JP2010228998A - Glass member with sealing material layer, electronic device using the same, and manufacturing method thereof - Google Patents

Abstract

When applying laser sealing, the adhesive strength between a glass substrate and a sealing layer can be increased even when the line width of the sealing layer and the interval between the glass substrates are reduced.
A glass substrate 3 has a groove 6 formed in a sealing region, and includes a fired layer of a sealing glass material containing a sealing glass, a low expansion filler, and a laser absorber in the groove 6. A sealing material layer 5 is provided. The sealing material layer 5 is provided so that the upper part protrudes from the groove 6. By laminating such a glass substrate 3 and a glass substrate 2 having an element forming region 2a including an electronic element, the sealing material layer 5 is irradiated with a laser beam 7 from the glass substrate 3 side to be melted, whereby a glass substrate is obtained. Seal between 2 and 3.
[Selection] Figure 2

Description

  The present invention relates to a glass member with a sealing material layer, an electronic device using the same, and a method for manufacturing the same.

  Flat-type display devices (FPD) such as organic electro-luminescence display (OELD), plasma display panel (PDP), liquid crystal display device (LCD), etc. are used for sealing glass substrates for elements on which light emitting elements are formed and for sealing It has a structure in which a light emitting element is sealed with a glass package in which a glass substrate is opposed to each other and these two glass substrates are sealed (see Patent Document 1). Further, in solar cells such as dye-sensitized solar cells, it has been studied to apply a glass package in which solar cell elements (photoelectric conversion elements) are sealed with two glass substrates (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. However, since the sealing temperature by the sealing glass is about 400 to 600 ° C., the characteristics of the electronic element part such as the OEL element are deteriorated when baked using a normal heating furnace. Therefore, a sealing glass material layer including a laser absorbing material is disposed between the sealing regions provided in the peripheral portions of the two glass substrates, and a sealing layer is formed by irradiating the laser beam to this and heating and melting it. Attempts have been made (see Patent Documents 1 and 2). Sealing by laser irradiation (laser sealing) has an advantage that thermal influence on the electronic element part can be suppressed.

  In applying laser sealing to a glass package such as an FPD or a solar cell, in order to increase the formation area of an electronic element such as an OEL element or a solar cell element, the width of the sealing region set on the glass substrate, The line width of the sealing layer tends to be narrowed to 3 mm or less, and further 1 mm or less. As the line width of the sealing layer decreases, the adhesion area between the glass substrate and the glass substrate decreases, so that the adhesive strength between the glass substrate and the sealing layer tends to decrease. The decrease in adhesive strength causes peeling or cracking at the interface between the glass substrate and the sealing layer.

  Further, in the FPD, in order to suppress the internal scattering of the light emitting elements in the glass package, it is required that the interval (gap) between the glass substrates is also narrowed, for example, 30 μm or less, further 10 μm or less. The sealing glass material is blended with a low expansion filler to match the thermal expansion coefficient between the glass substrate and the sealing glass, and it is necessary to make the filler particles finer as the distance between the substrates is reduced. Occurs. When the filler particles are made finer, the surface area is increased, the shear stress between the sealing glass softened by heating and the filler particles is increased, and the flow hardly occurs. This causes a decrease in the adhesion between the sealing material and the glass substrate. This also reduces the adhesive strength between the glass substrate and the sealing layer.

  Patent Document 1 describes that an uneven portion is formed in a sealing region (non-pixel region) of an element glass substrate having an OEL element formation region (pixel region). Here, a sealing glass material layer is formed on a sealing glass substrate that does not have an uneven portion, and sealing is performed by irradiating laser light from the sealing glass substrate side. In such a method, the closer to the recess from the laser light irradiation surface, the harder the softening glass material becomes, and it becomes difficult to sufficiently fill the recess with the sealing glass material. In this case, not only the adhesive strength cannot be sufficiently increased, but also the voids remaining in the recesses may become a starting point of peeling or cracking.

  In Patent Document 2, a groove is formed in a glass substrate for sealing, and after the glass material for sealing is filled in the groove, laser light is irradiated from the glass substrate side for sealing, and the glass material for sealing is used for the element. It is described that the glass substrates are sealed by being raised toward the glass substrates. In this method, it is inevitable that the width of the sealing layer becomes narrower than the groove width, and thus the adhesive strength between the glass substrate and the sealing layer cannot be sufficiently increased. Further, the surface of the sealing glass material filled in the groove is flattened before the laser sealing step, but it is inevitable that the glass substrate is damaged at that time, and the characteristics of the glass substrate are likely to deteriorate. There is a difficulty.

JP-T-2006-524419 JP 2008-115057 A Japanese Patent Application Laid-Open No. 2007-200838 International Publication No. 2005/122645

  The object of the present invention is to provide a sealing material layer that can sufficiently increase the adhesive strength between the glass substrate and the sealing layer even when the line width of the sealing layer and the interval between the glass substrates are reduced. An object of the present invention is to provide a glass member, an electronic device using the glass member, and a manufacturing method thereof.

  A glass member with a sealing material layer according to an aspect of the present invention includes a sealing substrate, a glass substrate having a groove formed continuously in the sealing region, a sealing glass provided in the groove, A frame-like sealing material layer made of a fired layer of a sealing glass material containing a low expansion filler and a laser absorber, and the sealing material layer is provided so that the upper part protrudes from the groove It is characterized by being.

  An electronic device according to an aspect of the present invention includes a first glass substrate having an element formation region including an electronic element, and a first sealing region provided along an outer periphery of the element formation region, and the first glass substrate. A second glass substrate having a second sealing region corresponding to the first sealing region of the glass substrate, and a groove formed continuously in the second sealing region; The first sealing region of the glass substrate and the second sealing region of the second glass substrate are formed so as to be sealed while providing a gap on the element formation region. A sealing layer composed of a melt-fixed layer of a glass material for sealing containing glass, a low expansion filler, and a laser absorber, and a part of the sealing layer is embedded in the groove It is characterized by.

  An electronic device manufacturing method according to an aspect of the present invention provides a first glass substrate having an element formation region including an electronic element and a first sealing region provided along an outer periphery of the element formation region. A step of performing, a second sealing region corresponding to the first sealing region of the first glass substrate, a groove formed continuously in the second sealing region, and an upper portion thereof A second sealing material layer provided in the groove so as to protrude from the groove and having a frame-shaped sealing material layer made of a fired layer of a sealing glass material containing a sealing glass, a low expansion filler, and a laser absorbing material; Preparing the glass substrate, laminating the first glass substrate and the second glass substrate through the sealing material layer while forming a gap on the element formation region, Irradiating the sealing material layer with a laser beam through a second glass substrate; By melting Kifugi material layer is characterized by comprising a step of forming a sealing layer for sealing between the second glass substrate and the first glass substrate.

  According to the glass member with the sealing material layer according to the aspect of the present invention, the electronic device using the glass member, and the manufacturing method thereof, the glass substrate even when the line width of the sealing layer and the interval between the glass substrates are reduced. Adhesive strength between the sealing layer and the sealing layer can be sufficiently increased. Accordingly, it is possible to provide an electronic device excellent in sealing performance and reliability with high reproducibility.

It is sectional drawing which shows the structure of the electronic device by embodiment of this invention. It is sectional drawing which shows the manufacturing process of the electronic device by embodiment of this invention. It is a top view which shows the 1st glass substrate used in the manufacturing process of the electronic device shown in FIG. It is sectional drawing along the AA line of FIG. It is a top view which shows the 2nd glass substrate used at the manufacturing process of the electronic device shown in FIG. It is sectional drawing along the AA line of FIG. It is sectional drawing which expands and shows a part of 2nd glass substrate shown in FIG. It is sectional drawing which expands and shows a part of electronic device shown in FIG.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. 1 is a diagram showing a configuration of an electronic device according to an embodiment of the present invention, FIG. 2 is a diagram showing a manufacturing process of the electronic device according to an embodiment of the present invention, and FIGS. 3 to 6 are first and second glasses used therefor. FIG. 7 is an enlarged view showing a part of the second glass substrate, and FIG. 8 is an enlarged view showing a sealing portion of the electronic device. The electronic device 1 shown in FIG. 1 constitutes an illuminating device (such as OEL illumination) using a light emitting element such as an OPD, PDP, LCD, or other FPD, or a solar cell such as a dye-sensitized solar cell. To do.

The electronic device 1 includes a first glass substrate (element glass substrate) 2 having an element formation region 2 a including an electronic element, and a second glass substrate (sealing glass substrate) 3. The first and second glass substrates 2 and 3 are made of, for example, non-alkali glass or soda lime glass. The alkali-free glass has a thermal expansion coefficient of about 35 to 40 × 10 ⁻⁷ / ° C. Soda lime glass has a thermal expansion coefficient of about 85 to 90 × 10 ⁻⁷ / ° C.

  In the element formation region 2a of the first glass substrate 2, an electronic element corresponding to the electronic device 1, for example, an OEL element for OELD or OEL illumination, a plasma light emitting element for PDP, a liquid crystal display element for LCD, In the case of a solar cell, a dye-sensitized photoelectric conversion unit and the like are formed. Electronic elements such as light emitting elements such as OEL elements and solar cell elements such as dye-sensitized photoelectric conversion units have various known structures, and are not limited to these element structures.

  As shown in FIGS. 3 and 4, the first glass substrate 2 has a first sealing region 2 b provided along the outer periphery of the element formation region 2 a. The first sealing region 2b is set so as to surround the element formation region 2a. As shown in FIGS. 5 and 6, the second glass substrate 3 has a second sealing region 3a. The second sealing region 3a corresponds to the first sealing region 2b. That is, when the first glass substrate 2 and the second glass substrate 3 are disposed to face each other, the first sealing region 2b and the second sealing region 3a are set to face each other, which will be described later. Thus, a sealing layer forming region (a sealing material layer forming region for the second glass substrate 3) is formed.

  The first glass substrate 2 and the second glass substrate 3 are disposed to face each other so as to form a gap on the element formation region 2a. The space between the first glass substrate 2 and the second glass substrate 3 is sealed with a sealing layer 4. That is, the sealing layer 4 is sealed between the sealing region 2b of the first glass substrate 2 and the sealing region 3a of the second glass substrate 3 while providing a gap on the element formation region 2a. Is formed. The electronic element formed in the element formation region 2 a is hermetically sealed with a glass panel constituted by the first glass substrate 2, the second glass substrate 3, and the sealing layer 4. Note that the gap between the first glass substrate 2 and the second glass substrate 3 is not limited to a space, and such a space may be filled with a transparent resin. The transparent resin may be adhered to the glass substrates 2 and 3 or may simply be in contact.

  The sealing layer 4 is a fusion fixing layer in which the sealing material layer 5 formed in the sealing region 3 a of the second glass substrate 3 is melted with a laser beam and fixed to the sealing region 2 b of the first glass substrate 2. It consists of That is, the frame-shaped sealing material layer 5 is formed in the sealing region 3a of the second glass substrate 3 used for manufacturing the electronic device 1 as shown in FIGS. By sealing the sealing material layer 5 formed in the sealing region 3a of the second glass substrate 3 to the sealing region 2b of the first glass substrate 2 with the heat of the laser beam, the first glass substrate is obtained. A sealing layer 4 that seals a space (element arrangement space) between 2 and the second glass substrate 3 is formed.

  The sealing material layer 5 is a fired layer of a sealing glass material containing a sealing glass, a low expansion filler, and a laser absorber. The glass material for sealing is obtained by blending a laser absorbing material and a low expansion filler into sealing glass as a main component. The glass material for sealing may contain additives other than these as required. For the sealing glass (glass frit), for example, low-melting glass such as tin-phosphate glass, bismuth glass, vanadium glass, lead glass or the like is used. Of these, tin-phosphate glass is used in consideration of sealing properties (adhesiveness) to the glass substrates 2 and 3, reliability thereof (adhesion reliability and sealing properties), and influence on the environment and human body. It is preferable to use sealing glass made of bismuth glass.

Tin-phosphate glass (glass frit) is composed of 20 to 68 mol% SnO, 0.5 to 5 mol% SnO ₂ and 20 to 40 mol% P ₂ O ₅ (basically a total amount of 100%). It is preferable to have a composition of (mol%). SnO is a component for lowering the melting point of glass. If the SnO content is less than 20 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 (gas 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). Preferably). 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 glass material for sealing contains a low expansion filler. As the low expansion filler, it is preferable to use at least one selected from silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate compound, soda lime glass, and borosilicate glass. Zirconium phosphate compounds include (ZrO) ₂ P ₂ O ₇ , AZr ₂ (PO ₄ ) ₃ (A is at least one selected from Na, K and Ca), NbZr ₂ (PO ₄ ) ₃ , Zr _2. (WO ₃ ) (PO ₄ ) ₂ , and complex compounds thereof. The low expansion filler has a lower thermal expansion coefficient than the sealing glass which is the main component of the sealing glass material.

The content of the low expansion filler is appropriately set so that the thermal expansion coefficient of the sealing glass approaches the thermal expansion coefficient of the glass substrates 2 and 3. The low expansion filler is preferably contained in the range of 15 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 2 and 3. When the glass substrates 2 and 3 are formed of alkali-free glass (thermal expansion coefficient: 35 to 40 × 10 ⁻⁷ / ° C.), a relatively large amount (for example, a range of 30 to 50% by volume) of a low expansion filler is used. It is preferable to add. When the glass substrates 2 and 3 are formed of soda lime glass (thermal expansion coefficient: 85 to 90 × 10 ⁻⁷ / ° C.), a relatively small amount (for example, a range of 15 to 40% by volume) of a low expansion filler is used. It is preferable to add.

  The glass material for sealing further contains a laser absorber. As the laser absorbing material, 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. The content of the laser absorber is preferably in the range of 0.1 to 10% by volume with respect to the sealing glass material. When the content of the laser absorber is less than 0.1% by volume, the sealing material layer 5 cannot be sufficiently melted at the time of laser irradiation. When the content of the laser absorbing material exceeds 10% by volume, the second glass substrate 3 is cracked or sealed due to local heat generation near the interface with the second glass substrate 3 during laser irradiation, or sealing. There is a possibility that the fluidity at the time of melting of the glass material is deteriorated and the adhesiveness with the first glass substrate 2 is lowered.

  The 2nd glass substrate 3 has the groove | channel 6 formed in the 2nd sealing area | region 3a, as shown to Fig.7 (a). The groove 6 is continuously formed along the entire circumference of the frame-shaped sealing region 3a and has a depth T1. The shape of the groove 6 is not limited to a square groove, but may be a stepped shape, an inclined shape, a curved shape, or the like. As shown in FIG. 7B, the sealing material layer 5 is provided in the groove 6, and the upper portion protrudes from the groove 6. Based on the height T3 of the portion protruding from the second glass substrate 3 (film thickness on the glass substrate 3 of the sealing material layer 5), between the first glass substrate 2 and the second glass substrate 3. The interval T2 is maintained.

  In this way, by using the sealing material layer 5 in which the groove 6 is partially filled, the sealing layer 4 and the glass substrate 2, 3 can be improved in adhesive strength. The effect of improving the adhesive strength by the sealing material layer 5 formed in the groove 6 will be described based on the sealing material layer 5 forming step and the sealing step by laser light (laser sealing step). The sealing material layer 5 is formed in the groove 6 provided in the sealing region 3a of the second glass substrate 3 as follows, for example.

  First, the groove 6 is formed in the sealing region 3 a of the second glass substrate 3. The method for forming the groove 6 is not particularly limited, and for example, sandblasting, etching, laser processing, or the like can be applied. The depth T1 of the groove 6 depends on the thickness of the second glass substrate 3 and the interval T2 between the first glass substrate 2 and the second glass substrate 3, but is in the range of, for example, 5 to 60 μm. It is preferable. When the depth T1 of the groove 6 is less than 5 μm, there is a possibility that the effect of expanding the adhesion area by the groove 6 or the anchor effect cannot be obtained sufficiently. Even if the groove 6 is formed so that the depth T1 exceeds 60 μm, the effect cannot be further increased, and the thickness of the glass substrate 3 is relatively reduced, so that the strength of the glass substrate 3 is reduced. May be reduced.

  Further, the depth T1 of the groove 6 preferably satisfies the relationship of T1 / (T1 + T2) ≧ 0.2 with respect to the substrate interval (gap) T2. When the ratio of T1 to (T1 + T2) is less than 0.2, the effect of improving the adhesive strength due to the formation of the groove 6 and the effect of improving the adhesive strength when the gap is narrowed cannot be sufficiently obtained. However, even if the ratio of T1 to (T1 + T2) is increased too much, the thickness of the glass substrate 3 is relatively reduced, and the strength of the glass substrate 3 may be reduced. It is preferable to satisfy the relationship of 0.2 ≦ T1 / (T1 + T2) ≦ 0.9.

  The width of the groove 6 is set according to the line width W of the sealing material layer 5. The groove 6 filled with a part of the sealing material layer 5 is effective when the line width W of the sealing material layer 5 is 3 mm or less, further 1 mm or less. Therefore, the width of the groove 6 is preferably 3 mm or less, more preferably 1 mm or less. The width of the groove 6 is preferably 0.1 mm or more practically. Even when the sealing material layer 5 having a narrow line width W is applied, that is, when the bonding area of the sealing layer 4 is small in the glass substrate 3 without the groove 6, the bonding area of the sealing layer 4 by the groove 6 The adhesion strength between the sealing layer 4 and the glass substrates 2 and 3 can be improved based on the expansion effect and the anchor effect.

  The state of the bottom surface of the groove 6 may be either a mirror surface or a rough surface, but is preferably appropriately roughened in order to obtain a laser light scattering effect during laser sealing. Specifically, the surface roughness of the bottom surface of the groove 6 is preferably 0.3 μm or more in terms of arithmetic average roughness Ra. According to the groove 6 having such a rough surface, the laser light applied to the sealing material layer 5 is scattered, and uniform heating can be performed in the line width direction of the sealing material layer 5. As a result, the residual stress generated in the heating / cooling step of the sealing material layer 5 can be reduced, and the heat shock resistance of the sealing layer 4 that is the melt-solidified layer of the sealing material layer 5 can be improved. Become.

  However, if the surface roughness of the bottom surface of the groove 6 is too large, the glass substrate 3 is easily broken starting from that portion. For this reason, the surface roughness of the bottom surface of the groove 6 is preferably less than 1 μm in terms of arithmetic average roughness Ra. When the surface roughness Ra of the bottom surface of the groove 6 exceeds 1 μm, the surface irregularities are likely to be the starting point of destruction. Therefore, the surface roughness of the bottom surface of the groove 6 is preferably in the range of 0.3 μm or more and less than 1 μm in terms of arithmetic average roughness Ra. Such a roughened groove 6 can be obtained by applying the above-described various forming methods. In particular, by forming the groove 6 by applying sandblasting or laser processing, the bottom surface is appropriately roughened. Can be

  Next, the sealing glass paste is prepared by mixing the sealing glass material with the vehicle. As the vehicle, for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, nitrocellulose or the like dissolved in a solvent such as terpineol, butyl carbitol acetate, ethyl carbitol acetate, or methyl (meth) An acrylic resin such as acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate or the like dissolved in a solvent such as methyl ethyl ketone, terpineol, butyl carbitol acetate, or ethyl carbitol acetate. Is used.

  The viscosity of the sealing material paste may be adjusted to the viscosity corresponding to the apparatus applied to the glass substrate 3, and can be adjusted by the ratio of the resin (binder component) and the solvent or the ratio of the sealing glass material and the vehicle. A known additive may be added to the sealing material paste as a glass paste such as an antifoaming agent or a dispersing agent. A known method using a rotary mixer equipped with a stirring blade, a roll mill, a ball mill or the like can be applied to the preparation of the sealing material paste.

  The sealing material paste described above is applied while filling the grooves 6 provided in the sealing region 3a of the second glass substrate 3, and is dried to form an application layer of the sealing material paste. The coating layer of the sealing material paste is formed so that the upper part protrudes from the groove 6. The sealing material paste is applied to the second sealing region 3a by applying a printing method such as screen printing or gravure printing, or is applied along the second sealing region 3a using a dispenser or the like. . The coating layer of the sealing material paste is dried, for example, at a temperature of 120 ° C. or more for 10 minutes or more. 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.

  The coating layer of the sealing material paste described above is fired to form the sealing material layer 5. In the firing step, first, the coating layer is heated to a temperature not higher than the glass transition point of sealing glass (glass frit), which is the main component of the sealing glass material, and the binder component in the coating layer is removed. The glass material for sealing is heated to a temperature equal to or higher than the softening point of the glass frit to melt and seal the glass material for sealing. In this way, the sealing material layer 5 is formed which is partially filled in the groove 6 having the depth T1 and is made of the fired layer of the sealing glass material having the thickness T3 on the glass substrate 3. To do. The overall film thickness of the sealing material layer 5 is (T1 + T3).

  Next, as shown to Fig.2 (a), the 2nd glass substrate 3 which has the sealing material layer 5, and the 1st glass substrate 2 which has the element formation area 2a provided with the electronic device produced separately from it, Is used to manufacture an electronic device 1 such as an OELD, PDP, LCD or other FPD, an illumination device using an OEL element, or a solar cell such as a dye-sensitized solar cell. That is, as shown in FIG. 2B, the first glass substrate 2 and the second glass substrate 3 are arranged such that the surface having the element formation region 2a and the surface having the sealing material layer 5 face each other. Laminate. On the element formation region 2a of the first glass substrate 2, a gap is formed based on the film thickness T3 of the sealing material layer 5 on the glass substrate 3.

  The film thickness T3 of the sealing material layer 5 on the glass substrate 3 is set according to the interval (gap) T2 between the first glass substrate 2 and the second glass substrate 3. This embodiment is particularly effective when the substrate interval T2 is 30 μm or less, and further 10 μm or less. Even when laser sealing is applied to the production of such a narrow gap glass package, since a part of the sealing material layer 5 is filled in the groove 6, the film thickness of the sealing material layer 5 as a whole. (T1 + T3) can be maintained. As will be described in detail later, this contributes not only to an increase in the bonding area of the sealing layer 4 but also to an improvement in the strength of the sealing layer 4 itself. Although the substrate interval T2 depends on the structure of the electronic device 1, it is preferably 5 μm or more in practice.

  Next, as shown in FIG. 2C, the sealing material layer 5 is irradiated with laser light 7 through the second glass substrate 3. The laser beam 7 is irradiated while scanning along the frame-shaped sealing material layer 5. Then, by irradiating the entire circumference of the sealing material layer 5 with the laser beam 7, as shown in FIG. 2 (d), a seal that seals between the first glass substrate 2 and the second glass substrate 3 is sealed. The wearing layer 4 is formed. In this way, an electronic device 1 in which an electronic element formed in the element formation region 2a is hermetically sealed with a glass panel constituted by the first glass substrate 2, the second glass substrate 3, and the sealing layer 4 is formed. Make it. The glass panel can be applied not only to the electronic device 1 but also to a sealing member of an electronic component or a glass member (building material or the like) such as vacuum pair glass.

  The laser beam 7 is not particularly limited, and a laser beam from a semiconductor laser, a carbon dioxide laser, an excimer laser, a YAG laser, a HeNe laser, or the like is used. The output of the laser beam 7 is appropriately set according to the thickness of the sealing material layer 5 and the like, but is preferably in the range of 2 to 150 W, for example. If the laser output is less than 2 W, the sealing material layer 5 may not be melted, and if it exceeds 150 W, cracks and cracks are likely to occur in the glass substrates 2 and 3. The output of the laser beam is more preferably in the range of 5 to 100W.

  When the laser beam 7 is irradiated through the second glass substrate 3, the sealing material layer 5 is remelted. At this time, since the interface between the first glass substrate 2 and the sealing material layer 5 becomes a new adhesive interface, relatively good adhesion can be obtained. On the other hand, since the interface between the second glass substrate 3 and the sealing material layer 5 becomes a fixed interface after remelting, the adhesion tends to be lowered. That is, when the sealing material layer 5 is remelted when the laser beam 7 is irradiated, a new thermal stress is generated at the interface with the second glass substrate 3. Furthermore, voids and crystal nuclei are likely to occur at the interface between the second glass substrate 3 and the sealing layer 4 as the sealing material layer 5 is remelted. These are factors that reduce the adhesive strength between the second glass substrate 3 and the sealing layer 4.

  On the other hand, since the sealing material layer 5 of this embodiment is partially filled in the groove 6, the adhesive strength between the second glass substrate 3 and the sealing layer 4 is improved. be able to. That is, since the bonding area between the sealing material layer 5 and the second glass substrate 3 is expanded by the groove 6, the heat capacity when the sealing material layer 5 is melted can be increased accordingly. This brings about an effect of relaxing the cooling rate after melting, and the generation of stress at the interface is suppressed, so that the adhesive strength between the second glass substrate 3 and the sealing layer 4 can be improved. Further, even if voids or crystal nuclei are generated at the interface, the bonding area is enlarged by the groove 6 and the anchor effect by the groove 6 is obtained. Therefore, the adhesion between the second glass substrate 3 and the sealing layer 4 is achieved. Strength is maintained.

  The effect of improving the adhesive strength between the second glass substrate 3 and the sealing layer 4 functions effectively particularly when the line width W of the sealing layer 4 and the substrate interval T2 are narrowed. As the line width W of the sealing layer 4 is reduced, the adhesion area between the sealing layer 4 and the glass substrates 2 and 3 decreases. Even when applying the laser sealing to the sealing material layer 5 having a narrow line width W by compensating for the decrease in the adhesion area with the groove 6 and obtaining various effects by the groove 6 described above, the second glass substrate. 3 and the sealing layer 4 can be sufficiently increased in adhesive strength. Therefore, this embodiment is effective when the line width W of the sealing layer 4 is 3 mm or less, and further 1 mm or less.

  When the substrate interval T2 is narrowed, the particle size of the low expansion filler particles cannot be made larger than the substrate interval T2 in the conventional package structure, and it is inevitably necessary to make the low expansion filler fine particles. As described above, this causes an increase in the surface area of the low expansion filler particles, a decrease in fluidity due to an increase in shear stress based on the increase, and a decrease in the adhesion between the sealing layer 4 and the glass substrates 2 and 3. Become. In this embodiment, since the film thickness (T1 + T3) as the whole sealing material layer 5 can be maintained even when the substrate interval T2 is narrowed, the low expansion filler having a particle size corresponding to this film thickness (T1 + T3) Can be used. Accordingly, the fluidity of the glass material for sealing can be maintained and the adhesion between the sealing layer 4 and the glass substrates 2 and 3 can be improved. This embodiment is effective when the substrate interval T2 is 30 μm or less, and further 10 μm or less.

  Furthermore, the low expansion filler having a particle size corresponding to the film thickness (T1 + T3) of the sealing material layer 5 as a whole and the film thickness (T1 + T2) of the sealing layer 4 as a whole based on the sealing material layer 5 is the sealing layer 4 itself. Contributes to the improvement of strength. That is, the sealing layer 4 embedded in the groove 6 may be broken along the surface of the glass substrate 3 when a shear stress or the like is applied. In contrast, the strength of the sealing layer 4 can be increased by using low-expansion filler particles having a large particle size that can be accommodated within the film thickness (T1 + T2). Such low-expansion filler particles impart a spacer effect to the sealing material layer 5, so that a decrease in film thickness due to melting and solidification of the sealing material layer 5 is suppressed. As a result, it is possible to suppress the generation of stress due to the decrease in film thickness.

  From this point, the low expansion filler does not contain particles (low expansion filler particles) having a particle size exceeding the film thickness (T1 + T2) of the sealing layer 4 as a whole, and the groove depth T1 and the substrate interval T2 It is preferable that the particle | grains which have a particle size which exceeds any one of these larger dimensions (T4) are contained in 0.05% or more of volume range. The low expansion filler having such a particle structure is obtained, for example, by classifying the low expansion filler powder by sieving or wind separation, or by mixing two or more types of low expansion filler powders having different particle size distributions. be able to.

  By using a low expansion filler containing 0.05% by volume or more of particles having a particle size exceeding T4 with respect to the film thickness (T1 + T2) of the sealing layer 4, the surface of the glass substrate 3 of the sealing layer 4 in particular. Can be prevented with good reproducibility. Therefore, the mechanical strength and reliability of the electronic device 1 having the sealing layer 4 can be improved. If the volume ratio of the particles having a particle size exceeding T4 is less than 0.05%, such an effect cannot be sufficiently obtained. It is more preferable that the volume ratio of the particles having a particle size exceeding T4 in the low expansion filler is 0.1% or more.

  However, if the volume ratio of the particles having a particle size exceeding T4 is excessively increased, the content of the low expansion filler particles having a particle size smaller than that is relatively reduced, and the low expansion filler in the sealing material layer 5 is reduced. There is a possibility that the distribution of particles becomes non-uniform. In this case, the thermal expansion coefficient of the sealing material layer 5 is partially increased, and cracks or the like are likely to occur in the sealing layer 4 itself. For this reason, the volume ratio of the particles having a particle size exceeding T4 is preferably 20% or less, and more preferably 5% or less considering the practicality of the low expansion filler.

  According to the electronic device 1 of this embodiment and its manufacturing process, the adhesive strength between the sealing layer 4 and the glass substrates 2 and 3, particularly the adhesive strength between the second glass substrate 3 can be sufficiently increased. The effect of improving the adhesive strength functions effectively particularly when the line width W of the sealing layer 4 and the substrate interval T2 are narrowed, and the line width W of the sealing layer 4 is narrowed to increase the area of the element formation region 2a. Also in the electronic device 1 that achieves the above and the electronic device 1 in which the substrate interval T2 is narrowed to suppress the internal scattering of light, the adhesive strength between the sealing layer 4 and the glass substrates 2 and 3 can be increased. Therefore, including the case where the line width W of the sealing layer 4 and the substrate interval T2 are narrowed, it is possible to improve the mechanical reliability, the hermetic sealing performance, and the reliability of the electronic device 1.

  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, SnO63.0 mol%, SnO ₂ 2.0 mol%, P ₂ O ₅ 29.5 mol%, ZnO5.0 mol%, Al ₂ O ₃ 0.3 mol%, of SiO ₂ 0.2 mol% Tin-phosphate glass frit having a composition and an average particle size of 3 μm (softening point: 399 ° C., specific gravity: 3.9), an average particle size (D50) of 9 μm as a low expansion filler, maximum particle size ( Dmax) 44 μm zirconium phosphate ((ZrO) ₂ P ₂ O ₇ ) powder, Fe ₂ O ₃ —Cr ₂ O ₃ —Co ₂ O ₃ —MnO composition, laser absorber with maximum particle size of 9 μm Prepared.

Glass material (thermal expansion coefficient: 45 × 10 ⁻⁷⁾ which is prepared by mixing 51 volume% of the tin-phosphate glass frit described above, 45.2 volume% of zirconium phosphate powder, and 3.8 volume% of the laser absorber. / ° C.). A sealing material paste was prepared by mixing 80% by mass of this glass material for sealing with 20% by mass of vehicle. The vehicle is obtained by dissolving 4% by mass of nitrocellulose as a binder component in 96% by mass of a solvent composed of butyl carbitol acetate.

Next, a second glass substrate (dimension: 90 × 90 × 0.7 mmt) made of alkali-free glass (thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C.) is prepared, and a sealing region (outer periphery) of this glass substrate is prepared. In the region), sandblasting was applied to form a groove having a depth T1 of 25 μm and a width of 0.5 mm. The groove was formed to be continuous over the entire circumference of the sealing region. When the surface roughness of the groove bottom surface was measured, it had an arithmetic average roughness Ra of 0.6 μm.

  Next, the sealing material paste was applied by screen printing in the grooves of the second glass substrate, and then dried under conditions of 130 ° C. × 5 minutes. The sealing material paste was applied so that a part thereof protruded from the groove. By baking this coating layer under the condition of 430 ° C. × 10 minutes, a sealing material layer in which the height T3 of the portion protruding from the groove is 21 μm and the film thickness including the portion filled in the groove (T1 + T3) is 46 μm Formed. The set value of the interval T2 between the glass substrates by the sealing layer is 20 μm. Therefore, the larger value (T4) of the groove depth T1 and the substrate interval T2 is 25 μm, which is the groove depth T1.

  The zirconium phosphate powder as the low expansion filler does not contain particles exceeding the total (45 μm) of the groove depth T1 and the substrate interval T2, and the larger one of the groove depth T1 and the substrate interval T2 is larger. It contains 3.4% by volume of particles exceeding the value T4 (groove depth T1: 25 μm). Therefore, a sealing glass material prepared by mixing such a low expansion filler with a tin-phosphate glass frit and a laser absorber contains 1.5% by volume of particles exceeding T4 (25 μm). Yes. The zirconium phosphate powder is pulverized with a ball mill, and the particle structure is adjusted by removing particles with a particle size exceeding 44 μm with an airflow classifier.

  The second glass substrate having the sealing material layer described above and a first glass substrate having an element formation region (region in which an OEL element is formed) (consisting of an alkali-free glass having the same composition and shape as the second glass substrate). Substrate). Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 35 W through the second glass substrate at a scanning speed of 10 mm / s to melt and rapidly solidify the sealing material layer. Thus, the first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

(Example 2)
Using a second glass substrate on which a groove (Ra = 0.6 μm) having a depth T1 of 35 μm was formed by sandblasting, a sealing material layer having a thickness (T1 + T3) of 46 μm was formed in the same manner as in Example 1. did. The set value of the substrate interval T2 in this example is 10 μm. The zirconium phosphate powder does not contain particles exceeding T1 + T2 (45 μm), and further contains 0.5% by volume of particles exceeding T4 (35 μm). The glass material for sealing produced using such a low expansion filler contains 0.2% by volume of particles exceeding T4 (35 μm).

  Next, the 2nd glass substrate which has a sealing material layer, and the 1st glass substrate which has an element formation area (area | region which formed the OEL element) were laminated | stacked. The first and second glass substrates are made of non-alkali glass as in the first embodiment. Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 35 W through the second glass substrate at a scanning speed of 10 mm / s to melt and rapidly solidify the sealing material layer. The first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

Example 3
A zirconium phosphate powder having an average particle diameter (D50) of 3 μm and a maximum particle diameter (Dmax) of 19 μm is used, and a second glass substrate in which grooves having a depth T1 of 15 μm are formed by etching is used. A sealing material layer having T1 + T3) of 21 μm was formed in the same manner as in Example 1. The surface roughness Ra of the groove bottom surface was 0.2 μm. The set value of the substrate interval T2 in this example is 5 μm. The zirconium phosphate powder does not contain particles exceeding T1 + T2 (20 μm), and further contains 0.8% by volume of particles exceeding T4 (15 μm). The glass material for sealing produced using such a low expansion filler contains 0.4% by volume of particles exceeding T4 (15 μm).

  Next, the 2nd glass substrate which has a sealing material layer, and the 1st glass substrate which has an element formation area (area | region which formed the OEL element) were laminated | stacked. The first and second glass substrates are made of non-alkali glass as in the first embodiment. Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 40 W through the second glass substrate at a scanning speed of 10 mm / s to melt and rapidly cool and solidify the sealing material layer. The first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

Example 4
A second glass substrate in which a zirconium phosphate powder having an average particle diameter (D50) of 3 μm and a maximum particle diameter (Dmax) of 19 μm is used, and a groove (Ra = 0.6 μm) having a depth T1 of 20 μm is formed by sandblasting. A sealing material layer having a film thickness (T1 + T3) of 25 μm was formed in the same manner as in Example 1. The set value of the substrate interval T2 in this example is 5 μm. The zirconium phosphate powder does not contain particles exceeding T1 + T2 (25 μm), and further does not contain particles exceeding T4 (25 μm).

  Next, the 2nd glass substrate which has a sealing material layer, and the 1st glass substrate which has an element formation area (area | region which formed the OEL element) were laminated | stacked. The first and second glass substrates are made of non-alkali glass as in the first embodiment. Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 35 W through the second glass substrate at a scanning speed of 10 mm / s to melt and rapidly solidify the sealing material layer. The first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

(Example 5)
52.5% by volume of tin-phosphate glass frit having the same composition as in Example 1, 44.6% by volume of silica (SiO ₂ ) powder having an average particle size (D50) of 4 μm and a maximum particle size (Dmax) of 31 μm, A glass material for sealing (thermal expansion coefficient: 49 × 10 ⁻⁷ / ° C.) was prepared by mixing 2.9% by volume of the laser absorber. A sealing material paste was prepared by mixing 80% by mass of this glass material for sealing with 20% by mass of the same vehicle as in Example 1. Next, an etching process is applied to the sealing region (outer peripheral region) of the second glass substrate made of non-alkali glass similar to that in Example 1, and a groove (Ra = 25 μm) having a depth T1 of 25 μm and a width of 0.5 mm. 0.3 μm) was formed.

  Next, a sealing material layer having a film thickness (T1 + T3) of 36 μm was formed in the same manner as in Example 1 using the above-described sealing material paste and glass substrate. The set value of the substrate interval T2 in this example is 10 μm. The silica powder does not contain particles exceeding T1 + T2 (35 μm), and further contains 0.2% by volume of particles exceeding T4 (25 μm). The glass material for sealing produced using such a low expansion filler contains 0.09% by volume of particles exceeding T4 (25 μm).

  Next, the 2nd glass substrate which has a sealing material layer, and the 1st glass substrate which has an element formation area (area | region which formed the OEL element) were laminated | stacked. The first and second glass substrates are made of non-alkali glass as in the first embodiment. Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 35 W through the second glass substrate at a scanning speed of 10 mm / s to melt and rapidly solidify the sealing material layer. The first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

(Example 6)
Bismuth glass frit having a composition of Bi ₂ O ₃ 82.0%, B ₂ O ₃ 6.5%, ZnO 11.0%, Al ₂ O ₃ 0.5% by mass ratio and an average particle diameter of 2 μm (Softening point: 420 ° C., specific gravity: 7.3), cordierite powder having an average particle size (D50) of 6 μm and a maximum particle size (Dmax) of 24 μm as a low expansion filler, and the same laser absorption as in Example 1. Materials were prepared.

Glass material (thermal expansion coefficient: 82 × 10 ⁻⁷ / ° C.) for sealing by mixing 80.4% by volume of the bismuth-based glass frit, 17.6% by volume of cordierite powder, and 2.0% by volume of the laser absorber. ) Was produced. A sealing material paste was prepared by mixing 80% by mass of this glass material for sealing with 20% by mass of vehicle. The vehicle was prepared by dissolving 5% by mass of ethyl cellulose as a binder component in 95% by mass of a mixed solvent of terpineol (31.6%) and propylene glycol diacetate (68.4%).

Next, a second glass substrate (dimensions: 100 × 100 × 1.1 mmt) made of soda lime glass (thermal expansion coefficient: 87 × 10 ⁻⁷ / ° C.) is prepared, and a sealing region (outer periphery) of this glass substrate is prepared. In the region), laser processing was applied to form a groove having a depth T1 of 5 μm and a width of 1 mm. The groove was formed to be continuous over the entire circumference of the sealing region. When the surface roughness of the groove bottom surface was measured, it had an arithmetic average roughness Ra of 1.0 μm.

  Next, the sealing material paste was applied by screen printing in the grooves of the second glass substrate, and then dried under conditions of 130 ° C. × 5 minutes. The sealing material paste was applied so that a part thereof protruded from the groove. By baking this coating layer under the conditions of 450 ° C. × 10 minutes, a sealing material layer in which the height T3 of the portion protruding from the groove is 21 μm and the film thickness including the portion filled in the groove (T1 + T3) is 26 μm Formed. The set value of the interval T2 between the glass substrates by the sealing layer is 20 μm. Therefore, the larger value (T4) of the groove depth T1 and the substrate interval T2 is 20 μm, which is the substrate interval T2.

  The cordierite powder does not contain particles exceeding the sum (25 μm) of the groove depth T1 and the substrate interval T2, and the larger value T4 (substrate interval T2: substrate interval T2: the groove depth T1 and the substrate interval T2). Particles containing more than 20 μm) are included in a volume ratio of 3.2%. The glass material for sealing produced using such a low expansion filler contains 0.6% by volume of particles exceeding T4 (20 μm). The cordierite powder is prepared by pulverizing with a ball mill and adjusting the particle structure by removing particles with a particle size exceeding 24 μm with an airflow classifier.

  The second glass substrate having the sealing material layer and the first glass substrate having the element formation region (region where the OEL element is formed) (soda lime glass having the same composition and shape as the second glass substrate). Substrate). Next, the sealing material layer is irradiated with laser light (semiconductor laser) having a wavelength of 940 nm and an output of 60 W through the second glass substrate at a scanning speed of 5 mm / s to melt and rapidly solidify the sealing material layer. Thus, the first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

(Example 7)
73.5% by volume of a bismuth glass frit having the same composition as in Example 6, 24.7% by volume of cordierite powder having an average particle size (D50) of 5 μm and a maximum particle size (Dmax) of 19 μm, and a laser absorber 1.8 A glass material (thermal expansion coefficient: 73 × 10 ⁻⁷ / ° C.) for sealing was prepared by mixing with volume%. A sealing material paste was prepared by mixing 80% by mass of this sealing glass material with 20% by mass of the same vehicle as in Example 6. Next, an etching process is applied to the sealing region (outer peripheral region) of the second glass substrate made of the same soda lime glass as in Example 6 to obtain a groove having a depth T1 of 15 μm and a width of 1 mm (Ra = 0. 6 μm) was formed.

  Next, a sealing material layer having a thickness (T1 + T3) of 20 μm was formed in the same manner as in Example 6 using the above-described sealing material paste and glass substrate. The set value of the substrate interval T2 in this example is 5 μm. The cordierite powder does not contain particles exceeding T1 + T2 (20 μm), and further contains 0.5% by volume of particles exceeding T4 (15 μm). The glass material for sealing produced using such a low expansion filler contains 0.12% by volume of particles exceeding T4 (15 μm).

  Next, the 2nd glass substrate which has a sealing material layer, and the 1st glass substrate which has an element formation area (area | region which formed the OEL element) were laminated | stacked. The first and second glass substrates are made of soda lime glass as in the sixth embodiment. Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 65 W through the second glass substrate at a scanning speed of 5 mm / s to melt and quench and solidify the sealing material layer. The first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

(Example 8)
Bismuth glass frit having the same composition as in Example 6 67.2% by volume, 31.1% by volume of cordierite powder having an average particle size (D50) of 11 μm and a maximum particle size (Dmax) of 52 μm, and a laser absorber 1.6 A glass material (thermal expansion coefficient: 63 × 10 ⁻⁷ / ° C.) for sealing was prepared by mixing with volume%. A sealing material paste was prepared by mixing 80% by mass of this sealing glass material with 20% by mass of the same vehicle as in Example 6. Next, a groove having a depth T1 of 45 μm and a width of 1 mm is applied to the sealing region (outer peripheral region) of a second glass substrate (plate thickness = 3 mm) made of soda-lime glass similar to that in Example 6 by applying sandblasting. (Ra = 0.8 μm) was formed.

  Next, a sealing material layer having a film thickness (T1 + T3) of 62 μm was formed in the same manner as in Example 6 using the above-described sealing material paste and glass substrate. The set value of the substrate interval T2 in this example is 15 μm. The cordierite powder does not contain particles exceeding T1 + T2 (60 μm), and further contains 1.3% by volume of particles exceeding T4 (45 μm). The glass material for sealing produced using such a low expansion filler contains 0.4% by volume of particles exceeding T4 (45 μm).

  Next, the 2nd glass substrate which has a sealing material layer, and the 1st glass substrate which has an element formation area (area | region which formed the OEL element) were laminated | stacked. The first and second glass substrates are made of soda lime glass as in the sixth embodiment. Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 65 W through the second glass substrate at a scanning speed of 5 mm / s to melt and quench and solidify the sealing material layer. The first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

(Comparative Example 1)
Using a tin-phosphate glass frit having the same composition as in Example 1, zirconium phosphate powder having an average particle diameter (D50) of 2 μm and a maximum particle diameter (Dmax) of 9 μm, and a laser absorber, Using a glass material for sealing produced in the same manner and a second glass substrate made of non-alkali glass with no groove formed (the thermal expansion coefficient and shape are the same as those in Example 1), the film thickness is A 10 μm sealing material layer was formed. The set value of the substrate interval T2 in this example is 10 μm. The zirconium phosphate powder does not contain particles exceeding the film thickness (10 μm) of the sealing material layer and further the film thickness of the sealing layer.

  Next, the 2nd glass substrate which has a sealing material layer, and the 1st glass substrate which has an element formation area (area | region which formed the OEL element) were laminated | stacked. The first and second glass substrates are made of non-alkali glass as in the first embodiment. Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 35 W through the second glass substrate at a scanning speed of 10 mm / s to melt and rapidly solidify the sealing material layer. The first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

(Comparative Example 2)
In the same manner as in Comparative Example 1 except that the output of the laser light (semiconductor laser) irradiated to the sealing material layer is changed to 50 W and the scanning speed of the laser light is changed to 5 mm / s, the first glass substrate and The second glass substrate was sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

(Comparative Example 3)
Laser absorption with 58.2% by volume of tin-phosphate glass frit having the same composition as in Example 1, 37.9% by volume of zirconium phosphate powder having an average particle size (D50) of 3 μm and a maximum particle size (Dmax) of 12 μm. A glass material for sealing (thermal expansion coefficient: 61 × 10 ⁻⁷ / ° C.) was prepared by mixing 3.9% by volume of the material. A sealing material paste was prepared by mixing 80% by mass of this glass material for sealing with 20% by mass of the same vehicle as in Example 1.

  Next, using the above-described sealing material paste and a second glass substrate made of non-alkali glass not forming grooves (thermal expansion coefficient and shape are the same as in Example 1), the film thickness is 16 μm. A sealing material layer was formed. The set value of the substrate interval T2 in this example is 15 μm. The zirconium phosphate powder does not contain particles exceeding the film thickness (16 μm) of the sealing material layer and further the film thickness (15 μm) of the sealing layer.

  Next, the 2nd glass substrate which has a sealing material layer, and the 1st glass substrate which has an element formation area (area | region which formed the OEL element) were laminated | stacked. The first and second glass substrates are made of non-alkali glass as in the first embodiment. Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 35 W through the second glass substrate at a scanning speed of 10 mm / s to melt and rapidly solidify the sealing material layer. The first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

  Next, about the external appearance of the glass panel of Examples 1-8 and Comparative Examples 1-3, the board | substrate crack and the crack of a sealing layer in the time of completion | finish of irradiation of a laser beam were evaluated. The appearance was evaluated by observing with an optical microscope. Moreover, the airtightness of each glass panel was measured. The airtightness was evaluated by applying a helium leak test. Furthermore, the peeling test shown below was implemented about the glass substrate (including the presence or absence of a groove | channel) used for each example, and the glass material for sealing, and adhesive strength was evaluated. These measurement / evaluation results are shown in Table 1, Table 2 and Table 3 together with the glass panel production conditions.

  The peel test was performed as follows. A 40 × 40 mm glass substrate (plate thickness is the same as in each example, and a grooved glass substrate is used in the evaluation of the examples), and the sealing material paste of each example is dispensed with a dispenser in a frame-like pattern with a side of 30 mm (Line width: 1 mm). After drying and baking this, the counter substrate was shifted and laser-sealed. Laser sealing was performed under conditions according to each example. One glass substrate of the peel test sample thus formed was fixed with a jig, a load (shear stress) was applied in the surface direction of the other glass substrate, and the fracture state at that time was observed. In the peel test, a 40 × 40 mm glass substrate was used to eliminate factors other than the adhesive strength of the sealing layer and the strength of the sealing layer itself.

  In the peeling test described above, it can be said that when the break mode is [break of glass substrate (substrate break)], it is a preferable adhesive state as a glass package (airtight container). When the destruction mode is [destruction of sealing layer], it can be used as a glass package (airtight container), but the mechanical reliability is slightly inferior to that of [substrate destruction]. When the failure mode is [peeling at the interface between the sealing layer and the substrate (interfacial peeling)], it can be determined that the adhesive strength at the interface is weak and is not suitable for a glass package (airtight container).

  As can be seen from Tables 1, 2 and 3, all of the glass panels according to Examples 1 to 8 are excellent in appearance and airtightness, and have better adhesive strength. In Example 4, since the particle size of the low expansion filler was small, the strength of the sealing layer was inferior to that of the other examples. In Example 3, since the laser scattering at the groove was small, it was necessary to increase the output of the laser beam. In Example 6, since the surface roughness of the groove portion was slightly large, breakage occurred from the groove portion in the peel test. On the other hand, it was confirmed that all of the glass panels of Comparative Examples 1 to 3 using a glass substrate in which no groove was formed did not have sufficient adhesive strength because interfacial peeling occurred in the peeling test.

  DESCRIPTION OF SYMBOLS 1 ... Electronic device, 2 ... 1st glass substrate, 2a ... Element formation area, 2b ... 1st sealing area, 3 ... 2nd glass substrate, 3a ... 2nd sealing area, 4 ... Sealing layer 5 ... Sealing material layer, 6 ... Groove, 7 ... Laser light.

Claims (13)

A glass substrate having a sealing region and a groove formed continuously in the sealing region;
A sealing material layer comprising a fired layer of a frame-like sealing glass material, which is provided in the groove and contains a sealing glass, a low expansion filler, and a laser absorber;
The glass member with a sealing material layer, wherein the sealing material layer is provided so that an upper portion thereof protrudes from the groove.   2. The glass member with a sealing material layer according to claim 1, wherein the groove has a depth in the range of 5 to 60 [mu] m and a width in the range of 3 mm or less.   3. The glass member with a sealing material layer according to claim 1, wherein the surface roughness of the bottom surface of the groove is in the range of 0.3 μm or more and less than 1 μm in terms of arithmetic average roughness Ra.   The low expansion filler is made of at least one selected from silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate compound, soda lime glass and borosilicate glass, and the sealing glass material is the low expansion 2. The glass member with a sealing material layer according to claim 1, comprising a filler in a range of 15 to 50% by volume.   The laser absorber is made of at least one metal selected from Fe, Cr, Mn, Co, Ni and Cu or a compound containing the metal, and the glass material for sealing contains 0.1 to 10 of the laser absorber. It contains in the range of volume%, The glass member with a sealing material layer of any one of Claim 1 thru | or 4 characterized by the above-mentioned.   6. The glass member with a sealing material layer according to claim 1, wherein the sealing glass is made of tin-phosphate glass or bismuth glass. A first glass substrate having an element formation region including an electronic element, and a first sealing region provided along an outer periphery of the element formation region;
A second glass substrate having a second sealing region corresponding to the first sealing region of the first glass substrate, and a groove formed continuously in the second sealing region;
Formed so as to seal between the first sealing region of the first glass substrate and the second sealing region of the second glass substrate while providing a gap on the element formation region. A sealing layer comprising a sealing glass, a low-expansion filler and a laser-absorbing material, and a sealing layer composed of a melt-fixed layer of a sealing glass material,
An electronic device, wherein a part of the sealing layer is embedded in the groove.   The groove has a depth T1 that satisfies a relationship of T1 / (T1 + T2) ≧ 0.2 with respect to an interval T2 between the first glass substrate and the second glass substrate. The electronic device according to claim 7.   9. The electronic device according to claim 7, wherein the groove has a depth in the range of 5 to 60 [mu] m and a width in the range of 3 mm or less.   The low-expansion filler having a particle diameter exceeding the total (T1 + T2) of the groove depth T1 and the interval T2 between the first glass substrate and the second glass substrate. The low-expansion filler particles not containing particles and having a particle diameter exceeding the larger dimension of either the depth T1 or the interval T2 are included in a volume ratio of 0.05% or more. The electronic device of any one of Claims 7 thru | or 9.   The electronic device according to claim 7, wherein the electronic device is an organic EL device or a solar cell device. Preparing a first glass substrate having an element forming region including an electronic element and a first sealing region provided along an outer periphery of the element forming region;
A second sealing region corresponding to the first sealing region of the first glass substrate, a groove formed continuously with the second sealing region, and an upper portion thereof protruding from the groove. A second glass substrate having a frame-shaped sealing material layer formed of a fired layer of a sealing glass material, which is provided in the groove and contains sealing glass, a low expansion filler, and a laser absorber. A process to prepare;
Laminating the first glass substrate and the second glass substrate through the sealing material layer while forming a gap on the element formation region;
Sealing that seals a gap between the first glass substrate and the second glass substrate by irradiating the sealing material layer with laser light through the second glass substrate to melt the sealing material layer. And a method of manufacturing an electronic device comprising:   The method of manufacturing an electronic device according to claim 12, wherein the electronic element is an organic EL element or a solar cell element.

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