JP2011051811A - Method for manufacturing glass member with sealing material layer and method for manufacturing electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a glass member with a sealing material layer by which even when the whole of a glass substrate cannot be heated, a sealing material layer can be formed satisfactorily. <P>SOLUTION: A sealing material paste prepared by mixing a sealing material containing a sealing glass and a laser absorbent with an organic binder is applied in a frame shape onto a sealing region of a glass substrate 2. The resulting coating layer 8 of the sealing material paste is selectively heated by irradiation with a first laser beam 9 along the coating layer 8 to remove the organic binder. The binder-freed layer 10 is selectively heated by irradiation with a second laser beam 11 along the binder-freed layer 10, whereby the sealing material is fired to form a sealing material layer 7. A gap between two glass substrates is sealed by using such a sealing material layer 7. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a glass member with a sealing material layer and a method for producing an electronic device.

  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). Even in a solar cell such as a dye-sensitized solar cell, it has been studied to apply a glass package in which a solar cell element (photoelectric conversion element) is 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. Since the sealing temperature by sealing glass is about 400-600 degreeC, when it bakes using a normal heating furnace, the characteristic of electronic element parts, such as an OEL element, will deteriorate. Therefore, a sealing material layer including sealing glass (glass frit) and a laser absorbing material is disposed between the sealing regions provided in the periphery of the two glass substrates, and this is irradiated with laser light. Attempts have been made to heat and melt the sealing material layer for sealing (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, and the sealing material layer is heated and melted. The electronic element part provided between the glass substrates is sealed.

  A heating furnace is generally used to form the sealing material layer. Patent Document 3 describes that 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 sealing material layer forming step. In the first temperature raising process, the glass substrate is heated from the back side thereof using a hot plate, an IR heater, a heating lamp, laser light, or the like. In the second temperature raising process, the entire glass substrate is heated using the heater in the heating furnace, as in the normal baking process. Also in the method described in Patent Document 3, the sealing material is baked by heating the entire glass substrate using a heating furnace.

  By the way, in an FPD glass package, an organic resin film such as a color filter is formed not only on an element glass substrate but also on a sealing glass substrate. In such a case, since the organic resin film is thermally damaged when the entire substrate is heated using a heating furnace, a general heating furnace is used even when the sealing material layer is formed on the sealing glass substrate. The used baking process cannot be applied. Further, in the dye-sensitized solar cell, since an element film or the like is formed also on the counter substrate side, it is required to suppress thermal deterioration of the element film or the like in the firing process. Furthermore, since a firing process using a heating furnace usually requires a long time and consumes a large amount of energy, improvements are required from the standpoint of reducing the number of manufacturing steps and manufacturing costs and saving energy.

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

  An object of the present invention is to provide a method for producing a glass member with a sealing material layer and an electronic device capable of satisfactorily forming a sealing material layer even when the entire glass substrate cannot be heated. It is to provide a method.

  In the method for producing a glass member with a sealing material layer according to an aspect of the present invention, a step of preparing a glass substrate having a sealing region, and a sealing material including a sealing glass and a laser absorber are mixed with an organic binder. A step of applying the sealing material paste prepared in a frame shape on the sealing region of the glass substrate, and irradiating a first laser beam along the coating layer of the frame-shaped sealing material paste Selectively heating and removing the organic binder in the coating layer; and selectively heating by irradiating a second laser beam along the coating layer from which the organic binder has been removed. And a step of baking the material to form a sealing material layer.

  An electronic device manufacturing method according to an aspect of the present invention includes a step of preparing a first glass substrate having a surface including a first sealing region, and a second sealing corresponding to the first sealing region. A step of preparing a second glass substrate having a surface with a region; and a sealing material paste prepared by mixing a sealing material containing a sealing glass and a laser absorber with an organic binder. A step of applying a frame shape on the second sealing region of the substrate, and selectively heating by applying a first laser beam along the coating layer of the frame-shaped sealing material paste, A step of removing the organic binder in the layer, and selectively heating by irradiating a second laser beam along the coating layer from which the organic binder has been removed, and firing the sealing material to seal the sealing material Forming a layer, the surface of the first glass substrate, and the A step of laminating the first glass substrate and the second glass substrate through the sealing material layer while facing the surface of the second glass substrate, and the first glass substrate or the first glass substrate Electrons provided between the first glass substrate and the second glass substrate by irradiating the sealing material layer with a third laser beam through the second glass substrate to melt the sealing material layer And a step of forming a sealing layer that seals the element portion.

  According to the method for manufacturing a glass member with a sealing material layer according to an aspect of the present invention, the sealing material layer can be satisfactorily formed even when the entire glass substrate cannot be heated. Therefore, even when such a glass substrate is used, it is possible to manufacture an electronic device excellent in reliability, sealing performance, and the like with high reproducibility.

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 shows the formation process of the sealing material layer to the 2nd glass substrate in the manufacturing process of the electronic device shown in FIG.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. 1 to 6 are views showing a manufacturing process of an electronic device according to an embodiment of the present invention. Here, as an electronic device to which the manufacturing method of the embodiment of the present invention is applied, a lighting device using a light emitting element such as an FPD such as an OELD, PDP, or LCD, or an OEL element, or a dye-sensitized solar cell is used. A sealed solar cell can be 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 30 to 40 × 10 ⁻⁷ / ° C. Soda lime glass has a thermal expansion coefficient of about 80 to 90 × 10 ⁻⁷ / ° C.

  As shown in FIGS. 2 and 3, the first glass substrate 1 has a surface 1 a on which an element region 3 is provided. The element region 3 is provided with an electronic element unit 4 corresponding to the electronic device that is the object. The electronic element unit 4 is, for example, an OEL element for OELD or OEL illumination, a plasma light-emitting element for PDP, a liquid crystal display element for LCD, and a dye-sensitized solar cell element (dye-sensitized type for solar cells). Photoelectric conversion element). The electronic element unit 4 including a light emitting element such as an OEL element, a dye-sensitized solar cell element, and the like has various known structures. This embodiment is not limited to the element structure of the electronic element unit 4.

  A first sealing region 5 is provided along the outer periphery of the element region 3 on the surface 1 a of the first glass substrate 1. The first sealing region 5 is provided so as to surround the element region 3. The second glass substrate 2 has a surface 2 a that faces the surface 1 a of the first glass substrate 1. As shown in FIGS. 4 and 5, a second sealing region 6 corresponding to the first sealing region 5 is provided on the surface 2 a of the second glass substrate 2. The first and second sealing regions 5 and 6 serve as a sealing layer forming region (a sealing material layer forming region for the second sealing region 6).

  The electronic element unit 4 is provided between the surface 1 a of the first glass substrate 1 and the surface 2 a of the second glass substrate 2. In the manufacturing process of the electronic device shown in FIG. 1, the first glass substrate 1 constitutes a glass substrate for an element, and an element structure such as an OEL element or a PDP element is formed as an electronic element portion 4 on the surface 1a. ing. The second glass substrate 2 constitutes a glass substrate for sealing the electronic element portion 4 formed on the surface 1 a of the first glass substrate 1. However, the configuration of the electronic element unit 4 is not limited to this.

  For example, when the electronic element unit 4 is a dye-sensitized solar cell element or the like, a wiring film or an electrode film that forms an element structure on each of the surfaces 1a and 2a of the first and second glass substrates 1 and 2 is used. An element film is formed. The element film constituting the electronic element unit 4 and the element structure based thereon are formed on at least one of the surfaces 1a and 2a of the first and second glass substrates 1 and 2. Furthermore, as described above, an organic resin film such as a color filter may be formed on the surface 2a of the second glass substrate 2 constituting the sealing glass substrate. The manufacturing method of this embodiment is particularly effective when an organic resin film, an element film, or the like is formed on the surface 2a of the second glass substrate 2.

  A frame-shaped sealing material layer 7 is formed in the sealing region 6 of the second glass substrate 2 as shown in FIGS. 1 (a), 4 and 5. The sealing material layer 7 is a fired layer of a sealing material containing 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 other fillers and additives as necessary.

  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. Among these, in view of sealing properties (adhesiveness) to glass substrates 1 and 2 and their reliability (adhesion reliability and hermetic sealing properties), influence on environment and human body, etc., tin-phosphate It is preferable to use a sealing glass made of glass or bismuth glass.

Tin - phosphate glass (glass frit) is 55 to 68 mass% of SnO, SnO ₂ of 0.5 to 5% by weight, and 20 to 40 wt% P ₂ O ₅ (the total amount is basically 100% by mass). SnO is a component for lowering the melting point of glass. When the SnO content is less than 55% by mass, the viscosity of the glass becomes high and the sealing temperature becomes too high, and when it exceeds 68% by mass, it does not vitrify.

SnO ₂ is a component for stabilizing the glass. When the content of SnO ₂ is less than 0.5% by mass, 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% by mass, 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. When the content of P ₂ O ₅ is less than 20% by mass, vitrification does not occur, and when the content exceeds 40% by mass, the weather resistance, which is a disadvantage specific to phosphate glass, may be deteriorated.

Here, the ratio (mass%) of SnO and SnO ₂ in the glass frit can be obtained 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% 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.

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 to widen the range of possible vitrified to form a skeleton of glass. 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 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. Also, other pigments may be used. The content of the laser absorber is preferably in the range of 0.1 to 10% by volume with respect to the sealing material. If the content of the laser absorber is less than 0.1% by volume, the sealing material layer 7 may not be sufficiently melted. If the content of the laser absorbing material exceeds 10% 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 to cause the first There exists a possibility that adhesiveness with the glass substrate 1 may fall.

Furthermore, the sealing material contains 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 appropriately 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 and the glass substrates 1 and 2, the low expansion filler is preferably contained in the range of 5 to 50% by volume with respect to the sealing material. When the glass substrates 1 and 2 are formed of alkali-free glass (thermal expansion coefficient: 30 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 1 and 2 are formed of soda lime glass (thermal expansion coefficient: 80 to 90 × 10 ⁻⁷ / ° C.), a relatively small amount (for example, in the range of 5 to 40% by volume) of a low expansion filler is used. It is preferable to add.

  The sealing material layer 7 is formed as follows. The formation process of the sealing material layer 7 is demonstrated with reference to FIG. FIG. 6 shows an embodiment of the glass member with a sealing material layer of the present invention. 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.

  Examples of the vehicle include those obtained by dissolving a resin such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, and nitrocellulose in a solvent such as terpineol, butyl carbitol acetate, and ethyl carbitol acetate. ) Acrylic resin such as acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc. dissolved in a solvent such as methyl ethyl ketone, terpineol, butyl carbitol acetate, ethyl carbitol acetate Used.

  The resin component in the vehicle functions as an organic 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 is adjusted by 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 do. 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. 6A, the sealing material paste is applied to the sealing region 6 of the second glass substrate 2 and dried to form the coating layer 8. The sealing material paste is applied onto the second sealing region 6 by applying a printing method such as screen printing or gravure printing, or is applied along the second sealing region 6 using a dispenser or the like. To do. The coating layer 8 is dried, for example, at a temperature of 120 ° C. or more for 10 minutes or more. The drying step is performed to remove the solvent in the coating layer 8. If the solvent remains in the coating layer 8, the organic binder may not be sufficiently removed in the subsequent firing step (laser firing step).

  Next, as shown in FIG. 6 (b), the first laser beam 9 is irradiated on the coating layer (dry film) 8 of the sealing material paste. By irradiating the first laser beam 9 along the coating layer 8 and thermally decomposing the organic binder in the coating layer 8, a layer (debide layer) 10 in which the organic binder is removed from the coating layer 8 is formed ( FIG. 6 (c)). The first laser light 9 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 second and third laser beams described later.

  The first laser beam 9 is such that the heating temperature of the coating layer 8 is (T1 + 200 ° C.) or higher (T2 + 120 ° C.) with respect to the thermal decomposition temperature T1 (° C.) of the organic binder and the softening temperature T2 (° C.) of the sealing glass. Irradiation at a scanning speed in the range of 0.1 mm / second or more and 1 mm / second or less along the coating layer 8 is preferable so that the temperature is in the following range. Here, the softening temperature T2 of the sealing glass indicates a temperature at which it softens and flows but does not crystallize. The temperature of the coating layer 8 when irradiated with the first laser light 9 is a value measured with a radiation thermometer. The same applies to the temperature of the removal layer 10 when the second laser light described later is irradiated.

  When the first laser light 9 is irradiated so that the temperature of the coating layer 8 is in the range of (T1 + 200 ° C.) or more and (T2 + 120 ° C.) or less, the organic binder in the coating layer 8 is thermally decomposed, and the pyrolysis component (Gas component) is volatilized and removed out of the layer. The obtained removal layer 10 is in a state of being fixed to the glass substrate 2 without being peeled off from the glass substrate 2. Under the irradiation condition of the laser light 9 that does not reach the temperature of the coating layer 8 (T1 + 200 ° C.), the thermal decomposition of the organic binder cannot be sufficiently progressed, and the binder component may remain. Under the irradiation conditions of the laser light 9 such that the temperature of the coating layer 8 exceeds (T2 + 120 ° C.), the melting of the sealing glass in the coating layer 8 proceeds, and the pyrolysis component of the organic binder is volatilized out of the layer. May interfere.

  Thus, the amount of carbon remaining in the sealing material layer 7 can be reduced by irradiating the coating layer 8 with the first laser light 9 to remove the organic binder. Residual carbon becomes a factor that increases the concentration of impurity gas in the glass panel. In realizing such an organic binder removal step, the first laser beam 9 is preferably irradiated at a scanning speed in the range of 0.1 mm / second to 1 mm / second. If the scanning speed of the first laser beam 9 is less than 0.1 mm / second, the glass substrate 2 may be excessively heated and cracks or cracks may occur.

  On the other hand, if the scanning speed of the first laser light 9 exceeds 1 mm / second, the organic binder cannot be sufficiently decomposed, and the binder component may remain. When the binder component remains in the debonding layer 10, bubbles are generated in the sealing material layer 7 formed in the subsequent baking process (second laser light irradiation process), or deformation due to the bubbles occurs on the surface. . Furthermore, since the amount of residual carbon in the sealing material layer 7 cannot be sufficiently reduced, the amount of gas generated when laser sealing between the glass substrates 1 and 2 may increase, and the airtightness may decrease. is there.

Further, with the first laser light 9 having a scanning speed of 0.1 mm / second or more and 1 mm / second or less, the heating temperature of the coating layer 8 is set to a range of (T1 + 200 ° C.) to (T2 + 120 ° C.). The first laser beam 9 preferably has a power density in the range of 190 to 250 W / cm ² . If the power density of the first laser beam 9 is less than 190 W / cm ² , the entire coating layer 8 cannot be heated uniformly. If the power density of the first laser light 9 exceeds 250 W / cm ² , it becomes difficult to achieve both the heating temperature and the scanning speed.

  Next, as shown in FIG. 6 (d), the second laser beam 11 is irradiated to the removal layer 10. By irradiating the second laser beam 11 along the removal layer 10, the sealing material is baked to form the sealing material layer 7 (FIG. 6E). The second laser beam 11 is removed so that the heating temperature of the debuy layer 10 is not less than (T2 + 120 ° C.) and not more than (T2 + 550 ° C.) with respect to the softening temperature T2 (° C.) of the sealing glass. It is preferable to irradiate along the bi-layer 10 at a scanning speed in the range of 0.1 mm / second or more and 50 mm / second or less.

  When the second laser light 11 is irradiated so that the temperature of the debonding layer 10 is in the range of (T2 + 120 ° C.) to (T2 + 550 ° C.), the sealing glass in the sealing material is melted and rapidly solidified. As a result, the sealing material is baked onto the second glass substrate 2 to form the sealing material layer 7. Under the irradiation condition of the laser beam 11 such that the temperature of the debuy layer 10 does not reach (T2 + 120 ° C.), only the surface portion of the debuy layer 10 is melted, and the entire debuy layer 10 cannot be melted uniformly. Under the irradiation condition of the laser beam 11 such that the temperature of the debonding layer 10 exceeds (T2 + 550 ° C.), the glass substrate 2 and the sealing material layer 7 are likely to be cracked or broken.

  On the other hand, if the scanning speed of the second laser beam 11 is less than 0.1 mm / second, the glass substrate 2 is excessively heated and cracks, cracks, and the like are likely to occur. On the other hand, if the scanning speed of the second laser beam 11 exceeds 50 mm / sec, there is a possibility that the entire removal layer 10 cannot be melted uniformly. Furthermore, since the sealing material paste is removed by the first laser beam 9 in advance, it is not necessary to consider the removal of the binder component when the second laser beam 11 is irradiated. Therefore, the scanning speed of the second laser beam 11 can be increased within a range in which the sealing glass can be melted, and more specifically, it is more preferably 10 mm / second or more. This makes it possible to further reduce the number of manufacturing steps and manufacturing costs of the sealing material layer 7.

Further, with the second laser light 11 having a scanning speed of 0.1 mm / second or more and 50 mm / second or less, the heating temperature of the removal layer 10 is set to a range of (T2 + 120 ° C.) to (T2 + 550 ° C.). At this time, the second laser beam 11 preferably has a power density in the range of 250 to 2000 W / cm ² . If the power density of the second laser beam 11 is less than 250 W / cm ² , the entire de-bye layer 10 cannot be heated uniformly, and only the surface portion melts, and bubbles and deformation are likely to occur. On the other hand, when the power density exceeds 2000 W / cm ² , the glass substrate 2 and the sealing material are excessively heated, and cracks and cracks are likely to occur.

  The formation process of the sealing material layer 7 is not limited to the film thickness of the coating layer 8, but the film thickness is such that the thickness after baking (the thickness of the sealing material layer 7) is less than 20 μm. It is effective for the coating layer 8 having. In the coating layer 8 having a thickness such that the thickness after firing is 20 μm or more, there is a possibility that the coating layer 8 or the entire removal layer 10 cannot be uniformly heated by the laser beams 9 and 11. In such a case, only the surface portion of the removal layer 10 is melted and vitrified at the time of irradiation with the second laser light 11, and bubbles are generated inside the sealing material layer 7. Deformation tends to occur. The film thickness of the sealing material layer 7 is preferably less than 20 μm, and more preferably 10 μm or less. Practically, the thickness of the sealing material layer 7 is preferably 5 μm or more.

  In the formation process of the sealing material layer 7 according to this embodiment, the coating layer 8 and the debuoyancy are removed by sequentially irradiating the coating layer 8 of the sealing material paste with the first laser beam 9 and the second laser beam 11. Layer 10 is selectively heated. 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 7 can be formed satisfactorily. Furthermore, since the organic binder is excellent in removability and the amount of residual carbon can be sufficiently reduced, it is possible to obtain the sealing material layer 7 having excellent sealing properties, reliability, and the like.

  Of course, in the step of forming the sealing material layer 7 using the first and second laser beams 9 and 11, no organic resin film, element film or the like is formed on the surface 2 a of the second glass substrate 2. Even in such a case, the sealing material layer 7 having excellent sealing properties and reliability can be obtained. Furthermore, the process of forming the sealing material layer 7 using the laser beams 9 and 11 (de-buying and baking process) consumes less energy than the baking process using the conventional heating furnace, and reduces the number of manufacturing steps and manufacturing costs. Also contribute. Therefore, the process of forming the sealing material layer 7 using the laser beams 9 and 11 is also effective from the viewpoint of energy saving and cost reduction.

  Next, the 1st glass substrate 1 produced separately from the 2nd glass substrate 2 is prepared, and the illuminating device using FPD, OEL elements, such as OELD, PDP, LCD, using these glass substrates 1 and 2. An electronic device such as a solar cell such as a dye-sensitized solar cell is manufactured. That is, as shown in FIG. 1B, the first glass substrate 1 and the second glass substrate 2 are laminated via the sealing material layer 7 so that the surfaces 1a and 2a face each other. . A gap is formed between the first glass substrate 1 and the second glass substrate 2 based on the thickness of the sealing material layer 7.

  Next, as shown in FIG. 1C, the sealing material layer 7 is irradiated with the third laser light 12 through the second glass substrate 2. The third laser beam 12 may be applied to the sealing material layer 7 through the first glass substrate 1. The third laser beam 12 is irradiated while scanning along the frame-shaped sealing material layer 7. The sealing material layer 7 is melted in order from the portion irradiated with the laser beam 12, and is rapidly cooled and solidified and fixed to the first glass substrate 1 when the irradiation with the laser beam 12 is completed. Then, by irradiating the third laser beam 12 over the entire circumference of the sealing material layer 7, the space between the first glass substrate 1 and the second glass substrate 2 is sealed as shown in FIG. The sealing layer 13 to be stopped is formed.

  In this way, a glass panel constituted by the first glass substrate 1, the second glass substrate 2 and the sealing layer 13 is arranged between the first glass substrate 1 and the second glass substrate 2. The electronic device 14 in which the electronic element unit 4 is hermetically sealed is produced. In addition, the glass panel of this embodiment is not restricted to the component of the electronic device 14, It is possible to apply also to glass members (building materials etc.) like a sealing body of electronic components, or vacuum pair glass. is there.

  According to the manufacturing process of the electronic device 14 of this embodiment, even when an organic resin film, an element film, or the like is formed on the surface 2a of the second glass substrate 2, they are not thermally damaged. The sealing material layer 7 and the sealing layer 13 can be formed satisfactorily. Therefore, the electronic device 14 having excellent hermetic sealing performance and reliability can be manufactured with good reproducibility without deteriorating the function of the electronic device 14 and its reliability.

  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
Bi ₂ O ₃ glass having a composition of 83.2% by mass of Bi ₂ O _3, 5.6% by mass of B ₂ O ₃ , 10.7% by mass of ZnO and 0.5% by mass of Al ₂ O ₃ and having an average particle diameter of 1 μm. Frit (softening temperature: 450 ° C.), cordierite powder having an average particle size of 2 μm as a low expansion filler, Fe ₂ O ₃ —Cr ₂ O ₃ —MnO—Co ₂ O ₃ composition, average particle size Was prepared with a 1 μm laser absorber.

  The above-mentioned bismuth glass frit 72.7% by volume, cordierite powder 22.0% by volume and laser absorber 5.3% by volume were mixed 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 thermal decomposition temperature of ethyl cellulose is 250 ° C.

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 sealed in a sealing region of this glass substrate. The coating material paste was applied by screen printing and then dried at 120 ° C. for 10 minutes. The sealing material paste was applied so that the film thickness after drying was 20 μm and the line width was 1 mm. A resin color filter is formed on the surface of the second glass substrate, and it is necessary to form a sealing layer in the sealing region of the second glass substrate without causing thermal damage to the color filter.

Next, an alkali-free glass substrate on which a sealing material paste coating layer has been formed is placed on an alumina substrate (thickness) on a sample holder of a laser irradiation apparatus LD-Heator L10060 (trade name, manufactured by Hamamatsu Photonics) using a semiconductor laser. 0.5 mm), and the coating layer was irradiated with laser light (first laser light) having a wavelength of 940 nm and a power density of 249 W / cm ² at a scanning speed of 1 mm / second to form a de-bye layer. When the heating temperature of the coating layer when irradiated with the first laser beam was measured with a radiation thermometer, the temperature of the coating layer was 560 ° C.

Subsequently, using the same laser irradiation apparatus, the laser light irradiation condition is changed to a power density of 746 W / cm ² and a scanning speed of 10 mm / second, and then the laser light (second laser light) along the debonding layer. Was applied to form a sealing material layer (sealing material fired layer) having a thickness of 12 μm. When the heating temperature of the removal layer when irradiated with the second laser beam was measured with a radiation thermometer, the temperature of the removal layer was 732 ° C.

  When the state of the sealing material layer thus obtained was observed with an SEM, it was confirmed that it was vitrified well. In the sealing material layer, generation of bubbles and surface deformation due to residual binder components was not observed. When the residual carbon amount of the sealing material layer was measured, it was confirmed that it was the same as the residual carbon amount when the coating layer of the same sealing material paste was baked in an electric furnace (250 ° C. × 40 minutes). Furthermore, it was confirmed that the color filter formed on the surface of the glass substrate was not damaged by heat.

  Next, a second glass substrate having the above-described sealing material layer and a first glass substrate having an element region (region in which an OEL element is formed) (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 (third laser beam) having a wavelength of 940 nm, an output of 60 W, and a spot diameter of 1.6 mm through the second glass substrate at a scanning speed of 10 mm / s for sealing. By melting and rapidly solidifying the material layer, the first glass substrate and the second glass substrate were sealed.

  The appearance of the glass panel thus produced was evaluated by observing cracks and cracks in the glass substrate and the sealing layer, the bonding state of the sealing layer, etc. with an optical microscope, and all were confirmed to be good. It was. When the hermeticity of the glass panel was measured by a helium leak test, it was confirmed that a good hermetic state was obtained. Moreover, when the joining strength of a glass substrate and a sealing layer was measured, it was confirmed that the intensity | strength equivalent to the glass panel produced using the sealing layer baked with the above-mentioned electric furnace was obtained.

(Example 2)
The debuying process of the coating layer of the sealing material paste in the same manner as in Example 1 except that the irradiation condition of the second laser beam on the debuying layer is changed to a power density of 1742 W / cm ² and a scanning speed of 50 mm / sec. And the sealing material layer whose film thickness is 12 micrometers was formed by implementing the baking process of a debuy layer. The temperature of the removal layer when irradiated with the second laser beam was 870 ° C. The temperature of the coating layer when irradiated with the first laser beam was the same as in Example 1.

  When the state of the sealing material layer thus obtained was observed with an SEM, it was confirmed that it was vitrified well. In addition, no bubbles or surface deformation due to the organic binder was observed in the sealing material layer. Furthermore, 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 (250 ° C. × 40 minutes). It was.

  Next, in the same manner as in Example 1, the second glass substrate having the sealing material layer and the first glass substrate having the element region were laminated, and then the second glass substrate was passed through the second glass substrate to the sealing material layer. The first glass substrate and the second glass substrate were sealed by irradiating the laser beam 3. The first and second glass substrates are made of alkali-free glass as in Example 1. The obtained glass panel was excellent in appearance, airtightness, bonding strength and the like as in Example 1.

(Example 3)
The sealing material paste was applied in the same manner as in Example 1 except that the irradiation condition of the first laser beam on the coating layer of the sealing material paste was changed to a power density of 199 W / cm ² and a scanning speed of 0.5 mm / second. A sealing material layer having a film thickness of 12 μm was formed by carrying out a coating layer removal process and a removal layer baking process. The temperature of the coating layer when irradiated with the first laser light was 560 ° C., and the temperature of the removal layer when irradiated with the second laser light was 730 ° C.

  When the state of the sealing material layer thus obtained was observed with an SEM, it was confirmed that it was vitrified well. In addition, no bubbles or surface deformation due to the organic binder was observed in the sealing material layer. Furthermore, 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 (250 ° C. × 40 minutes). It was.

  Next, in the same manner as in Example 1, the second glass substrate having the sealing material layer and the first glass substrate having the element region were laminated, and then the second glass substrate was passed through the second glass substrate to the sealing material layer. The first glass substrate and the second glass substrate were sealed by irradiating the laser beam 3. The first and second glass substrates are made of alkali-free glass as in Example 1. The obtained glass panel was excellent in appearance, airtightness, bonding strength and the like as in Example 1.

(Reference Example 1)
The coating layer of the sealing material paste was applied in the same manner as in Example 1 except that the irradiation condition of the first laser beam on the coating layer of the sealing material paste was changed to a power density of 149 W / cm ² and a scanning speed of 1 mm / second. The sealing material layer having a film thickness of 12 μm was formed by carrying out the removal process and the firing process of the removal layer. The temperature of the coating layer when irradiated with the first laser beam was 428 ° C., and the temperature of the removal layer when irradiated with the second laser beam was 730 ° C.

  When the state of the obtained sealing material layer was observed with an SEM, it was confirmed that it was vitrified, but deformation due to bubbles derived from the organic binder was observed on the surface, and bubbles remained inside. It was confirmed that When such a sealing material layer was used and the laser sealing process of the first glass substrate and the second glass substrate was performed under the same conditions as in Example 1, good sealing state and airtightness were obtained. I couldn't.

(Reference Example 2)
The sealing material paste was applied in the same manner as in Example 1 except that the irradiation condition of the first laser beam on the coating layer of the sealing material paste was changed to a power density of 149 W / cm ² and a scanning speed of 0.5 mm / second. A sealing material layer having a film thickness of 12 μm was formed by carrying out a coating layer removal process and a removal layer baking process. The temperature of the coating layer when irradiated with the first laser beam was 428 ° C., and the temperature of the removal layer when irradiated with the second laser beam was 730 ° C.

  When the state of the obtained sealing material layer was observed with an SEM, it was confirmed that it was vitrified, but deformation due to bubbles derived from the organic binder was observed on the surface, and bubbles remained inside. It was confirmed that When such a sealing material layer was used and the laser sealing process of the first glass substrate and the second glass substrate was performed under the same conditions as in Example 1, good sealing state and airtightness were obtained. I couldn't.

  DESCRIPTION OF SYMBOLS 1 ... 1st glass substrate, 1a ... surface, 2 ... 2nd glass substrate, 2a ... surface, 3 ... element area | region, 4 ... electronic element part, 5 ... 1st sealing area | region, 6 ... 2nd sealing Stop region, 7 ... Sealing material layer, 8 ... Sealing material paste coating layer, 9 ... First laser beam, 10 ... Deviating layer, 11 ... Second laser beam, 12 ... Second laser beam, 13 ... sealing layer, 14 ... electronic device.

Claims (10)

Preparing a glass substrate having a sealing region;
A step of applying a sealing material paste prepared by mixing a sealing glass material including a sealing glass and a laser absorber with an organic binder in a frame shape on the sealing region of the glass substrate;
Irradiating the first laser beam along the coating layer of the frame-shaped sealing material paste and selectively heating it, and removing the organic binder in the coating layer;
Irradiating and selectively heating a second laser beam along the coating layer from which the organic binder has been removed, and firing the sealing glass material to form a sealing material layer. A method for producing a glass member with a sealing material layer.   When the thermal decomposition temperature of the organic binder is T1 (° C.) and the softening temperature of the sealing glass is T2 (° C.), the heating temperature of the coating layer is (T1 + 200 ° C.) in the first laser light irradiation step. The first laser beam is irradiated at a scanning speed in the range of 0.1 mm / second to 1 mm / second so that the temperature is in the range of (T2 + 120 ° C.) or less. In the irradiation step, the second laser light is in the range of 0.1 mm / second to 50 mm / second so that the heating temperature of the coating layer is in the range of (T2 + 120 ° C.) to (T2 + 550 ° C.). 2. The method for producing a glass member with a sealing material layer according to claim 1, wherein the irradiation is performed at a scanning speed of 5. 2. The first laser light has an energy density in a range of 190 to 250 W / cm < ² >, and the second laser light has an energy density in a range of 250 to 2000 W / cm < ² >. Or the manufacturing method of the glass member with a sealing material layer of Claim 2.   The said sealing material layer has thickness less than 20 micrometers, The manufacturing method of the glass member with a sealing material layer of any one of Claim 1 thru | or 3 characterized by the above-mentioned.   The glass with a sealing material layer according to any one of claims 1 to 4, wherein the sealing glass material includes the sealing glass made of tin-phosphate glass or bismuth glass. Manufacturing method of member.   The glass material for sealing contains the laser absorber made of at least one metal selected from Fe, Cr, Mn, Co, Ni and Cu or a compound containing the metal in a range of 0.1 to 10% by volume. The method for producing a glass member with a sealing material layer according to any one of claims 1 to 5, wherein:   The glass material for sealing is selected from silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, cordierite, eucryptite, spodumene, zirconium phosphate compound, quartz solid solution, soda lime glass, and borosilicate glass. The method for producing a glass member with a sealing material layer according to any one of claims 1 to 6, wherein the low expansion filler composed of at least one kind is contained in an amount of 5 to 50% by volume. Providing a first glass substrate having a surface with a first sealing region;
Providing a second glass substrate having a surface with a second sealing region corresponding to the first sealing region;
A sealing material paste prepared by mixing a sealing glass 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. Process,
Irradiating the first laser beam along the coating layer of the frame-shaped sealing material paste and selectively heating it, and removing the organic binder in the coating layer;
Irradiating and selectively heating a second laser beam along the coating layer from which the organic binder has been removed, and firing the sealing glass material to form a sealing material layer;
The first glass substrate and the second glass substrate are stacked via the sealing material layer while the surface of the first glass substrate and the surface of the second glass substrate are opposed to each other. Process,
The sealing material layer is irradiated with a third laser beam through the first glass substrate or the second glass substrate, and the sealing material layer is melted, so that the first glass substrate and the second glass are melted. And a step of forming a sealing layer for sealing the electronic element portion provided between the substrate and the substrate.   When the thermal decomposition temperature of the organic binder is T1 (° C.) and the softening temperature of the sealing glass is T2 (° C.), the heating temperature of the coating layer is (T1 + 200 ° C.) in the first laser light irradiation step. The first laser beam is irradiated at a scanning speed in the range of 0.1 mm / second to 1 mm / second so that the temperature is in the range of (T2 + 120 ° C.) or less. In the irradiation step, the second laser light is in the range of 0.1 mm / second to 50 mm / second so that the heating temperature of the coating layer is in the range of (T2 + 120 ° C.) to (T2 + 550 ° C.). The method of manufacturing an electronic device according to claim 8, wherein irradiation is performed at a scanning speed of 10.   10. The method of manufacturing an electronic device according to claim 8, wherein the sealing material layer has a thickness of less than 20 [mu] m.

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