JP2013053032A - Airtight member and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an airtight member by which a sealing layer excellent in airtight sealing performance can be formed with good reproducibility, when laser heating is applied to a step of forming a sealing material layer and a sealing layer.SOLUTION: A sealing material layer 5 is formed by irradiating laser light for firing from a first irradiation starting position LS1 of the frame-like coating layer to a first irradiation finishing position LF1 while being scanned along a frame-like coating layer of a sealing material paste. A first glass substrate and a second glass substrate 2 are stacked via the sealing material layer 5, and a sealing layer is formed, by irradiating from a second irradiation starting position LS2 being set at a position different from the first irradiation starting position LS1 and the first irradiation finishing position LF1 to a second irradiation finishing position LF2, being irradiated with laser light 8 for sealing while being scanned along the sealing material layer 5.

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 (see Patent Document 2).

  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 Documents 1 and 2).

  When laser sealing is applied, first, a sealing material is mixed with a vehicle to prepare a sealing material paste, which is applied to the sealing region of one glass substrate, and then the firing temperature of the sealing material ( The sealing glass is melted and baked on a glass substrate to form a sealing material layer. Further, the organic binder is thermally decomposed and removed in the process of raising the sealing material to the firing temperature. 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, the electronic element portion or the like provided between the glass substrates is hermetically sealed.

  A heating furnace is generally used for forming the sealing material layer. Patent Document 3 describes that, in the sealing material layer forming step, a first temperature raising process for removing the organic binder and a second temperature raising process for baking the sealing material are performed. In the first temperature raising process, the glass substrate is heated from the back side thereof using a hot plate, an infrared heater, a heating lamp, laser light, or the like. In the second temperature raising process for baking the sealing material, a heating furnace for heating the entire glass substrate is used. In Patent Document 4, a sealing material paste in which a low-melting glass (sealing glass), a binder and a solvent are mixed is applied to one panel substrate, and then the coating layer of the sealing material paste is baked with laser light. Forming a sealing material layer.

  When forming a sealing material layer to be used for laser sealing, when applying local heating by laser light to firing the coating layer of the sealing material paste, the sealing glass has surface tension or There is a risk that a gap (gap) may be generated at the position where the firing laser light is irradiated due to shrinkage due to a decrease in the gap. The gap generated in the sealing material layer becomes a factor of reducing the hermetic sealing performance of the hermetic member in the subsequent sealing process. Furthermore, when laser sealing is applied, depending on the irradiation conditions of the sealing laser light, the stress is locally increased based on gaps generated in the sealing material layer, and thus the glass substrate is not easily cracked. There is a risk.

JP-T-2006-524419 JP 2008-115057 A JP 2003-068199 A JP 2002-366050 A

  An object of the present invention is to form a sealing layer with excellent reproducibility and yield in applying a laser beam heating in both the sealing material layer forming step and the sealing layer forming step. An object of the present invention is to provide a method for manufacturing an airtight member that enables this, and an airtight member that is excellent in airtight sealing performance and reliability.

  The method for manufacturing an airtight member of the present invention includes a step of preparing a first glass substrate having a first surface provided with a first sealing region, and a second corresponding to the first sealing region. A step of preparing a second glass substrate having a second surface provided with a sealing region, and a sealing material paste prepared by mixing a sealing material including a sealing glass and a laser absorber with an organic binder Is applied in a frame shape on the second sealing region of the second glass substrate, and the first irradiation end position from the first irradiation start position of the frame-shaped coating layer of the sealing material paste. Until the laser beam for firing is irradiated while scanning along the frame-shaped coating layer, and the whole of the frame-shaped coating layer is heated with the laser beam for firing, thereby removing the organic binder in the frame-shaped coating layer. A step of baking the sealing material to form a sealing material layer while removing the sealing material layer; A step of laminating the first glass substrate and the second glass substrate through the sealing material layer while the first surface and the second surface are opposed to each other; and the sealing material layer From the second irradiation start position set to a position different from the first irradiation end position and the first irradiation end position, the sealing laser beam is transmitted from the first irradiation end position to the second irradiation end position. Irradiation is performed while scanning along the sealing material layer through the glass substrate, and the sealing material layer is melted to hermetically seal a gap between the first glass substrate and the second glass substrate. And a step of forming a deposition layer.

  The hermetic member of the present invention includes a first glass substrate having a first surface including a first sealing region, and a second surface including a second sealing region corresponding to the first sealing region. A second glass substrate disposed on the first glass substrate with a predetermined gap so that the second surface faces the first surface, and the first glass The first sealing region of the first glass substrate and the second sealing region of the second glass substrate so as to hermetically seal a gap between the substrate and the second glass substrate. And a sealing layer made of a material obtained by melting and solidifying a sealing material containing a sealing glass and a laser absorber, and a retardation value generated by the formation of the sealing layer is 100 nm or less It is characterized by being.

  According to the method for producing an airtight member of the present invention, when applying heating by laser light in both the sealing material layer forming step and the sealing layer forming step, the sealing layer having excellent hermetic sealing properties is formed. It can be formed with good reproducibility and yield. Therefore, it is possible to provide an airtight member excellent in airtight sealing performance and reliability and the like with a high yield.

It is sectional drawing which shows the manufacturing method of the airtight member by embodiment of this invention. It is a top view which shows the 1st glass substrate used with the manufacturing method of the airtight member shown in FIG. It is a top view which shows the 2nd glass substrate used with the manufacturing method of the airtight member shown in FIG. It is sectional drawing along the AA line of FIG. It is sectional drawing which shows the formation process of the sealing material layer to the 2nd glass substrate in the manufacturing method of the airtight member shown in FIG. It is a figure which shows the scanning example of the laser beam for baking in the manufacturing method of the airtight member shown in FIG. It is a figure which shows the scanning example of the laser beam for sealing in the manufacturing method of the airtight member shown in FIG. It is a figure which shows the other scanning example of the laser beam for baking in the manufacturing method of the airtight member shown in FIG. 1, and the laser beam for sealing. It is a figure which shows the irradiation completion position of the laser beam for baking in the formation process of the sealing material layer of embodiment of this invention. It is a figure for demonstrating the completion | finish area | region of the laser beam for baking in the formation process of the sealing material layer of embodiment of this invention. It is a figure for demonstrating the scanning speed of the completion | finish area | region of the laser beam for baking in the formation process of the sealing material layer of embodiment of this invention.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. 1 to 7 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, as shown in FIG. 1A, a first glass substrate 1 and a second glass substrate 2 are prepared. For the first and second glass substrates 1 and 2, for example, glass substrates formed of alkali-free glass or soda lime glass having various known compositions are used. The alkali-free glass has a thermal expansion coefficient of about 35 to 40 × 10 ⁻⁷ / K. Soda lime glass has a thermal expansion coefficient of about 80 to 90 × 10 ⁻⁷ / K. At least one of the first and second glass substrates 1 and 2 may be a chemically strengthened glass substrate or the like.

  As shown in FIG. 2, a frame-shaped first sealing region 3 is provided on the surface 1 a of the first glass substrate 1 along the outer peripheral region. As shown in FIGS. 3 and 4, a frame-shaped second sealing region 4 corresponding to the first sealing region 3 is provided on the surface 2 a of the second glass substrate 2. The first and second sealing regions 3 and 4 are regions for forming a sealing layer (for the second sealing region 4, a region for forming a sealing material 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 arranged. The space | interval of the 1st glass substrate 1 and the 2nd glass substrate 2 is suitably set according to the use etc. of an airtight member.

  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 hermetic member is used as an airtight package of the reflecting mirror, a metal reflecting 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.

  As shown in FIGS. 1A, 3, and 4, a frame-shaped sealing material layer 5 is formed in the sealing region 6 of the second glass substrate 2. The sealing material layer 5 is a layer made of a material obtained by baking a sealing material including a sealing glass and a laser absorbing material. The sealing material is obtained by blending a sealing material as a main component with a laser absorbing material and, if necessary, an inorganic filler such as a low expansion filler. The sealing material may contain additives other than these as required.

  As the sealing glass (glass frit), 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. Of these, tin-phosphate glass in consideration of sealing properties (adhesiveness) to glass substrates 1 and 2, reliability thereof (adhesion reliability and sealing properties), influence on the environment and human body, etc. It is preferable to use sealing glass made of bismuth glass.

Tin - phosphate glass (glass frit) is 55 to 68 mol% of SnO, 0.5 to 5 mol% of SnO _2, and 20 to 40 mol% of P ₂ O ₅ (the total amount is basically 100 mol%) is preferable. 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 glass frit can be determined as follows. First, after the glass frit (low melting point glass powder) is acid-decomposed, the total amount of Sn atoms contained in the glass frit 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 (glass frit) is composed of 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 100% by mass). It is preferable to have a composition of 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.

  The sealing material contains a laser absorber. As the laser absorber, a compound such as at least one metal selected from Fe, Cr, Mn, Co, Ni, and Cu or an oxide containing the metal is used. Moreover, pigments other than these may be used. The content of the laser absorbing material is preferably in the range of 0.1 to 40% by volume with respect to the sealing material. If the content of the laser absorbing material is less than 0.1% by volume, the sealing material layer 5 may not be sufficiently melted. If the content of the laser absorbing material exceeds 40% by volume, there is a risk of locally generating heat in the vicinity of the interface with the second glass substrate 2, and the fluidity at the time of melting of the sealing material deteriorates, resulting in the first There exists a possibility that adhesiveness with the glass substrate 1 may fall. Preferably it is 37 volume% or less.

Furthermore, the sealing material may contain a low expansion filler as required. Low expansion filler selected from 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 preferably set so that the thermal expansion coefficient of the sealing glass approaches the thermal expansion coefficient of the glass substrates 1 and 2. Although it depends on the thermal expansion coefficient of the sealing glass or 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 material. The content of the low expansion filler can be appropriately changed depending on the thickness of the sealing material layer 5 and the like. However, if the content of the low expansion filler exceeds 50% by volume, the fluidity at the time of melting of the sealing material may be deteriorated and the adhesiveness with the first glass substrate 1 may be lowered. Preferably it is 45 volume% or less. Since the content of the low expansion filler affects the total content with the laser absorber, the total content is preferably in the range of 0.1 to 50% by volume.

  The sealing material layer 5 is formed as follows. The formation process of the sealing material layer 5 is demonstrated with reference to FIG. First, a sealing material is prepared by blending a sealing glass with a laser absorbing material or a low expansion filler, and this is mixed with a vehicle to prepare a sealing material paste. 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. .

  The resin component in the vehicle functions as a binder for the sealing material and needs to be removed before firing the sealing material. The viscosity of the sealing material paste may be adjusted to the viscosity corresponding to the apparatus applied to the glass substrate 2, and depends on the ratio of the resin component (organic binder) and the solvent (organic solvent, etc.) and the ratio of the sealing material and the vehicle. Can be adjusted. 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.

  As shown in FIG. 5A, a sealing material paste is applied to the sealing region 4 of the second glass substrate 2 and dried to form a frame-shaped coating layer 6. The sealing material paste is applied onto the second sealing region 4 by applying a printing method such as screen printing or gravure printing, or is applied along the second sealing region 4 using a dispenser or the like. To do. The coating layer 6 is preferably dried at a temperature of 120 ° C. or more for 10 minutes or more, for example. The drying process is performed to remove the solvent in the coating layer 6. If the solvent remains in the coating layer 6, the organic binder may not be sufficiently removed in the subsequent baking step (laser baking step).

  Next, as shown in FIG. 5B, the coating layer (dry film) 6 of the sealing material paste is irradiated with a laser beam 7 for firing. The sealing material is baked to form the sealing material layer 5 while removing the organic binder in the coating layer 6 by irradiating the laser beam 7 for firing along the coating layer 6 and selectively heating. (FIG. 5C). The laser beam 7 for firing is not particularly limited, and laser light from a semiconductor laser, a carbon dioxide gas laser, an excimer laser, a YAG laser, a HeNe laser, or the like is used. The same applies to sealing laser light described later.

  The firing process of the coating layer 6 by the laser light 7 is not necessarily limited to the film thickness of the coating layer 6, but the thickness after firing (the thickness of the sealing material layer 5) is 20 μm or less. This is particularly effective for the coating layer 6 having a film thickness. When the thickness after baking exceeds 20 μm, there is a possibility that the entire coating layer 6 cannot be uniformly heated with the laser light 7. However, if the coating layer 6 has a thickness of 150 μm or less by adjusting the formation conditions of the coating layer 6 and the irradiation conditions of the laser beam 7, the coating layer 6 is fired with the laser beam 7. Can do. Practically, the thickness of the sealing material layer 5 is preferably 1 μm or more.

  In the step of forming the sealing material layer 5 according to this embodiment, the frame-shaped coating layer 6 of the sealing material paste is selectively heated by irradiating the laser beam 7 for firing. Therefore, even when an organic resin film such as a color filter or an element film is formed on the surface 2a of the second glass substrate 2, the organic resin film or the element film is not damaged by heat. The sealing material layer 5 can be formed satisfactorily. Furthermore, since it is excellent also in the removability of an organic binder, the sealing material layer 5 excellent in sealing property, reliability, etc. can be obtained.

  Of course, the step of forming the sealing material layer 5 using the firing laser beam 7 can be applied even when an organic resin film or an element film is not formed on the surface 2a of the second glass substrate 2. Even in such a case, it is possible to obtain the sealing material layer 5 having excellent sealing properties and reliability. Furthermore, the firing process using the laser light 7 consumes less energy than the firing process using the conventional heating furnace, and contributes to the reduction of manufacturing steps and manufacturing costs. Therefore, the process of forming the sealing material layer 5 using the laser light 7 is also effective from the viewpoint of energy saving and cost reduction.

  When the sealing material layer 5 is formed with the laser beam 7 for firing, first, as shown in FIG. 6, the laser beam 7 is irradiated to the irradiation start position LS1 of the frame-shaped coating layer 6 of the sealing material paste. Next, the laser beam 7 is irradiated while scanning along the frame-shaped coating layer 6. Then, the laser beam 7 is scanned to the irradiation end position LF1 at least partially overlapping with the irradiation start position LS1, and after the entire frame-shaped coating layer 6 is heated, the irradiation of the laser beam 7 is ended. In this way, by irradiating the entire frame-shaped coating layer 6 with the laser beam 7, the organic binder in the frame-shaped coating layer 6 is thermally decomposed and removed, and the sealing glass is melted and rapidly cooled and solidified for sealing. The material layer 5 is formed. In addition, the specific baking conditions of the frame-shaped coating layer 6 by the laser beam 7 for baking are mentioned later.

  When the sealing material paste is applied by applying screen printing, gravure printing, or the like, the sealing material paste is applied to the sealing region 4 of the second glass substrate 2 at one time, so that a laser for firing is used. The irradiation start position LS1 of the light 7 is not particularly limited. When the sealing material paste is applied along the second sealing region 4 with a dispenser or the like, an application start position AS and an application end position AF of the sealing material paste are generated as shown in FIG. In the portion where the coating start position AS and the coating end position AF overlap, the film thickness of the frame-shaped coating layer 6 tends to vary, and stress concentration tends to occur when the laser beam 7 is irradiated. When the irradiation start position LS1 and the irradiation end position LF1 of the laser beam 7 where stress tends to concentrate on such a part are set, the local stress further increases or the gap of the sealing material layer 5 shown below is expanded. There is a risk.

  That is, the irradiation end position LF1 of the firing laser light 7 is set so as to at least partially overlap the irradiation start position LS1 in order to heat the entire frame-shaped coating layer 6. While the laser beam 7 is scanned along the frame-shaped coating layer 6, the irradiation start position LS1 where the sealing glass has been melted is cooled and solidified. For this reason, when the laser beam 7 reaches the irradiation end position LF1 at least partially overlapping with the irradiation start position LS1, the surface tension is superior to the fluidity of the heated and melted sealing glass. It is considered that the sealing glass shrinks and a gap is generated. If the film thickness variation of the frame-shaped coating layer 6 occurs in such a portion, there is a possibility that the shrinkage of the sealing glass is increased and the gap is enlarged.

  Therefore, when the sealing material paste is applied along the second sealing region 4 with a dispenser or the like, the irradiation start position LS1 of the laser light 7 is the application start position AS and the application of the sealing material paste in the frame-shaped coating layer 6. It is preferable to set a position different from the end position AF. As a result, the irradiation of the laser beam 7 for firing is started from a portion where the film thickness of the frame-shaped coating layer 6 is uniform, so that an increase in local stress of the second glass substrate 2 and the sealing material layer 5 Expansion of the gap can be suppressed. The irradiation start position LS1 of the laser beam 7 is obtained from the application start position AS and the application end position AF of the sealing material paste in order to obtain the effect of suppressing the influence of the stress dispersion effect and the film thickness variation of the frame-shaped application layer 6. It is preferable to set the position at a distance of 3 mm or more.

  Next, as shown in FIG.1 (b), the 1st glass substrate 1 and the 2nd glass substrate 2 are laminated | stacked through the sealing material layer 5 so that surface 1a, 2a may oppose. Thereafter, as shown in FIG. 1C, the sealing material layer 5 is irradiated with the sealing laser beam 8 through the second glass substrate 2. The sealing material layer 5 may be irradiated with the laser light 8 through the first glass substrate 1. As shown in FIG. 1 (d), the sealing laser beam 8 is irradiated while scanning along the frame-shaped sealing material layer 5, and the sealing material layer 5 is sequentially melted and rapidly cooled and solidified. An airtight member 10 is produced by forming a sealing layer 9 that hermetically seals the gap between the glass substrate 1 and the second glass substrate 2. A space 11 between the first glass substrate 1 and the second glass substrate 2 is hermetically sealed by a sealing layer 9.

  As shown in FIG. 7, the sealing laser beam 8 is first irradiated to the irradiation start position LS <b> 2 of the frame-shaped sealing material layer 5. The sealing laser beam 8 is irradiated while scanning along the sealing material layer 5, and is scanned to the irradiation end position LF2 at least partially overlapping with the irradiation start position LS2. The irradiation start position LS2 of the sealing laser light 8 is set to a position different from the irradiation start position LS1 and the irradiation end position LF1 of the firing laser light 7 in the sealing material layer 5. Since stress tends to concentrate on the irradiation start / end positions LS2 and LF2 of the sealing laser beam 8, the laser is set by setting the stresses at positions different from the irradiation start / end positions LS1 and LF1 of the firing laser beam 7. Stress due to the start and end of the light 7 and 8 is dispersed, and the reliability of the airtight member 10 is improved.

  Furthermore, when the irradiation start position LS2 of the sealing laser beam 8 is set in a portion where the gap of the sealing material layer 5 is generated, the heat of the sealing laser beam 8 is excessively transmitted to the first glass substrate 1 and is locally There is a possibility that the stress increases further. By setting the irradiation start / end positions LS2 and LF2 of the sealing laser beam 8 to positions different from the irradiation start / end positions LS1 and LF1 of the firing laser beam 7, local portions caused by the gap of the sealing material layer 5 Increase in stress can be suppressed. The irradiation start position LS2 of the sealing laser beam 8 is used to obtain the effect of suppressing the effects of stress dispersion and the influence of the gap of the sealing material layer 5, so that the irradiation start position LS1 and the irradiation end position LF1 of the firing laser beam 7 are obtained. It is preferable to set the position at a distance of 3 mm or more.

  As described above, there is a possibility that a gap is generated at the irradiation end position LF1 of the firing laser beam 7 in the sealing material layer 5 due to shrinkage of the sealing glass due to surface tension, void reduction, or the like. When the irradiation start position LS <b> 2 of the sealing laser beam 8 is set in a portion where the gap is generated, the heat of the sealing laser beam 7 is excessively transmitted to the first glass substrate 1 due to the gap of the sealing material layer 5. The stress may increase locally. Such an increase in local stress causes the glass substrate 1 to crack. By setting the irradiation start position LS2 of the sealing laser beam 8 to a position different from the irradiation start position LS1 and the irradiation end position LF1 of the firing laser beam 7, an increase in local stress and the glass substrate 1 based on the increased stress Cracking can be suppressed.

  In FIG. 7, the application start position AS and the application end position AF of the sealing material paste are set to the first side 4a of the second sealing region 4, and the irradiation start position LS1 and the irradiation end position of the firing laser beam 7 are set. LF1 is set to the second side 4b of the second sealing region 4, and the irradiation start position LS2 and the irradiation end position LF2 of the sealing laser beam 8 are set to the third side 4c of the second sealing region 4. Shows the state. In this way, the application start / end positions AS, AF of the sealing material paste, the irradiation start / end positions LS1, LF1, and the irradiation start / end positions LS2, LF2 of the sealing laser beam 7 By separately setting the sides 4a, 4b, and 4c of the sealing region 4 of 2, the stress is distributed to the sides of the sealing layer 9, and thus the glass substrate 1 can be more reliably suppressed from cracking. In addition, the reliability of the airtight member 10 can be further enhanced.

  Application start / end positions AS, AF of the sealing material paste, irradiation start / end positions LS1, LF1 of the firing laser beam 7, and irradiation start / end positions LS2, LF2 of the sealing laser beam 8 are as shown in FIG. Alternatively, it may be set to one side 4 a of the second sealing region 4. In this case, the irradiation start position LS1 of the firing laser light 7 is preferably set at a position 3 mm or more away from the application start / end positions AS, AF of the sealing material paste, and the irradiation start position LS2 of the sealing laser light 8 Is preferably set at a position 3 mm or more away from the irradiation start / end positions LS1, LS2 of the firing laser beam 7. When the hermetic member 10 is used as a package of an electronic device, each position is set to one side 4a of the second sealing region 4 and wirings that are vulnerable to stress are arranged on the other side, thereby The degree of freedom of the wiring pattern can be increased.

  Next, specific conditions for the process of forming the sealing material layer 5 using the firing laser beam 7 will be described. The heating temperature when the frame-shaped coating layer 6 is irradiated with the laser beam 7 for baking is set to a range of (T + 80 ° C.) or more and (T + 550 ° C.) or less with respect to the softening temperature T (° C.) of the sealing glass. preferable. The softening temperature T of the sealing glass indicates a temperature at which it softens and flows but does not crystallize. The temperature of the frame-shaped coating layer 6 when irradiated with the laser light 7 is a value measured with a radiation thermometer. Under the irradiation condition of the laser beam 7 such that the temperature of the frame-shaped coating layer 6 does not reach (T + 80 ° C.), only the surface portion of the frame-shaped coating layer 6 is melted and the entire frame-shaped coating layer 6 cannot be melted uniformly. There is a fear. Under the irradiation conditions of the laser light 7 such that the temperature of the frame-shaped coating layer 6 exceeds (T + 550 ° C.), cracks and cracks are likely to occur in the glass substrate 2 and the sealing material layer (firing layer) 5.

  The organic binder in the frame-shaped coating layer 6 is thermally decomposed and removed by irradiating the laser beam 7 while scanning so that the heating temperature of the frame-shaped coating layer 6 of the sealing material paste falls within the above range. . Since the laser beam 7 is irradiated while scanning along the frame-shaped coating layer 6, the portion located in front of the traveling direction of the laser beam 7 is preheated appropriately. The thermal decomposition of the organic binder proceeds not only when the frame-shaped coating layer 6 is directly irradiated with the laser beam 7 but also with a preheated portion in front of the traveling direction of the laser beam 7. As a result, the organic binder in the frame-shaped coating layer 6 is effectively and efficiently removed, and the amount of residual carbon in the sealing material layer 5 can be reduced. Residual carbon becomes a factor which raises the impurity gas concentration in an airtight member.

  The laser beam 7 is preferably irradiated while scanning along the frame-shaped coating layer 6 at a scanning speed in the range of 3 to 20 mm / second. When the scanning speed of the laser beam 7 when scanning along the frame-shaped coating layer 6 is less than 3 mm / second, the baking rate of the frame-shaped coating layer 6 by the laser beam 7 is reduced, and the sealing material layer 5 is made efficient. It cannot be formed well. On the other hand, when the scanning speed of the laser beam 7 exceeds 20 mm / second, only the surface portion may be melted and vitrified before the entire frame-shaped coating layer 6 is uniformly heated. The release of gas generated by decomposition to the outside is reduced. For this reason, bubbles are easily generated inside the sealing material layer 5, and deformation due to the bubbles is likely to occur on the surface. The amount of residual carbon in the sealing material layer 5 is also likely to increase. If the sealing material layer 5 having a poor organic binder removal state is used to seal between the glass substrates 1 and 2, the bonding strength between the glass substrates 1 and 2 and the sealing layer is reduced, or the airtightness of the airtight member is reduced. May decrease.

  The scanning speed of the laser beam 7 is preferably adjusted according to the film thickness of the frame-shaped coating layer 6. For example, in the case of the frame-shaped coating layer 6 such that the film thickness after firing is less than 5 μm, the scanning speed of the laser light 7 can be increased to 15 mm / second or more. Further, in the case of the frame-shaped coating layer 6 having a film thickness after firing exceeding 20 μm, the scanning speed of the laser light 7 is preferably 5 mm / second or less. The scanning speed of the laser beam 7 when firing the frame-shaped coating layer 6 in which the film thickness after firing is in the range of 5 to 20 μm is preferably in the range of 5 to 15 mm / second.

Further, when the heating temperature of the frame-shaped coating layer 6 is set to the range of (T + 80 ° C.) to (T + 550 ° C.) with the laser beam 7 having a scanning speed of 3 to 20 mm / second, the laser beam 7 is 100 to It preferably has a power density in the range of 1100 W / cm ² . If the output density of the laser beam 7 is less than 100 W / cm ² , the entire frame-shaped coating layer 6 may not be heated uniformly. When the output density of the laser beam 7 exceeds 1100 W / cm ² , the glass substrate 2 is excessively heated, and cracks, cracks, and the like are likely to occur.

  Although FIG. 5 shows a state in which the laser beam 7 is irradiated from above the frame-shaped coating layer 6, the laser beam 7 may be irradiated to the frame-shaped coating layer 6 through the glass substrate 2. For example, in order to shorten the baking time of the frame-shaped coating layer 6, it is effective to increase the output of the laser beam 7 and increase the scanning speed. For example, when the high-power laser beam 7 is irradiated from above the frame-shaped coating layer 6, only the surface portion of the frame-shaped coating layer 6 may be vitrified. Vitrification of only the surface portion of the frame-shaped coating layer 6 causes various problems as described above. With respect to such a point, when the frame-shaped coating layer 6 is irradiated with the laser beam 7 from the glass substrate 2 side, even if the portion irradiated with the laser beam 7 is vitrified, the gas generated by the thermal decomposition of the organic binder Can be released from the surface of the frame-shaped coating layer 6. It is also effective to irradiate the laser beam 7 from the upper and lower surfaces of the frame-shaped coating layer 6.

  The beam shape of the laser beam 7 (irradiation spot shape) is not particularly limited. The beam shape of the laser beam 7 is generally circular, but is not limited to circular. The beam shape of the laser beam 7 may be an ellipse having a minor axis in the width direction of the frame-shaped coating layer 6. According to the laser beam 7 whose beam shape is shaped into an ellipse, the irradiation area of the laser beam 7 on the frame-shaped coating layer 6 can be enlarged, and the scanning speed of the laser beam 7 can be increased. By these, it becomes possible to shorten the baking time of the frame-shaped coating layer 6.

  As described above, a gap may be generated at the irradiation end position LF1 of the firing laser beam 7 due to the surface tension of the sealing glass, the decrease in the gap, or the like. If the gap generated in the sealing material layer 5 is wide, the hermetic sealing property may be lowered in the subsequent laser sealing step. For such a point, it is effective to keep the flow state of the sealing glass at the end of the irradiation time of the firing laser beam 7. The molten state of the sealing glass when the laser beam 7 reaches the irradiation end position LF1 is maintained, and the time for contacting the sealing glass in which the molten sealing glass is solidified is increased, in other words, the molten sealing is performed. By causing the glass to flow on the sealing glass solidifying the glass, it is possible to suppress the occurrence of a gap due to the surface tension of the sealing glass.

  Specifically, the irradiation end position LF1 of the laser beam 7 in the frame-shaped coating layer 6 is set at least at least one of the already baked portion of the frame-shaped coating layer 6 (the portion that has already been irradiated with the laser beam 7 and melted and solidified). When the part is set at the overlapping position, the scanning speed of the laser beam 7 in the end region from the position close to the irradiation end position LF1 to the irradiation end position LF1 is set in the scanning region along the frame-shaped coating layer 6 excluding the end region. It is preferable to decelerate from the scanning speed of the laser beam 7. Thus, by reducing the scanning speed of the laser beam 7 in the end region, the molten sealing glass is caused to flow toward the already-solidified sealing glass, and the molten sealing glass is solidified. It is possible to make sufficient contact with the sealing glass. Therefore, the gap width generated by shrinkage due to insufficient fluidity of the sealing glass at the irradiation end position LF1 can be reduced.

  As shown in FIG. 9A, the irradiation end position LF1 of the firing laser beam 7 in the frame-shaped coating layer 6 corresponds to the already baked portion of the frame-shaped coating layer 6 (basically the irradiation start position LS1). To a position where at least a part overlaps. Thereby, the sealing glass can be integrated in a fluid state. The irradiation end position LF1 of the laser beam 7 is preferably set to a position where the amount of overlap (area ratio) with the irradiation start position LS1 is 50% or more as shown in FIG. 9B. The irradiation end position LF1 of the laser beam 7 is set to a position overlapping the irradiation start position LS1 as shown in FIG. 9C, or set to a position exceeding the irradiation start position LS1 as shown in FIG. 9D. More preferably. The molten sealing glass in the end region can be brought into better contact with the fired portion of the frame-shaped coating layer 6 (solidified sealing glass).

As shown in FIG. 9D, when the irradiation end position LF1 of the firing laser light 7 is set to a position beyond the irradiation start position LS1, the length of the region where the laser light 7 is irradiated repeatedly is particularly large. It is not limited. However, even if the overlapping irradiation region of the laser beam 7 is made too long, not only can the contact improvement between the molten sealing glass and the solid sealing glass be improved, but also the sealing material. The formation time of the layer 5 is extended correspondingly, and the formation efficiency is lowered. For this reason, the overlapping irradiation region of the laser beam 7 is preferably set to a distance not more than 20 times the beam diameter D of the laser beam 7 from the center of the irradiation start position LS1 with the beam center of the laser beam 7 as a reference. More preferably, the distance is 5 times or less the beam diameter D. The beam shape of the laser beam 7 is defined by a region where the intensity is 1 / e ² of the maximum beam intensity.

  As shown in FIG. 10A, the position at which the speed of the laser beam 7 is decelerated (the start position of the end region) is the firing portion (firing end) of the frame-shaped coating layer 6 with the beam center of the laser beam 7 as a reference. To a position at least 1.2 times before the beam diameter D of the laser beam 7. When the laser beam 7 is decelerated from a position less than 1.2 times the beam diameter D, the contact time between the molten sealing glass and the solid sealing glass in the end region may be insufficient. is there. The deceleration start position of the laser beam 7 may be a position at least 1.2 times the beam diameter D of the laser beam 7 from the firing end of the frame-shaped coating layer 6, and from a position 1.2 times the beam diameter D. Furthermore, you may decelerate from the near position (position farther from the firing end).

  However, when decelerating from a position that is too far from the firing end of the frame-shaped coating layer 6, the scanning time of the laser light 7 in the state of being decelerated by that amount increases, and the formation time of the sealing material layer 5 is that much. The formation efficiency is lowered. For this reason, the deceleration start position of the laser beam 7 is, as shown in FIG. 10B, the beam diameter D of the laser beam 7 before the firing end of the frame-shaped coating layer 6 with the beam center of the laser beam 7 as a reference. It is preferable to set the position 20 times or less. Thus, it is preferable to set the deceleration start position of the laser beam 7 within a range of 1.2 times or more and 20 times or less of the beam diameter D of the laser beam 7 before the firing end of the frame-shaped coating layer 6. It is more preferable to set within a range of 1.2 times to 5 times the beam diameter D.

  As described above, the scanning speed of the laser beam 7 (scanning speed of the laser beam 7 in the scanning region) when scanning along the frame-shaped coating layer 6 is preferably in the range of 3 to 20 mm / second. It is preferable to reduce the scanning speed of the laser beam 7 to 2 mm / second or less in the end region with respect to the scanning speed of the laser beam 7 in such a scanning region. Thereby, the molten sealing glass in the end region can be brought into good contact with the fired portion of the frame-shaped coating layer 6 (solidified sealing glass). More preferably, the scanning speed of the laser beam 7 in the end region is reduced to 0.5 mm / second or less. The lower limit value of the scanning speed of the laser beam 7 in the end region is not particularly limited, but is 0.1 mm / second or more (beam diameter D) in consideration of excessive heating of the glass substrate 2 and a decrease in the formation efficiency of the sealing material layer 5. It is preferable that the position reference is 1.2 times before.

  As shown in FIGS. 11A and 11B, the scanning speed of the laser beam 7 in the end region is from the firing portion (firing end) of the frame-shaped coating layer 6 with the beam center of the laser beam 7 as a reference. It is preferably 2 mm / second or less at a position 1.2 times before the beam diameter D of the laser beam 7. Since the deceleration start position of the laser beam 7 may be a position 1.2 times or more the beam diameter D of the laser beam 7 from the firing end of the frame-shaped coating layer 6 as described above, FIG. As shown, a position (position farther from the firing end) than the position 1.2 times before the beam diameter D of the laser beam 7, that is, 1.2 times or more and 20 times the beam diameter D of the laser beam 7. The laser beam 7 may be scanned at a speed of 2 mm / second or less from a position within the following range.

  FIG. 11B and FIG. 11C show a state in which the laser beam 7 in the end region is scanned at a constant speed that is decelerated from the scanning speed of the scanning region, for example, a constant speed of 2 mm / second or less. As shown in FIG. 11D, the laser beam 7 is irradiated at a predetermined deceleration from the deceleration start position of the laser beam 7 (within a range of 1.2 to 20 times the beam diameter D) to the irradiation end position LF1. The scanning speed may be reduced. Also in this case, the scanning speed when the beam center of the laser beam 7 reaches a position 1.2 times before the beam diameter D of the laser beam 7 from the firing end of the frame-shaped coating layer 6 is set to 2 mm / second or less. It is preferable. In any case, it is preferable to set the scanning speed of the laser light 7 at a position 1.2 times before the beam diameter D of the laser light 7 to 2 mm / second or less, and thereby the gap width generated at the irradiation end position LF1. Can be narrowed with good reproducibility.

  As described above, in the end region, the scanning speed of the laser beam 7 is made lower than the scanning speed of the laser beam 7 in the scanning region. Therefore, the heating temperature of the frame-shaped coating layer 6 is the same as the laser beam 7 in the scanning region. May be too high. In such a case, it is preferable to lower the output density of the laser light 7 in the end region than in the scanning region. As a result, overheating of the frame-shaped coating layer 6 and cracks and cracks of the glass substrate 2 and the sealing material layer (firing layer) 5 caused thereby can be suppressed. However, if the heating temperature of the frame-shaped coating layer 6 in the end region is within the above range, the laser beam 7 may be irradiated under the same conditions as in the scanning region.

The gap generated at the irradiation end position LF1 of the firing laser beam 7 can be suppressed by reducing the scanning speed of the laser beam 7 in the end region from that in the scanning region. Furthermore, the gap width at the irradiation end position LF1 is also affected by the ease of flow of the sealing material. The flow state of the sealing material is affected by the content and particle size of the laser absorbing material and low expansion filler added to the sealing glass. Therefore, the fluidity-inhibiting factor of the sealing material represented by the sum of the products of the content (mass%) of the laser absorbing material and the low expansion filler and the specific surface area (m ² / g) should be 300 or less. Is more preferable, and 250 or less is more preferable. Thereby, since the fluidity of the sealing material is improved, the gap width can be further narrowed.

  Next, the specific conditions of the formation process of the sealing layer 9 by the sealing laser beam 8 will be described. The heating temperature when the sealing material layer 5 is irradiated with the sealing laser beam 8 may be in the range of (T + 80 ° C.) to (T + 550 ° C.) with respect to the softening temperature T (° C.) of the sealing glass. preferable. Under the irradiation condition of the laser beam 8 such that the temperature of the sealing material layer 5 does not reach (T + 80 ° C.), the adhesion between the glass substrates 1 and 2 and the sealing glass may be insufficient. On the other hand, under the irradiation condition of the laser light 8 such that the temperature of the sealing material layer 5 exceeds (T + 550 ° C.), the glass substrates 1 and 2 and the sealing layer 9 are likely to be cracked or broken.

The laser beam 8 is preferably irradiated while scanning along the sealing material layer 5 at a scanning speed in the range of 3 to 15 mm / second. The output density of the laser beam 8 is preferably in the range of 700 to 5200 W / cm ² . The irradiation end position LF2 of the laser beam 8 is preferably set to a position overlapping the irradiation start position LS2 or a position exceeding the irradiation start position LS2. In particular, by setting the irradiation end position LF2 of the laser light 8 to a position beyond the irradiation start position LS2, the stress caused by the irradiation start / end positions LS2 and LF2 of the laser light 8 can be dispersed. The overlapping irradiation region of the laser beam 8 is preferably set to a distance not more than 20 times the beam diameter D of the laser beam 8 from the center of the irradiation start position LS2 with the beam center of the laser beam 8 as a reference. More preferably, the distance is 5 times or less of D.

  According to the manufacturing method of this embodiment, since the stress caused by the start and end of the laser beams 7 and 8 can be dispersed, the increase in local stress caused by the formation of the sealing layer 9 can be suppressed. it can. As a result, it is possible to increase the reliability of the airtight member 10 having the sealing layer 9 in addition to suppressing the cracking of the glass substrates 1 and 2 when the sealing layer 9 is formed. Specifically, when the retardation value of the glass substrates 1 and 2 after forming the sealing layer 9 is observed with a polarizing microscope or the like, the retardation value of the portion where the sealing layer 9 is formed should be 100 nm or less. Can do. That is, the retardation value generated in the glass substrates 1 and 2 by the formation of the sealing layer 9 can be set to 100 nm or less.

  In particular, at the sealing material paste application start / end positions AS, AF, the irradiation start / end positions LS1, LF1 of the firing laser beam 7, and the irradiation start / end positions LS2, LF2 of the sealing laser beam 8, the sealing layer The retardation value produced in the glass substrates 1 and 2 by formation of 9 can be 3-100 nm or less. Thereby, the reliability of the airtight member 10 having the sealing layer 9 can be enhanced. By setting the retardation value at each position to 100 nm or less, sealing properties and reliability after sealing can be improved. In addition, since the lower limit value of the retardation value is a rapid cooling process, it is difficult to make it less than 3 nm.

  A birefringence imaging system (manufactured by CRi, apparatus name: Abrio) is used to measure the retardation value generated by the formation of the sealing layer 9 described above. In this method, the sample is placed in the order of the glass substrate 1, the sealing layer 9, and the glass substrate 2 with respect to the optical axis of the birefringence imaging system, and a light source and a circle are placed in front of the sample (on the glass substrate 2 side). A configuration in which a polarizing filter is arranged and an elliptical ellipsometer and a CCD camera are arranged behind the sample (on the glass substrate 1 side) is used. In this configuration, the state of the liquid crystal optical element in the ellipsometer is changed, a plurality of images that have passed through the ellipsometer are acquired by a CCD camera, and these images are compared and calculated. Can be quantified. When the thickness of the sealing layer 9 is thick or when the concentration of the laser absorber is high, it is difficult to measure the retardation of the glass substrates 1 and 2 inside and below the sealing layer 9. The retardation value at the side of 2 sealing layer 9 is used. The retardation value at this time will be further described. It is assumed that the retardation value is highest in a range within 2 mm from the end of the sealing layer 9.

  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
Bismuth glass frit 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 and having an average particle diameter of 1 μm (softening temperature: 410 ° C.) A cordierite powder having an average particle size of 0.9 μm and a specific surface area of 12.4 m ² / g as a low expansion filler, an Fe ₂ O ₃ —Al ₂ O ₃ —MnO—CuO composition, A laser absorber having a diameter of 1.9 μm and a specific surface area of 8.3 m ² / g was prepared.

The specific surface areas of the cordierite powder and the laser absorbing material were measured using a BET specific surface area measuring device (manufactured by Mountec, apparatus name: Macsorb HM model-1201). Measurement conditions are adsorbate: nitrogen, carrier gas: helium, measurement method: flow method (BET one-point method), degassing temperature: 200 ° C., degassing time: 20 minutes, degassing pressure: N ₂ gas flow / atmospheric pressure The sample mass was 1 g. The same applies to the following examples.

Bismuth glass frit 66.9% by volume (79.8% by mass), cordierite powder 19.2% by volume (8.8% by mass), and laser absorber 13.9% by volume (11.4% by mass) To prepare a sealing material. A sealing material paste was prepared by mixing 80% by mass of the sealing material with 20% by mass of the vehicle. The vehicle is obtained by dissolving ethyl cellulose (2.5% by mass) as a binder component in a solvent (97.5% by mass) made of terpineol. The sum of the products of the cordierite and laser absorber content (mass%) and the specific surface area (m ² / g) (the fluidity-inhibiting factor of the sealing material) is 203.7.

Next, a second glass substrate (dimension: 90 × 90 × 0.7 mmt) made of alkali-free glass (thermal expansion coefficient: 38 × 10 ⁻⁷ / K) is prepared and sealed in a sealing region of the glass substrate. The coating material paste was applied to a 70 × 70 mm frame by screen printing, and then dried under the conditions of 120 ° C. × 10 minutes. The sealing material paste was applied so that the film thickness after drying was 6.4 μm. An alkali-free glass substrate on which a frame-shaped coating layer of a sealing material paste was formed was placed on a sample holder of a laser irradiation device via an alumina substrate having a thickness of 0.5 mm.

Next, a circular laser beam having a wavelength of 940 nm, an output density of 679 W / cm ² , and a beam shape of 1.5 mm in diameter was irradiated along the frame-shaped coating layer of the sealing material paste. The irradiation start position of the laser beam was set at the first side of the sealing region. The scanning speed of the laser beam was 5 mm / second. The heating temperature of the frame-shaped coating layer at this time is 740 ° C. When the laser beam reached a position 5 mm from the baking end of the frame-shaped coating layer, the scanning speed was reduced to 0.5 mm / second, and the laser beam was irradiated to the irradiation end position at this scanning speed. During deceleration, the output density of the laser beam was reduced to 425 W / cm ² . The heating temperature of the frame-shaped coating layer at this time is 740 ° C. The irradiation end position of the laser beam was set so that the overlapping irradiation distance was 5 mm. In this way, the entire frame-shaped coating layer of the sealing material paste was baked with laser light, thereby forming a sealing material layer having a film thickness of 3.8 μm.

  When the state of the obtained sealing material layer was observed with SEM, it was confirmed that the entire sealing material layer was vitrified well. In the sealing material layer, no bubbles or surface deformation due to the organic binder was observed. Furthermore, when the gap width at the irradiation end position was measured with a side-length microscope, it was confirmed that no gap was generated at the laser beam irradiation end position (gap width = 0 μm). When the amount of residual carbon in the sealing material layer was measured, it was confirmed that it was the same as the amount of residual carbon when the coating layer of the same sealing material paste was baked in an electric furnace (300 ° C. × 40 minutes).

Next, a second glass substrate having a sealing material layer and a first glass substrate (a substrate made of non-alkali glass having the same composition and shape as the second glass substrate) were stacked. Next, a laser beam having a wavelength of 940 nm, an output density of 1982 W / cm ² and a beam shape of 1.5 mm in diameter is irradiated while scanning along the sealing material layer through the second glass substrate, and the sealing material layer is irradiated with the laser beam. The first glass substrate and the second glass substrate were sealed by melting and rapid solidification. The irradiation start position of the laser beam was set at the second side of the sealing region. The scanning speed of the laser beam was 10 mm / second. The irradiation end position of the laser beam was set so that the overlapping irradiation distance was 3 mm.

  When laser sealing of 10 airtight members was carried out in this way, it was confirmed that none of the airtight members were found to have cracks or cracks in the glass substrate or the sealing layer, and had excellent airtightness. It was. Furthermore, the retardation value of the irradiation start position of the firing laser beam and the irradiation start position of the sealing laser beam was measured according to the method described above using the airtight member that was able to seal well. As a result, it was confirmed that the retardation value at the irradiation start position of the firing laser light was 20 nm and the retardation value at the irradiation start position of the sealing laser light was 15 nm, both of which were small in distortion and stress was dispersed. .

(Example 2)
The sealing material paste prepared in the same manner as in Example 1 is framed along the sealing region of the second glass substrate having the same composition and shape as Example 1 using a dispenser (manufactured by Hitachi Plant Technology). It was applied to the shape. The application conditions using the dispenser were nozzle diameter: 0.45 mm, nozzle speed: 30 mm / second, and discharge pressure: 70-80 kPa. Under such conditions, a coating film having a dry film thickness of 12 to 15 μm and a line width of 500 to 600 μm was formed. This coating film was dried under the same conditions as in Example 1 and then laser-fired under the same conditions as in Example 1 to form a sealing material layer. The irradiation start position of the laser beam for firing was set at the second side of the sealing region.

  Next, after laminating a second glass substrate having a sealing material layer and a first glass substrate (a substrate made of alkali-free glass having the same composition and shape as the second glass substrate), Example 1 and An airtight member was produced by laser sealing under the same conditions. The irradiation start position of the sealing laser beam was set at the third side of the sealing region. In this way, 10 airtight members were laser-sealed, and the number of good products by laser sealing was examined. Moreover, the retardation value of the application | coating start position of sealing material paste, the irradiation start position of the laser beam for baking, and the irradiation start position of the sealing laser beam was measured similarly to Example 1 using the good airtight member. . The results are shown in Table 1.

(Example 3)
Bismuth glass frit having a composition of 82% by mass of Bi ₂ O _3, 6% by mass of B ₂ O ₃ , 10% by mass of ZnO, 1% by mass of Al ₂ O _3, 1% by mass of SiO ₂ and having an average particle diameter of 1 μm ( Softening temperature: 410 ° C.), cordierite powder having an average particle size of 0.9 μm and a specific surface area of 12.4 m ² / g as a low expansion filler, and Fe ₂ O ₃ —Al ₂ O ₃ —MnO—CuO composition And a laser absorber having an average particle diameter of 0.8 μm and a specific surface area of 8.3 m ² / g. Subsequently, 66.9 volume% of bismuth-type glass frit, 19.1 volume% of cordierite powder, and 13.9 volume% of laser absorbers were mixed, and the sealing material was produced. 80% by mass of this sealing material was mixed with 20% by mass of a vehicle having the same composition as in Example 1 to prepare a sealing material paste.

  Except for using the above-mentioned sealing material paste, under the same conditions as in Example 2, application of the sealing material paste with a dispenser, laser firing of the coating film, and laser sealing using the sealing material layer formed thereby We performed wearing. In this way, 10 airtight members were laser-sealed, and the number of good products by laser sealing was examined. Moreover, the retardation value of the application | coating start position of sealing material paste, the irradiation start position of the laser beam for baking, and the irradiation start position of the sealing laser beam was measured similarly to Example 1 using the good airtight member. . The results are shown in Table 1.

(Examples 4 to 6)
An airtight member was produced under the same conditions as in Example 2 except that the output density of the laser light applied to the sealing material layer was changed to the conditions shown in Table 1. In this way, 10 airtight members were laser-sealed, and the number of good products by laser sealing was examined. Moreover, the retardation value of the application | coating start position of sealing material paste, the irradiation start position of the laser beam for baking, and the irradiation start position of the sealing laser beam was measured similarly to Example 1 using the good airtight member. . The results are shown in Table 1.

(Example 7)
The same conditions as in Example 2 except that the application start position of the sealing material paste, the irradiation start position of the firing laser light, and the irradiation start position of the sealing laser light are all set to one side of the sealing region. An airtight member was produced. However, the distance between the application start position of the sealing material paste and the irradiation start position of the firing laser light is 35 mm, and the distance between the irradiation start position of the firing laser light and the irradiation start position of the sealing laser light is 15 mm. did. In this way, 10 airtight members were laser-sealed, and the number of good products by laser sealing was examined. Using a non-defective airtight member, the retardation values of the application start position of the sealing material paste, the irradiation start position of the firing laser beam, and the irradiation start position of the sealing laser beam were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
An airtight member was produced under the same conditions as in Example 1 except that the irradiation start position of the firing laser light and the irradiation start position of the sealing laser light were set to the same position on one side of the sealing region. In this way, 10 airtight members were laser-sealed, and the number of good products by laser sealing was examined. Using a non-defective airtight member, the retardation values of the application start position of the sealing material paste, the irradiation start position of the firing laser beam, and the irradiation start position of the sealing laser beam were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
The same conditions as in Example 2 except that the application start position of the sealing material paste, the irradiation start position of the firing laser light, and the irradiation start position of the sealing laser light are set to the same position on one side of the sealing region. An airtight member was produced. In this way, 10 airtight members were laser-sealed, and the number of good products by laser sealing was examined. Using a non-defective airtight member, the retardation values of the application start position of the sealing material paste, the irradiation start position of the firing laser beam, and the irradiation start position of the sealing laser beam were measured in the same manner as in Example 1. The results are shown in Table 1.

  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 ... Sealing material layer, 6 ... Frame-shaped coating layer of sealing material paste, 7 ... Laser light for firing, 8 ... Laser light for sealing, 9 ... Sealing layer, 10 ... Airtight member, 11 ... Airtight space.

Claims (15)

Preparing a first glass substrate having a first surface provided with a first sealing region;
Preparing a second glass substrate having a second surface provided with a second sealing region corresponding to the first sealing region;
A step of applying a sealing material paste prepared by mixing a sealing material containing a sealing glass and a laser absorber with an organic binder in a frame shape on the second sealing region of the second glass substrate. When,
From the first irradiation start position to the first irradiation end position of the frame-shaped coating layer of the sealing material paste, the laser beam for baking is irradiated while scanning along the frame-shaped coating layer, and the laser beam for baking And heating the entire frame-shaped coating layer to remove the organic binder in the frame-shaped coating layer while firing the sealing material to form a sealing material layer;
Laminating the first glass substrate and the second glass substrate through the sealing material layer while facing the first surface and the second surface;
From the second irradiation start position set to a position different from the first irradiation start position and the first irradiation end position of the sealing material layer, the sealing laser beam is supplied from the second irradiation end position to the second irradiation end position. Irradiation is performed while scanning along the sealing material layer through the first or second glass substrate, the sealing material layer is melted, and the gap between the first glass substrate and the second glass substrate is hermetically sealed. And a step of forming a sealing layer to be sealed.   The said 2nd irradiation start position is set to the position 3 mm or more away from the said 1st irradiation start position and the said 1st irradiation end position, The manufacture of the airtight member of Claim 1 characterized by the above-mentioned. Method.   In the step of forming the sealing material layer, the scanning speed of the firing laser light in the end region from the position approaching the first irradiation end position to the first irradiation end position is excluded from the end region. The method for manufacturing an airtight member according to claim 1, wherein the airtight member is decelerated from a scanning speed of the firing laser light in a scanning region along the frame-shaped coating layer.   The scanning speed of the firing laser light in the scanning region is controlled in a range of 3 to 20 mm / second, and the scanning speed of the firing laser light in the end region is changed from the first irradiation start position to the firing laser. 4. The method of manufacturing an airtight member according to claim 3, wherein a control is performed so that a scanning speed of the firing laser light at a position 1.2 times before the beam diameter of the light is 2 mm / second or less.   From the position where the first irradiation end position of the firing laser light partially overlaps the first irradiation start position, the overlapping irradiation region of the firing laser light is 20 times the beam diameter of the firing laser light. The method for manufacturing an airtight member according to any one of claims 1 to 4, wherein the airtight member is set within a range up to a position that becomes the following.   From the position where the second irradiation end position of the sealing laser light partially overlaps the second irradiation start position, the overlapping irradiation region of the sealing laser light is 20 times the beam diameter of the sealing laser light. The method for manufacturing an airtight member according to any one of claims 1 to 5, wherein the airtight member is set within a range up to a position which becomes the following.   Application start set at a position different from the first irradiation start position, the first irradiation end position, the second irradiation start position, and the second irradiation end position of the second sealing region. The method for manufacturing an airtight member according to any one of claims 1 to 6, wherein the sealing material paste is applied along the second sealing region from a position to an application end position.   The application start position is set to a position 3 mm or more away from the first irradiation start position, the first irradiation end position, the second irradiation start position, and the second irradiation end position. The manufacturing method of the airtight member of Claim 7 characterized by these.   The application start position is set to the first side of the second sealing region, the first irradiation start position is set to the second side of the second sealing region, and The method for manufacturing an airtight member according to claim 7 or 8, wherein the second irradiation start position is set at a third side of the second sealing region.   9. The application start position, the first irradiation start position, and the second irradiation start position are set on one side of the second sealing region, respectively. The manufacturing method of the airtight member as described in 1 ..   The sealing material includes 0.1 to 40% by volume of the laser absorber and a low expansion filler in the range of 0 to 50% by volume as a total amount of the laser absorber and the low expansion filler. The method for producing an airtight member according to any one of claims 1 to 10, wherein the content is in the range of 0.1 to 50% by volume. 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
In order to hermetically seal a gap between the first glass substrate and the second glass substrate,
A sealing material formed between the first sealing region of the first glass substrate and the second sealing region of the second glass substrate and including a sealing glass and a laser absorbing material; A sealing layer made of a melted and solidified material,
An airtight member, wherein a retardation value generated by forming the sealing layer is 100 nm or less. The sealing layer is formed by irradiating laser light for sealing along the fired layer of the sealing material formed in the first or second sealing region,
The airtight member according to claim 12, wherein the retardation value at the irradiation start position and irradiation end position of the sealing laser light with respect to the fired layer of the sealing material is 3 to 100 nm. The firing layer of the sealing material is formed by irradiating the firing laser light along the paste coating layer containing the sealing material formed in the first or second sealing region. Yes,
14. The airtight member according to claim 13, wherein the retardation value at the irradiation start position and the irradiation end position of the firing laser light on the paste coating layer is 3 to 100 nm. The application layer of the paste is formed by applying the paste along the first or second sealing region,
The airtight member according to claim 14, wherein the retardation value at the application start position and the application end position of the paste is 3 to 100 nm.

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