JP5516194B2 - Light heat sealing glass, glass member with sealing material layer, electronic device and method for producing the same - Google Patents

Description

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

  Flat display devices (FPD) such as organic EL displays (Organic Electro-Luminescence Display: OELD), field emission displays (Feed Emission Display: FED), plasma display panels (PDP), liquid crystal display devices (LCD), and illumination An organic light emitting diode (OLED) is a glass package in which a glass substrate for an element on which a display element and a light emitting element are formed and a glass substrate for sealing are arranged opposite to each other, and the two glass substrates are sealed. The display element is sealed. 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 (dye-sensitized photoelectric conversion element) is sealed with two glass substrates.

  As a material for sealing between two glass substrates, resin has generally been used. However, since organic EL (OEL) elements and the like are easily deteriorated by moisture, sealing with glass having excellent moisture resistance and the like. Application of materials is underway. When sealing with a glass material, it is necessary to heat to a temperature at which the glass softens and flows. Since the temperature at which the glass softens and flows is generally about 400 ° C. or higher, the heat treatment using a normal firing furnace deteriorates the characteristics of the electronic element portion such as the OEL element. Accordingly, a laser sealing technique has been developed in which only the sealing portion is locally heated and sealed using laser light.

  As a material used for laser sealing, a sealing material containing a laser absorbing material in sealing glass (see Patent Document 1), a sealing material containing a transition metal component having laser absorbing ability in sealing glass ( Patent Document 2), sealing materials in which black Sn colloid is contained in sealing glass (see Patent Document 3) and the like are known. Among these, since the sealing material containing the laser absorbing material is liable to decrease the fluidity when the glass is melted, it is necessary to increase the sealing temperature to some extent. Moreover, since the conventional transition metal component needs to be contained in a relatively large amount in order to blacken the sealing material, an increase in the glass transition temperature of the sealing material is inevitable.

  The tin-phosphate glass described in Patent Document 3 has attracted attention as a material that can lower the sealing temperature. However, the laser beam absorptance of the sealing material is not always sufficient, and preheating is required even for a low-temperature sealing material, and there is a concern about damage and adverse effects on an electronic element portion such as an OEL element. As the FPD is made thinner, the thickness of the sealing portion is required to be several tens of μm or less, which further reduces the absorption rate of the laser beam.

  In addition, when a pigment is added as a laser absorber to tin-phosphate glass, it is necessary to reduce the particle size of the pigment in order to realize a thin sealing portion. The fine-particle pigment decreases the fluidity of the sealing glass and becomes a factor of deteriorating hermetic sealing properties. Furthermore, since the conventional tin-phosphate glass is easy to crystallize, it is necessary to use it as a strip to reduce the specific surface area of the sealing material. For this reason, the glass powder is suitable for mass production. Has a drawback that it cannot be made into a paste and applied to the sealing process. In addition, it is desired for the sealing material to further reduce the sealing temperature in laser sealing.

JP 2008-115057 A JP 2006-524419 A JP 2008-186697 A

  An object of the present invention is to provide an optical heating sealing that has a sufficient light absorption rate in a wide wavelength range and can reduce the sealing temperature when applied to optical heating sealing typified by laser sealing. The object of the present invention is to provide a wearing glass, a glass member with a sealing material layer and an electronic device using the same, and a method for producing the same.

The glass for optical heat sealing of the present invention is expressed in mol% on the basis of oxide, 27 to 33% P ₂ O ₅ , 50 to 70% SnO, 0.5 to 3% TeO ₂ , 0 to 10%. ZnO, 0-5% CaO, 0-5% SrO, 0-5% B ₂ O ₃ , 0-5% Ga ₂ O ₃ , 0-3% GeO ₂ , 0-3% It is characterized by comprising a glass composition containing In ₂ O ₃ , 0 to 3% La ₂ O ₃ , and 0 to 3% WO ₃ .

  The glass member with a sealing material layer of the present invention includes a glass substrate having a sealing region, the glass for light heating sealing of the present invention, and a low expansion filler provided on the sealing region of the glass substrate. And a sealing material layer made of a fired layer of the sealing material.

  An electronic device according to the present invention includes a first glass substrate having a first surface including a first sealing region, and a second surface including a second sealing region corresponding to the first sealing region. A second glass substrate disposed on the first glass substrate with a predetermined gap so that the second surface faces the first surface, and the first glass An electronic element provided between the substrate and the second glass substrate; and the first sealing region of the first glass substrate and the second so as to seal the electronic element. A sealing layer formed between the second sealing region of the glass substrate and made of a melt-fixed layer of a sealing material containing the light heat sealing glass of the present invention and a low expansion filler. It is characterized by that.

  The electronic device manufacturing method of the present invention includes a step of preparing a first glass substrate having a first surface including a first sealing region, and a second sealing corresponding to the first sealing region. And a sealing material layer formed on the second sealing region and comprising a fired layer of a sealing material containing the light heat sealing glass of the present invention and a low expansion filler. Preparing a second glass substrate having a surface; and sealing the first glass substrate and the second glass substrate so that the first surface and the second surface face each other. A step of laminating through the material layer, and heating the sealing material layer by irradiating the sealing material layer with light through the first glass substrate or the second glass substrate, thereby melting the sealing material layer and Sealing for sealing an electronic element portion provided between the glass substrate and the second glass substrate It is characterized by comprising a step of forming a.

Since the glass for light heat sealing of the present invention is blackened with a relatively small amount of TeO ₂ , a sufficient light absorption rate can be obtained in a wide wavelength region while suppressing an increase in the glass transition temperature. Therefore, sealing by light heating at a low temperature can be realized.

It is sectional drawing which shows 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 a figure which shows the relationship between the wavelength of the glass for sealing by embodiment of this invention, and the light transmittance compared with the conventional glass for sealing.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. FIG. 1 is a view showing an electronic device according to an embodiment of the present invention, FIG. 2 is a view showing a manufacturing process of the electronic device, and FIGS. 3 to 6 are views showing a configuration of a glass substrate used therefor. The electronic device 1 shown in FIG. 1 constitutes a lighting device using a light emitting element such as an FPD such as an OELD, FED, PDP, or LCD, or an OEL element, or a solar cell such as a dye-sensitized solar cell. is there.

The electronic device 1 includes a first glass substrate 2 and a second glass substrate 3. The first and second glass substrates 2 and 3 are made of, for example, soda lime glass or non-alkali glass having various known compositions. Soda lime glass has a thermal expansion coefficient of about 80 to 90 × 10 ⁻⁷ / ° C. The alkali-free glass has a thermal expansion coefficient of about 35 to 40 × 10 ⁻⁷ / ° C. However, the material of the glass substrates 2 and 3 is not particularly limited.

  An electronic element portion (not shown) corresponding to the electronic device 1 is provided between the surface 2a of the first glass substrate 2 and the surface 3a of the second glass substrate 3 facing it. The electronic element unit 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, or a dye-sensitized solar cell element (dye-sensitized photoelectric element for solar cells). Conversion unit element) and the like. An electronic element portion including a display element, a light emitting element, a dye-sensitized solar cell element, and the like has various known structures. The electronic device 1 of this embodiment is not limited to the element structure of the electronic element part.

  The electronic element part in the electronic device 1 is composed of an element film, an electrode film, a wiring film, and the like formed on at least one of the surfaces 2a and 3a of the first and second glass substrates 2 and 3. In OELD, FED, PDP, etc., an electronic element part is comprised by the element structure formed in the surface 3a (2a) of one glass substrate 3 (2). In this case, the other glass substrate 2 (3) serves as a sealing substrate, but a filter film or the like may be formed. In addition, in LCDs and dye-sensitized solar cell elements, element films, electrode films, wiring films and the like that form element structures are formed on the surfaces 2a and 3a of the glass substrates 2 and 3, respectively. Is configured.

  As shown in FIG. 3, a first sealing region 4 is provided on the surface 2 a of the first glass substrate 2 used for manufacturing the electronic device 1. As shown in FIG. 5, a second sealing region 5 corresponding to the first sealing region 4 is provided on the surface 3 a of the second glass substrate 3. The first and second sealing regions 4 and 5 serve as a sealing layer forming region (a sealing material layer forming region for the second sealing region 5). A portion surrounded by the first and second sealing regions 4 and 5 becomes an element region, and an electronic element portion is provided in the element region.

  The first glass substrate 2 and the second glass substrate 3 have a predetermined gap so that the surface 2a having the first sealing region 4 and the surface 3a having the second sealing region 5 face each other. Is arranged. A gap between the first glass substrate 2 and the second glass substrate 3 is sealed with a sealing layer 6. The sealing layer 6 is formed between the sealing region 4 of the first glass substrate 2 and the sealing region 5 of the second glass substrate 3 so as to seal the electronic element portion. The electronic element portion provided between the first glass substrate 2 and the second glass substrate 3 is a glass panel composed of the first glass substrate 2, the second glass substrate 3, and the sealing layer 6. It is hermetically sealed.

  The sealing layer 6 was fixed to the sealing region 4 of the first glass substrate 2 by melting and solidifying the sealing material layer 7 formed on the sealing region 5 of the second glass substrate 3. It consists of a melt-fixed layer. The sealing material layer 7 is melted by local heating using light such as laser light. That is, a frame-shaped sealing material layer 7 is formed in the sealing region 5 of the second glass substrate 3 used for manufacturing the electronic device 1 as shown in FIGS. The sealing material layer 7 formed in the sealing region 5 of the second glass substrate 3 is rapidly heated / cooled with a laser beam or the like, and melted and fixed to the sealing region 5 of the first glass substrate 2. A sealing layer 6 that hermetically seals the space (element arrangement space) between the first glass substrate 2 and the second glass substrate 3 is formed.

The sealing material layer 7 is a fired layer of a sealing material containing sealing glass and a low expansion filler. The sealing material contains a low expansion filler in order to match the coefficient of thermal expansion with the coefficient of thermal expansion of the glass substrates 2 and 3. The sealing material may contain additives other than the low expansion filler as necessary. The sealing glass as the main component of the sealing material includes 27 to 33% P ₂ O ₅ , 50 to 70% SnO, 0.5 to 3% TeO ₂ , expressed in terms of mol% based on oxide. 0-10% ZnO, 0-5% CaO, 0-5% SrO, 0-5% B ₂ O ₃ , 0-5% Ga ₂ O ₃ , 0-3% GeO ₂ , 0 A tin-phosphate glass composition containing ˜3% In ₂ O ₃ , 0 to 3% La ₂ O ₃ , and 0 to 3% WO ₃ is used.

In the sealing glass (tin-phosphate glass composition) used in this embodiment, P ₂ O ₅ is an essential component that stabilizes the glass by forming a glass skeleton, and 27 to 33 in the sealing glass. It is contained in the range of mol%. When the content of P ₂ O ₅ is less than 27 mol%, the glass transition temperature (Tg) increases. When the content of P ₂ O ₅ exceeds 33 mol%, durability against the environment (especially moisture) decreases. Considering the stability of the glass and the durability to the environment, the content of P ₂ O ₅ is particularly preferably in the range of 30 to 32 mol%.

SnO is an essential component that lowers the softening temperature of the glass and improves the fluidity of the glass, and is contained in the sealing glass in the range of 50 to 70 mol%. When the content of SnO is less than 50 mol%, the softening temperature of the glass increases, and the fluidity of the glass in the sealing step decreases. Furthermore, since the light transmittance when the blackened glass is thinned is increased and the absorptivity of the laser beam or the like is reduced, it is difficult to sufficiently heat the laser beam or the like. If the SnO content exceeds 70 mol%, vitrification becomes difficult. The content of SnO is more preferably set so that the total content with P ₂ O ₅ is in the range of 85 to 99 mol%, thereby further reducing the glass transition temperature (Tg). .

TeO ₂ is an essential component for blackening the glass, and is contained in the sealing glass in a range of 0.5 to 3 mol%. If the TeO ₂ content is less than 0.5 mol%, the light absorption rate of the glass cannot be sufficiently improved, and heating by light irradiation tends to be insufficient. Sex is reduced. When the content of TeO ₂ exceeds 3 mol%, vitrification becomes difficult. The content of TeO ₂ is particularly preferably in the range of 0.5 to 1 mol%, thereby stabilizing a black glass having a further lowered glass transition temperature (Tg), that is, a glass having a high light absorption rate. Can be obtained.

The glass composition formed of the above-described three components (basic components) is excellent in the ability to absorb laser light and the like, has a low glass transition temperature (Tg), and is suitable as a material for light heating sealing at low temperatures. In addition, optional components such as ZnO, CaO, SrO, B ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , In ₂ O ₃ , La ₂ O ₃ , and WO ₃ may be further contained. However, if the total content of the optional components is too large, the glass becomes unstable and devitrification occurs during glass production, and the crystallization tendency of the glass becomes too strong even if devitrification does not occur. Since the glass may crystallize without softening and flowing in the middle, the total content of optional components is preferably 20 mol% or less, more preferably 15 mol% or less, particularly preferably 12 mol% or less. It is.

  Since ZnO has effects such as improving the water resistance of the glass and lowering the thermal expansion coefficient, it is preferably contained in the range of 0 to 10 mol%. When the content of ZnO exceeds 10 mol%, devitrification tends to occur. In order to obtain the effect of improving the water resistance of the glass by ZnO, the content of ZnO is preferably 1 mol% or more. The ZnO content is preferably 1/7 or less of the SnO content. If the ZnO content exceeds 1/7 of the SnO content, the glass softening temperature may become too high, or crystallization may be promoted.

  CaO is a component that suppresses crystallization of glass and lowers the thermal expansion coefficient, and is preferably contained in the range of 0 to 5 mol%. If the content of CaO exceeds 5 mol%, the glass becomes unstable. In order to obtain an effect of suppressing crystallization by CaO, the content of CaO is preferably 0.5 mol% or more, more preferably 1 mol% or more. In particular, when the CaO content is in the range of 0.5 to 3 mol%, sealing in a wide temperature range is possible.

B ₂ O ₃ may be contained in a range of 5 mol% or less as a component that supports suppression of crystallization by CaO. When the content of B ₂ O ₃ exceeds 5 mol%, the refractive index of the glass becomes small and the chemical durability such as water resistance may be lowered.

  SrO may be contained in a range of 5 mol% or less as a component for suppressing crystallization of glass. If the SrO content exceeds 5 mol%, the glass may become unstable or the thermal expansion coefficient may become too large.

Ga ₂ O ₃ may be contained in a range of 5 mol% or less as a component for improving water resistance and stabilizing the glass. When the content of Ga ₂ O ₃ exceeds 5 mol%, the glass softening temperature increases and the glass transition temperature (Tg) may exceed, for example, 310 ° C., so that the sealing property at low temperatures is lowered. The content of Ga ₂ O ₃ is more preferably 4 mol% or less, and particularly preferably 3 mol% or less.

GeO ₂ may be contained in the range of 3 mol% or less as a component for improving water resistance and stabilizing the glass. When the content of GeO ₂ exceeds 3 mol%, the softening temperature of the glass increases, and the glass transition temperature (Tg) may exceed, for example, 310 ° C. The content of GeO ₂ is more preferably 2 mol% or less, and particularly preferably 1 mol% or less.

In ₂ O ₃ may be contained in a range of 3 mol% or less as a component for improving water resistance and stabilizing the glass. When the content of In ₂ O ₃ exceeds 3 mol%, the glass softening temperature increases and the glass transition temperature (Tg) may exceed, for example, 310 ° C., so that the sealing property at low temperatures is lowered. The content of In ₂ O ₃ is more preferably 2 mol% or less, and particularly preferably 1 mol% or less.

La ₂ O ₃ may be contained in the range of 3 mol% or less as a component for improving water resistance and stabilizing the glass. When the content of La ₂ O ₃ exceeds 3 mol%, the softening temperature of the glass becomes high and the glass transition temperature (Tg) may exceed, for example, 310 ° C., so that the sealing property at a low temperature is lowered. The content of La ₂ O ₃ is more preferably 2 mol% or less, and particularly preferably 1 mol% or less.

WO ₃ may be contained in a range of 3 mol% or less as a component for improving water resistance and stabilizing the glass. When the content of WO ₃ exceeds 3 mol%, the softening temperature of the glass becomes high and the glass transition temperature (Tg) may exceed, for example, 310 ° C., so that the sealing property at a low temperature is lowered. The content of WO ₃ is more preferably 2 mol% or less, and particularly preferably 1 mol% or less.

The tin-phosphate glass composition used as the sealing glass is substantially composed of the above-described components, but other components such as MgO, Bi ₂ O ₃ , Y ₂ within the range not impairing the purpose. O ₃ , Gd ₂ O ₃ , Ce ₂ O ₃ , CeO ₂ , TiO ₂ , Ta ₂ O _{5 and the} like may be contained. In addition, it is preferable that the glass for sealing does not contain PbO substantially. Further, it is preferable that the sealing glass does not contain Li ₂ O, Na ₂ O, the K ₂ O or the like substantially. If these compounds are present in a significant amount in the glass, ions may diffuse into the electrodes, wirings, etc. of the electronic element part at the time of sealing, and the electronic element part may be deteriorated or deteriorated in characteristics.

In the tin-phosphate glass composition described above, the reason why the glass turns black is not necessarily fully ^{understood, but} a part of Te ⁴⁺ ions or Te ⁴⁺ ions in a high-temperature molten state during the glass production process. It is considered that a part of the Sn ²⁺ ions have a metastable valence, and a semiconductor-like structure is locally generated. Since the glass blackened with TeO ₂ exhibits a sufficient light absorption rate in a wide wavelength range of, for example, 400 to 1600 nm, it can be satisfactorily heated with a light beam emitted from a laser light source or a high-intensity light source. The tin-phosphate glass composition of this embodiment has a light absorption with a linear light transmittance of 10% or less in a wavelength range of 400 to 1600 nm when it is vitrified and formed into a mirror-polished plate having a thickness of 2 mm. It has the ability.

Figure 7 is the light transmittance of the glass prepared by blending the TeO ₂ in the glass composition composed mainly of a P ₂ O ₅ and SnO, instead of glass not blended TeO _2, also the TeO ₂ Fe ₂ O ₃ and is a graph showing by comparison with the light transmittance of the glass compounded with CuO. As can be seen from FIG. 7, the glass blended with TeO ₂ has a low light transmittance in a wide wavelength range of 400 to 1600 nm, specifically 10% or less. In contrast, the glass containing Fe ₂ O ₃ has a reduced light transmittance around 1050 nm, and can absorb, for example, Nd: YAG laser light, etc., but compared with glass containing TeO _2. It can be seen that the wavelength range in which the transmitted light intensity decreases is narrow, and the decrease in light transmittance is insufficient. Further, it can be seen that the light transmittance of the glass blended with CuO is almost the same as that of the glass before blending although the ultraviolet absorption edge is on the long wavelength side.

Moreover, tin TeO ₂ content - phosphate glass composition, since it is possible to blacken a relatively small amount of TeO _2, to maintain a low softening temperature by the fundamental component (P ₂ O ₅ and SnO) And an increase in the glass transition temperature (Tg) can be suppressed. The glass transition temperature (Tg) of the sealing glass is preferably in the range of 240 to 310 ° C. By using the sealing glass made of the tin-phosphate glass composition of this embodiment, it becomes possible to lower the sealing temperature by the light beam emitted from the laser light source or the high-intensity light source. Moreover, since it is hard to crystallize compared with the conventional tin-phosphate type glass composition, it becomes possible to apply the paste of sealing material to a sealing process. This contributes to the improvement of mass productivity in the sealing process.

The sealing material contains the sealing glass (tin-phosphate glass composition) and the low expansion filler described above. The low expansion filler is at least one selected from silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, cordierite, eucryptite, spodumene, zirconium phosphate compound, tin oxide compound, and quartz solid solution. It is preferable to use seeds. 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 , Na _0.5 Nb _0.5 Zr _1.5 ( PO ₄ ) ₃ , K _0.5 Nb _0.5 Zr _1.5 (PO ₄ ) ₃ , Ca _0.25 Nb _0.5 Zr _1.5 (PO ₄ ) ₃ , NbZr (PO ₄ ) ₃ , Zr ₂ (WO ₃ ) (PO ₄ ) ₂ , these Examples include complex compounds. The low expansion filler has a lower thermal expansion coefficient than the sealing glass which is the main component of the sealing material.

  The content of the low expansion filler is preferably in the range of 0.1 to 50% by volume with respect to the sealing material. When the content of the low expansion filler is less than 0.1% by volume, the thermal expansion coefficient of the sealing material cannot be sufficiently reduced. When the thermal expansion coefficient of the sealing material is large, residual stress is likely to be generated at or near the bonding interface between the glass substrates 2 and 3 and the sealing layer 6 due to a local rapid heating / quenching process using a light beam. Residual stress generated at or near the bonding interface may cause cracks or cracks in the glass substrates 2, 3 and the sealing layer 6, and the bonding strength and bonding reliability between the glass substrates 2, 3 and the sealing layer 6. It will cause the decrease. When the content of the low expansion filler exceeds 50% by volume, the fluidity at the time of melting of the sealing material is lowered, and cracks and cracks of the glass substrates 2 and 3 and the sealing layer 6 are generated. Decrease in adhesion strength and adhesion reliability with the sealing layer is likely to occur.

  As described above, the sealing material containing the sealing glass composed of the tin-phosphate glass composition of this embodiment is such that the sealing glass has a sufficient light absorption rate in a wide wavelength range and has a glass transition. Since temperature (Tg) is low, the sealing process using the light beam irradiated from a laser light source or a high-intensity light source can be implemented at low temperature. Moreover, since the sealing glass itself has a sufficient light absorption rate, it is not necessary to add a light absorbing material separately, and the fluidity of the sealing material during the sealing process is increased as compared with the case where a light absorbing material is added. be able to. Therefore, it is possible to achieve both the lowering of the formation temperature (sealing temperature) of the sealing layer 6 and the improvement of the hermetic sealing property by the sealing layer 6.

  The electronic device 1 of this embodiment is manufactured as follows, for example. First, as shown in FIG. 2A, a first glass substrate 2 and a second glass substrate 3 having a sealing material layer 7 are prepared. The sealing material layer 7 is prepared by mixing a sealing material containing a sealing glass and a low expansion filler with a vehicle to prepare a sealing material paste, which is then applied to the sealing region 5 of the second glass substrate 3. It is formed by drying and baking after coating. The specific configurations of the sealing glass and the low expansion filler are as described above.

  Vehicles used for the preparation of the sealing material paste include resins such as methylcellulose, ethylcellulose, carboxymethylcellulose, oxyethylcellulose, benzylcellulose, propylcellulose, and nitrocellulose, and solvents such as terpineol, butylcarbitol acetate, and ethylcarbitol acetate. Acrylic resins such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl methacrylate, and the like dissolved in methyl ethyl ketone, terpineol, butyl carbitol acetate, ethyl carbitol acetate And those dissolved in a solvent such as

  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 and the ratio of the sealing material and the vehicle. A known additive may be added to the sealing material paste as a glass paste such as a solvent for dilution, 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.

  A sealing material paste is applied to the sealing region 5 of the second glass substrate 3 and dried to form an application layer of the sealing material paste. The sealing material paste is applied onto the second sealing region 5 by applying a printing method such as screen printing or gravure printing, or is applied along the second sealing region 5 using a dispenser or the like. To do. The coating layer of the sealing material paste is preferably dried at a temperature of 120 ° C. or more for 10 minutes or more, for example. A drying process is implemented in order to remove the solvent in an application layer. If the solvent remains in the coating layer, the binder component may not be sufficiently removed in the subsequent firing step.

  The sealing material layer 7 is formed by baking the coating layer of the sealing material paste described above. In the firing step, first, the coating layer is heated to a temperature not higher than the glass transition temperature (Tg) of the sealing glass (tin-phosphate glass composition) which is the main component of the sealing material, and the binder component in the coating layer is heated. After the removal, the sealing material is heated to a temperature equal to or higher than the softening temperature of the sealing glass, and the sealing material is melted and baked on the glass substrate 3. In this way, the sealing material layer 7 composed of the fired layer of the sealing material is formed.

  Next, as shown in FIG.2 (b), the 1st glass substrate 2 and the 2nd glass substrate 3 are laminated | stacked through the sealing material layer 7 so that those surfaces 2a and 3a may oppose. To do. Next, as shown in FIG. 2C, the sealing material layer 7 is irradiated with a light beam 8 such as a laser beam through the second glass substrate 3 (or the first glass substrate 2). For example, the light beam 8 is irradiated while scanning along the frame-shaped sealing material layer 7. The laser light is not particularly limited, and laser light from a semiconductor laser, carbon dioxide laser, excimer laser, YAG laser, HeNe laser, or the like is used. The light beam is not limited to 8 laser light, and may be a light beam emitted from a high-luminance light source.

  The sealing material layer 7 is melted in order from the portion irradiated with the light beam 8 scanned along the sealing material layer 7, and is rapidly solidified at the end of the irradiation of the light beam 8 to be fixed to the first glass substrate 2. Then, by irradiating the entire circumference of the sealing material layer 7 with the light beam 8, the sealing between the first glass substrate 2 and the second glass substrate 3 is sealed as shown in FIG. A landing layer 6 is formed. In this way, the electronic device 1 in which the electronic element portion is hermetically sealed with the glass panel constituted by the first glass substrate 2, the second glass substrate 3, and the sealing layer 6 is produced. The sealing glass is not limited to the sealing of the electronic device 1 but can be applied to sealing of an electronic component package, a lighting bulb, a glass member such as a multilayer glass, and the like.

  Next, specific examples of the present invention and evaluation results thereof will be described. The following description does not limit the present invention.

(Examples 1-31)
Sn ₂ P ₂ O ₇ , SnO, ZnO, TeO ₂ , Zn (PO ₃ ) ₂ , Ca (PO ₃ ) ₂ , SrCO ₃ , B ₂ O ₃ , Ga ₂ so that the compositions shown in Tables 1 to 3 are obtained. Each raw material powder of O ₃ , GeO ₂ , In ₂ O ₃ , La ₂ O ₃ , and WO ₃ was prepared so that the total amount of all components was 200 g, and these preparations were mixed well. Each mixed powder was put into a quartz crucible, covered with a quartz lid, and melted in an electric furnace at 950 ° C. for 30 minutes. Thereafter, the lid was removed, and the melt was poured onto the carbon plate and quenched to obtain glasses. The above steps were all performed in a glove box with a dry nitrogen atmosphere.

  About each obtained glass, the glass transition temperature (Tg) and the light transmittance were measured as follows. The glass transition temperature (Tg) was measured at a rate of temperature increase of 10 ° C./min using a differential thermal analyzer (product name: Thermo Plus TG8110) filled with 250 mg of a sample processed into a powder form in a platinum pan. . The light transmittance is obtained by measuring the linear light transmittance in the wavelength range of 400 to 1600 nm with a spectrophotometer (manufactured by PerkinElmer, product name: Lambda 950) for a sample obtained by processing glass to a thickness of 2 mm and mirroring the front and back surfaces. ). Tables 1 to 3 show the glass transition temperature (Tg) and light transmittance of each glass.

(Comparative Examples 1-4)
As shown in Table 3, a formulation not containing TeO ₂ (Comparative Examples 1 and 2) and a formulation containing Fe ₂ O ₃ (Comparative Example 3) and CuO (Comparative Example 4) instead of TeO ₂ Using the product, a glass was produced in the same manner as in Example 1. For these glasses, the glass transition temperature (Tg) and light transmittance were measured in the same manner as in Example 1. The results are also shown in Table 3.

As is clear from Tables 1 to 3, it can be seen that all the glasses according to Examples 1 to 31 have low light transmittance and have sufficient light absorption ability in a wide wavelength range. Further, as compared with Comparative Examples 1-2 not blended with TeO _2, it can be seen increase in glass transition temperature (Tg) of is also negligible. Therefore, it turns out that the glass composition of Examples 1-31 is suitable for the glass for sealing heated with light beams, such as a laser beam.

(Example 32)
The black glass produced in Example 1 was crushed and sieved to obtain a tin-phosphate glass powder having an average particle size of about 6 μm (maximum particle size of 40 to 70 μm). Next, 60% by mass of tin-phosphate glass powder and 40% by mass of zirconium phosphate powder were mixed to prepare a sealing material (sealing glass material). A sealing material paste was prepared by mixing 90% by mass of the sealing material and 10% by mass of the vehicle. The vehicle is obtained by dissolving nitrocellulose (1.2% by mass) as a binder component in a solvent (98.8% by mass) such as butyl carbitol acetate.

  Next, a sealing material paste was applied to a glass substrate made of soda lime glass by a screen printing method so as to have a line width of 1 mm, and then dried at 120 ° C. for 10 minutes. The coating layer of the sealing material paste after drying was heated to 250 ° C. at a temperature rising rate of 15 ° C./min and treated to remove the binder, and then heated to 460 ° C. at a temperature rising rate of 30 ° C./min. Baked for 10 minutes. In this way, a sealing material layer having a film thickness of 65 μm was formed.

  A test sample was prepared by laminating the glass substrate on which the sealing material layer described above was formed and a glass substrate made of soda lime glass having the same composition. Next, the sealing material layer is irradiated with a semiconductor laser having a wavelength of 940 nm while scanning at a scanning speed of 5 mm / second through the glass substrate, and the sealing material layer is melted and rapidly cooled and solidified, thereby sealing the glass substrate. A wearing test was conducted. Table 4 shows the results of the sealing test with each output semiconductor laser.

(Example 33)
Similarly to Example 32, a test sample was prepared using the black glass of Example 2. However, the film thickness of the sealing material layer after firing was 52 μm. Next, a sealing test of the glass substrate is performed by irradiating the adhesive material layer through the glass substrate while scanning with a semiconductor laser having a wavelength of 940 nm at a scanning speed of 5 mm / second to melt and rapidly solidify the sealing material layer. Went. Table 4 shows the results of the sealing test with each output semiconductor laser.

  As is apparent from Table 4, when the black glass of Example 1 was used, it was able to adhere (seal) well in the range of output 70 to 150 W. In this test, the glass substrate was not broken, and it was confirmed that the glass could be used for sealing. Moreover, when the black glass of Example 2 was used, although the adhesion was insufficient at an output of 70 W or less, it was able to be adhered (sealed) well in the range of an output of 75 to 150 W. In this test, it was found that there is no condition that the glass substrate breaks, and that the glass can be used for high output. As is clear from the results of these Examples, it can be seen that various types of glass panels produced using the sealing glass of Examples are effective for electronic devices.

  DESCRIPTION OF SYMBOLS 1 ... Electronic device, 2 ... 1st glass substrate, 2a ... 1st surface, 3 ... 2nd glass substrate, 3a ... 2nd surface, 4 ... 1st sealing area | region, 5 ... 2nd sealing Stop region, 6 ... sealing layer, 7 ... sealing material layer, 8 ... light beam.

Claims (10)

27 to 33% P ₂ O ₅ , 50 to 70% SnO, 0.5 to 3% TeO ₂ , 0 to 10% ZnO, 0 to 5% CaO, expressed as mole percent on an oxide basis. 0-5% SrO, 0-5% B ₂ O ₃ , 0-5% Ga ₂ O ₃ , 0-3% GeO ₂ , 0-3% In ₂ O ₃ , 0-3% A glass for light heat sealing, comprising a glass composition containing La ₂ O ₃ and 0 to 3% of WO ₃ .   The light heating according to claim 1, wherein when the glass composition is vitrified and mirror-polished to a 2 mm thick plate, the linear light transmittance in a wavelength range of 400 to 1600 nm is 10% or less. Glass for sealing. 3. The glass for heat sealing according to claim 1, wherein the total content of P ₂ O ₅ and SnO in the glass composition is in the range of 85 to 99% in terms of mol% based on oxide. . The content of P ₂ O _{5 in} the glass composition is in the range of 30 to 32% in terms of mol% on the basis of oxides, and is sealed by light heating according to any one of claims 1 to 3. Glass.   5. The photosealing seal according to claim 1, wherein the CaO content of the glass composition is in the range of 0.5 to 3% in terms of oxide-based mol%. Glass.   The glass for glass for heat-sealing according to any one of claims 1 to 5, wherein the glass transition temperature is in the range of 240 to 310 ° C. A glass substrate having a sealing region;
The sealing material which consists of a baking layer of the sealing material which is provided on the said sealing area | region of the said glass substrate, and contains the glass for light heating sealing of any one of Claim 1 thru | or 6, and a low expansion filler. A glass member with a sealing material layer.   The low expansion filler is selected from silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, cordierite, eucryptite, spodumene, zirconium phosphate compound, tin oxide compound, quartz solid solution, and mica. The glass member with a sealing material layer according to claim 7, comprising at least one kind, wherein the sealing material contains the low expansion filler in a range of 0.1 to 50% by mass. A first glass substrate having a first surface with a first sealing region;
The first glass substrate has a second surface including a second sealing region corresponding to the first sealing region, and the second surface faces the first surface. A second glass substrate disposed with a predetermined gap between
An electronic element unit provided between the first glass substrate and the second glass substrate;
2. The device is formed between the first sealing region of the first glass substrate and the second sealing region of the second glass substrate so as to seal the electronic element portion. An electronic device comprising: a sealing layer formed of a melt-fixed layer of a sealing material containing the glass for light heat sealing according to any one of 1 to 6 and a low expansion filler. Providing a first glass substrate having a first surface with a first sealing region;
The second sealing region corresponding to the first sealing region and the second heat-sealing glass and the low expansion formed on the second sealing region, respectively. Providing a second glass substrate having a second surface comprising a sealing material layer comprising a fired layer of a sealing material containing a filler;
Laminating the first glass substrate and the second glass substrate via the sealing material layer such that the first surface and the second surface are opposed to each other;
The sealing material layer is irradiated with laser light through the first glass substrate or the second glass substrate and heated to melt the sealing material layer, thereby the first glass substrate and the second glass. And a step of forming a sealing layer for sealing an electronic element portion provided between the substrate and the substrate.

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