JP2014005177A - Airtight member and method of manufacturing the same - Google Patents

Abstract

Provided is a manufacturing method in which when a pair of glass substrates is hermetically sealed by local heating using electromagnetic waves, the adhesion of a sealing layer to both glass substrates and the reliability thereof are improved.
Sealing material layers made of a fired layer of a sealing glass material having electromagnetic wave absorbing ability are formed in the sealing regions of first and second glass substrates. While the first sealing material layer 5 and the second sealing material layer 6 are in contact with each other, the first glass substrate 1 and the second glass substrate 2 are laminated. The first glass is formed by irradiating the first and second sealing material layers 5 and 6 with electromagnetic waves and locally heating them to melt and solidify the first and second sealing material layers 5 and 6. A sealing layer 8 that hermetically seals the gap between the substrate 1 and the second glass substrate 2 is formed.
[Selection] Figure 1

Description

  The present invention relates to an airtight member and a manufacturing method thereof.

  In a flat panel display device (FPD) such as an organic EL display (Organic Electro-Luminescence Display: OELD), a field emission display (Feed Emission Display: FED), a plasma display panel (PDP), a liquid crystal display device (LCD), etc. A structure in which a device glass substrate on which an element is formed and a sealing glass substrate are arranged to face each other and a display element is sealed with an airtight member (glass package) in which the two glass substrates are sealed is applied. (See Patent Document 1). Even in a solar cell such as a dye-sensitized solar cell, application of an airtight member in which a solar cell element (photoelectric conversion element) is sealed with two glass substrates has been studied.

  As a sealing material for sealing between two glass substrates, application of sealing glass excellent in moisture resistance or the like is being promoted. Since the sealing temperature by the sealing glass is about 400 to 600 ° C., the characteristics of the electronic element parts such as the OEL element and the dye-sensitized solar cell element may be deteriorated when baked using a heating furnace. . Therefore, a sealing material layer including a sealing glass and a laser absorbing material is disposed between the sealing regions provided in the periphery of the two glass substrates, and the sealing material layer is irradiated with laser light. Attempts have been made to form a sealing layer by heating and melting (see Patent Document 1).

  In order to apply laser sealing, first, a sealing material paste containing a sealing material is applied to the sealing region of one glass substrate, and then the firing temperature of the sealing material (a temperature equal to or higher than the softening temperature of the sealing glass). The sealing material layer is formed by raising the temperature to 1. Next, after laminating the glass substrate having the sealing material layer and the other glass substrate through the sealing material layer, the laser material is irradiated from one glass substrate side to heat and melt the sealing material layer. Thus, a sealing layer for hermetically sealing the electronic element portion and the like is formed. While laser sealing can suppress the thermal effect on the electronic device part, etc., it is a process in which the sealing material layer is locally heated and rapidly cooled, so the sealing material layer provided on one glass substrate The wettability of the molten / solidified layer (sealing layer) with respect to the other glass substrate cannot be sufficiently increased. This becomes a factor of reducing the adhesion strength and adhesion reliability between the sealing layer and the other glass substrate.

  Moreover, in the glass package which comprises FPD and a solar cell, the space | interval of two glass substrates may be made wide as 50 micrometers or more depending on the structure of a display element or a solar cell element. It is difficult to seal such a wide interval with only a single sealing layer. In contrast, Patent Document 2 describes forming a plurality of sealing material layers having different laser light transmittances on one glass substrate. In this case, although the meltability of the sealing material layer is improved by irradiating the laser beam from the sealing material layer side having a high laser light transmittance, the wettability of the sealing layer to the other glass substrate is sufficient. It cannot be increased.

  In Patent Document 3, at least one of a glass substrate that forms a sealing material layer and a sealing material layer, and a glass substrate that contacts the sealing material layer and a sealing material layer, for example, from a glass substrate It describes that a base portion made of glass having a low softening point and a higher softening point than the sealing glass in the sealing material layer is provided. By providing the base on at least one glass substrate, the thickness of the sealing material layer can be reduced, so that the meltability and formability of the sealing material layer are improved. However, the wettability of the sealing layer to the other glass substrate or the base is the same as in the case of irradiating the sealing material layer directly provided on one glass substrate with laser light. The wetting angle with the glass substrate or the base cannot be made sufficiently small.

JP-T-2006-524419 JP 2010-140848 A JP 2011-029131 A

  The object of the present invention is to improve the adhesion of the sealing layer to both glass substrates and the reliability thereof when hermetically sealing between a pair of glass substrates by local heating using electromagnetic waves such as laser light. It is in providing a member and its manufacturing method.

  A method for manufacturing an airtight member according to an aspect of the present invention includes a first sealing region and a first sealing formed of a fired layer of a sealing glass material formed in the first sealing region and having electromagnetic wave absorption ability. A step of preparing a first glass substrate having a first surface with a material layer; a second sealing region corresponding to the first sealing region; and a second sealing region formed in the second sealing region A step of preparing a second glass substrate having a second surface comprising a second sealing material layer made of a fired layer of a sealing glass material having electromagnetic wave absorbing ability; the first surface; The first glass substrate and the second glass substrate are stacked while facing the second surface and bringing the first sealing material layer and the second sealing material layer into contact with each other. And the first and second through the first glass substrate or the second glass substrate. By irradiating the sealing material layer with an electromagnetic wave and locally heating it, and melting and solidifying the first and second sealing material layers, the first glass substrate and the second glass substrate And a step of forming a sealing layer that hermetically seals the gap.

  An airtight member according to the first aspect of the present invention includes a first glass substrate having a first surface including a first sealing region, and a second sealing region corresponding to the first sealing region. And a second glass substrate disposed on the first glass substrate with a predetermined gap so that the second surface faces the first surface, The electromagnetic wave absorbing ability is formed between the first sealing region and the second sealing region so as to hermetically seal a gap between the first glass substrate and the second glass substrate. And a sealing layer made of a fused and fixed layer of a glass material for sealing, wherein the sealing layer has a wetting angle of 45 degrees or less with respect to each of the first and second glass substrates.

  An airtight member according to a second aspect of the present invention includes a first glass substrate having a first surface including a first sealing region, and a second sealing region corresponding to the first sealing region. And a second glass substrate disposed on the first glass substrate with a predetermined gap so that the second surface faces the first surface, An electromagnetic wave formed between the first sealing region and the second sealing region so as to hermetically seal a gap between the first glass substrate and the second glass substrate. A sealing layer composed of a melt-fixed layer of a sealing glass material having an absorbing ability, wherein the sealing layer is at least selected from a sealing glass composed of a low-melting glass, an electromagnetic wave absorbing material and a low expansion filler. Containing one kind of inorganic filler, and the sealing layer is bonded to the first glass substrate, A first layer containing an inorganic filler, a second layer bonded to the second glass substrate and containing the inorganic filler, and formed between the first layer and the second layer. And an intermediate layer composed of a single glass layer not containing the inorganic filler.

  According to the hermetic member and the manufacturing method thereof of the present invention, when local heating using electromagnetic waves is applied to hermetically seal between a pair of glass substrates, the adhesion of the sealing layer to both glass substrates and its reliability Can increase the sex. Therefore, it is possible to provide an airtight member excellent in airtight sealing performance and reliability with high reproducibility.

It is sectional drawing which shows the manufacturing method of the airtight member by embodiment of this invention. It is a top view of the 1st glass substrate used with the manufacturing method of the airtight member by the embodiment of the present invention. It is sectional drawing along the AA line of FIG. It is a top view of the 2nd glassy board | substrate used with the manufacturing method of the airtight member by embodiment of this invention. It is sectional drawing along the AA line of FIG. It is sectional drawing which expands and shows the sealing material layer shown to FIG. 3 and FIG. It is sectional drawing which expands and shows a part of lamination process of the 1st glass substrate and 2nd glass substrate in the manufacturing method of the airtight member shown in FIG. It is sectional drawing which expands and shows the sealing layer of the airtight member by embodiment of this invention. It is a figure for demonstrating the wetting angle with respect to the glass substrate of a sealing layer. 4 is an electron microscope image showing a wetting angle of a sealing layer of an airtight member according to Example 1. FIG. 3 is an optical microscope image showing an intermediate layer in a sealing layer of an airtight member according to Example 1. FIG. 6 is an electron microscopic image showing a wetting angle of a sealing layer of an airtight member according to Comparative Example 1.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. 1 to 5 are views showing a method of manufacturing an airtight member according to an embodiment of the present invention. Here, as an airtight member to which the manufacturing method of the embodiment of the present invention is applied, a glass package for airtightly sealing a display element in an FPD such as OELD, FED, PDP, LCD, and a light emitting element such as an OEL element are hermetically sealed. Glass packages for lighting devices, glass packages for hermetically sealing solar cell elements in sealed solar cells such as dye-sensitized solar cells, thin-film silicon solar cells, compound semiconductor solar cells, hermetic packages for reflectors, A multilayer glass etc. are mentioned.

First, a first glass substrate 1 and a second glass substrate 2 are prepared as constituent members of an airtight member. For the first and second glass substrates 1 and 2, soda lime glass, alkali-free glass, silicate glass, borate glass, borosilicate glass, phosphate glass, etc. having various known compositions are applied. can do. Soda lime glass has a thermal expansion coefficient (50 to 250 ° C.) of about 80 to 90 (× 10 ⁻⁷ / ° C.), and non-alkali glass has a thermal expansion coefficient of about 35 to 40 (× 10 ⁻⁷ / ° C.). (50 to 250 ° C.). At least one of the first and second glass substrates 1 and 2 may be a chemically strengthened glass substrate or the like.

  The symbol “˜” indicating a numerical range is used in the sense of including the numerical values described before and after the numerical value as a lower limit value and an upper limit value. Unless otherwise specified, the symbol “˜” in this specification has the same meaning. Unless otherwise specified, the thermal expansion coefficient indicates an average linear expansion coefficient at 50 to 250 ° C., and is simply expressed as “thermal expansion coefficient (50 to 250 ° C.)”.

  On the surface 1a of the first glass substrate 1, as shown in FIG. 2, a first sealing region 3 is provided along the outer peripheral region. As shown in FIG. 4, a second sealing region 4 corresponding to the first sealing region 3 is provided on the surface 2 a of the second glass substrate 2. It is preferable that the 1st and 2nd sealing area | regions 3 and 4 are formed over the perimeter of the outer peripheral area | region of the glass substrates 1 and 2, respectively. The sealing regions 3 and 4 are regions for forming a sealing material layer and a sealing layer. The first glass substrate 1 and the second glass substrate 2 have a predetermined gap so that the surface 1a having the first sealing region 3 and the surface 2a having the second sealing region 4 face each other. Is placed.

  When the hermetic member manufactured in this embodiment is used as a glass package of an electronic device or the like, it corresponds to the electronic device between the surface 1a of the first glass substrate 1 and the surface 2a of the second glass substrate 2. An electronic element part is provided. The electronic element section includes, for example, an OEL element for OELD and OEL illumination, an electron emitting element for FED, a plasma light emitting element for PDP, a liquid crystal display element for LCD, and a solar cell element for solar cell. Is. Various known structures are applied to the electronic element portion, and the structure is not limited thereto. Further, when the airtight member is used as an airtight package of the reflecting mirror, a reflective film is provided on at least one of the surface 1a of the first glass substrate 1 and the surface 2a of the second glass substrate 2.

  Frame-shaped sealing material layers 5 and 6 are respectively formed in the sealing region 3 of the first glass substrate 1 and the sealing region 4 of the second glass substrate 2. That is, the first sealing material layer 5 is formed in the sealing region 3 of the first glass substrate 1 as shown in FIG. 1A, FIG. 2 and FIG. A second sealing material layer 6 is formed in the sealing region 4 of the second glass substrate 2 as shown in FIGS. 1B, 4 and 5. The first and second sealing material layers 5 and 6 are layers (fired layers of the sealing glass material) made of a material obtained by firing the sealing glass material.

  The glass material for sealing is obtained by adding an inorganic filler such as an electromagnetic wave absorbing material or a low expansion filler that absorbs electromagnetic waves such as laser light and infrared rays to sealing glass made of low melting glass. When the sealing glass itself has electromagnetic wave absorbing ability, the addition of the electromagnetic wave absorbing material can be omitted. The glass material for sealing may contain additives other than these as necessary. It is preferable that the glass material for sealing contains sealing glass and at least one inorganic filler selected from an electromagnetic wave absorbing material and a low expansion filler.

  As the sealing glass, for example, low-melting glass such as tin-phosphate glass, bismuth glass, vanadium glass, lead glass, zinc borate alkali glass or the like is used. Among these, in consideration of the adhesiveness to the first and second glass substrates 1 and 2 and their reliability (adhesion reliability and hermetic sealing), influence on the environment and human body, etc., tin-phosphate glass It is preferable to use sealing glass made of bismuth glass.

Tin-phosphate glass is expressed in terms of mol% in terms of the following oxides: 55 to 68 mol% SnO, 0.5 to 5 mol% SnO ₂ , and 20 to 40 mol% P ₂ O ₅ (basic In particular, the total amount is preferably 100 mol%). SnO is a component for lowering the melting point of glass. If the SnO content is less than 55 mol%, the viscosity of the glass will be high and the sealing temperature will be too high, and if it exceeds 68 mol%, it will not vitrify.

SnO ₂ is a component for stabilizing the glass. If the content of SnO ₂ is less than 0.5 mol%, SnO ₂ is separated and precipitated in the glass that has been softened and melted during the sealing operation, the fluidity is impaired and the sealing workability is lowered. If the content of SnO ₂ exceeds 5 mol%, SnO ₂ is likely to precipitate during melting of the low-melting glass. P ₂ O ₅ is a component for forming a glass skeleton. If the content of P ₂ O ₅ is less than 20 mol%, the glass does not vitrify, and if the content exceeds 40 mol%, the weather resistance, which is a disadvantage specific to phosphate glass, may be deteriorated.

Here, the ratio (mol%) of SnO and SnO ₂ in the low-melting glass can be determined as follows. First, after acid decomposition of the low melting glass powder, the total amount of Sn atoms contained in the low melting glass is measured by ICP emission spectroscopic analysis. Next, since Sn ²⁺ (SnO) is obtained by acidimetric decomposition, Sn ⁴⁺ (SnO ₂ ) is obtained by subtracting the obtained Sn ²⁺ from the total amount of Sn atoms.

The glass formed of the above three components has a low glass transition point and is suitable for a low-temperature sealing material. However, a component that forms a glass skeleton such as SiO ₂ , ZnO, B ₂ O ₃ , Al _{2 O 3, WO 3, MoO} 3, Nb 2 O 5, TiO 2, ZrO 2, Li 2 O, stabilizing _{Na 2 O, K 2 O,} Cs 2 O, MgO, CaO, SrO, the glass BaO, etc. The component to be made may be contained as an optional component. However, if the content of any component is too large, the glass becomes unstable and devitrification may occur, and the glass transition point and softening point may increase. Therefore, the total content of any component is 30 mol%. The following is preferable. The glass composition in this case is adjusted so that the total amount of the basic component and the optional component is basically 100 mol%.

Bismuth-based glass is expressed in terms of mol% in terms of the following oxides, and is 70 to 90% by mass of Bi ₂ O ₃ , 1 to 20% by mass of ZnO, and 2 to 12% by mass of B ₂ O ₃ (basically The total amount is preferably 100% by mass). Bi ₂ O ₃ is a component that forms a glass network. When the content of Bi ₂ O ₃ is less than 70% by mass, the softening point of the low-melting glass becomes high and sealing at a low temperature becomes difficult. When the content of Bi ₂ O ₃ exceeds 90% by mass, it becomes difficult to vitrify and the thermal expansion coefficient tends to be too high.

ZnO is a component that lowers the thermal expansion coefficient and the like. Vitrification becomes difficult when the content of ZnO is less than 1% by mass. When the content of ZnO exceeds 20% by mass, stability during low-melting glass molding is lowered, and devitrification is likely to occur. B ₂ O ₃ is a component that increases the range in which vitrification is possible by forming a glass skeleton. If the content of B ₂ O ₃ is less than 2% by mass, vitrification becomes difficult, and if it exceeds 12% by mass, the softening point becomes too high, and even if a load is applied during sealing, sealing is performed at a low temperature. It becomes difficult.

The glass formed of the above three components has a low glass transition point and is suitable for a sealing material for low temperature. Al ₂ O ₃ , CeO ₂ , SiO ₂ , Ag ₂ O, MoO ₃ , Nb ₂ O ₃ , Ta ₂ O ₅ , Ga ₂ O ₃ , Sb ₂ O ₃ , Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, CaO, SrO, BaO, WO ₃ , P ₂ O ₅ , SnO _x (X is 1 or 2) etc. may be contained. However, if the content of any component is too large, the glass becomes unstable and devitrification may occur, and the glass transition point and softening point may increase. Therefore, the total content of any component is 30% by mass. The following is preferable. The glass composition in this case is adjusted so that the total amount of the basic component and the optional component is basically 100% by mass.

Low expansion fillers include the group consisting of silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, cordierite, eucryptite, spodumene, zirconium phosphate compounds, quartz solid solution, soda lime glass and borosilicate glass It is preferable to use at least one selected from the above. Zirconium phosphate compounds include (ZrO) ₂ P ₂ O ₇ , NaZr ₂ (PO ₄ ) ₃ , KZr ₂ (PO ₄ ) ₃ , Ca _0.5 Zr ₂ (PO ₄ ) ₃ , NbZr (PO ₄ ) ₃ , Zr ₂ (WO ₃ ) (PO ₄ ) ₂ , and complex compounds thereof can be mentioned. The low expansion filler has a lower thermal expansion coefficient than the sealing glass. The content of the low expansion filler is appropriately set so that the thermal expansion coefficient of the sealing glass material approaches that of the glass substrates 1 and 2. The low expansion filler is preferably contained in the range of 0.1 to 50% by volume with respect to the sealing glass material, although it depends on the thermal expansion coefficient of the sealing glass and the glass substrates 1 and 2.

As the electromagnetic wave absorber, at least one metal (including an alloy) selected from the group consisting of Fe, Cr, Mn, Co, Ni and Cu, or an oxide containing the metal, such as FeO, Fe ₂ O ₃ , At least one selected from compounds such as CoO, Co ₂ O ₃ , Mn ₂ O ₃ , MnO, and CuO is used. Other materials may be used. The content of the electromagnetic wave absorbing material is preferably in the range of 0.1 to 40% by volume with respect to the sealing glass material. Furthermore, the total content of the low expansion filler and the electromagnetic wave absorbing material is preferably set to a range of 50% by volume or less with respect to the sealing glass material. If the content of the electromagnetic wave absorbing material is less than 0.1% by volume, the sealing material layers 5 and 6 may not be sufficiently melted. When the total content of the low expansion filler and the electromagnetic wave absorbing material exceeds 50% by volume, the fluidity at the time of melting of the glass material for sealing deteriorates, and adhesion between the first and second sealing material layers 5 and 6 occurs. May decrease.

  The first and second sealing material layers 5 and 6 are formed as follows, for example. A sealing glass material is prepared by blending an inorganic filler such as an electromagnetic wave absorbing material or a low expansion filler with the sealing glass to prepare a sealing glass material, and mixing it with a vehicle. The vehicle is obtained by dissolving a resin as a binder component in a solvent. Examples of the resin for the vehicle include cellulose resins such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, nitrocellulose, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate, An organic resin such as an acrylic resin obtained by polymerizing one or more acrylic monomers such as 2-hydroxyethyl acrylate is used. As the solvent for the vehicle, terpineol, butyl carbitol acetate, ethyl carbitol acetate, etc. are used in the case of a cellulose resin, and methyl ethyl ketone, terpineol, butyl carbitol acetate, ethyl carbitol acetate, etc. are used in the case of an acrylic resin. Used.

  The resin component in the vehicle functions as a binder for the sealing glass material, and is preferably removed before firing the sealing glass material. The viscosity of the sealing material paste may be adjusted to the viscosity corresponding to the apparatus applied to the glass substrates 1 and 2, the ratio of the resin component (organic binder) and the solvent (organic solvent, etc.), the sealing glass material and the vehicle It can be adjusted according to the ratio. A known additive may be added to the sealing material paste as a glass paste such as an antifoaming agent or a dispersing agent. For preparing the sealing material paste, a known method using a rotary mixer equipped with a stirring blade, a roll mill, a ball mill, or the like can be applied.

  The sealing material paste described above is applied to the sealing regions 3 and 4 of the glass substrates 1 and 2 and dried to form an application layer of the sealing material paste. The sealing material paste is applied onto the sealing regions 3 and 4 by applying a printing method such as screen printing or gravure printing, or is applied along the sealing regions 3 and 4 using a dispenser or the like. The coating layer of the sealing material paste is preferably dried at a temperature of 120 ° C. or more for 10 minutes or more, for example. A drying process is implemented in order to remove the solvent in an application layer. If the solvent remains in the coating layer, the binder component may not be sufficiently removed in the subsequent firing step. Next, by firing the coating layer of the sealing material paste, the sealing regions 3 and 4 of the first and second glass substrates 1 and 2 are formed as shown in FIGS. 1 (a) and 1 (b). Sealing material layers 5 and 6 are formed, respectively.

  In the firing step, the glass substrates 1 and 2 on which the coating layer of the sealing material paste is formed are placed in a firing furnace, heated to a temperature below the glass transition point of the sealing glass, and the binder component in the coating layer is removed. After the removal, the glass is heated to a temperature equal to or higher than the softening point of the sealing glass, and the sealing glass is melted and baked on the glass substrates 1 and 2. In this manner, sealing material layers 5 and 6 made of a fired layer of glass material for sealing are formed in the sealing regions 3 and 4 of the glass substrates 1 and 2, respectively. Next, as shown in FIG. 1C, the surface 1a of the first glass substrate 1 and the surface 2a of the second glass substrate 2 are made to face each other, and the first sealing material layer 5 and the second sealing material 2 are sealed. The first glass substrate 1 and the second glass substrate 2 are laminated while the material layer 6 is in contact with the first material.

  Next, as shown in FIG. 1 (d), the first and second sealing material layers 5, 6 are irradiated with electromagnetic waves 7 such as laser light and infrared rays through the glass substrate 1 from above the glass substrate 1. The electromagnetic wave 7 may be irradiated through the glass substrate 2. When laser light is used as the electromagnetic wave 7, the laser light is irradiated while scanning along the frame-shaped sealing material layers 5 and 6. The laser light is not particularly limited, and laser light from a semiconductor laser, carbon dioxide laser, excimer laser, YAG laser, HeNe laser, or the like is used. When infrared rays are used as the electromagnetic waves 7, it is preferable to selectively irradiate the sealing material layers 5 and 6 with infrared rays by masking portions other than the formation portions of the sealing material layers 5 and 6 with an infrared reflecting film or the like. .

  When laser light is used as the electromagnetic wave 7, the sealing material layers 5 and 6 are melted in order from the portion irradiated with the laser light scanned along the sealing material layers, and are rapidly cooled and solidified simultaneously with the end of the laser light irradiation. 8 is formed. When infrared rays are used as the electromagnetic wave 7, the sealing material layers 5 and 6 are locally heated and melted based on the irradiation of infrared rays, and are rapidly cooled and solidified simultaneously with the end of the irradiation of infrared rays to form the sealing layer 8. . The sealing layer 8 is composed of a melt-fixed layer of the sealing material layers 5 and 6, and the sealing regions 3 and 4 are sealed so as to hermetically seal the gap between the first glass substrate 1 and the second glass substrate 2. It is formed over the entire circumference. In this manner, an airtight member 10 having a space 9 hermetically sealed with the first and second glass substrates 1 and 2 and the sealing layer 8 as shown in FIG.

  The step of forming the sealing layer 8 will be described in detail. Since the sealing material layers 5 and 6 are formed by heat-treating the glass substrates 1 and 2 on which the coating layer of the sealing material paste is formed in a baking furnace, both ends of the sealing material layers 5 and 6 are glass substrates 1 as shown in FIG. 2 has a shape that spreads wet with respect to 2, specifically a trapezoidal cross-sectional shape. That is, the sealing material layers 5 and 6 have a shape with a sharp wetting angle with respect to the glass substrates 1 and 2. As shown in FIG. 7, the first sealing material layer 5 and the second sealing material layer 6 having a trapezoidal cross section are opposed to each other, and the first sealing material layer 5 and the second sealing material layer are disposed. 6 upper surfaces (surfaces including the upper side of the trapezoid) are brought into contact with each other. When the sealing material layers 5 and 6 are irradiated with the electromagnetic wave 7 in this state, the sealing glass in the sealing material layers 5 and 6 melts and flows, respectively, so that the first and second sealing material layers 5 are flown. , 6 are integrated.

At this time, if the difference in line width between the first sealing material layer 5 and the second sealing material layer 6 is large, even if the sealing glass is melted and flowed, the first sealing material layer 5 There is a possibility that the upper surface and the upper surface of the second sealing material layer 6 cannot be integrated. That is, the upper surface of the sealing material layer with a narrow line width may be integrated with only a part of the upper surface of the sealing material layer with a large line width. In such a case, the contact angle between the side surface of the sealing material layer having a narrow line width and the upper surface of the sealing material layer having a wide line width becomes an acute angle, and breakage or the like is likely to occur from this portion. Therefore, when the average line width of the first sealing material layer 5 is W1, the average line width of the second sealing material layer 6 is W2, and W1 ≧ W2, it is expressed by the following formula (1). The difference in average line width between the first and second sealing material layers 5 and 6 is preferably 80% or less.
Formula 1: (W1-W2) / W1 * 100 (%)
If the difference in average line width is 80% or less, the sealing glass melts and flows, so that the contact interface between the upper surface of the first sealing material layer 5 and the upper surface of the second sealing material layer 6 Are integrated as a whole.

  Since the sealing layer 8 is formed by quenching and solidifying from a state in which the contact interfaces of the first and second sealing material layers 5 and 6 are integrated, the first and second glass substrates of the sealing layer 8 are formed. As for the interface shape with 1 and 2, the shape which spreads wet with respect to the glass substrates 1 and 2 of the sealing material layers 5 and 6 is maintained. Therefore, as shown in FIG. 8, a sealing layer 8 having a cross-sectional shape with acute wetting angles with respect to the first and second glass substrates 1 and 2 is obtained. According to the sealing layer 8 having a small wetting angle with respect to the first and second glass substrates 1 and 2, respectively, the adhesion strength between the sealing layer 8 and the first and second glass substrates 1 and 2 is improved, Furthermore, adhesion reliability can be improved.

  The wetting angles of the sealing layer 8 with respect to the first and second glass substrates 1 and 2 are preferably 45 degrees or less, respectively. Thereby, the adhesive strength between the sealing layer 8 and the glass substrates 1 and 2 can be further improved, and the adhesion reliability against bending stress or thermal stress applied from the outside can be further effectively increased. Here, the wetting angle of the sealing layer 8 with respect to the glass substrates 1 and 2 is 1/10 of the height of the sealing layer 8 and the tip of the sealing layer 8 in the cross section of the sealing layer 8 as shown in FIG. The angle α between the line connecting the points and the surfaces of the glass substrates 1 and 2 is defined.

Here, if the difference in thickness between the first sealing material layer 5 and the second sealing material layer 6 is too large, stress concentrates on one of the sealing material layers and the sealing layer is destroyed. There is a fear. Therefore, when the average thickness of the first sealing material layer 5 is H1, the average thickness of the second sealing material layer 6 is H2, and H1 ≧ H2, the following expression (2) is satisfied. The difference in average thickness between the first and second sealing material layers 5 and 6 is preferably 80% or less.
Formula 2: (H1-H2) / H1 × 100 (%)
Furthermore, the difference in average thickness between the first and second sealing material layers 5 and 6 is more preferably 50% or less. Thereby, the difference in the amount of distortion generated in the first and second glass substrates 1 and 2 can be reduced, and the adhesion reliability can be increased.

  Furthermore, when integrating the contact interfaces of the first and second sealing material layers 5 and 6, by flowing only the fused sealing glass in the sealing material layers 5 and 6, An intermediate layer made of a single glass layer not containing an inorganic filler is formed at the contact interface between the sealing material layers 5 and 6. That is, as shown in FIG. 8, the first layer 81 bonded to the first glass substrate 1 and containing an inorganic filler, and the second layer bonded to the second glass substrate 2 and containing an inorganic filler. 82 and an intermediate layer 83 formed between the first layer 81 and the second layer 82 and made of a single glass layer not containing an inorganic filler is obtained. The intermediate layer 83 made of a single glass layer is formed for the first time by melting and integrating the contact interfaces of the sealing material layers 5 and 6.

  Since the sealing layer 8 having the intermediate layer 83 composed of such a single glass layer is formed by applying a relatively low heating temperature at which only the sealing glass flows, the sealing layer 8 and the glass substrate are formed. The stress generated at the contact interface with 1 and 2 can be reduced. In other words, according to the sealing layer 8 having the intermediate layer 83 made of a single glass layer, the stress generated at the contact interface between the sealing layer 8 and the glass substrates 1 and 2 is reduced. The adhesion strength and adhesion reliability with the first and second glass substrates 1 and 2 can be further enhanced.

  In forming the sealing layer 8 having the intermediate layer 83 made of a single glass layer, the heating temperature when the sealing material layers 5 and 6 are irradiated with the electromagnetic wave 7 is set to the softening temperature T (° C.) of the sealing glass. Thus, it is preferable to set the temperature in the range of (T + 50 ° C.) to (T + 400 ° C.). Under the irradiation conditions of the electromagnetic wave 7 such that the temperature of the sealing material layers 5 and 6 does not reach (T + 50 ° C.), the adhesion between the sealing material layers 5 and 6 may be reduced. On the other hand, under the irradiation conditions of the electromagnetic wave 7 such that the temperature of the sealing material layers 5 and 6 exceeds (T + 400 ° C.), the inorganic filler also flows in addition to the molten sealing glass, and an intermediate layer composed of a single glass layer. 83 cannot be clearly formed.

  The thickness of the intermediate layer 83 made of a single glass layer is preferably in the range of 50 to 5000 nm. When the thickness of the intermediate layer 83 is less than 50 nm, a steep temperature distribution is formed in the vicinity of the intermediate layer 83, and there is a possibility that the sealing reliability is lowered. On the other hand, if the thickness of the intermediate layer 83 exceeds 5000 nm, the sealing state may be destroyed due to stress due to a difference in thermal expansion coefficient between the sealing glass material containing the inorganic filler and the sealing glass. The thickness of the intermediate layer 83 is more preferably 1000 nm or less. The thickness of the intermediate layer 83 is measured for the adhesion region of the sealing material layers 5 and 6, and the minimum value and the maximum value at that time may be within the above-described range.

  As described above, according to the sealing layer 8 formed using the first and second sealing material layers 5 and 6, the adhesive strength and adhesion reliability with respect to the first and second glass substrates 1 and 2 can be improved. In addition to the improvement, even when the gap between the first glass substrate 1 and the second glass substrate 2 is wide, it can be hermetically sealed. For this reason, the sealing layer 8 is more effective when the gap between the first glass substrate 1 and the second glass substrate 2 is 50 μm or more. However, even when the gap between the glass substrates 1 and 2 is narrow, the effect of improving the adhesion strength and adhesion reliability of the sealing layer 8 to the glass substrates 1 and 2 can be obtained. Accordingly, the thickness of the sealing layer 8 is preferably in the range of 5 μm to 200 μm. If the gap between the glass substrates 1 and 2 exceeds 200 μm, the sound sealing layer 8 may not be formed even if the first and second sealing material layers 5 and 6 are used.

  Next, specific examples of the present invention and evaluation results thereof will be described. In addition, the following description does not limit this invention, The modification | change in the form along the meaning of this invention is possible.

Example 1
First, bismuth glass (softening point: 410 ° C.) having a composition of 83% by mass of Bi ₂ O _3, 5% by mass of B ₂ O ₃ , 11% by mass of ZnO, and 1% by mass of Al ₂ O _{3 in} terms of oxide. A cordierite powder having an average particle size (D50) of 4.3 μm and a specific surface area of 1.6 m ² / g as a low expansion filler, and a composition of Fe ₂ O ₃ —MnO—CuO—Al ₂ O ₃ ; A laser absorber having an average particle diameter (D50) of 1.2 μm and a specific surface area of 6.1 m ² / g was prepared. The average particle size was measured using a laser diffraction / scattering particle size measuring device (manufactured by Nikkiso Co., Ltd., Microtrac HRA). The specific surface area was measured using a BET specific surface area measuring device (Macsorb HM model-1201, manufactured by Mountec Co., Ltd.).

By mixing 66.8% by volume of the above-described bismuth-based glass, 32.2% by volume of cordierite powder, and 1.0% by volume of the laser absorber, a glass material for sealing (thermal expansion coefficient (50 to 250 ° C.): 66 × 10 ⁻⁷ / ° C.). Next, 83% by mass of this glass material for sealing was mixed with 17% by mass of a vehicle to prepare a sealing material paste. The vehicle is obtained by dissolving ethyl cellulose (5% by mass) as a binder component in a solvent (95% by mass) composed of diethylene glycol mono-2-ethylhexyl ether.

Next, first and second glass substrates (dimensions: outer dimensions 100 × 100 mm, thickness 1.8 mm) made of soda lime glass (thermal expansion coefficient (50 to 250 ° C.): 85 × 10 ⁻⁷ / ° C.) The sealing material paste was applied to each of the sealing regions of the glass substrate by a screen printing method. Screen printing was performed using a screen plate having a mesh size of 325 and an emulsion thickness of 20 μm. The pattern of the screen plate was a 70 mm × 70 mm frame pattern with a line width of 0.5 mm, and the curvature radius of the corner portion was 2 mm. Next, the first and second glass substrates were placed in a firing furnace and dried under conditions of 120 ° C. × 10 minutes. Thereafter, the coating layer of the sealing material paste was baked under conditions of 480 ° C. × 10 minutes. In this way, sealing material layers (first and second sealing material layers) having an average line width of 0.55 mm and an average film thickness of 15 μm in the sealing regions of the first and second glass substrates, respectively. Formed.

The above-mentioned first glass substrate having the first sealing material layer and second glass substrate having the second sealing material layer are combined with the first sealing material layer and the second sealing material layer glass. The layers were laminated so that their surfaces were in close contact with each other. Next, in a state where a pressure of 0.25 MPa is applied from above the first glass substrate, a wavelength of 808 nm, a spot is formed on the first and second sealing material layers from above the first glass substrate through the first glass substrate. A laser beam (semiconductor laser) having a diameter of 1.85 mm and an output density of 3.79 W / mm ² is irradiated at a scanning speed of 4 mm / second, and the first and second sealing materials are melted and rapidly cooled and solidified. A sealing layer for sealing the gap between the first glass substrate and the second glass substrate was formed. The intensity distribution of the laser beam was not shaped uniformly, and a laser beam having a protruding intensity distribution was used. The heating temperature (measured with a radiation thermometer) of the first and second sealing material layers at the time of laser light irradiation was 530 ° C.

  When the appearance of the glass substrate and the sealing layer was observed after laser sealing, the occurrence of cracks or cracks was not observed, and the adhesiveness of the sealing layer to the first and second glass substrates was good. It was confirmed that. When the airtightness of the airtight member in which the gap between the first and second glass substrates was sealed with a sealing layer was evaluated by a helium leak test, it was confirmed that good airtightness was obtained. Furthermore, the strain amount of the part in which the sealing layer was formed was measured using the optical strain meter (CRi company make, Abrio-Micro), and the residual stress value was calculated | required from the strain amount and the thickness of the glass substrate. The residual stress value will be described later.

  In addition, the airtight member produced in Example 1 was cleaved, and after embedding an epoxy resin (trade name: Epochure, manufactured by Buehler) in the gap between the first glass substrate and the second glass substrate, Both sides were polished with a polishing machine (Buhler). Polishing finishing was performed using alumina having a particle size of 0.05 μm (Bueller, trade name: Master Prep). Next, the cross section of the polished sample was observed using a field emission scanning electron microscope (Hitachi, S4300). FIG. 10 shows an electron microscope image. When the wetting angles (total of four locations) at both ends of the sealing layer with respect to the first and second glass substrates were measured, the maximum value was 24 degrees, and the structure was such that stress concentration did not easily occur due to bending or the like. It was confirmed that As described above, the wetting angle of the sealing layer with respect to the glass substrate was defined by the angle between the line connecting the tip of the sealing layer and a point that is 1/10 of the height of the sealing layer and the surface of the glass substrate.

  Next, the sealing layer of the sample sealed under the same conditions as in Example 1 was observed using an optical microscope (manufactured by Olympus, BX51) under conditions of an objective lens 20 times and an eyepiece 10 times. An observation result (an optical microscope image) is shown in FIG. As shown in FIG. 11, it is confirmed that a glass single layer (a black linear portion in the central portion of the sealing layer in FIG. 11) in which no inorganic filler is present is formed as an intermediate layer in the central portion of the sealing layer. It was done. Furthermore, when the thickness of the glass single layer (intermediate layer) at the center of the sample was measured over 300 μm using an electron microscope, it was confirmed that the minimum value was 300 nm and the maximum value was 500 nm. It was.

(Example 2)
The first glass substrate in the same manner as in Example 1 except that the first and second sealing material layers having an average film thickness of 30 μm are used and the laser light irradiation conditions are changed to the conditions shown in Table 1. A sealing layer was formed to seal the gap between the first glass substrate and the second glass substrate. When the appearance of the glass substrate and the sealing layer was observed after laser sealing, the occurrence of cracks or cracks was not observed, and the adhesiveness of the sealing layer to the first and second glass substrates was good. It was confirmed that. Further, in the same manner as in Example 1, helium leak test, measurement of residual stress value, measurement of the wetting angle of the sealing layer with respect to the first and second glass substrates, observation of the sealing layer, and glass alone in the sealing layer The thickness of the layer (intermediate layer) was measured. The results are shown in Table 1.

(Comparative Example 1)
The first glass was formed in the same manner as in Example 1 except that the sealing material layer having an average film thickness of 30 μm was formed only on the first glass substrate and the laser light irradiation conditions were changed to the conditions shown in Table 1. A sealing layer for sealing the gap between the substrate and the second glass substrate was formed. In the same manner as in Example 1, helium leak test, measurement of residual stress value, measurement of the wetting angle of the sealing layer with respect to the first and second glass substrates, observation of the sealing layer, and a single glass layer in the sealing layer ( Measurement of the thickness of the intermediate layer was performed. The results are shown in Table 1. The residual stress value is shown as a relative value where the value of Example 1 is 1. FIG. 12 shows an electron microscope image when the wetting angle of Comparative Example 1 is measured.

  As shown in Table 1, since the airtight members according to Examples 1 and 2 have a small wetting angle with respect to the glass substrate of the sealing layer and a reduced residual stress value, the structure has excellent adhesion reliability of the sealing layer. It was confirmed that Furthermore, it was confirmed that the sealing layer has a glass single layer as an intermediate layer. In Comparative Example 1 in which the sealing material layer was formed only on one glass substrate, the presence of an intermediate layer composed of a single glass layer was not confirmed.

  DESCRIPTION OF SYMBOLS 1 ... 1st glass substrate, 1a ... 1st surface, 2 ... 2nd glass substrate, 2a ... 2nd surface, 3 ... 1st sealing area | region, 4 ... 2nd sealing area | region, 5 ... 1st sealing material layer, 6 ... 2nd sealing material layer, 7 ... Electromagnetic wave, 8 ... Sealing layer, 81 ... 1st layer, 82 ... 2nd layer, 83 ... Intermediate | middle consisting of glass single layer Layers 9 ... Airtight space, 10 ... Airtight member.

Claims (13)

A first surface having a first surface comprising a first sealing region and a first sealing material layer formed of a fired layer of a sealing glass material formed in the first sealing region and having electromagnetic wave absorbing ability. Preparing a glass substrate of 1;
A second sealing material layer comprising a second sealing region corresponding to the first sealing region and a fired layer of a sealing glass material formed in the second sealing region and having an electromagnetic wave absorption capability Providing a second glass substrate having a second surface comprising:
While the first surface and the second surface are opposed to each other and the first sealing material layer and the second sealing material layer are in contact with each other, the first glass substrate and the second surface Laminating a glass substrate of
The first and second sealing material layers are irradiated with electromagnetic waves through the first glass substrate or the second glass substrate and locally heated to melt the first and second sealing material layers. And a step of forming a sealing layer that hermetically seals a gap between the first glass substrate and the second glass substrate by solidifying. A method for manufacturing an airtight member.   The method for manufacturing an airtight member according to claim 1, wherein the sealing layer has a wetting angle of 45 degrees or less with respect to the first and second glass substrates.   The airtight member according to claim 1 or 2, wherein the glass material for sealing contains a sealing glass made of a low melting point glass and at least one inorganic filler selected from an electromagnetic wave absorbing material and a low expansion filler. Manufacturing method.   The first and second sealing material layers are formed so that a glass single layer not containing the inorganic filler is formed at the contact interface between the first sealing material layer and the second sealing material layer. The manufacturing method of the airtight member of Claim 3 which heats. When the average line width of the first sealing material layer is W1, the average line width of the second sealing material layer is W2, and W1 ≧ W2,
Formula 1: (W1-W2) / W1 * 100 (%)
The airtight member according to any one of claims 1 to 4, wherein a difference in average line width between the first sealing material layer and the second sealing material layer represented by the formula is 80% or less. Manufacturing method. When the average thickness of the first sealing material layer is H1, the average thickness of the second sealing material layer is H2, and H1 ≧ H2,
Formula 2: (H1-H2) / H1 × 100 (%)
The airtight member according to any one of claims 1 to 5, wherein a difference in average thickness between the first sealing material layer and the second sealing material layer represented by the formula is 80% or less. Manufacturing method.   The manufacturing method of the airtight member of any one of Claim 1 thru | or 6 which irradiates a laser beam as said electromagnetic wave, scanning along the said 1st and 2nd sealing material layer. A first glass substrate having a first surface with a first sealing region;
The first glass substrate has a second surface including a second sealing region corresponding to the first sealing region, and the second surface faces the first surface. A second glass substrate disposed with a predetermined gap between
It is formed between the first sealing region and the second sealing region so as to hermetically seal a gap between the first glass substrate and the second glass substrate, and has an electromagnetic wave absorption capability. Comprising a sealing layer composed of a melt-fixed layer of glass material for sealing,
The airtight member, wherein the sealing layer has a wetting angle of 45 degrees or less with respect to the first and second glass substrates.   The airtight member according to claim 8, wherein the sealing layer contains a sealing glass made of a low melting point glass and at least one inorganic filler selected from an electromagnetic wave absorbing material and a low expansion filler.   The sealing layer is bonded to the first glass substrate and includes the first layer including the inorganic filler; the second layer bonded to the second glass substrate and including the inorganic filler; The airtight member according to claim 9, further comprising an intermediate layer formed between the first layer and the second layer and made of a single glass layer not including the inorganic filler. A first glass substrate having a first surface with a first sealing region;
The first glass substrate has a second surface including a second sealing region corresponding to the first sealing region, and the second surface faces the first surface. A second glass substrate disposed with a predetermined gap between
Electromagnetic wave absorption formed between the first sealing region and the second sealing region so as to hermetically seal a gap between the first glass substrate and the second glass substrate. Comprising a sealing layer composed of a melt-fixed layer of a sealing glass material having a function,
The sealing layer contains a sealing glass made of low-melting glass, and at least one inorganic filler selected from an electromagnetic wave absorbing material and a low expansion filler,
The sealing layer is bonded to the first glass substrate and includes the first layer including the inorganic filler; the second layer bonded to the second glass substrate and including the inorganic filler; An airtight member comprising an intermediate layer formed between the first layer and the second layer and made of a single glass layer not containing the inorganic filler.   The airtight member according to claim 11, wherein the thickness of the intermediate layer is in the range of 50 nm to 5000 nm.   The airtight member according to any one of claims 8 to 12, wherein a thickness of the sealing layer is in a range of 5 µm to 200 µm.

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