JP6156675B2 - Manufacturing method of glass package - Google Patents

Description

  The present invention relates to a method for manufacturing a glass package, and more specifically to a method for manufacturing a glass package for performing a sealing process using a laser (hereinafter referred to as laser sealing).

  In recent years, organic EL devices such as organic EL displays have attracted attention. Non-silicon type solar cells such as dye-sensitized solar cells and thin film compound solar cells are also attracting attention. At present, these glass packages have been put to practical use.

  The organic EL display can be driven by a DC voltage, so that the drive circuit can be simplified. Unlike the liquid crystal display, the organic EL display has advantages such as no dependency on the viewing angle, bright due to self-emission, and high response speed. . Currently, organic EL displays are mainly used in small portable devices such as mobile phones, but in the future, application to ultra-thin televisions is expected. Note that the organic EL display is mainly driven by disposing an active element such as a thin film transistor (TFT) in each pixel in the same manner as a liquid crystal display.

  The organic EL display is composed of two glass substrates, a negative electrode such as metal, an organic light emitting layer, a positive electrode such as ITO, and an adhesive material. Conventionally, an organic resin adhesive material such as an epoxy resin having a low temperature curability or an ultraviolet curable resin has been used as the adhesive material. However, organic resin adhesive materials cannot completely block gas intrusion. For this reason, when an organic resin adhesive material is used, the airtightness inside the organic EL display cannot be maintained, and as a result, the organic light emitting layer having low water resistance is easily deteriorated, and the organic EL display There is a problem that the display characteristics of the display deteriorate with time. In addition, the organic resin-based adhesive material has an advantage that the glass substrates can be bonded to each other at a low temperature. However, since the water resistance is low, when the organic EL display is used for a long time, the reliability of the display is likely to be lowered. .

Further, the dye-sensitized solar cell includes a glass substrate on which a transparent conductive film is formed, and a porous oxide semiconductor electrode composed of a porous oxide semiconductor layer (mainly a TiO ₂ layer) formed on the glass substrate. And a dye such as Ru dye adsorbed on the porous oxide semiconductor electrode, an iodine electrolyte containing iodine, a glass substrate on which a catalyst film and a transparent conductive film are formed, and the like.

  A conventional dye-sensitized solar cell has a structure in which the outer peripheral edges of a pair of glass substrates are bonded with an organic resin-based adhesive material. However, when an organic resin adhesive material is used, the organic resin adhesive material is eroded by the iodine electrolyte solution, and the iodine electrolyte solution leaks from the dye-sensitized solar cell, which may significantly deteriorate the battery characteristics.

In a thin film compound solar cell, for example, a CIGS solar cell, a chalcopyrite compound semiconductor made of Cu, In, Ga, and Se, Cu (InGa) Se ₂ is formed on a glass substrate as a photoelectric conversion film. These non-silicon type solar cells have a structure sandwiched between a pair of glass substrates.

Conventional thin-film compound solar cells have a structure in which the outer peripheral edges of a pair of glass substrates are bonded with an organic resin-based adhesive material. As described above, the organic resin-based adhesive material cannot completely block gas intrusion. For this reason, when an organic resin adhesive material is used, the long-term reliability of the thin-film compound solar cell may be reduced due to intrusion of gas (H ₂ O or the like).

  When the outer peripheral edges of the pair of glass substrates are hermetically sealed with an inorganic sealing material, the above-described problems can be solved. As such a sealing material, a sealing material containing glass powder and a refractory filler is promising.

  In the case of hermetically sealing using this sealing material, it is necessary to heat-treat the sealing material to soften and flow.

  However, if the sealing material is heat-treated to a temperature range where it softens and flows with an electric furnace or the like, the characteristics of the organic EL device and the elements of the non-silicon type solar cell may be thermally deteriorated.

JP 2008-166197 A

  In view of the above circumstances, in recent years, laser sealing has been studied as a sealing method for sealing materials. According to laser sealing, since only the portion to be sealed can be locally heated, it is possible to hermetically seal the glass substrates together while preventing thermal degradation of the elements and the like.

  However, with laser sealing, it is difficult to obtain a desired sealing strength. This is because the material strength of the sealing material layer is lower than the strength of the glass substrate, and due to the difference in thermal expansion coefficient between the glass substrate and the sealing material layer, undue stress is applied to the glass substrate and the sealing material layer after laser sealing. Is due to residual.

  By the way, glass packages such as organic EL displays and non-silicon type solar cells are rapidly increasing in size and thickness, and along with this, the size and thickness of glass substrates are also increasing rapidly. When the glass substrate becomes larger and thinner, the glass substrate is likely to be bent. Therefore, in the glass package, the glass substrates may come into contact with each other, and there is a possibility that an element or the like may be damaged. In order to prevent contact between the glass substrates, the gap between the glass substrates needs to be large to some extent, and the gap needs to be kept uniform.

  However, when using the above sealing material, it is difficult to increase the gap between the glass substrates, and it is also difficult to increase the accuracy. And it becomes difficult to ensure sealing strength, so that the gap between glass substrates is large.

  Therefore, the present invention has been made in view of the above circumstances, and its technical problem is that the gap between the glass substrates can be easily widened, the gap can be easily uniformed, and the glass substrates can be hermetically sealed. It is to secure the reliability of a large and thin glass package by creating a glass glass manufacturing method that can be used.

As a result of intensive studies, the inventors have arranged a glass film between glass substrates and a sealing material layer between the glass substrate and the laser to form a large gap with high accuracy. The present inventors have found that the above technical problem can be solved by sealing, and propose as the present invention. That is, the glass package manufacturing method of the present invention is a glass package manufacturing method in which the first glass substrate and the second glass substrate are hermetically sealed, and a step of forming a glass film by a downdraw method, The first glass substrate is the first sealing material layer, the second glass substrate is the second sealing material layer, and the glass film is the first sealing material layer and the second sealing material layer. laminating placed it in contact respectively against the first sealing material layer from the first glass substrate is irradiated with laser, it possesses a step of dissolving the first sealing material layer, The first sealing material layer and the second sealing material layer are sintered bodies of the sealing material, and the sealing material contains bismuth glass containing at least 5 to 30 mol% of CuO + Fe ₂ O _3. characterized in that it. Here, the “glass film” refers to glass having a thickness of 5 to 500 μm. In the present invention, as long as the first glass substrate, the first sealing material layer, the glass film, the second sealing material layer, and the second glass substrate are stacked in this order, the first It does not matter whether the member on which the sealing material layer is formed is the first glass substrate or the glass film. Similarly, it does not matter whether the member on which the second sealing material layer is formed is the second glass substrate or the glass film.

  By irradiating the first sealing material layer with laser from the first glass substrate side, it becomes possible to hermetically seal the first glass substrate and the glass film, and the second glass substrate and the glass film. Can be hermetically sealed between the first glass substrate and the second glass substrate. Further, the glass film can secure a large gap and increase the dimensional accuracy of the gap. The glass film can reduce the thickness of the first sealing material layer and the second sealing material layer, and as a result, the residual stress of the sealing material layer (sealing portion) is reduced. This makes it easier to ensure the desired sealing strength.

Various lasers can be used as the laser. In particular, a semiconductor laser, a YAG laser, a CO ₂ laser, an excimer laser, an infrared laser, and the like are preferable in terms of easy handling.

  It is preferable that the second glass substrate has no heat sensitive elements or the like formed thereon. If it does in this way, when irradiating a laser from the 1st glass substrate side, an element etc. become difficult to thermally deteriorate.

  FIG. 1 is a conceptual cross-sectional view for explaining an example of a method for producing a glass package 1 of the present invention. In FIG. 1A, a first sealing material layer 11 and a second sealing material layer 12 are formed on both surfaces of the glass film 13. In FIG. 1B, a glass film 13 is interposed between the first glass substrate 14 and the second glass substrate 15, and the first glass substrate 14 is interposed between the first glass substrate 14 and the first glass substrate 14. The sealing material layer 11 is interposed, and the second sealing material layer 12 is interposed between the glass film 13 and the second glass substrate 15. In FIG. 1B, a gap is provided between the first sealing material layer 11 and the first glass substrate 14 and between the second sealing material layer 12 and the second glass substrate 15. Although in actual arrangements, they are in contact. FIG. 1C shows the glass package 1 after the first glass substrate 14 and the second glass substrate 15 are hermetically sealed by irradiating a laser from the first glass substrate 14 side of FIG. FIG.

  FIG. 2 is a conceptual cross-sectional view for explaining an example of the method for manufacturing the glass package 1 of the present invention. In FIG. 2A, the first sealing material layer 11 is formed on one surface of the glass film 13. In FIG. 2B, the glass film 13 is interposed between the first glass substrate 14 and the second glass substrate 15. In addition, the first sealing material layer 11 is interposed between the glass film 13 and the first glass substrate 14. The second sealing material layer 12 is interposed between the glass film 13 and the second glass substrate 15, and the second sealing material layer 12 is formed on the surface of the second glass substrate 15. ing. In FIG. 2B, spaces are provided between the first sealing material layer 11 and the first glass substrate 14 and between the glass film 13 and the second sealing material layer 12. However, in an actual arrangement, they are in contact. FIG. 2C shows the glass package 1 after the first glass substrate 14 and the second glass substrate 15 are hermetically sealed by laser irradiation from the first glass substrate 14 side of FIG. FIG.

  In the method for producing a glass package of the present invention, the first sealing material layer and the second sealing material layer are irradiated by irradiating a laser to the first sealing material layer from the first glass substrate side. It is preferable to dissolve. In this way, since the glass package is hermetically sealed by a single laser irradiation, the manufacturing efficiency of the glass package is improved.

  It is preferable that the manufacturing method of the glass package of this invention has the process of irradiating a laser with respect to a 2nd sealing material layer from the 2nd glass substrate side, and melt | dissolving a 2nd sealing material layer. . In this way, the sealing strength between the second glass substrate and the second sealing material layer is improved.

  The method for producing a glass package of the present invention preferably includes a step of forming a first sealing material layer and / or a second sealing material layer on the surface of the glass film. In this way, it is not necessary to form a sealing material layer on the surface of the glass substrate, and the productivity of the device is improved. In addition, when the sealing material layer is formed only on one surface of the glass film, one glass substrate (side on which the sealing material layer is not formed on the glass film) in order to ensure the airtight reliability of the device. A sealing material layer may be formed on the surface.

  In the method for producing a glass package of the present invention, the step of forming the first sealing material layer on the surface of the first glass substrate and / or the formation of the second sealing material layer on the surface of the second glass substrate. It is preferable to provide a process. If it does in this way, the sealing strength between a glass substrate and a sealing material layer will improve, and it will become difficult to peel a glass substrate and a sealing material layer.

  The method for producing a glass package of the present invention includes a step of mixing a sealing material and a vehicle to produce a sealing material paste, sintering the sealing material paste, and a first sealing material layer and / or Or it is preferable to provide the process of forming a 2nd sealing material layer. If it does in this way, it will become easy to reduce the thickness of a sealing material layer. Further, the surface accuracy of the sealing material layer is improved, and the gap between the first glass substrate and the second glass substrate is easily made uniform.

  In the method for producing a glass package of the present invention, the glass film, the first sealing material layer, and the second sealing material layer are preferably disposed on the outer peripheral edges of the first glass substrate and the second glass substrate. . In this way, the effective surface of the glass package is increased, and laser sealing can be performed efficiently. If a frame-shaped glass film is used, the glass film, the first sealing material layer, and the second sealing material layer can be disposed on the outer peripheral edges of the first glass substrate and the second glass substrate. It becomes easy.

The method of manufacturing glass package of the present invention, the first sealing material layer and / or the second sealing material layer including a transition metal oxide.

  In the method for producing a glass package of the present invention, the thickness of the second sealing material layer is preferably smaller than the thickness of the first sealing material layer. In this way, the glass package can be easily hermetically sealed by a single laser irradiation.

  In the method for producing a glass package of the present invention, the content of the transition metal oxide in the second sealing material layer is preferably made larger than the content of the transition metal oxide in the first sealing material layer. In this way, the glass package can be easily hermetically sealed by a single laser irradiation.

  A glass package according to the present invention is a glass package manufactured by the method for manufacturing a glass package of the present invention, wherein the first glass substrate and the second glass substrate are hermetically sealed, A glass film is interposed between the one glass substrate and the second glass substrate, and the first glass substrate and the glass film are sealed and integrated by the first sealing material layer; and The second glass substrate and the glass film are sealed and integrated by the second sealing material layer. If it does in this way, it becomes easy to achieve the enlargement and thickness reduction of a glass package, after ensuring the reliability of a glass package.

  The glass package according to the present invention preferably has a glass film thickness of 300 μm or less. If it does in this way, it will become easy to achieve thickness reduction of a glass package.

  In the glass package according to the present invention, the thickness of the first sealing material layer and the second sealing material layer is preferably 20 μm or less. In this way, the laser sealing property is improved and the residual stress in the sealing material layer is reduced, so that a desired sealing strength can be easily ensured.

  In the glass package according to the present invention, the glass film is preferably alkali-free glass. Since alkali-free glass has a low coefficient of thermal expansion, it is difficult for a glass film to crack during laser sealing. Furthermore, since alkali-free glass has a high strain point and hardly undergoes thermal shrinkage or the like, the size of the glass film hardly changes even after the heat treatment step, and as a result, the gap between the glass substrates hardly changes.

  In the glass package according to the present invention, the first glass substrate and the second glass substrate are preferably alkali-free glass. Since alkali-free glass has a low coefficient of thermal expansion, it is difficult for a glass substrate to crack during laser sealing. Further, since the alkali-free glass has a high strain point and hardly undergoes thermal shrinkage or the like, the size of the glass substrate hardly changes even after the heat treatment step, and as a result, the gap between the glass substrates hardly changes.

  In the glass package according to the present invention, the glass package is preferably an organic EL device or a non-silicon type solar cell.

It is a cross-sectional conceptual diagram for demonstrating an example of the manufacturing method of the glass package of this invention. It is a cross-sectional conceptual diagram for demonstrating an example of the manufacturing method of the glass package of this invention. It is a schematic diagram which shows the softening point Ts when it measures with a macro type | mold DTA apparatus.

  In the manufacturing method of the glass package of this invention, the thickness of a glass film is 5-500 micrometers, Preferably it is 10-300 micrometers, Especially 50-200 micrometers. If it does in this way, it will become easy to achieve thickness reduction of a glass package, after preventing contact between glass substrates. In addition, when the thickness of a glass film is too small, it will become difficult to ensure the gap between glass substrates.

  In the method for producing a glass package of the present invention, the shape of the glass film is not limited, and may be a strip shape, a frame shape, or the like. Among them, the shape of the glass film is preferably a frame shape. In particular, it is preferable that the outer dimensions of the frame are substantially the same as the outer dimensions of the first glass substrate and / or the second glass substrate. This facilitates the alignment of the first glass substrate and / or the second glass substrate and the glass film, improves the manufacturing efficiency of the glass package, and improves the reliability of laser sealing (for example, airtight reliability). Property).

  The material of the glass film is not particularly limited, and alkali-free glass, borosilicate glass, soda lime glass, or the like can be used. Among these, alkali-free glass is preferable for the above reasons. Moreover, it is preferable that the material of a glass film is the same as the material of a 1st glass substrate and / or a 2nd glass substrate. In this way, the residual stress in the sealing material layer can be reduced.

The thermal expansion coefficient of the glass film is preferably 40 × 10 ^{−7 to} 90 × 10 ⁻⁷ / ° C. If it does in this way, while a glass film becomes difficult to break at the time of laser sealing, unreasonable residual stress becomes difficult to produce in the 1st glass substrate, the 2nd glass substrate, a glass film, and a sealing material layer.

  The glass film can be produced by a known method, but the glass film according to the present invention is produced by a down draw method (redraw method, slot down draw method, overflow down draw method).

  If the molding is performed by the downdraw method (redraw method, slot downdraw method, overflow downdraw method), the surface accuracy of the glass film is improved and the thickness of the glass film is easily uniformed.

  The first sealing material layer according to the present invention is preferably formed by sintering the sealing material on the surface of the first glass substrate or glass film, and sintering the powder-shaped sealing material. It is preferable to become. Further, the second sealing material layer according to the present invention is preferably formed by sintering the sealing material on the surface of the second glass substrate or glass film, and sintering the powder-shaped sealing material. It is preferable to let it be. In this way, it becomes easy to hermetically seal the glass substrates together by laser sealing. If it does in this way, it will become easy to reduce the thickness of a sealing material layer. Further, the surface accuracy of the sealing material layer is improved, and the gap between the first glass substrate and the second glass substrate is easily made uniform.

  In the sealing material according to the present invention, the softening point is preferably 460 ° C. or lower, 420 ° C. or lower, and particularly preferably 400 ° C. or lower. When the softening point is too high, the laser sealing property tends to be lowered. The lower limit of the softening point is not particularly limited, but the softening point is preferably 350 ° C. or higher in consideration of the thermal stability of the glass powder, particularly the SnO-containing glass powder. The “softening point” refers to a value measured with a macro-type differential thermal analysis (DTA) apparatus in a nitrogen atmosphere. DTA starts measurement from room temperature, and the rate of temperature rise is 10 ° C./min. And the softening point measured with the macro type | mold DTA apparatus points out the temperature (Ts) of the 4th bending point shown in FIG.

The thermal expansion coefficient of the sealing material (the first sealing material layer and / or the second sealing material layer) is preferably 40 × 10 ^{−7 to} 90 × 10 ⁻⁷ / ° C. If it does in this way, it will become difficult to produce an undue residual stress in a glass substrate, a glass film, and a sealing material layer.

Sealing materials, you containing glass powder. In this way, the glass substrates can be hermetically sealed by laser sealing.

Glass powder according to the present invention, bismuth-based glass can be used. In addition, "... series glass" refers to the glass which contains 10 mol% or more of an explicit component.

Bismuth-based glass in order to soften flow at low temperatures, tend to reduce heat damage of the electrode or the like at the time of laser sealing.

The bismuth-based glass powder is, as a glass composition, in terms of the following oxide, in mol%, Bi ₂ O ₃ 20 to 60%, B ₂ O ₃ 10 to 35%, ZnO 5 to 40%, CuO + Fe ₂ O ₃ 5 It is preferable to contain 30%. If it does in this way, while the softening point of glass powder will fall, a sealing material layer will absorb laser energy directly, and can be efficiently converted into thermal energy. As a result, laser sealing can be completed at a low temperature in a short time, and the sealing strength can be increased during laser sealing. The reason for limiting the content of each component as described above will be described below. In the description of the glass composition range, “%” indicates mol% unless otherwise specified.

Bi ₂ O ₃ is a main component for lowering the softening point, and its content is preferably 20 to 60%, 25 to 55%, particularly 30 to 55%. If the content of Bi ₂ O ₃ is less than 20%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with a laser. On the other hand, when the content of Bi ₂ O ₃ is more than 60%, the glass becomes thermally unstable, and the glass is easily devitrified at the time of melting or laser sealing.

B ₂ O ₃ is a component that forms a glass network of bismuth-based glass, and the content thereof is preferably 10 to 35%, 15 to 30%, particularly 15 to 28%. When the content of B ₂ O ₃ is less than 10%, the glass becomes thermally unstable, and the glass tends to be devitrified at the time of melting or laser sealing. On the other hand, if the content of B ₂ O ₃ is more than 35%, the softening point becomes too high and the glass is difficult to soften even when irradiated with a laser.

  ZnO is a component that suppresses devitrification at the time of melting or laser sealing and lowers the coefficient of thermal expansion, and its content is preferably 5 to 40%, 5 to 35%, particularly 5 to 33%. It is. If the ZnO content is less than 5%, it is difficult to obtain the above effect. On the other hand, when the ZnO content is more than 40%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.

CuO + Fe ₂ O ₃ is a component having light absorption characteristics, and when irradiated with a laser having a predetermined emission center wavelength, CuO + Fe ₂ O ₃ is a component that absorbs the laser and softens the glass. CuO + Fe ₂ O ₃ is a component that suppresses devitrification at the time of melting or laser sealing. The content of CuO + Fe ₂ O ₃ is 5 to 30% , preferably 7 to 25%, particularly 10 to 20%. When the content of CuO + Fe ₂ O ₃ is less than 5%, the light absorption characteristics are poor, and the glass is difficult to soften even when irradiated with a laser. On the other hand, when the content of CuO + Fe ₂ O ₃ is more than 30%, is impaired balance of components in the glass composition, the glass is liable to devitrify reversed.

  CuO is a component having light absorption characteristics. When irradiated with a laser having a predetermined emission center wavelength, CuO is a component that absorbs the laser and softens the glass, and loses it when melted or sealed. It is a component that suppresses see-through. The content of CuO is preferably 0 to 25%, 5 to 25%, 10 to 25%, particularly 10 to 20%. When there is more content of CuO than 25%, the component balance in a glass composition will be impaired, and it will become easy to devitrify glass conversely. If the CuO content is regulated to 5% or more, the light absorption characteristics are improved, and the glass is easily softened during laser sealing.

Fe ₂ O ₃ is a component having light absorption characteristics. When irradiated with a laser having a predetermined emission center wavelength, it is a component that absorbs the laser and softens the glass, and at the time of melting or laser sealing. It is a component that suppresses devitrification. The content of Fe ₂ O ₃ is preferably 0 to 10%, 0.1 to 10%, 0.2 to 10%, particularly 0.5 to 10%. When the content of Fe ₂ O ₃ is more than 10%, is impaired balance of components in the glass composition, the glass is liable to devitrify reversed. If the content of Fe ₂ O ₃ is regulated to 0.1% or more, the light absorption characteristics are improved, and the glass is easily softened during laser sealing.

Fe ions in iron oxide exist in the state of Fe ²⁺ or Fe ³⁺ . In the present invention, Fe ions in iron oxide are not limited to either Fe ²⁺ or Fe ³⁺ , and may be any. Therefore, in the present invention, even Fe ²⁺ is handled after being converted to Fe ₂ O ₃ . In particular, when an infrared laser is used as the irradiation light, since Fe ²⁺ has an absorption peak in the infrared region, the ratio of Fe ²⁺ is preferably large. For example, the ratio of Fe ²⁺ / Fe ^{3+ in} iron oxide is 0. It is preferable to regulate to 0.03 or more (preferably 0.08 or more).

  In addition to the above components, for example, the following components may be added.

SiO ₂ is a component that improves water resistance. The content of SiO ₂ is preferably 0 to 10%, in particular 0 to 3%. If the content of SiO ₂ is more than 10%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with a laser.

Al ₂ O ₃ is a component that improves water resistance. The content of Al ₂ O ₃ is preferably 0 to 5%, particularly 0 to 2%. When the content of Al ₂ O ₃ is more than 5%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with a laser.

  MgO + CaO + SrO + BaO (total amount of MgO, CaO, SrO and BaO) is a component that suppresses devitrification at the time of melting or laser sealing, and the content of MgO + CaO + SrO + BaO is preferably 0 to 20%, particularly 0 to 15%. It is. If the content of MgO + CaO + SrO + BaO is more than 20%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with a laser.

  MgO, CaO and SrO are components that suppress devitrification during melting or laser sealing. The content of each component is preferably 0 to 5%, particularly 0 to 2%. If the content of each component is more than 5%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with a laser.

  BaO is a component that suppresses devitrification during melting or laser sealing. The content of BaO is preferably 0 to 15%, in particular 0 to 10%. When the content of BaO is more than 15%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with a laser.

CeO ₂ and Sb ₂ O ₃ are components that suppress devitrification during melting or laser sealing. The content of each component is preferably 0 to 5%, 0 to 2%, particularly 0 to 1%. When there is more content of each component than 5%, the component balance in a glass composition will be impaired, and conversely, it will become easy to devitrify glass. From the viewpoint of enhancing the thermal stability, it is preferable to add a small amount of Sb ₂ O ₃ , and specifically, it is preferable to add 0.05% or more of Sb ₂ O ₃ .

WO ₃ is a component that suppresses devitrification at the time of melting or laser sealing. The content of WO ₃ is preferably 0 to 10%, in particular 0 to 2%. When the content of WO ₃ is more than 10%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.

In ₂ O ₃ + Ga ₂ O ₃ (total amount of In ₂ O ₃ and Ga ₂ O ₃ ) is a component that suppresses devitrification during melting or laser sealing. The content of In ₂ O ₃ + Ga ₂ O ₃ is preferably 0 to 5%, particularly 0 to 3%. If the content of In ₂ O ₃ + Ga ₂ O ₃ is more than 5%, the batch cost increases. In addition, the content of In ₂ O ₃ is more preferably 0 to 1%, and the content of Ga ₂ O ₃ is more preferably 0 to 0.5%.

  The oxides of Li, Na, K, and Cs are components that lower the softening point. However, since they have an action of promoting devitrification at the time of melting, the total amount is preferably regulated to less than 1%.

P ₂ O ₅ is a component that suppresses devitrification at the time of melting. However, if the content of P ₂ O ₅ is more than 1%, the glass tends to undergo phase separation during melting.

La ₂ O ₃ , Y ₂ O ₃ and Gd ₂ O ₃ are components that suppress phase separation at the time of melting. However, if the total amount thereof is more than 3%, the softening point becomes too high, and the laser Even when irradiated, the glass becomes soft and difficult to soften.

NiO, V ₂ O ₅ , CoO, MoO ₃ , TiO ₂ and MnO ₂ are components having light absorption characteristics, and when irradiated with a laser having a predetermined emission center wavelength, the laser is absorbed and the glass is softened. It is a component that facilitates. The content of each component is preferably 0 to 7%, particularly 0 to 3%. If the content of each component is more than 7%, the glass tends to be devitrified during laser sealing.

  Even if it is a component other than the above, you may add to 5%, for example in the range which does not impair glass characteristics.

  When adding a pigment, it is preferable that a transition metal oxide is not substantially included in a glass composition. If it does in this way, it will become easy to improve thermal stability. Here, “substantially no transition metal oxide” refers to the case where the content of the transition metal oxide in the glass composition is less than 3000 ppm (mass), preferably less than 1000 ppm (mass).

The average particle diameter _{D 50} of the glass powder is 1.0 to 3.0 m, particularly 1.5~2.5μm is preferred. When the average particle diameter D ₅₀ of the glass powder is too small, the glass is easily devitrified during the formation of the sealing material layer, there is a possibility that the softening flow of the sealing material layer is inhibited. Further, the glass powder tends to aggregate during pulverization and classification, and remains as an aggregate after kneading the sealing material paste, which may cause clogging of the screen mesh during screen printing. On the other hand, when the average particle diameter D ₅₀ of the glass powder is too large, unevenness of sealing material layer during the screen printing (wet film) becomes too large, the surface smoothness of the sealing material layer tends to decrease Since the sealing material is softened and hardly flows during the formation of the sealing material layer, it is necessary to raise the firing temperature. In this case, thermal damage to the sealed object is likely to increase, which contributes to high costs. obtain. “Average particle diameter D ₅₀ ” refers to a value measured by the laser diffraction method. In the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the cumulative amount is 50% cumulative from the smaller particle. Represents the particle size.

The 90% particle size D ₉₀ of the glass powder is preferably 7.0 μm or less, particularly preferably 5.0 μm or less. In this way, it becomes easy to reduce the thickness of the sealing material layer, in this case, the time required for laser sealing is shortened, and even if there is a difference in the thermal expansion coefficient between the glass substrate and the sealing material, Cracks and the like hardly occur in the glass substrate and the sealing material layer. Here, “90% particle diameter D ₉₀ ” indicates a value measured by laser diffraction method, and in the volume-based cumulative particle size distribution curve when measured by laser diffraction method, the accumulated amount is accumulated from the smaller particle. Represents a particle size of 90%.

The maximum particle size D ₉₉ of the glass powder is preferably 15 μm or less, particularly preferably 10 μm or less. In this way, it becomes easy to reduce the thickness of the sealing material layer, in this case, the time required for laser sealing is shortened, and even if there is a difference in the thermal expansion coefficient between the glass substrate and the sealing material, Cracks and the like hardly occur in the glass substrate and the sealing material layer. Here, the “maximum particle diameter D ₉₉ ” indicates a value measured by the laser diffraction method. In the cumulative particle size distribution curve based on the volume when measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle. Represents a particle size of 99%.

  It is preferable that glass powder does not contain PbO substantially in a glass composition from an environmental viewpoint. Here, “substantially does not contain PbO” refers to a case where the content of PbO in the glass composition is less than 1000 ppm (mass).

  The sealing material according to the present invention preferably contains a refractory filler in addition to the glass powder. In this way, the thermal expansion coefficient of the sealing material layer can be reduced, and the mechanical strength of the sealing material layer (sealing portion) can be increased. The content of the refractory filler in the sealing material is preferably 5 to 60% by volume, particularly preferably 10 to 45% by volume. If the content of the refractory filler is too small, it will be difficult to enjoy the above effects and it will be difficult to match the thermal expansion coefficient of the object to be sealed (for example, glass substrate), so there will be cracks in the glass substrate or sealing material layer. It becomes easy to generate | occur | produce and it becomes difficult to ensure the airtightness of a glass package. On the other hand, when there is too much content of a refractory filler, the softening flow of a sealing material layer will be inhibited and the surface smoothness of a sealing material layer will fall easily. As a result, the laser sealing property tends to be lowered.

The average particle diameter _{D 50} of the refractory filler is 0.5 to 2.0 [mu] m, particularly 0.5~1.8μm is preferred. When the average particle diameter D ₅₀ of the refractory filler is too small, the refractory filler is easily dissolves in the glass during the formation of the sealing material layer, there is a possibility that the softening flow of the sealing material layer is inhibited. Further, the refractory filler easily aggregates during pulverization and classification, and remains as an aggregate after kneading the sealing material paste, which may cause clogging of the screen mesh during screen printing. On the other hand, when the average particle diameter D ₅₀ of the refractory filler is too large, unevenness of sealing material layer during the screen printing becomes too large, the surface smoothness of the sealing material layer tends to decrease.

Zircon, zirconia, tin oxide, quartz, β-spodumene, cordierite, mullite, quartz glass, β-eucryptite, β-quartz, zirconium phosphate, zirconium phosphate tungstate, zirconium tungstate as refractory filler NbZr (PO ₄ ) _{3 and} other compounds having a basic structure of [AB ₂ (MO ₄ ) ₃ ],
A: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, Mn etc. B: Zr, Ti, Sn, Nb, Al, Sc, Y etc. M: P, Si, W, Mo etc. Alternatively, these solid solutions can be used.

  The sealing material according to the present invention preferably contains a pigment in addition to the glass powder. If it does in this way, it will become easy to convert the light of a laser into heat energy, and laser sealing nature will improve.

The pigment is preferably an inorganic pigment, and _one or more selected from carbon, Co ₃ O ₄ , CuO, Cr ₂ O ₃ , Fe ₂ O ₃ , MnO ₂ , SnO, TinO _2n-1 (n is an integer) More preferably, carbon is particularly preferable. These pigments have excellent color developability and good laser absorptivity. Carbon also has the effect of preventing the SnO-containing glass powder from being altered during laser sealing, that is, the effect of preventing the oxidation of SnO in the glass composition to SnO ₂ during laser sealing. As carbon, amorphous carbon or griffite is preferable. These carbon has a property of easily processing the average particle diameter _{D 50} of the primary particles in the 1 to 100 nm.

The average particle diameter D50 of the primary particles of the pigment is preferably 1 to 100 nm, 3 to 70 nm, 5 to 60 nm, and particularly preferably 10 to ₅₀ nm. When the average particle diameter D ₅₀ of the primary particles of the pigment is too small, the pigment each other tend to aggregate, pigment becomes difficult to uniformly disperse, sealing material layer during the laser sealing is not locally softened flow risk There is. On the other hand, too large an average particle diameter D ₅₀ of the primary particles of the pigment, the pigment is difficult to uniformly disperse, sealing material during laser sealing there is a possibility not to locally soften flow.

  The pigment content is preferably 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass. When there is too little content of a pigment, it will become difficult to convert the light of a laser into heat energy. On the other hand, if the content of the pigment is too large, the sealing material layer becomes difficult to soften and flow during laser sealing, and it becomes difficult to increase the sealing strength.

  The pigment preferably contains substantially no Cr-based oxide from the environmental viewpoint. Here, “substantially does not contain Cr-based oxide” refers to a case where the content of Cr-based oxide in the pigment is less than 1000 ppm (mass).

  In the method for producing a glass package of the present invention, it is preferable to regulate the surface roughness Ra of the sealing material layer (first sealing material layer and / or second sealing material layer) to 0.6 μm or less. If it does in this way, it will become easy to equalize the gap between the 1st glass substrate and the 2nd glass substrate. In addition, "surface roughness Ra" points out the value measured by the method based on JISB0601: 2001.

  In the method for producing a glass package of the present invention, it is preferable that the surface roughness RMS of the sealing material layer (the first sealing material layer and / or the second sealing material layer) is regulated to 1.0 μm or less. If it does in this way, it will become easy to equalize the gap between the 1st glass substrate and the 2nd glass substrate. Here, “surface roughness Ra” refers to a value measured by a method based on JIS B0601: 2001. “Surface roughness RMS” refers to a value measured by a method based on JIS B0601: 2001.

  The sealing material according to the present invention is preferably kneaded with a vehicle, processed into a sealing material paste, applied to the surface of the glass film, and then debindered and fired (sintered). If it does in this way, a sealing material layer (a 1st sealing material layer and / or a 2nd sealing material layer) can be produced efficiently.

  As the resin used for the vehicle, acrylic ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, polypropylene carbonate, methacrylic ester and the like can be used.

  Solvents are N, N'-dimethylformamide, ethylene glycol, dimethyl sulfoxide, dimethyl carbonate, propylene carbonate, butyrolactone, caprolactone, N-methyl-2-pyrrolidone, phenyl diglycol (PhDG), dibutyl phthalate (DBP) , One or more selected from benzyl glycol (BzG), benzyl diglycol (BzDG), and phenyl glycol (PhG) are preferred. These solvents have a characteristic that it is difficult to denature glass powder, particularly SnO-containing glass powder, during binder removal or laser sealing. In particular, among these solvents, one or two selected from propylene carbonate, phenyl diglycol (PhDG), dibutyl phthalate (DBP), benzyl glycol (BzG), benzyl diglycol (BzDG), and phenyl glycol (PhG). The above is preferable. These solvents have a boiling point of 240 ° C. or higher. Therefore, when these solvents are used, it becomes easy to suppress the volatilization of the solvent during the coating operation such as screen printing, and as a result, the sealing material paste can be used stably over a long period of time. Furthermore, phenyl diglycol (PhDG), dibutyl phthalate (DBP), benzyl glycol (BzG), benzyl diglycol (BzDG), and phenyl glycol (PhG) have high affinity with pigments. For this reason, even if the addition amount of these solvents is small, the situation where a pigment separates in the sealing material paste can be suppressed.

  In the method for producing a glass package of the present invention, the thickness of the sealing material layer (first sealing material layer and / or second sealing material layer) is preferably 20 μm or less, 15 μm or less, particularly 1 to 10 μm. It is preferable to do. The smaller the thickness of the sealing material layer, the lower the residual stress in the sealing material layer. If the thickness of the sealing material layer is too small, it becomes difficult to ensure airtight reliability.

  In the method for producing a glass package of the present invention, the material configuration (softening point, light absorption characteristics, etc.) of the first sealing material layer and the second sealing material layer may be the same or different. Also good. Moreover, the thickness of the first sealing material layer and the second sealing material layer may be the same or different. For example, if the softening point of the second sealing material layer is set lower than the softening point of the first sealing material layer, the sealing operation can be easily completed by one laser irradiation. Moreover, if the laser absorption characteristic of the second sealing material layer is made higher than the laser absorption characteristic of the first sealing material layer, the sealing operation can be easily completed by one laser irradiation. In addition, if the content of the transition metal oxide in the sealing material layer is increased, the laser absorption characteristics can be improved. Further, if the content of the pigment in the sealing material layer is increased, the laser absorption characteristics can be enhanced. Moreover, if the thickness of the second sealing material layer is made smaller than the thickness of the first sealing material layer, the sealing operation can be easily completed by one laser irradiation.

In the method for producing a glass package of the present invention, the difference in thermal expansion coefficient between the sealing material layer (the first sealing material layer and / or the second sealing material layer) and the glass film is preferably 50 × 10 ^−7. / ° C. or lower, 40 × 10 ⁻⁷ / ° C. or lower, particularly 5 × 10 ⁻⁷ to 30 × 10 ⁻⁷ / ° C. If it does in this way, it will become difficult to produce an unreasonable residual stress in a glass film or a sealing material layer.

  In the method for producing a glass package of the present invention, the sealing material layer (the first sealing material layer and / or the second sealing material layer) may be formed on the entire surface of the glass film. And may be formed on a part of the surface of the glass film.

In the method for producing a glass package of the present invention, a sealing material layer (first sealing material layer and / or second sealing material layer) and a glass substrate (first glass substrate and / or second glass substrate) ) Is preferably 50 × 10 ⁻⁷ / ° C. or less, 40 × 10 ⁻⁷ / ° C. or less, particularly 5 × 10 ⁻⁷ to 30 × 10 ⁻⁷ / ° C. If it does in this way, it will become difficult to produce an undue residual stress in a glass substrate or a sealing material layer.

  The material of the glass substrate (first glass substrate and / or second glass substrate) is not particularly limited, and alkali-free glass, borosilicate glass, soda lime glass, or the like can be used. Among these, alkali-free glass is preferable for the above reasons. If it does in this way, it will become difficult to break a glass substrate at the time of laser sealing.

The thermal expansion coefficient of the glass substrate (the first glass substrate and / or the second glass substrate) is preferably 40 × 10 ^{−7 to} 90 × 10 ⁻⁷ / ° C. If it does in this way, it will become difficult to produce an unreasonable residual stress in a 1st glass substrate, a 2nd glass substrate, a glass film, and a sealing material layer.

  The glass substrate (first glass substrate and / or second glass substrate) can be produced by a known method. For example, it can be produced by a method such as a float method, a downdraw method (redraw method, slot downdraw method, overflow downdraw method), a rollout method, or the like.

  Among them, the downdraw method (redraw method, slot downdraw method, overflow downdraw method) is preferable. If it does in this way, the surface accuracy of a glass film will become favorable and it will become easy to equalize the thickness of a glass substrate.

  The glass substrate (first glass substrate and / or second glass substrate) is preferably unpolished on the surface (the surface of the effective surface). In this way, the gap between the first glass substrate and the second glass substrate can be easily made uniform, and the sealing strength can be increased.

  The glass package according to the present invention is a glass package produced by the method for producing a glass package of the present invention, and a glass film is interposed between the first glass substrate and the second glass substrate, The first glass substrate and the glass film are sealed and integrated by the first sealing material layer, and the second glass substrate and the glass film are sealed and integrated by the second sealing material layer. It is characterized by.

  In the glass package according to the present invention, the gap between the first glass substrate and the second glass substrate is preferably 10 to 500 μm, 70 to 400 μm, particularly 100 to 300 μm. If it does in this way, after achieving the enlargement and thickness reduction of a glass package, it will become easy to prevent the situation where a glass substrate contacts and damage to an element etc. arises. In addition, when the gap between the first glass substrate and the second glass substrate is too small, it is difficult to prevent a situation in which the glass substrates are in contact with each other and the elements are damaged. On the other hand, if the gap between the first glass substrate and the second glass substrate is too large, it is difficult to achieve an increase in size and thickness of the device.

  The value of (thickness of glass film) / (thickness of first sealing material layer) is preferably 1 or more, 2 or more, 4 or more, and particularly 5 or more. The value of (thickness of glass film) / (thickness of first sealing material layer) is preferably 1 or more, 2 or more, 4 or more, particularly 5 or more. If it does in this way, it will become difficult to produce the residual stress of a glass film and a sealing material layer after laser irradiation.

  Hereinafter, the present invention will be described in detail based on examples. The following examples are merely illustrative. The present invention is not limited to the following examples.

A sealing material was produced as follows. First, a predetermined glass composition (mol% in terms of the following oxide, Bi ₂ O ₃ 37%, B ₂ O ₃ 26%, ZnO 17.5%, CuO 14%, BaO 5%, Fe ₂ O ₃ 0.5 %), After preparing the raw material, this mixed raw material was put in a platinum crucible and melted at 1000 ° C. for 1 to 2 hours in an air atmosphere. Next, the obtained molten glass was formed into a film shape with a water-cooled roller. Subsequently, the film obtained by the ball mill was pulverized and classified to obtain a bismuth glass powder. The density of the obtained bismuth-based glass powder was 6.99 g / cm ³ , average particle diameter D ₅₀ : 1.2 μm, and maximum particle diameter D ₉₉ : 2.9 μm. The particle size is a value measured with a laser diffraction particle size distribution meter (the same applies hereinafter).

The bismuth glass powder and the refractory filler were mixed at a volume ratio of 75:25 to prepare a sealing material. Cordierite was used for the refractory filler. The cordierite density was 2.63 g / cm ³ , and the particle size was an average particle size D ₅₀ : 1.0 μm and a maximum particle size D ₉₉ : 2.3 μm.

  The softening point of the obtained sealing material was 450 ° C. The softening point is a value measured with a macro DTA apparatus. The conditions of the macro type DTA were as follows: measurement atmosphere: air atmosphere, temperature rising rate: 10 ° C./min, measurement temperature range: room temperature to 600 ° C.

The obtained sealing material had a thermal expansion coefficient of 79 × 10 ⁻⁷ / ° C. A thermal expansion coefficient is the value measured in the temperature range of 30-300 degreeC using the push rod type | mold TMA apparatus. In addition, as the measurement sample, a material obtained by precisely sintering the sealing material was used.

Subsequently, four types of glass films (thickness 20 μm, 30 μm, 50 μm, 100 μm) were prepared. The material of the glass film was OA-10G (thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C.) manufactured by Nippon Electric Glass Co., Ltd.

  A sealing material layer was formed as follows. First, the sealing material and the vehicle are kneaded so that the viscosity is about 70 Pa · s (25 ° C., Shear rate: 4), and then kneaded until uniform with a three-roll mill to obtain a sealing material paste. It was. Ethyl cellulose was used as a resin component in the vehicle, and butyl carbitol acetate (BCA) and α-terpineol were used as solvent components. Next, the obtained sealing material paste was applied to the surface of the glass film with a screen printer. During screen printing, the sealing material paste was applied linearly to the central portion of the glass film. After screen printing, drying at 120 ° C. for 30 minutes, followed by baking at 490 ° C. for 10 minutes to form a sealing material layer having a thickness of about 5 μm and a width of about 0.6 mm on both surfaces of the glass film. Each composite sealing material was obtained. The surface roughness (Ra, RMS) of the sealing material layer was 0.04 μm and 0.09 μm, respectively. The thickness of the sealing material layer is an average value measured with a non-contact type laser film thickness meter. The surface roughness (Ra, RMS) of the sealing material layer is a value measured with a surface roughness meter.

(Experiment No. 1)
As a glass substrate, an alkali-free glass substrate (OA-10G manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C., thickness: 0.5 mm) was prepared. Next, while arranging the glass film with a sealing material layer (thickness 20 μm) in a frame shape along the outer peripheral edge of the alkali-free glass substrate between two alkali-free glass substrates of the same size, 2 A piece of alkali-free glass substrate was accurately stacked. Next, a semiconductor laser is irradiated along the sealing material layer (corresponding to the first sealing material layer) from the upper alkali-free glass substrate (corresponding to the first glass substrate) side, and the alkali-free glass is irradiated. The substrates were sealed together. In addition, the laser was not irradiated from the lower alkali-free glass substrate (equivalent to a 2nd glass substrate).

  The wavelength of the semiconductor laser was 808 nm, the laser output was 12 W, and the laser scanning speed was 10 mm / s.

  About the obtained glass package, laser sealing property was evaluated. For laser sealing, the sealing state of the glass package after laser sealing is observed, and the obtained glass package is subjected to a high-temperature, high-humidity and high-pressure test: HAST test (Highly Accelerated Temperature and Humidity Stress test). Evaluation was made by observing the presence or absence of peeling of both sealing material layers (first sealing material layer and second sealing material layer). The conditions of the HAST test are 121 ° C., humidity 100%, 2 atm, and 24 hours. The alkali-free glass substrates were hermetically sealed, and both the sealing material layers were not peeled off after the HAST test was “◯”, while the alkali-free glass substrates were hermetically sealed. A case where any of the sealing material layers was peeled after the test was evaluated as “Δ”, and a case where the alkali-free glass substrates were not hermetically sealed was evaluated as “X”. As a result, the evaluation of laser sealing property was “◯”.

(Experiment No. 2)
As a glass substrate, an alkali-free glass substrate (OA-10G manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C., thickness: 0.5 mm) was prepared. Next, while arranging the glass film with a sealing material layer (thickness 30 μm) in a frame shape along the outer peripheral edge of the alkali-free glass substrate between two alkali-free glass substrates of the same size, 2 A piece of alkali-free glass substrate was accurately stacked. Next, a semiconductor laser is irradiated along the sealing material layer (corresponding to the first sealing material layer) from the upper alkali-free glass substrate (corresponding to the first glass substrate) side, and the alkali-free glass is irradiated. The substrates were sealed together. In addition, the laser was not irradiated from the lower alkali-free glass substrate (equivalent to a 2nd glass substrate).

  The wavelength of the semiconductor laser was 808 nm, the laser output was 12 W, and the laser scanning speed was 10 mm / s.

  About the obtained glass package, laser sealing property was evaluated as mentioned above. As a result, the evaluation of laser sealing property was “◯”.

(Experiment No. 3)
As a glass substrate, an alkali-free glass substrate (OA-10G manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C., thickness: 0.5 mm) was prepared. Next, between the two alkali-free glass substrates of the same size, the glass film with a sealing material layer (thickness 50 μm) is arranged in a frame shape along the outer peripheral edge of the alkali-free glass substrate. A piece of alkali-free glass substrate was accurately stacked. Next, a semiconductor laser is irradiated along the sealing material layer (corresponding to the first sealing material layer) from the upper alkali-free glass substrate (corresponding to the first glass substrate) side, and the alkali-free glass is irradiated. The substrates were sealed together. In addition, the laser was not irradiated from the lower alkali-free glass substrate (equivalent to a 2nd glass substrate).

  The wavelength of the semiconductor laser was 808 nm, the laser output was 12 W, and the laser scanning speed was 10 mm / s.

  About the obtained glass package, laser sealing property was evaluated as mentioned above. As a result, the evaluation of laser sealing property was “◯”.

(Experiment No. 4)
As a glass substrate, an alkali-free glass substrate (OA-10G manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C., thickness: 0.5 mm) was prepared. Next, while placing the glass film with a sealing material layer (thickness: 100 μm) in a frame shape along the outer peripheral edge of the alkali-free glass substrate between two alkali-free glass substrates of the same size, 2 A piece of alkali-free glass substrate was accurately stacked. Next, a semiconductor laser is irradiated along the sealing material layer (corresponding to the first sealing material layer) from the upper alkali-free glass substrate (corresponding to the first glass substrate) side, and the alkali-free glass is irradiated. The substrates were sealed together. In addition, the laser was not irradiated from the lower alkali-free glass substrate (equivalent to a 2nd glass substrate).

  The wavelength of the semiconductor laser was 808 nm, the laser output was 12 W, and the laser scanning speed was 10 mm / s.

  About the obtained glass package, laser sealing property was evaluated as mentioned above. As a result, the evaluation of laser sealing property was “◯”.

(Experiment No. 5)
As a glass substrate, an alkali-free glass substrate (OA-10G manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C., thickness: 0.5 mm) was prepared. Next, the sealing material paste was applied 10 times to the outer peripheral edge of the alkali-free glass substrate by screen printing. After screen printing, drying at 120 ° C. for 30 minutes, followed by baking at 490 ° C. for 10 minutes, a sealing material layer having a thickness of about 50 μm and a width of about 0.6 mm was formed on the surface of the alkali-free glass substrate. . Subsequently, an alkali-free glass substrate of the same size was stacked on the alkali-free glass substrate with the sealing material layer so as to be in contact with the sealing material layer. Furthermore, the alkali-free glass substrates were sealed by irradiating a semiconductor laser along the sealing material layer from the alkali-free glass substrate side on which the sealing material layer was not formed. Immediately after the semiconductor laser irradiation, the alkali-free glass substrate and the sealing material layer were observed, and innumerable cracks were generated.

  The wavelength of the semiconductor laser was 808 nm, the laser output was 12 W, and the laser scanning speed was 10 mm / s.

  About the obtained glass package, laser sealing property was evaluated as mentioned above. As a result, the laser sealing property was evaluated as “x”, and the sealing material layer was completely peeled off.

First, four types of glass films (thickness 20 μm, 30 μm, 50 μm, 100 μm) were prepared. The material of the glass film was OA-10G (thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C.) manufactured by Nippon Electric Glass Co., Ltd.

  A sealing material layer (corresponding to the first sealing material layer) was produced as follows. First, the sealing material prepared in [Example 1] and the vehicle were kneaded so that the viscosity was about 70 Pa · s (25 ° C., Shear rate: 4), and then kneaded until it became uniform with a three-roll mill. Thus, a sealing material paste was obtained. Ethyl cellulose was used as a resin component in the vehicle, and butyl carbitol acetate (BCA) and α-terpineol were used as solvent components. Next, the obtained sealing material paste was applied to one surface of the glass film with a screen printer. During screen printing, the sealing material paste was applied linearly to the central portion of the glass film. After screen printing, drying at 120 ° C. for 30 minutes, followed by baking at 490 ° C. for 10 minutes, a sealing material layer having a thickness of about 5 μm and a width of about 0.6 mm was formed on one surface of the glass film. . The surface roughness (Ra, RMS) of the sealing material layer was 0.04 μm and 0.09 μm, respectively. The thickness of the sealing material layer is an average value measured with a non-contact type laser film thickness meter. The surface roughness (Ra, RMS) of the sealing material layer is a value measured with a surface roughness meter.

Subsequently, a sealing material layer (corresponding to a second sealing material layer) was formed on the alkali-free glass substrate. First, the sealing material prepared in [Example 1] and the vehicle were kneaded so that the viscosity was about 70 Pa · s (25 ° C., Shear rate: 4), and then kneaded until it became uniform with a three-roll mill. Thus, a sealing material paste was obtained. Ethyl cellulose was used as a resin component in the vehicle, and butyl carbitol acetate (BCA) and α-terpineol were used as solvent components. Next, the obtained sealing material paste was screened on one surface of an alkali-free glass substrate (OA-10G manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C., thickness: 0.5 mm). It was applied with a printing machine. During screen printing, the sealing material paste was applied linearly to the outer peripheral edge portion of the alkali-free glass substrate. After screen printing, drying at 120 ° C. for 30 minutes, followed by baking at 490 ° C. for 10 minutes, a sealing material layer having a thickness of about 5 μm and a width of about 0.6 mm is formed on one surface of the alkali-free glass substrate. Formed. The surface roughness (Ra, RMS) of the sealing material layer was 0.04 μm and 0.09 μm, respectively. The thickness of the sealing material layer is an average value measured with a non-contact type laser film thickness meter. The surface roughness (Ra, RMS) of the sealing material layer is a value measured with a surface roughness meter.

(Experiment No. 6)
Non-alkali glass substrate having the same size as the non-alkali glass substrate with a sealing material layer (OA-10G manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C., thickness: 0.5 mm, sealing material layer A non-alkali glass substrate on which is not formed) was prepared. Further, between the two alkali-free glass substrates, along the outer peripheral edge of the alkali-free glass substrate, the above-mentioned glass film with a sealing material layer (thickness 20 μm) is arranged in a frame shape. The glass substrates were accurately stacked. In addition, it arrange | positioned so that the sealing material layer formed in the non-alkali glass substrate might contact the surface of the glass film in which the sealing material layer is not formed. Further, the alkali-free glass substrates were sealed by irradiating a semiconductor laser along the sealing material layer formed on the glass film from the alkali-free glass substrate side on which the sealing material layer was not formed. In addition, the laser was not irradiated from the alkali-free glass substrate side on which the sealing material was formed.

  The wavelength of the semiconductor laser was 808 nm, the laser output was 12 W, and the laser scanning speed was 10 mm / s.

  About the obtained glass package, laser sealing property was evaluated as mentioned above. As a result, the evaluation of laser sealing property was “◯”.

(Experiment No. 7)
Non-alkali glass substrate having the same size as the non-alkali glass substrate with a sealing material layer (OA-10G manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C., thickness: 0.5 mm, sealing material layer A non-alkali glass substrate on which is not formed) was prepared. Further, between the two alkali-free glass substrates, along the outer peripheral edge of the alkali-free glass substrate, the above-mentioned glass film with a sealing material layer (thickness 30 μm) is arranged in a frame shape, and the two alkali-free glass substrates are arranged. The glass substrates were accurately stacked. In addition, it arrange | positioned so that the sealing material layer formed in the non-alkali glass substrate might contact the surface of the glass film in which the sealing material layer is not formed. Further, the alkali-free glass substrates were sealed by irradiating a semiconductor laser along the sealing material layer formed on the glass film from the alkali-free glass substrate side on which the sealing material layer was not formed. In addition, the laser was not irradiated from the alkali-free glass substrate side on which the sealing material was formed.

  The wavelength of the semiconductor laser was 808 nm, the laser output was 12 W, and the laser scanning speed was 10 mm / s.

  About the obtained glass package, laser sealing property was evaluated as mentioned above. As a result, the evaluation of laser sealing property was “◯”.

(Experiment No. 8)
Non-alkali glass substrate having the same size as the non-alkali glass substrate with a sealing material layer (OA-10G manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C., thickness: 0.5 mm, sealing material layer A non-alkali glass substrate on which is not formed) was prepared. Further, between the two alkali-free glass substrates, along the outer peripheral edge of the alkali-free glass substrate, the above-mentioned glass film with a sealing material layer (thickness 50 μm) is arranged in a frame shape, and the two alkali-free glass substrates are arranged. The glass substrates were accurately stacked. In addition, it arrange | positioned so that the sealing material layer formed in the non-alkali glass substrate might contact the surface of the glass film in which the sealing material layer is not formed. Further, the alkali-free glass substrates were sealed by irradiating a semiconductor laser along the sealing material layer formed on the glass film from the alkali-free glass substrate side on which the sealing material layer was not formed. In addition, the laser was not irradiated from the alkali-free glass substrate side on which the sealing material was formed.

  The wavelength of the semiconductor laser was 808 nm, the laser output was 12 W, and the laser scanning speed was 10 mm / s.

  About the obtained glass package, laser sealing property was evaluated as mentioned above. As a result, the evaluation of laser sealing property was “◯”.

(Experiment No. 9)
Non-alkali glass substrate having the same size as the non-alkali glass substrate with a sealing material layer (OA-10G manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C., thickness: 0.5 mm, sealing material layer A non-alkali glass substrate on which is not formed) was prepared. Further, between the two alkali-free glass substrates, along the outer peripheral edge of the alkali-free glass substrate, the above-mentioned glass film with a sealing material layer (thickness: 100 μm) is arranged in a frame shape, and the two alkali-free glass substrates are arranged. The glass substrates were accurately stacked. In addition, it arrange | positioned so that the sealing material layer formed in the non-alkali glass substrate might contact the surface of the glass film in which the sealing material layer is not formed. Further, the alkali-free glass substrates were sealed by irradiating a semiconductor laser along the sealing material layer formed on the glass film from the alkali-free glass substrate side on which the sealing material layer was not formed. In addition, the laser was not irradiated from the alkali-free glass substrate side on which the sealing material was formed.

  The wavelength of the semiconductor laser was 808 nm, the laser output was 12 W, and the laser scanning speed was 10 mm / s.

  About the obtained glass package, laser sealing property was evaluated as mentioned above. As a result, the evaluation of laser sealing property was “◯”.

  The method for producing a glass package of the present invention is suitable for producing, for example, organic EL displays, organic EL lighting, dye-sensitized solar cells, non-silicon solar cells such as thin film compound solar cells, and lithium ion secondary batteries. is there.

DESCRIPTION OF SYMBOLS 1 Glass package 11 1st sealing material layer 12 2nd sealing material layer 13 Glass film 14 1st glass substrate 15 2nd glass substrate

Claims (15)

A method of manufacturing a glass package in which a first glass substrate and a second glass substrate are hermetically sealed,
Forming a glass film by a downdraw method;
The first glass substrate is the first sealing material layer, the second glass substrate is the second sealing material layer, and the glass film is the first sealing material layer and the second sealing material layer. A step of laminating and arranging each in a state of contact
Relative to the first sealing material layer from the first glass substrate is irradiated with laser, possess a step of dissolving the first sealing material layer,
The first sealing material layer and the second sealing material layer are sintered bodies of the sealing material,
Encapsulating adhesive material, method of manufacturing a glass package, characterized in that it contains a bismuth glass containing 5 to 30 mol% of CuO + _Fe 2 _{O 3} in the glass composition.   2. The first sealing material layer and the second sealing material layer are dissolved by irradiating a laser to the first sealing material layer from the first glass substrate side. The manufacturing method of the glass package of description.   The glass package according to claim 1, further comprising a step of irradiating a laser to the second sealing material layer from the second glass substrate side to dissolve the second sealing material layer. Manufacturing method.   The glass package according to any one of claims 1 to 3, further comprising a step of forming a first sealing material layer and / or a second sealing material layer on a surface of the glass film. Production method.   The method includes forming a first sealing material layer on the surface of the first glass substrate and / or forming a second sealing material layer on the surface of the second glass substrate. The manufacturing method of the glass package of any one of 1-4.   A step of mixing a sealing material and a vehicle to produce a sealing material paste, and sintering the sealing material paste to form a first sealing material layer and / or a second sealing material layer The manufacturing method of the glass package of any one of Claims 1-5 characterized by including the process to do.   The glass film, the first sealing material layer, and the second sealing material layer are disposed on the outer peripheral edges of the first glass substrate and the second glass substrate, respectively. The manufacturing method of the glass package of 1 item | term. The method for producing a glass package according to any one of claims 1 to 7 , wherein the thickness of the second sealing material layer is made smaller than the thickness of the first sealing material layer. Second any one of claims 1-8, characterized by more than the content of the transition metal oxide content first sealing material layer of the transition metal oxide of the sealing material layer The manufacturing method of the glass package of description. Method for manufacturing a glass package according to any one of claim 1 to 9, characterized in that shaping the glass film at a redraw method. The thickness of a glass film is 300 micrometers or less, The manufacturing method of the glass package of any one of Claims 1-10 characterized by the above-mentioned. Method for manufacturing a glass package according to any one of claim 1 to 11, the thickness of the first sealing material layer and the second sealing material layer, characterized in that at 20μm or less. Glass film, method of manufacturing a glass package according to any one of claim 1 to 12, characterized in that an alkali-free glass. The method for manufacturing a glass package according to any one of claims 1 to 13 , wherein the first glass substrate and the second glass substrate are non-alkali glass. The method for producing a glass package according to any one of claims 1 to 14 , wherein the glass package is used for an organic EL device or a non-silicon type solar cell.