar concentration of elements other than oxygen, and is constant. The second glass layer is formed on the surface facing the target object of the first glass layer, and Si molar concentration thereof varies in a direction orthogonal to said surface facing the target object. The thickness of the first glass layer is 1 μm or greater. The thickness of the second glass layer is 5-300 nm. The Si molar concentration in the surface facing the target object of the second glass layer is higher than the Si molar concentration of the first glass layer.

Description

接合用ガラス体、及び接合体Glass body for joining and joining body
　本開示は、接合用ガラス体、及び接合体に関する。 This disclosure relates to a glass body for joining and a joining body.
　特許文献１には、２つの基体を原子拡散法で接合する接合方法が開示されている。その接合方法は、２つの基体のそれぞれの平滑面に接合膜と保護膜とをこの順番で形成することと、保護膜同士が接触するように２つの基体を重ね合わせることとを含む。保護膜は、Ａｕ又はＡｕ合金からなる。接合膜は、Ａｕ以外の単金属又はＡｕ合金以外の合金からなる。保護膜のＡｕの原子拡散により、接合膜の原子を再配列する。 Patent Document 1 discloses a joining method for joining two substrates by an atomic diffusion method. The bonding method includes forming a bonding film and a protective film on the smooth surface of each of the two substrates in this order, and superimposing the two substrates so that the protective films are in contact with each other. The protective film is made of Au or Au alloy. The bonding film is made of a single metal other than Au or an alloy other than Au alloy. The atoms of the bonding membrane are rearranged by the atomic diffusion of Au in the protective film.
　特許文献２には、２つの基板を表面活性化法で接合する接合方法が開示されている。その接合方法は、２つの基板のそれぞれの互いに接合される接合面の少なくとも一方を親水化することと、親水化の後で２つの基板を接合することと、を含む。親水化することは、酸素ガスを用いた反応性イオンエッチングと、窒素ガスを用いた反応性イオンエッチングと、窒素ラジカルの照射と、を含む。 Patent Document 2 discloses a joining method for joining two substrates by a surface activation method. The joining method includes hydrophilizing at least one of the joining surfaces of the two substrates to be joined to each other, and joining the two substrates after hydrophilization. Hydrophilization includes reactive ion etching using oxygen gas, reactive ion etching using nitrogen gas, and irradiation with nitrogen radicals.
　特許文献３には、２つの基板を表面活性化法で接合する接合方法が開示されている。その接合方法は、一対の基板の両方又はいずれか一方の接合面に金属酸化物の薄膜を形成することと、その薄膜を介して基板の接合面を互いに接触させて、貼り合わせることと、を含む。基板は、ＳｉＯ２を含むガラス、強化ガラス等である。 Patent Document 3 discloses a joining method for joining two substrates by a surface activation method. The joining method is to form a thin film of metal oxide on the joining surface of both or one of the pair of substrates, and to bring the joining surfaces of the substrates into contact with each other through the thin film and bond them together. include. The substrate is glass containing SiO 2 , tempered glass, or the like.
日本国特開２０１６－０８７６６４号公報Japanese Patent Application Laid-Open No. 2016-087664 国際公開第２０１８／０８４２８５号International Publication No. 2018/084285 日本国特開２０１９－１１９０８６号公報Japanese Patent Application Laid-Open No. 2019-119086
　本開示の一態様は、ＳｉＯ２とＳｉＯ２以外の成分とを含むガラスの接合強度を改善する、技術を提供する。 One aspect of the present disclosure provides a technique for improving the bonding strength of a glass containing SiO 2 and a component other than SiO 2 .
　本開示の一態様に係る接合用ガラス体は、対象物体と接合されるものである。接合用ガラス体は、第１ガラス層と、第２ガラス層とを含む。前記第１ガラス層は、Ｓｉモル濃度が酸素以外の元素のモル濃度よりも高く、且つ一定である。前記第２ガラス層は、前記第１ガラス層における前記対象物体との対向面に形成され、その対向面に直交する方向にＳｉモル濃度が変化するものである。前記第１ガラス層の厚みが、１μｍ以上である。前記第２ガラス層の厚みが、５ｎｍ～３００ｎｍである。前記第２ガラス層の前記対象物体との対向面におけるＳｉモル濃度が、前記第１ガラス層のＳｉモル濃度よりも高い。 The joining glass body according to one aspect of the present disclosure is to be joined to the target object. The glass body for joining includes a first glass layer and a second glass layer. The first glass layer has a Si molar concentration higher than the molar concentration of an element other than oxygen and is constant. The second glass layer is formed on a surface of the first glass layer facing the target object, and the Si molar concentration changes in a direction orthogonal to the facing surface. The thickness of the first glass layer is 1 μm or more. The thickness of the second glass layer is 5 nm to 300 nm. The Si molar concentration on the surface of the second glass layer facing the target object is higher than the Si molar concentration of the first glass layer.
　本開示の一態様によれば、ＳｉＯ２とＳｉＯ２以外の成分とを含むガラスのＳｉモル濃度を局所的に石英ガラスのＳｉモル濃度に近づけることで、ガラスの接合強度を改善できる。 According to one aspect of the present disclosure, the bonding strength of the glass can be improved by locally bringing the Si molar concentration of the glass containing SiO 2 and a component other than SiO 2 closer to the Si molar concentration of the quartz glass.
図１（Ａ）は一実施形態に係る接合用ガラス体を示す図であり、図１（Ｂ）はＳｉモル濃度の分布の一例を示す図であり、図１（Ｃ）はＣモル濃度の分布の一例を示す図である。FIG. 1 (A) is a diagram showing a glass body for joining according to an embodiment, FIG. 1 (B) is a diagram showing an example of a Si molar concentration distribution, and FIG. 1 (C) is a diagram showing a C molar concentration. It is a figure which shows an example of a distribution. 図２（Ａ）は第１変形例に係る接合用ガラス体を示す図であり、図２（Ｂ）は第２変形例に係る接合用ガラス体を示す図であり、図２（Ｃ）は第３変形例に係る接合用ガラス体を示す図である。FIG. 2A is a diagram showing a bonding glass body according to the first modification, FIG. 2B is a diagram showing a bonding glass body according to the second modification, and FIG. 2C is a diagram showing the bonding glass body. It is a figure which shows the glass body for joining which concerns on the 3rd modification. 図３（Ａ）は一実施形態に係る接合体を示す図であり、図３（Ｂ）は第１変形例に係る接合体を示す図であり、図３（Ｃ）は第２変形例に係る接合体を示す図であり、図３（Ｄ）は第３変形例に係る接合体を示す図である。FIG. 3A is a diagram showing a bonded body according to an embodiment, FIG. 3B is a diagram showing a bonded body according to a first modification, and FIG. 3C is a diagram showing a second modification. It is a figure which shows the said joint body, and FIG. 3 (D) is a figure which shows the joint body which concerns on the 3rd modification. 図４（Ａ）は第４変形例に係る接合体を示す図であり、図４（Ｂ）は第５変形例に係る接合体を示す図であり、図４（Ｃ）は第６変形例に係る接合体を示す図であり、図４（Ｄ）は第７変形例に係る接合体を示す図である。FIG. 4 (A) is a diagram showing a bonded body according to a fourth modified example, FIG. 4 (B) is a diagram showing a bonded body according to a fifth modified example, and FIG. 4 (C) is a diagram showing a sixth modified example. 4 (D) is a diagram showing a bonded body according to the seventh modification. 図５は、接合強度の測定方法の一例を示す断面図である。FIG. 5 is a cross-sectional view showing an example of a method for measuring the joint strength.
　以下、本開示の実施形態について図面を参照して説明する。なお、各図面において同一の又は対応する構成には同一の符号を付し、説明を省略することがある。明細書中、数値範囲を示す「～」は、その前後に記載された数値を下限値及び上限値として含むことを意味する。 Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In each drawing, the same or corresponding configurations may be designated by the same reference numerals and description thereof may be omitted. In the specification, "-" indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
　先ず、図１を参照して、本実施形態に係る接合用ガラス体１０について説明する。接合用ガラス体１０は、対象物体２０に接合されるものである。接合用ガラス体１０を、以下、単にガラス体１０とも呼ぶ。ガラス体１０は、第１ガラス層１１を含む。第１ガラス層１１は、いわゆる多成分ガラスであり、ＳｉＯ２を主成分とするシリケートガラスである。シリケートガラスは、ソーダライムガラス、無アルカリガラス、又はホウケイ酸ガラスなどである。ガラス組成は、一般的なものである。 First, the bonding glass body 10 according to the present embodiment will be described with reference to FIG. 1. The bonding glass body 10 is bonded to the target object 20. Hereinafter, the bonding glass body 10 is also simply referred to as a glass body 10. The glass body 10 includes the first glass layer 11. The first glass layer 11 is a so-called multi-component glass, which is a silicate glass containing SiO 2 as a main component. The silicate glass is soda lime glass, non-alkali glass, borosilicate glass and the like. The glass composition is general.
　例えば、第１ガラス層１１は、モル％表示で、ＳｉＯ２を５８．４％～６６．０％、Ａｌ２Ｏ３を１５．３％～２２．０％、Ｂ２Ｏ３を５．０％～１２．０％、ＭｇＯを０．０％～６．５％、ＣａＯを０．０％～７．０％、ＳｒＯを４．０％～１２．５％、ＢａＯを０．０％～２．０％含み、アルカリ土類金属酸化物（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）を９．０％～１８．０％含む。 For example, in the first glass layer 11, in mol% representation, SiO 2 is 58.4% to 66.0%, Al 2 O 3 is 15.3% to 22.0%, and B 2 O 3 is 5.0. % To 12.0%, MgO 0.0% to 6.5%, CaO 0.0% to 7.0%, SrO 4.0% to 12.5%, BaO 0.0% to It contains 2.0% and contains 9.0% to 18.0% of alkaline earth metal oxides (MgO + CaO + SrO + BaO).
　また、第１ガラス層１１は、モル％表示で、ＳｉＯ２を５０％～７０％、Ａｌ２Ｏ３を２％～８％、Ｂ２Ｏ３を０％～５％、ＭｇＯを０％～５％、ＣａＯを０％～６％、ＳｒＯを４％～２０％、ＢａＯを１４％～３５％含み、アルカリ土類金属酸化物（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）を２５％～４０％含んでもよい。 Further, in the first glass layer 11, in mol% representation, SiO 2 is 50% to 70%, Al 2 O 3 is 2% to 8%, B 2 O 3 is 0% to 5%, and MgO is 0% to 0%. It may contain 5%, CaO 0% to 6%, SrO 4% to 20%, BaO 14% to 35%, and alkaline earth metal oxide (MgO + CaO + SrO + BaO) 25% to 40%.
　第１ガラス層１１のガラス組成は、ガラス体１０の用途に応じて選択される。ヤング率などの機械的特性、熱膨張率などの熱的特性、光透過率などの光学的特性など、ガラス体１０の用途に応じて、求められる物性が異なるからである。 The glass composition of the first glass layer 11 is selected according to the use of the glass body 10. This is because the required physical properties differ depending on the application of the glass body 10, such as mechanical properties such as Young's modulus, thermal properties such as thermal expansion coefficient, and optical properties such as light transmittance.
　第１ガラス層１１は、Ｓｉモル濃度が、酸素以外の元素のモル濃度よりも高く、且つ一定であればよい。第１ガラス層１１のＳｉモル濃度は、例えば１６％以上である。Ｓｉモル濃度１６％に相当するＳｉＯ２モル濃度は４８％である。第１ガラス層１１のＳｉモル濃度は、好ましくは２０％以上である。また、第１ガラス層１１のＳｉモル濃度は、３３％未満である。第１ガラス層１１のＳｉモル濃度のバラツキは、±１％以内である。 The first glass layer 11 may have a Si molar concentration higher than the molar concentration of an element other than oxygen and may be constant. The Si molar concentration of the first glass layer 11 is, for example, 16% or more. The SiO 2 molar concentration corresponding to the Si molar concentration of 16% is 48%. The Si molar concentration of the first glass layer 11 is preferably 20% or more. Further, the Si molar concentration of the first glass layer 11 is less than 33%. The variation in the Si molar concentration of the first glass layer 11 is within ± 1%.
　第１ガラス層１１は、構成元素として、例えば、Ｂ、Ｃ、Ｓｉ、Ｐ、Ｖ、Ｇｅ、Ａｓ、Ｓｅ、Ｚｒ、Ｓｂ、Ａｌ、Ｔｉ、Ｓｎ、Ｔｅ、Ｔｌ、Ｐｂ、Ｂｉ、Ｌｉ、Ｂｅ、Ｎａ、Ｍｇ、Ｋ、Ｃａ、Ｓｃ、Ｃｕ、Ｚｎ、Ｇａ、Ｒｂ、Ｓｒ、Ｙ、Ａｇ、Ｃｄ、Ｉｎ、Ｃｓ、Ｂａ、Ｌａ、Ａｕ、Ｈｇから選ばれる１つ以上を含む。 The first glass layer 11 has, as constituent elements, for example, B, C, Si, P, V, Ge, As, Se, Zr, Sb, Al, Ti, Sn, Te, Tl, Pb, Bi, Li, Be. , Na, Mg, K, Ca, Sc, Cu, Zn, Ga, Rb, Sr, Y, Ag, Cd, In, Cs, Ba, La, Au, Hg.
　Ｂ、Ｃ、Ｓｉ、Ｐ、Ｖ、Ｇｅ、Ａｓ、Ｓｅ、Ｚｒ、及びＳｂの酸化物は、ネットワークフォーマーと呼ばれ、周期性のない三次元の網目構造を形成する。その網目構造が、ガラスの骨格となる。 Oxides of B, C, Si, P, V, Ge, As, Se, Zr, and Sb are called network formers and form a three-dimensional network structure without periodicity. The network structure becomes the skeleton of glass.
　一方、Ｌｉ、Ｂｅ、Ｎａ、Ｍｇ、Ｋ、Ｃａ、Ｓｃ、Ｃｕ、Ｚｎ、Ｇａ、Ｒｂ、Ｓｒ、Ｙ、Ａｇ、Ｃｄ、Ｉｎ、Ｃｓ、Ｂａ、Ｌａ、Ａｕ、及びＨｇの酸化物は、ネットワークモディファイアーと呼ばれ、網目構造の中に存在している。 On the other hand, the oxides of Li, Be, Na, Mg, K, Ca, Sc, Cu, Zn, Ga, Rb, Sr, Y, Ag, Cd, In, Cs, Ba, La, Au, and Hg are networks. It is called a modifier and exists in the network structure.
　Ａｌ、Ｔｉ、Ｓｎ、Ｔｅ、Ｔｌ、Ｐｂ、及びＢｉの酸化物は、中間酸化物と呼ばれ、ネットワークフォーマーとネットワークモディファイアーの中間的な性質を有する。 Oxides of Al, Ti, Sn, Te, Tl, Pb, and Bi are called intermediate oxides and have intermediate properties between network formers and network modifiers.
　第１ガラス層１１の厚みは、１μｍ以上である。第１ガラス層１１の厚みが１μｍ以上であれば、ガラス体１０の用途に適した物性が得られる。第１ガラス層１１の厚みは、好ましくは３０μｍ以上である。また、第１ガラス層１１の厚みは、好ましくは３０ｍｍ以下である。 The thickness of the first glass layer 11 is 1 μm or more. When the thickness of the first glass layer 11 is 1 μm or more, physical properties suitable for the use of the glass body 10 can be obtained. The thickness of the first glass layer 11 is preferably 30 μm or more. The thickness of the first glass layer 11 is preferably 30 mm or less.
　ガラス体１０は、対象物体２０との接合強度を向上すべく、第２ガラス層１２を含む。第２ガラス層１２は、第１ガラス層１１における対象物体２０との対向面１１ａに形成され、その対向面１１ａに直交する方向に、Ｓｉモル濃度が変化する。例えば、第１ガラス層１１からの距離が遠いほど、第２ガラス層１２のＳｉモル濃度が増加する（図１（Ｂ）参照）。なお、第２ガラス層１２の途中でのＳｉモル濃度の変化は特に限定されず、後述するＭ２がＭ１よりも高ければよい。 The glass body 10 includes a second glass layer 12 in order to improve the bonding strength with the target object 20. The second glass layer 12 is formed on the facing surface 11a of the first glass layer 11 with the target object 20, and the Si molar concentration changes in the direction orthogonal to the facing surface 11a. For example, as the distance from the first glass layer 11 increases, the Si molar concentration of the second glass layer 12 increases (see FIG. 1 (B)). The change in the Si molar concentration in the middle of the second glass layer 12 is not particularly limited, and M2, which will be described later, may be higher than M1.
　第２ガラス層１２は、例えば、第１ガラス層１１における対象物体２０との対向面１１ａに対して酸を供給し、Ｓｉ以外の所望の元素をガラスから酸に溶出するリーチングによって形成される。それゆえ、第２ガラス層１２は、第１ガラス層１１における対象物体２０との対向面１１ａに直交する方向に、Ｓｉモル濃度が変化する。 The second glass layer 12 is formed by, for example, leaching to supply an acid to the surface 11a facing the target object 20 in the first glass layer 11 and elute a desired element other than Si from the glass to the acid. Therefore, the Si molar concentration of the second glass layer 12 changes in the direction orthogonal to the surface 11a facing the target object 20 in the first glass layer 11.
　例えば、酸の供給によりリーチング処理する場合、酸は、酸性水溶液として供給されてもよいし、酸性蒸気として供給されてもよく、酸性蒸気を添加したガスのプラズマ、ラジカルあるいはイオンであってもよい。酸性水溶液は、例えば、硫酸、塩酸、蓚酸、マレイン酸、リン酸、クエン酸、又は混酸を含む。混酸は、硫酸、塩酸若しくは蓚酸とフッ酸との混酸でもよいし、塩酸と硝酸との混酸でもよい。酸性蒸気は、硫化水素、又は亜硫酸を含む。酸は、例えばガラスのネットワークモディファイアーを溶出させる。ガラスのネットワークフォーマーは残る。リーチング処理で使用するリーチング溶液は、リーチング処理されるガラスの組成に応じて選定し、酸性溶液の他、ガラスのネットワークフォーマーを選択的に残存させることができる中性あるいはアルカリ性の溶液であってもよい。以下、酸を用いたリーチング処理を、酸リーチング処理とも呼ぶ。 For example, in the case of leaching treatment by supplying an acid, the acid may be supplied as an acidic aqueous solution, may be supplied as an acidic vapor, or may be a plasma, radical or ion of a gas to which the acidic vapor is added. .. The acidic aqueous solution contains, for example, sulfuric acid, hydrochloric acid, oxalic acid, maleic acid, phosphoric acid, citric acid, or mixed acid. The mixed acid may be sulfuric acid, hydrochloric acid, a mixed acid of oxalic acid and hydrofluoric acid, or a mixed acid of hydrochloric acid and nitric acid. The acidic vapor contains hydrogen sulfide or sulfurous acid. The acid elutes, for example, the network modifier of glass. The glass network former remains. The leaching solution used in the leaching process is a neutral or alkaline solution that can be selected according to the composition of the glass to be leached, and can selectively leave the network former of the glass in addition to the acidic solution. May be good. Hereinafter, the leaching process using an acid is also referred to as an acid leaching process.
　第２ガラス層１２の対象物体２０との対向面１２ａにおけるＳｉモル濃度Ｍ２は、第１ガラス層１１のＳｉモル濃度Ｍ１よりも高く、例えば１７％～３３％であり、好ましくは２５％～３３％である。ガラス体１０のＳｉモル濃度を局所的に石英ガラスのＳｉモル濃度に近づけることで、ガラス体１０と対象物体２０の接合強度を改善できる。 The Si molar concentration M2 on the surface of the second glass layer 12 facing the target object 20 is higher than the Si molar concentration M1 of the first glass layer 11, for example, 17% to 33%, preferably 25% to 33. %. By locally bringing the Si molar concentration of the glass body 10 close to the Si molar concentration of quartz glass, the bonding strength between the glass body 10 and the target object 20 can be improved.
　なお、第２ガラス層１２は、リーチング処理以外の方法で形成されてもよく、例えばＣＶＤ（Ｃｈｅｍｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ）法、ＡＬＤ（Ａｔｏｍｉｃ　Ｌａｙｅｒ　Ｄｅｐｏｓｉｔｉｏｎ）法、又はＰＶＤ（Ｐｈｙｓｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｏｎ）法などで形成されてもよい。これらの方法で形成された第２ガラス層１２は、第１ガラス層１１との界面での相互拡散を促進するために加熱処理されてもよい。加熱処理すると、接合界面付近の原子の固体拡散によりＳｉモル濃度を連続的に変化させることができる。加熱処理は２５℃より高い温度で実施し、１００℃以上５００℃以下が好ましい。加熱処理時間は適宜調整される。なお、リーチング処理によれば、第２ガラス層１２のＳｉモル濃度を連続的に変化させることができる。 The second glass layer 12 may be formed by a method other than the leaching process, and is formed by, for example, a CVD (Chemical Vapor Deposition) method, an ALD (Atomic Layer Deposition) method, or a PVD (Physical Vapor Deposition) method. You may. The second glass layer 12 formed by these methods may be heat-treated in order to promote mutual diffusion at the interface with the first glass layer 11. When heat-treated, the Si molar concentration can be continuously changed by solid diffusion of atoms near the bonding interface. The heat treatment is carried out at a temperature higher than 25 ° C, preferably 100 ° C or higher and 500 ° C or lower. The heat treatment time is adjusted as appropriate. According to the leaching process, the Si molar concentration of the second glass layer 12 can be continuously changed.
　ところで、第２ガラス層１２を形成する際に、第２ガラス層１２にアルカリ土類金属の水酸化物が生成することがある。その水酸化物は、大気中の二酸化炭素と反応し、炭酸塩を生成する。その結果、第２ガラス層１２に、Ｃが取り込まれることがある。第２ガラス層１２のＣモル濃度は、リーチング処理の後に行われる洗浄、リンス、乾燥の処理によって調整できる。洗浄は第２ガラス層１２の表面を薬液で処理し、リンスは薬液と第２ガラス層１２との反応生成物を洗い流し、乾燥は表面を乾燥させる。 By the way, when the second glass layer 12 is formed, a hydroxide of an alkaline earth metal may be formed on the second glass layer 12. The hydroxide reacts with carbon dioxide in the atmosphere to produce carbonate. As a result, C may be incorporated into the second glass layer 12. The C molar concentration of the second glass layer 12 can be adjusted by a washing, rinsing and drying treatment performed after the leaching treatment. Washing treats the surface of the second glass layer 12 with a chemical solution, rinsing flushes the reaction product between the chemical solution and the second glass layer 12, and drying dries the surface.
　第２ガラス層１２がＣを含む場合、含まない場合に比べて、ＳｉとＯの結合が減少し、機械的な強度が低下する。例えば、ネットワークモディファイアーであるＣａＯに比べて、炭酸塩であるＣａＣＯ３は、密度が低く、機械的な強度が低下する。従って、ガラス体１０と対象物体２０との接合後に、第１ガラス層１１と対象物体２０とを剥離する際に、第２ガラス層１２を選択的に破壊でき、第１ガラス層１１と対象物体２０の破壊を防止できる。 When the second glass layer 12 contains C, the bond between Si and O is reduced and the mechanical strength is lowered as compared with the case where C is not contained. For example, the carbonate CaCO 3 has a lower density and lower mechanical strength than the network modifier CaO. Therefore, after the glass body 10 and the target object 20 are joined, the second glass layer 12 can be selectively destroyed when the first glass layer 11 and the target object 20 are separated from each other, and the first glass layer 11 and the target object 20 can be selectively destroyed. 20 can be prevented from being destroyed.
　第２ガラス層１２がＣを含む場合、第２ガラス層１２のＣモル濃度の最大値Ｃｍａｘは例えば０．１％～２０％である。Ｃｍａｘが０．１％以上であれば、第１ガラス層１１と対象物体２０とを剥離する際に、第２ガラス層１２を選択的に破壊できる。また、Ｃｍａｘが２０％以下であれば、意図しない剥離を防止できる。Ｃｍａｘは、好ましくは３％～２０％である。 When the second glass layer 12 contains C, the maximum value Cmax of the C molar concentration of the second glass layer 12 is, for example, 0.1% to 20%. When Cmax is 0.1% or more, the second glass layer 12 can be selectively destroyed when the first glass layer 11 and the target object 20 are separated from each other. Further, when Cmax is 20% or less, unintended peeling can be prevented. Cmax is preferably 3% to 20%.
　なお、ガラス体１０と対象物体２０との接合後に、第１ガラス層１１と対象物体２０とを剥離する予定がない場合、第２ガラス層１２はＣを実質的に含まなくてもよい。ここで、第２ガラス層１２がＣを実質的に含まないとは、第２ガラス層１２のＣモル濃度の最大値Ｃｍａｘが０．１％未満であることを意味する。Ｃｍａｘが０．１％未満であれば、高い接合強度が得られる。 If there is no plan to separate the first glass layer 11 and the target object 20 after joining the glass body 10 and the target object 20, the second glass layer 12 may not substantially contain C. Here, the fact that the second glass layer 12 does not substantially contain C means that the maximum value Cmax of the C molar concentration of the second glass layer 12 is less than 0.1%. When Cmax is less than 0.1%, high bonding strength can be obtained.
　第２ガラス層１２の厚みは、例えば５ｎｍ～３００ｎｍであり、好ましくは２５ｎｍ～１５０ｎｍである。 The thickness of the second glass layer 12 is, for example, 5 nm to 300 nm, preferably 25 nm to 150 nm.
　ガラス体１０は、第２ガラス層１２における対象物体２０との対向面１２ａに形成される結晶性又は非結晶性（アモルファス性）の金属酸化物層１３を更に含んでもよい。金属酸化物層１３は、例えばＳｉＯ２である。金属酸化物層１３は、Ｓｉ以外の元素がドーピングされたＳｉＯ２であってもよい。金属酸化物層１３は、ＣＶＤ法、ＡＬＤ法、又はＰＶＤ法などで形成される。また、金属酸化物層１３は、ガラス体１０のリーチング処理によって形成してもよい。リーチング処理では、元素ごとに溶出速度が異なることを利用して、Ｓｉモル濃度を高めることが可能である。 The glass body 10 may further include a crystalline or non-crystalline (amorphous) metal oxide layer 13 formed on the surface 12a of the second glass layer 12 facing the target object 20. The metal oxide layer 13 is, for example, SiO 2 . The metal oxide layer 13 may be SiO 2 doped with an element other than Si. The metal oxide layer 13 is formed by a CVD method, an ALD method, a PVD method, or the like. Further, the metal oxide layer 13 may be formed by a leaching treatment of the glass body 10. In the leaching process, it is possible to increase the Si molar concentration by utilizing the fact that the elution rate differs for each element.
　金属酸化物層１３における対象物体２０との対向面１３ａが、ガラス体１０の接合面である。接合面の表面粗さＲａは、例えば、０．１ｎｍよりも大きく１０ｎｍよりも小さい。Ｒａは、好ましくは０．２ｎｍ～１．０ｎｍである。Ｒａは、日本工業規格ＪＩＳ　Ｂ０６０１：１９９４に記載の「算術平均粗さ」である。 The facing surface 13a of the metal oxide layer 13 with the target object 20 is the joining surface of the glass body 10. The surface roughness Ra of the joint surface is, for example, greater than 0.1 nm and less than 10 nm. Ra is preferably 0.2 nm to 1.0 nm. Ra is the "arithmetic mean roughness" described in Japanese Industrial Standards JIS B0601: 1994.
　金属酸化物層１３のＳｉモル濃度Ｍ３は、第２ガラス層１２の対象物体２０との対向面１２ａにおけるＳｉモル濃度Ｍ２と同等以上であり、且つ一定である。金属酸化物層１３は、ガラス体１０と対象物体２０との接合強度を向上し、また、Ｓｉ以外の金属などが第１ガラス層１１から対象物体２０に拡散するのを抑制する。 The Si molar concentration M3 of the metal oxide layer 13 is equal to or higher than the Si molar concentration M2 on the surface 12a facing the target object 20 of the second glass layer 12, and is constant. The metal oxide layer 13 improves the bonding strength between the glass body 10 and the target object 20, and also suppresses the diffusion of metals other than Si from the first glass layer 11 to the target object 20.
　Ｍ３は、例えば１７％～３３％であり、好ましくは３０％～３３％であり、より好ましくは３３％である。金属酸化物層１３がＳｉＯ２である場合、Ｍ３は３３％であり、高い接合強度が得られる。金属酸化物層１３のＳｉモル濃度のバラツキは、±１％以内である。 M3 is, for example, 17% to 33%, preferably 30% to 33%, and more preferably 33%. When the metal oxide layer 13 is SiO 2 , M3 is 33%, and high bonding strength can be obtained. The variation in the Si molar concentration of the metal oxide layer 13 is within ± 1%.
　金属酸化物層１３の厚みは、例えば０．１ｎｍ～５００μｍであり、好ましくは１０ｎｍ～１μｍである。 The thickness of the metal oxide layer 13 is, for example, 0.1 nm to 500 μm, preferably 10 nm to 1 μm.
　ガラス体１０におけるＳｉモル濃度の分布は、Ｘ線光電分光分析装置（ＸＰＳ：Ｘ－ｒａｙ　Ｐｈｏｔｏｅｌｅｃｔｒｏｎ　Ｓｐｅｃｔｒｏｓｃｏｐｙ）／ＥＳＣＡ（Ｅｌｅｃｔｒｏｎ　Ｓｐｅｃｔｒｏｓｃｏｐｙ　ｆｏｒ　Ｃｈｅｍｉｃａｌ　Ａｎａｌｙｓｉｓ））で測定する。測定点の間隔は、例えば１０ｎｍ以下であり、好ましくは５ｎｍ以下である。 The distribution of the Si molar concentration in the glass body 10 is measured by an X-ray photoelectric spectroscopic analyzer (XPS: X-ray Photoelectron Spectroscopic) / ESCA (Electron Spectroscopic for Chemical Analysis). The interval between measurement points is, for example, 10 nm or less, preferably 5 nm or less.
　なお、Ｓｉモル濃度の分布は、Ｘ線光電分光分析装置に加えて、透過型電子顕微鏡（ＴＥＭ：Ｔｒａｎｓｍｉｓｓｉｏｎ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ）を併用して、測定してもよい。 The distribution of Si molar concentration may be measured by using a transmission electron microscope (TEM: Transmission Electron Microscope) in addition to the X-ray photoelectric spectroscopic analyzer.
　第１ガラス層１１と第２ガラス層１２の境界は、Ｓｉモル濃度の分析の結果を用いて決める。第１ガラス層１１におけるＳｉモル濃度は、回帰直線（ｙ＝ａ１ｘ＋ｂ１）で表す。その回帰直線は、最小二乗法で求める。ａ１は、±０．０３５０（％／ｎｍ）以内の範囲で設定する。一方、第２ガラス層１２におけるＳｉモル濃度は、近似曲線で表す。近似曲線は、最小二乗法で求められ、多項式で近似する。なお、近似曲線は、隣り合う２つの測定点を直線で結んだものであってもよい。各測定点のデータは、生データではなく、移動平均データであってもよい。直線（ｙ＝ａ１ｘ＋ｂ１＋σ１）と、近似曲線との交点が、第１ガラス層１１と第２ガラス層１２の境界である。σ１は、第１ガラス層１１におけるＳｉモル濃度の標準偏差である。 The boundary between the first glass layer 11 and the second glass layer 12 is determined using the result of the analysis of the Si molar concentration. The Si molar concentration in the first glass layer 11 is represented by a regression line (y = a1x + b1). The regression line is obtained by the method of least squares. a1 is set within the range of ± 0.0350 (% / nm). On the other hand, the Si molar concentration in the second glass layer 12 is represented by an approximate curve. The approximate curve is obtained by the least squares method and approximated by a polynomial. The approximate curve may be a straight line connecting two adjacent measurement points. The data at each measurement point may be moving average data rather than raw data. The intersection of the straight line (y = a1x + b1 + σ1) and the approximate curve is the boundary between the first glass layer 11 and the second glass layer 12. σ1 is the standard deviation of the Si molar concentration in the first glass layer 11.
　同様に、第２ガラス層１２と金属酸化物層１３の境界は、Ｓｉモル濃度の分析の結果を用いて決める。金属酸化物層１３におけるＳｉモル濃度は、回帰直線（ｙ＝ａ２ｘ＋ｂ２）で表す。その回帰直線は、最小二乗法で求める。ａ２は、±０．０３５０（％／ｎｍ）以内の範囲で設定する。一方、第２ガラス層１２におけるＳｉモル濃度は、近似曲線で表す。近似曲線は、最小二乗法で求められ、多項式で近似する。なお、近似曲線は、隣り合う２つの測定点を直線で結んだものであってもよい。各測定点のデータは、生データではなく、移動平均データであってもよい。直線（ｙ＝ａ２ｘ＋ｂ２－σ２）と、近似曲線との交点が、金属酸化物層１３と第２ガラス層１２の境界である。σ２は、金属酸化物層１３におけるＳｉモル濃度の標準偏差である。 Similarly, the boundary between the second glass layer 12 and the metal oxide layer 13 is determined using the result of the analysis of the Si molar concentration. The Si molar concentration in the metal oxide layer 13 is represented by a regression line (y = a2x + b2). The regression line is obtained by the method of least squares. a2 is set within the range of ± 0.0350 (% / nm). On the other hand, the Si molar concentration in the second glass layer 12 is represented by an approximate curve. The approximate curve is obtained by the least squares method and approximated by a polynomial. The approximate curve may be a straight line connecting two adjacent measurement points. The data at each measurement point may be moving average data rather than raw data. The intersection of the straight line (y = a2x + b2-σ2) and the approximate curve is the boundary between the metal oxide layer 13 and the second glass layer 12. σ2 is the standard deviation of the Si molar concentration in the metal oxide layer 13.
　次に、図２を参照して、変形例に係る接合用ガラス体１０について説明する。図２（Ａ）に示すように、接合用ガラス体１０は、第１ガラス層１１と第２ガラス層１２とを含み、金属酸化物層１３を含まなくてもよい。この場合、第２ガラス層１２における対象物体２０との対向面１２ａが、ガラス体１０の接合面である。 Next, with reference to FIG. 2, the joining glass body 10 according to the modified example will be described. As shown in FIG. 2A, the bonding glass body 10 includes the first glass layer 11 and the second glass layer 12, and may not include the metal oxide layer 13. In this case, the surface 12a facing the target object 20 in the second glass layer 12 is the joint surface of the glass body 10.
　また、図２（Ｂ）に示すように、接合用ガラス体１０は、第１ガラス層１１を挟んで両側に第２ガラス層１２を含んでもよい。第１ガラス層１１の両側に対象物体２０を接合することができる。更に、図２（Ｃ）に示すように、接合用ガラス体１０は、第１ガラス層１１を挟んで両側に金属酸化物層１３を含んでもよい。 Further, as shown in FIG. 2B, the bonding glass body 10 may include the second glass layer 12 on both sides of the first glass layer 11. The target object 20 can be joined to both sides of the first glass layer 11. Further, as shown in FIG. 2C, the bonding glass body 10 may include the metal oxide layers 13 on both sides of the first glass layer 11.
　次に、図３及び図４を参照して、一実施形態とその変形例に係る接合体３０について説明する。図３などに示すように、接合体３０は、ガラス体１０と、ガラス体１０に接合された対象物体２０と、を含む。 Next, with reference to FIGS. 3 and 4, the bonded body 30 according to the embodiment and its modified example will be described. As shown in FIG. 3 and the like, the bonded body 30 includes a glass body 10 and a target object 20 bonded to the glass body 10.
　対象物体２０は、例えば、図３（Ａ）に示すように、ガラス体１０と同様に、第１ガラス層２１と、第２ガラス層２２と、金属酸化物層２３と、を含んでもよい。第１ガラス層２１は第１ガラス層１１と同様に形成され、第２ガラス層２２は第２ガラス層１２と同様に形成され、金属酸化物層２３は金属酸化物層１３と同様に形成される。多成分ガラス同士の接合強度を改善できる。 For example, as shown in FIG. 3A, the target object 20 may include a first glass layer 21, a second glass layer 22, and a metal oxide layer 23, similarly to the glass body 10. The first glass layer 21 is formed in the same manner as the first glass layer 11, the second glass layer 22 is formed in the same manner as the second glass layer 12, and the metal oxide layer 23 is formed in the same manner as the metal oxide layer 13. The glass. The bonding strength between multi-component glasses can be improved.
　対象物体２０は、図３（Ａ）に示すように、ガラス体１０に直接に接している。この場合、ガラス体１０の接合面１３ａと、対象物体２０の接合面２３ａとは、予め、表面活性化法によって活性化される。表面活性化法は、例えば、特許文献１に記載の技術、いわゆるシーケンシャルプラズマ法を含む。シーケンシャルプラズマ法は、例えば、酸素ガスを用いた反応性イオンエッチングと、窒素ガスを用いた反応性イオンエッチングと、窒素ラジカルの照射と、を含む。 As shown in FIG. 3A, the target object 20 is in direct contact with the glass body 10. In this case, the joint surface 13a of the glass body 10 and the joint surface 23a of the target object 20 are activated in advance by the surface activation method. The surface activation method includes, for example, the technique described in Patent Document 1, the so-called sequential plasma method. The sequential plasma method includes, for example, reactive ion etching using oxygen gas, reactive ion etching using nitrogen gas, and irradiation with nitrogen radicals.
　シーケンシャルプラズマ法は、ガラス等の接合面を活性化する。活性化した接合面が水蒸気又は水などに接触すると、親水基であるＯＨ基が接合面に生成される。その後、接合時にＯＨ基同士の水素結合が生じ、高い接合強度が得られる。接合の後、アニール処理が実施されてもよい。アニール処理によって、水素結合が共有結合に変わり、より高い接合強度が得られる。 The sequential plasma method activates the joint surface of glass or the like. When the activated joint surface comes into contact with water vapor, water, or the like, OH groups, which are hydrophilic groups, are generated on the joint surface. After that, hydrogen bonds between OH groups are generated at the time of bonding, and high bonding strength is obtained. After joining, annealing may be performed. By the annealing treatment, the hydrogen bond is changed to a covalent bond, and higher bond strength is obtained.
　なお、表面活性化法は、シーケンシャルプラズマ法には限定されない。表面活性化法は、例えば、酸素ガスを用いた反応性イオンエッチングのみを含んでもよい。この場合も、活性化した接合面が水蒸気又は水などに接触すると、親水基であるＯＨ基が接合面に生成される。その後、接合時にＯＨ基同士の水素結合が生じ、水素結合の脱水縮合反応で共有結合が生じることで、高い接合強度が得られる。 The surface activation method is not limited to the sequential plasma method. The surface activation method may include, for example, only reactive ion etching using oxygen gas. Also in this case, when the activated joint surface comes into contact with water vapor or water, an OH group, which is a hydrophilic group, is generated on the joint surface. After that, hydrogen bonds between OH groups are generated at the time of bonding, and covalent bonds are generated by the dehydration condensation reaction of the hydrogen bonds, so that high bonding strength can be obtained.
　図３（Ｂ）に示すように、ガラス体１０と、対象物体２０とは、無機物の中間層４０を介して接合されもよい。中間層４０は、ガラス体１０の接合面に予め形成される接合層４１と、対象物体２０の接合面に予め形成される接合層４２と、を含む。 As shown in FIG. 3B, the glass body 10 and the target object 20 may be joined via an intermediate layer 40 of an inorganic substance. The intermediate layer 40 includes a joint layer 41 previously formed on the joint surface of the glass body 10 and a joint layer 42 previously formed on the joint surface of the target object 20.
　接合層４１、４２は、例えば、Ａｌ、Ｓｉ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｙ、Ｚｒ、Ｈｆ、及びＴａのうち１つ以上の元素を含む、金属で形成される。金属は、合金を含む。金属の原子拡散を利用して、ガラス体１０と対象物体２０とを接合できる。接合層４１、４２は、それぞれ、複数の金属層を含んでもよい。 The bonding layers 41 and 42 are formed of a metal containing, for example, one or more elements of Al, Si, Ti, V, Cr, Mn, Fe, Y, Zr, Hf, and Ta. Metals include alloys. The glass body 10 and the target object 20 can be joined by utilizing the atomic diffusion of the metal. The bonding layers 41 and 42 may each include a plurality of metal layers.
　また、接合層４１、４２は、Ａｌ、Ｓｉ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｙ、Ｚｒ、Ｈｆ、及びＴａのうち１つ以上の元素を含む、金属酸化物で形成されてもよい。金属酸化物は、スパッタ法、反応性スパッタ法、又はＡＬＤ法などの成膜方法で形成される。スパッタ法は、金属酸化物のターゲットと、不活性ガスとを用いる。反応性スパッタ法は、金属のターゲットと、希ガス等の不活性ガスと反応性ガス（例えば酸素ガス）との混合ガスとを用いる。 Further, the bonding layers 41 and 42 may be formed of a metal oxide containing one or more elements of Al, Si, Ti, V, Cr, Mn, Fe, Y, Zr, Hf, and Ta. .. The metal oxide is formed by a film forming method such as a sputtering method, a reactive sputtering method, or an ALD method. The sputtering method uses a metal oxide target and an inert gas. The reactive sputtering method uses a metal target and a mixed gas of an inert gas such as a rare gas and a reactive gas (for example, oxygen gas).
　接合層４１、４２が金属酸化物である場合、金属酸化物を成膜する過程で発現する金属酸化物の表面活性を利用し、真空、大気、不活性ガスなどの雰囲気下で接合を実施してもよいし、上記の表面活性化法により接合層４１、４２の表面を活性化したうえで、接合を実施してもよい。上記の表面活性化法によって活性化された接合面が水蒸気又は水などに接触すると、親水基であるＯＨ基が接合面に生成される。その後、接合時にＯＨ基同士の水素結合が生じ、更に水素結合の脱水縮合反応で共有結合が生じることで高い接合強度が得られる。 When the bonding layers 41 and 42 are metal oxides, the surface activity of the metal oxide developed in the process of forming the metal oxide is utilized, and the bonding is performed in an atmosphere such as vacuum, atmosphere, or an inert gas. Alternatively, the surface of the bonding layers 41 and 42 may be activated by the above-mentioned surface activation method, and then the bonding may be performed. When the bonding surface activated by the above surface activation method comes into contact with water vapor, water, or the like, OH groups, which are hydrophilic groups, are generated on the bonding surface. After that, hydrogen bonds between OH groups are generated at the time of bonding, and further, a covalent bond is generated by the dehydration condensation reaction of the hydrogen bonds, so that high bonding strength can be obtained.
　接合層４１、４２が金属である場合、接合層４１、４２を原子拡散法により接合した後に、接合層４１、４２をガラス体１０に含まれる酸素で酸化してもよい。酸化を促進するために接合体３０が加熱処理されてもよい。接合層４１、４２を酸化することで、光透過率、電気伝導率、熱伝導率、熱膨張係数などの物理的特性を変化させることができる。 When the bonding layers 41 and 42 are made of metal, the bonding layers 41 and 42 may be bonded by an atomic diffusion method, and then the bonding layers 41 and 42 may be oxidized with oxygen contained in the glass body 10. The bonded body 30 may be heat-treated to promote oxidation. By oxidizing the bonding layers 41 and 42, physical properties such as light transmittance, electric conductivity, thermal conductivity, and coefficient of thermal expansion can be changed.
　図３（Ｃ）及び図３（Ｄ）に示すように、対象物体２０は、ガラス板ではなくてもよく、例えば、Ｓｉ、ＧａＮ、ＳｉＣ、若しくはＧａ２Ｏ３などの半導体基板、ＬｉＴａＯ３、ＬｉＮｂＯ３、若しくはＡｌＮなどの圧電基板、Ａｌ２Ｏ３などの酸化物基板、又はＳｉＮなどの窒化物基板であってもよい。ガラス体１０と対象物体２０とは、図３（Ｃ）に示すように直接に接してもよいし、図３（Ｄ）に示すように中間層４０を介して接合されてもよい。 As shown in FIGS. 3C and 3D, the target object 20 does not have to be a glass plate, and is, for example, a semiconductor substrate such as Si, GaN, SiC, or Ga 2 O 3 , LiTaO 3 . It may be a piezoelectric substrate such as LiNbO 3 or AlN, an oxide substrate such as Al 2 O 3 , or a nitride substrate such as SiN. The glass body 10 and the target object 20 may be in direct contact with each other as shown in FIG. 3C, or may be joined via an intermediate layer 40 as shown in FIG. 3D.
　また、図４（Ａ）～図４（Ｂ）に示すように、対象物体２０は、ガラス体１０と同様に、第１ガラス層２１と第２ガラス層２２とを含み、金属酸化物層２３とを含まなくてもよい。ガラス体１０と対象物体２０とは、図４（Ａ）に示すように直接に接してもよいし、図４（Ｂ）に示すように中間層４０を介して接合されてもよい。 Further, as shown in FIGS. 4A to 4B, the target object 20 includes the first glass layer 21 and the second glass layer 22 and the metal oxide layer 23, similarly to the glass body 10. And may not be included. The glass body 10 and the target object 20 may be in direct contact with each other as shown in FIG. 4 (A), or may be joined via an intermediate layer 40 as shown in FIG. 4 (B).
　図４（Ｃ）～図４（Ｄ）に示すように、対象物体２０は、ガラス板ではなくてもよく、例えば、Ｓｉ、ＧａＮ、ＳｉＣ、若しくはＧａ２Ｏ３などの半導体基板、ＬｉＴａＯ３、ＬｉＮｂＯ３、若しくはＡｌＮなどの圧電基板、Ａｌ２Ｏ３などの酸化物基板、又はＳｉＮなどの窒化物基板であってもよい。ガラス体１０と対象物体２０とは、図４（Ｃ）に示すように直接に接してもよいし、図４（Ｄ）に示すように中間層４０を介して接合されてもよい。 As shown in FIGS. 4 (C) to 4 (D), the target object 20 does not have to be a glass plate, and is, for example, a semiconductor substrate such as Si, GaN, SiC, or Ga 2 O 3 , LiTaO 3 . It may be a piezoelectric substrate such as LiNbO 3 or AlN, an oxide substrate such as Al 2 O 3 , or a nitride substrate such as SiN. The glass body 10 and the target object 20 may be in direct contact with each other as shown in FIG. 4 (C), or may be joined via an intermediate layer 40 as shown in FIG. 4 (D).
　図示しないが、ガラス体１０又は対象物体２０は、その接合面に、凹部又は貫通穴を有してもよい。 Although not shown, the glass body 10 or the target object 20 may have a recess or a through hole in the joint surface thereof.
　接合体３０の接合強度は、図５に示すクラックオープニング法により測定する。クラックオープニング法では、互いに接合されたガラス体１０と対象物体２０の接合界面に、外側からカミソリの刃のようなブレードＢＬを挿入し、剥離長さＬを測定する。剥離長さＬが短いほど、接合強度が高い。接合強度が十分に高い場合、ブレードＢＬの挿入によってガラス体１０又は対象物体２０が破壊されることもある。 The joint strength of the joint 30 is measured by the crack opening method shown in FIG. In the crack opening method, a blade BL like a razor blade is inserted from the outside at the bonding interface between the glass body 10 and the target object 20 bonded to each other, and the peeling length L is measured. The shorter the peeling length L, the higher the bonding strength. If the bonding strength is sufficiently high, the glass body 10 or the target object 20 may be destroyed by the insertion of the blade BL.
　剥離長さＬから接合強度γを算出する際には、下記式（１）の関係式を使用する。 When calculating the bonding strength γ from the peeling length L, the relational expression of the following equation (1) is used.
Figure JPOXMLDOC01-appb-M000001
 上記式（１）において、Ｅ１はガラス体１０のヤング率であり、Ｅ２は対象物体２０のヤング率であり、ｔ１はガラス体１０の厚みであり、ｔ２は対象物体２０の厚みであり、ｔ０はブレードＢＬの厚みである。接合強度γは接合界面の表面エネルギーとして求められ、接合強度γの単位はＪ／ｍ２である。
Figure JPOXMLDOC01-appb-M000001
 In the above formula (1), E1 is the Young's modulus of the glass body 10, E2 is the Young's modulus of the target object 20, t1 is the thickness of the glass body 10, t2 is the thickness of the target object 20, and t0. Is the thickness of the blade BL. The bonding strength γ is obtained as the surface energy of the bonding interface, and the unit of the bonding strength γ is J / m 2 .
　以下、実験データについて説明する。まず、実験で用いた２種類のガラスＡ～Ｂの組成を表１に示す。 The experimental data will be explained below. First, Table 1 shows the compositions of the two types of glasses A to B used in the experiment.
Figure JPOXMLDOC01-appb-T000002
 　ガラスＡは、無アルカリガラスであり、より詳細にはアルミノボロシリケートガラスである。ガラスＢも、無アルカリガラスであり、より詳細にはアルミノシリケートガラスである。ガラスＡ～Ｂは、いずれも、ＳｉＯ２含有量が７０ｍｏｌ％以下である。実験では、ガラスＡ、Ｂ以外に、ＳｉＯ２含有量が１００ｍｏｌ％の石英ガラスも用意した。
Figure JPOXMLDOC01-appb-T000002
 The glass A is a non-alkali glass, and more specifically, an aluminum noborosilicate glass. Glass B is also non-alkali glass, more specifically aluminosilicate glass. Each of the glasses A to B has a SiO 2 content of 70 mol% or less. In the experiment, in addition to the glasses A and B, quartz glass having a SiO 2 content of 100 mol% was also prepared.
　下記の例１～例９では、表１に記載のガラス同士の接合を実施した。接合条件及び評価結果を、表２～表３に示す。下記の例２～例５及び例７～例９が実施例であり、下記の例１、及び例６が参考例である。 In Examples 1 to 9 below, the glasses shown in Table 1 were joined together. The joining conditions and evaluation results are shown in Tables 2 to 3. Examples 2 to 5 and 7 to 9 below are examples, and examples 1 and 6 below are reference examples.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
 　表２及び表３において、密着性と剥離性は、接合強度で評価した。
Figure JPOXMLDOC01-appb-T000004
 In Tables 2 and 3, the adhesion and the peelability were evaluated by the bonding strength.
　密着性が「Ａ」であることは接合強度が２．０Ｊ／ｍ２以上あるいは測定限界を上回る接合強度であることを意味し、密着性が「Ｂ」であることは接合強度が０．８Ｊ／ｍ２以上２．０Ｊ／ｍ２未満であることを意味し、密着性が「Ｃ」であることは接合強度が０．８Ｊ／ｍ２未満であることを意味する。接合強度が０．８Ｊ／ｍ２以上であれば、ＭＩＬ－ＳＴＤ－８８３規格等の工業規格に従った、切断した接合体のダイシェア強度試験で良好な結果を得られる。 When the adhesion is "A", it means that the bonding strength is 2.0J / m 2 or more or exceeds the measurement limit, and when the adhesion is "B", the bonding strength is 0.8J. It means that it is more than / m 2 and less than 2.0 J / m 2 , and that the adhesion is "C" means that the bonding strength is less than 0.8 J / m 2 . When the joint strength is 0.8 J / m 2 or more, good results can be obtained in the die shear strength test of the cut joint according to the industrial standard such as MIL-STD-883 standard.
　また、剥離性が「Ａ」であることは接合強度が０．３Ｊ／ｍ２未満であることを意味し、剥離性が「Ｂ」であることは接合強度が０．３Ｊ／ｍ２以上１．０Ｊ／ｍ２未満であることを意味し、剥離性が「Ｃ」であることは接合強度が１．０Ｊ／ｍ２以上であることを意味する。接合強度が１．０Ｊ／ｍ２未満であれば、接合界面にブレードを挿入することによりガラス同士を剥離することが可能である。なお、実験で使用したブレードＢＬは厚みｔ０が０．１ｍｍであった。 Further, when the peelability is "A", it means that the bonding strength is less than 0.3 J / m 2 , and when the peeling property is "B", the bonding strength is 0.3 J / m 2 or more 1 It means that it is less than 0.0 J / m 2 , and that the peelability is "C" means that the bonding strength is 1.0 J / m 2 or more. If the bonding strength is less than 1.0 J / m 2 , the glasses can be separated from each other by inserting a blade into the bonding interface. The blade BL used in the experiment had a thickness t0 of 0.1 mm.
　以下、例１～例９の接合条件及び評価結果について詳細に説明する。なお、例１～例５では、表面活性化法で接合を実施した。一方、例６～例９では、原子拡散法で接合を実施した。 Hereinafter, the joining conditions and evaluation results of Examples 1 to 9 will be described in detail. In Examples 1 to 5, joining was carried out by the surface activation method. On the other hand, in Examples 6 to 9, the bonding was carried out by the atomic diffusion method.
　例１では、２つの石英ガラスを接合した。石英ガラスは、ガラス体の厚みが０．５ｍｍであり、第２ガラス層と金属酸化物を有さなかった。接合前に、２つの石英ガラスの互いに対向する接合面を、酸素ガスを用いた反応性イオンエッチングのみで活性化し、水蒸気に曝した。酸素ガスを用いた反応性イオンエッチングの処理時間は、１２０秒であった。その後、大気中で、２つの石英ガラスを接合した。接合強度は１．５Ｊ／ｍ２以上であり、密着性の評価は「Ｂ」であり、剥離性の評価は「Ｃ」であった。 In Example 1, two quartz glasses were joined. Quartz glass had a glass body thickness of 0.5 mm and did not have a second glass layer and a metal oxide. Prior to joining, the opposing surfaces of the two quartz glasses were activated only by reactive ion etching using oxygen gas and exposed to water vapor. The processing time for reactive ion etching using oxygen gas was 120 seconds. Then, two quartz glasses were joined in the atmosphere. The bonding strength was 1.5 J / m 2 or more, the evaluation of adhesion was "B", and the evaluation of peelability was "C".
　例２では、２つのガラスＡを接合した。ガラスＡは、ガラス体の厚みが０．５ｍｍであり、第２ガラス層の厚みが４５ｎｍであった。接合前に、２つのガラスＡの互いに対向する接合面を酸リーチング処理した。酸リーチング処理の後にカーボンが残存しないように、各接合面を洗浄した。その後、酸素ガスを用いた反応性イオンエッチングのみで各接合面を活性化し、続いて各接合面を水蒸気に曝した。酸素ガスを用いた反応性イオンエッチングの処理時間は、１２０秒であった。その後、大気中で、２つのガラスＡを接合した。接合強度は０．９Ｊ／ｍ２であり、密着性の評価は「Ｂ」であり、剥離性の評価は「Ｂ」であった。 In Example 2, two glasses A were joined. In the glass A, the thickness of the glass body was 0.5 mm, and the thickness of the second glass layer was 45 nm. Prior to joining, the joining surfaces of the two glasses A facing each other were subjected to acid leaching treatment. Each joint surface was washed so that no carbon remained after the acid leaching treatment. Then, each joint surface was activated only by reactive ion etching using oxygen gas, and then each joint surface was subsequently exposed to water vapor. The processing time for reactive ion etching using oxygen gas was 120 seconds. Then, the two glasses A were joined in the atmosphere. The bonding strength was 0.9 J / m 2 , the evaluation of adhesion was "B", and the evaluation of peelability was "B".
　例３では、２つのガラスＢを接合した。ガラスＢは、ガラス体の厚みが０．５ｍｍであり、第２ガラス層の厚みが６０ｎｍであった。接合前に、２つのガラスＢの互いに対向する接合面を酸リーチング処理した。酸リーチング処理の後にカーボンが残存しないように、各接合面を洗浄した。その後、酸素ガスを用いた反応性イオンエッチングのみで各接合面を活性化し、続いて各接合面を水蒸気に曝した。酸素ガスを用いた反応性イオンエッチングの処理時間は、１２０秒であった。その後、大気中で、２つのガラスＢを接合した。接合強度は０．２Ｊ／ｍ２であり、密着性の評価は「Ｃ」であり、剥離性の評価は「Ａ」であった。 In Example 3, two glasses B were joined. In the glass B, the thickness of the glass body was 0.5 mm, and the thickness of the second glass layer was 60 nm. Prior to joining, the joining surfaces of the two glasses B facing each other were subjected to acid leaching treatment. Each joint surface was washed so that no carbon remained after the acid leaching treatment. Then, each joint surface was activated only by reactive ion etching using oxygen gas, and then each joint surface was subsequently exposed to water vapor. The processing time for reactive ion etching using oxygen gas was 120 seconds. Then, the two glasses B were joined in the atmosphere. The bonding strength was 0.2 J / m 2 , the evaluation of adhesion was "C", and the evaluation of peelability was "A".
　例４では、２つのガラスＡを接合した。ガラスＡは、ガラス体の厚みが０．５ｍｍであり、第２ガラス層の厚みが４５ｎｍであり、金属酸化物層が１５ｎｍであった。接合前に、２つのガラスＡの互いに対向する接合面を酸リーチング処理した。酸リーチング処理の後にカーボンが残存していた。その後、各接合面に、ＳｉＯ２ターゲットを用いたスパッタ法で非結晶性のＳｉＯ２膜である金属酸化物層を形成し、酸素ガスを用いた反応性イオンエッチングのみで各ＳｉＯ２膜の表面を活性化し、続いて各ＳｉＯ２膜の表面を水蒸気に曝した。酸素ガスを用いた反応性イオンエッチングの処理時間は、１２０秒であった。その後、大気中で、２つのＳｉＯ２膜を介して２つのガラスＡを接合した。接合強度は０．９Ｊ／ｍ２であり、密着性の評価は「Ｂ」であり、剥離性の評価は「Ｂ」であった。 In Example 4, two glasses A were joined. In the glass A, the thickness of the glass body was 0.5 mm, the thickness of the second glass layer was 45 nm, and the thickness of the metal oxide layer was 15 nm. Prior to joining, the joining surfaces of the two glasses A facing each other were subjected to acid leaching treatment. Carbon remained after the acid leaching treatment. After that, a metal oxide layer, which is a non-crystalline SiO 2 film, is formed on each joint surface by a sputtering method using a SiO 2 target, and the surface of each SiO 2 film is obtained only by reactive ion etching using oxygen gas. Was activated, and subsequently the surface of each SiO 2 film was exposed to steam. The processing time for reactive ion etching using oxygen gas was 120 seconds. Then, in the atmosphere, two glasses A were joined via two SiO 2 films. The bonding strength was 0.9 J / m 2 , the evaluation of adhesion was "B", and the evaluation of peelability was "B".
　例５では、２つのガラスＡに対して酸リーチング処理を実施せず、ｐＨ＝１１のアルカリ溶液で２つのガラスＡをエッチング処理した後に中性溶液でガラス表面をリーチング処理し、Ｃｍａｘを２０モル％に調整した後にＳｉＯ２ターゲットを用いたスパッタ法で非結晶性のＳｉＯ２膜である金属酸化物層を形成した。酸素ガスを用いた反応性イオンエッチングのみで各ＳｉＯ２膜の表面を活性化し、続いて各ＳｉＯ２膜の表面を水蒸気に曝した。酸素ガスを用いた反応性イオンエッチングの処理時間は、１２０秒であった。その後、大気中で、２つのＳｉＯ２膜を介して２つのガラスＡを接合した。ガラスＡは、ガラス体の厚みが０．５ｍｍであり、第２ガラス層の厚みが２５ｎｍであり、金属酸化物層の厚みが１５ｎｍであった。剥離は第２ガラス層の破壊により生じ、その接合強度は０．１Ｊ／ｍ２であり、密着性の評価は「Ｃ」であり、剥離性の評価は「Ａ」であった。 In Example 5, the acid leaching treatment is not performed on the two glasses A, the two glasses A are etched with an alkaline solution having a pH of 11, and then the glass surface is leached with a neutral solution to obtain a Cmax of 20 mol. After adjusting to%, a metal oxide layer which is a non-crystalline SiO 2 film was formed by a sputtering method using a SiO 2 target. The surface of each SiO 2 film was activated only by reactive ion etching using oxygen gas, and then the surface of each SiO 2 film was exposed to steam. The processing time for reactive ion etching using oxygen gas was 120 seconds. Then, in the atmosphere, two glasses A were joined via two SiO 2 films. In the glass A, the thickness of the glass body was 0.5 mm, the thickness of the second glass layer was 25 nm, and the thickness of the metal oxide layer was 15 nm. The peeling was caused by the fracture of the second glass layer, the bonding strength thereof was 0.1 J / m 2 , the evaluation of the adhesion was “C”, and the evaluation of the peelability was “A”.
　例６では、２つの石英ガラスを接合した。石英ガラスは、ガラス体の厚みが０．５ｍｍであり、第２ガラス層と金属酸化物を有さなかった。接合前に、２つの石英ガラスの互いに対向する接合面に、厚み２ｎｍのＴｉ膜と、厚み５０ｎｍのＡｕ膜とをこの順番で、スパッタ法で成膜した。その後、大気中で、２つの石英ガラスを接合した。接合強度は、測定限界を上回っており、ブレードを接合界面に挿入すると接合体が破壊し測定できなかった。密着性の評価は「Ａ」であり、剥離性の評価は「Ｃ」であった。 In Example 6, two quartz glasses were joined. Quartz glass had a glass body thickness of 0.5 mm and did not have a second glass layer and a metal oxide. Before joining, a Ti film having a thickness of 2 nm and an Au film having a thickness of 50 nm were formed on the bonding surfaces of the two quartz glasses facing each other by a sputtering method in this order. Then, two quartz glasses were joined in the atmosphere. The joint strength exceeded the measurement limit, and when the blade was inserted into the joint interface, the joint body broke and could not be measured. The evaluation of adhesion was "A", and the evaluation of peelability was "C".
　例７では、２つのガラスＡを接合した。ガラスＡは、ガラス体の厚みが０．５ｍｍであり、第２ガラス層の厚みが４５ｎｍであった。接合前に、２つのガラスＡの互いに対向する接合面を酸リーチング処理した。酸リーチング処理の後にカーボンが残存しないように、各接合面を洗浄した。その後、各接合面に、厚み２ｎｍのＴｉ膜と、厚み５０ｎｍのＡｕ膜とをこの順番で、スパッタ法で成膜した。その後、大気中で、２つのガラスＡを接合した。接合強度は２．０Ｊ／ｍ２であり、密着性の評価は「Ａ」であり、剥離性の評価は「Ｃ」であった。 In Example 7, two glasses A were joined. In the glass A, the thickness of the glass body was 0.5 mm, and the thickness of the second glass layer was 45 nm. Prior to joining, the joining surfaces of the two glasses A facing each other were subjected to acid leaching treatment. Each joint surface was washed so that no carbon remained after the acid leaching treatment. Then, a Ti film having a thickness of 2 nm and an Au film having a thickness of 50 nm were formed on each joint surface in this order by a sputtering method. Then, the two glasses A were joined in the atmosphere. The bonding strength was 2.0 J / m 2 , the evaluation of adhesion was "A", and the evaluation of peelability was "C".
　例８では、２つのガラスＡを接合した。ガラスＡは、ガラス体の厚みが０．５ｍｍであり、第２ガラス層の厚みが４５ｎｍであり、金属酸化物層が１５ｎｍであった。接合前に、２つのガラスＡの互いに対向する接合面を酸リーチング処理した。酸リーチング処理の後にカーボンが残存していた。その後、各接合面に、ＳｉＯ２ターゲットを用いたスパッタ法で非結晶性のＳｉＯ２膜である金属酸化物層を形成し、続いて、厚み２ｎｍのＴｉ膜と、厚み５０ｎｍのＡｕ膜とをこの順番で、スパッタ法で成膜した。その後、大気中で、２つのガラスＡを接合した。接合強度は０．９Ｊ／ｍ２であり、密着性の評価は「Ｂ」であり、剥離性の評価は「Ｂ」であった。 In Example 8, two glasses A were joined. In the glass A, the thickness of the glass body was 0.5 mm, the thickness of the second glass layer was 45 nm, and the thickness of the metal oxide layer was 15 nm. Prior to joining, the joining surfaces of the two glasses A facing each other were subjected to acid leaching treatment. Carbon remained after the acid leaching treatment. After that, a metal oxide layer which is a non-crystalline SiO 2 film is formed on each joint surface by a sputtering method using a SiO 2 target, and then a Ti film having a thickness of 2 nm and an Au film having a thickness of 50 nm are formed. In this order, a film was formed by a sputtering method. Then, the two glasses A were joined in the atmosphere. The bonding strength was 0.9 J / m 2 , the evaluation of adhesion was "B", and the evaluation of peelability was "B".
　例９では、２つのガラスＡに対して酸リーチング処理を実施せず、ｐＨ＝１１のアルカリ溶液で２つのガラスＡをエッチング処理した後に中性溶液でガラス表面をリーチング処理し、Ｃｍａｘを２０モル％に調整した後にＳｉＯ２ターゲットを用いたスパッタ法で非結晶性のＳｉＯ２膜である金属酸化物層を形成し、続いて、厚み２ｎｍのＴｉ膜と、厚み５０ｎｍのＡｕ膜とをこの順番で、スパッタ法で成膜した。その後、大気中で、２つのガラスＡを接合した。ガラスＡは、ガラス体の厚みが０．５ｍｍであり、第２ガラス層の厚みが２５ｎｍであり、金属酸化物層の厚みが１５ｎｍであった。剥離はガラスＡの第２ガラス層と第２ガラス層上に製膜したＴｉ膜の界面で生じ、その接合強度は０．１Ｊ／ｍ２であり、密着性の評価は「Ｃ」であり、剥離性の評価は「Ａ」であった。 In Example 9, the two glasses A are not subjected to the acid leaching treatment, the two glasses A are etched with an alkaline solution having a pH of 11, and then the glass surface is leached with a neutral solution to obtain a Cmax of 20 mol. After adjusting to%, a metal oxide layer which is a non-crystalline SiO 2 film is formed by a sputtering method using a SiO 2 target, and then a Ti film having a thickness of 2 nm and an Au film having a thickness of 50 nm are formed in this order. Then, a film was formed by the sputtering method. Then, the two glasses A were joined in the atmosphere. In the glass A, the thickness of the glass body was 0.5 mm, the thickness of the second glass layer was 25 nm, and the thickness of the metal oxide layer was 15 nm. Peeling occurs at the interface between the second glass layer of glass A and the Ti film formed on the second glass layer, the bonding strength thereof is 0.1 J / m 2 , and the evaluation of adhesion is "C". The evaluation of peelability was "A".
　なお、リーチング処理しなかった２つのガラス体を表面活性化法ならびに原子拡散法で接合したところ、ガラス体に含まれるＳｉ以外の成分がガラス体の接合面に表出してＳｉＯ２結合の阻害要因となり、十分な接合強度を得られなかった。 When the two glass bodies not subjected to the reaching treatment were joined by the surface activation method and the atomic diffusion method, components other than Si contained in the glass body appeared on the joint surface of the glass body, which was a factor of inhibiting the SiO 2 bond. Therefore, sufficient bonding strength could not be obtained.
　以上、本開示に係る接合用ガラス体、及び接合体について説明したが、本開示は上記実施形態等に限定されない。特許請求の範囲に記載された範疇内において、各種の変更、修正、置換、付加、削除、及び組み合わせが可能である。それらについても当然に本開示の技術的範囲に属する。 Although the joining glass body and the joining body according to the present disclosure have been described above, the present disclosure is not limited to the above-described embodiment and the like. Various changes, modifications, replacements, additions, deletions, and combinations are possible within the scope of the claims. Of course, they also belong to the technical scope of the present disclosure.
　本出願は、２０２０年１２月１８日に日本国特許庁に出願した特願２０２０－２０９９６１号に基づく優先権を主張するものであり、特願２０２０－２０９９６１号の全内容を本出願に援用する。 This application claims priority based on Japanese Patent Application No. 2020-20961, which was filed with the Japan Patent Office on December 18, 2020, and the entire contents of Japanese Patent Application No. 2020-20961 are incorporated into this application. ..
１０　　接合用ガラス体
１１　　第１ガラス層
１１ａ　対向面
１２　　第２ガラス層 10 Glass body for joining 11 First glass layer 11a Facing surface 12 Second glass layer

Claims (9)

  1. 　対象物体と接合される接合用ガラス体であって、
    　Ｓｉモル濃度が酸素以外の元素のモル濃度よりも高く、且つ一定である第１ガラス層と、
    　前記第１ガラス層における前記対象物体との対向面に形成され、その対向面に直交する方向にＳｉモル濃度が変化する第２ガラス層と、を含み、
    　前記第１ガラス層の厚みが、１μｍ以上であり、
    　前記第２ガラス層の厚みが、５ｎｍ～３００ｎｍであり、
    　前記第２ガラス層の前記対象物体との対向面におけるＳｉモル濃度が、前記第１ガラス層のＳｉモル濃度よりも高い、接合用ガラス体。     A glass body for joining that is joined to the target object.
    The first glass layer whose Si molar concentration is higher and constant than the molar concentration of elements other than oxygen,
    The first glass layer includes a second glass layer formed on a surface facing the target object and having a Si molar concentration changing in a direction orthogonal to the facing surface.
    The thickness of the first glass layer is 1 μm or more, and the thickness is 1 μm or more.
    The thickness of the second glass layer is 5 nm to 300 nm, and the thickness is 5 nm to 300 nm.
    A glass body for bonding in which the Si molar concentration on the surface of the second glass layer facing the target object is higher than the Si molar concentration of the first glass layer.
  2. 　前記第１ガラス層のＳｉモル濃度が、１６％以上であり、
    　前記第２ガラス層の前記対象物体との対向面におけるＳｉモル濃度が、１７％～３３％である、請求項１に記載の接合用ガラス体。     The Si molar concentration of the first glass layer is 16% or more.
    The bonding glass body according to claim 1, wherein the Si molar concentration on the surface of the second glass layer facing the target object is 17% to 33%.
  3. 　前記第２ガラス層の前記対象物体との対向面に形成される結晶性又は非結晶性の金属酸化物層を更に含み、
    　前記金属酸化物層の厚みが、０．１ｎｍ～５００μｍであり、
    　前記金属酸化物層のＳｉモル濃度が、前記第２ガラス層の前記対象物体との対向面におけるＳｉモル濃度と同等以上であり、且つ一定である、請求項１又は２に記載の接合用ガラス体。     Further comprising a crystalline or amorphous metal oxide layer formed on the surface of the second glass layer facing the target object.
    The thickness of the metal oxide layer is 0.1 nm to 500 μm.
    The bonding glass according to claim 1 or 2, wherein the Si molar concentration of the metal oxide layer is equal to or higher than the Si molar concentration on the surface of the second glass layer facing the target object and is constant. body.
  4. 　前記第２ガラス層のＣモル濃度の最大値が、０．１％～２０％である、請求項１～３のいずれか１項に記載の接合用ガラス体。 The bonding glass body according to any one of claims 1 to 3, wherein the maximum value of the C molar concentration of the second glass layer is 0.1% to 20%.
  5. 　前記第２ガラス層は、前記第１ガラス層を挟んで両側に形成される、請求項１～４のいずれか１項に記載の接合用ガラス体。 The bonding glass body according to any one of claims 1 to 4, wherein the second glass layer is formed on both sides of the first glass layer.
  6. 　前記対象物体との接合面の表面粗さが、０．１ｎｍよりも大きく１０ｎｍよりも小さい、請求項１～５のいずれか１項に記載の接合用ガラス体。 The bonding glass body according to any one of claims 1 to 5, wherein the surface roughness of the bonding surface with the target object is larger than 0.1 nm and smaller than 10 nm.
  7. 　請求項１～６のいずれか１項に記載の接合用ガラス体と、前記接合用ガラス体に接合された前記対象物体と、を含む接合体であって、
    　前記接合用ガラス体と、前記対象物体とは、直接に接しているか、又は無機物の中間層を介して接合されている、接合体。     A bonded body including the bonding glass body according to any one of claims 1 to 6 and the target object bonded to the bonding glass body.
    A bonded body in which the bonding glass body and the target object are in direct contact with each other or are bonded via an intermediate layer of an inorganic substance.
  8. 　前記中間層は、Ａｌ、Ｓｉ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｙ、Ｚｒ、Ｈｆ、及びＴａのうち１つ以上の元素を含む、金属又は金属酸化物で形成される、請求項７に記載の接合体。 7. The intermediate layer is formed of a metal or a metal oxide containing one or more elements of Al, Si, Ti, V, Cr, Mn, Fe, Y, Zr, Hf, and Ta. The joined body described in.
  9. 　前記接合用ガラス体又は前記対象物体は、その接合面に、凹部又は貫通穴を有する、請求項７又は８に記載の接合体。 The joint body according to claim 7 or 8, wherein the joint glass body or the target object has a recess or a through hole in the joint surface thereof.
PCT/JP2021/044500 2020-12-18 2021-12-03 Glass body for joining and joined body WO2022131028A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1036141A (en) * 1996-07-25 1998-02-10 Fujitsu Ltd Production of transparent conductive layer and liquid crystal display device
JP2008277789A (en) * 2007-04-03 2008-11-13 Semiconductor Energy Lab Co Ltd Soi substrate and manufacturing method, and semiconductor device
JP2009088497A (en) * 2007-09-14 2009-04-23 Semiconductor Energy Lab Co Ltd Semiconductor device and electronic appliance

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1036141A (en) * 1996-07-25 1998-02-10 Fujitsu Ltd Production of transparent conductive layer and liquid crystal display device
JP2008277789A (en) * 2007-04-03 2008-11-13 Semiconductor Energy Lab Co Ltd Soi substrate and manufacturing method, and semiconductor device
JP2009088497A (en) * 2007-09-14 2009-04-23 Semiconductor Energy Lab Co Ltd Semiconductor device and electronic appliance

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