JP2015023263A - Method for manufacturing electric element package and electric element package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve reliability of an electric element package by providing a method for increasing adhesive strength between an element substrate and a sealing material layer without causing deterioration of element characteristics even when an element substrate is metal or ceramic.SOLUTION: A method for manufacturing an electric element package comprises the steps of: preparing a glass substrate and forming a sealing material layer on the glass substrate; preparing an element substrate composed of metal or ceramic and forming a reaction film on the element substrate; arranging the glass substrate and the element substrate so that the sealing material layer comes into contact with the reaction film; and sealing the glass substrate and the element substrate by reacting the sealing material layer and the reaction film by irradiating the sealing material layer with a laser beam from the glass substrate side.

Description

  The present invention relates to an electrical element package manufacturing method and an electrical element package. Specifically, by performing sealing treatment with laser light (hereinafter referred to as laser sealing), an ambient environment such as an organic EL element and a piezoelectric vibration element is provided. The present invention relates to a method of manufacturing an electric element package for hermetically sealing a sensitive electric element and the electric element package.

  As is well known, various studies and developments have been made on organic EL lighting, and some have already been put into practical use.

  The organic EL element (organic EL layer) used for this organic EL illumination is a sensitive element that easily deteriorates when exposed to oxygen and moisture in the surrounding environment. Therefore, it has been studied to incorporate an organic EL element in an organic EL illumination in an airtight state so as to maintain the characteristics and extend the life of the organic EL illumination.

  As a structure of organic EL lighting in which an organic EL element is hermetically sealed, a glass substrate is disposed oppositely on an element substrate on which the organic EL element is disposed, and in this state, the organic EL element is disposed on the element substrate. A structure in which a gap between a glass substrate and an element substrate is hermetically sealed with a sealing material layer so as to surround the periphery of the organic EL element. Glass is generally used as the element substrate, but ceramic or metal may be used in some cases.

  The piezoelectric vibrator element is also a sensitive element that easily deteriorates when exposed to oxygen and moisture in the surrounding environment. Therefore, it has been studied to incorporate the piezoelectric vibrator element into the piezoelectric vibrator package in an airtight state so as to maintain the characteristics of the piezoelectric vibrator package and extend its life.

  As a structure of the piezoelectric vibrator package in which the piezoelectric vibrator elements are hermetically sealed, a glass substrate is disposed oppositely on the element substrate on which the piezoelectric vibrator elements are arranged, and in this state, on the element substrate. A structure in which a gap between a glass substrate and an element substrate is hermetically sealed with a sealing material layer so as to surround the periphery of the arranged piezoelectric vibrator element has been studied. Note that ceramic, for example, alumina is generally used as the element substrate.

  Organic EL elements and piezoelectric vibration elements are known to have low heat resistance. Therefore, if the glass substrate and the element substrate are sealed by firing in the softening flow temperature range of the sealing material layer, the characteristics of the element may be thermally deteriorated.

  Therefore, in recent years, laser sealing has been studied as a sealing method. According to laser sealing, only the portion to be sealed can be locally heated, so that the glass substrate and the element substrate can be sealed while preventing thermal degradation of the element and the like.

JP 2008-186697 A

  As a method for forming a sealing material layer on a glass substrate, a sealing material paste is applied on the glass substrate to form a sealing material film, and then the sealing material film is dried and the solvent is volatilized. Further, a method is generally used in which the resin component in the sealing material paste is incinerated (debinding treatment) and the sealing material is sintered (fixed) by firing at a temperature higher than the softening point of the sealing material. By this firing step, the adhesive strength between the glass substrate and the sealing material layer is sufficiently increased. However, as described above, in this method, there is a possibility that the characteristics of the element are thermally deteriorated.

  On the other hand, when laser sealing is performed, thermal degradation of the element can be suppressed during sealing, but it is difficult to increase the adhesive strength between the element substrate and the sealing material layer. And when an element substrate is a metal or a ceramic, it is still more difficult to raise the adhesive strength of an element substrate and a sealing material layer.

  Laser sealing is a method in which the sealing material layer is locally heated to soften and flow the sealing material layer, so that the time required for sealing is shortened and the element substrate and the sealing material layer react with each other. The time to do is also short. As a result, the reaction layer is not sufficiently generated at the interface between the element substrate and the sealing material layer, and the adhesive strength between the element substrate and the sealing material layer is lowered.

  Further, the sealing material usually contains a low melting point glass. This low melting point glass erodes the surface layer of the element substrate at the time of laser sealing, and a reaction layer is generated. When the element substrate is made of glass, a reaction layer is generated to some extent by laser sealing, and the adhesive strength can be ensured. However, when the element substrate is made of metal or ceramic, the low melting point glass hardly erodes the surface layer of the element substrate at the time of laser sealing, and the reaction layer is not sufficiently formed. As a result, the adhesive strength decreases, and it becomes difficult to ensure the airtightness of the electric element package.

  The present invention has been made in view of the above circumstances, and the technical problem thereof is that the element substrate and the sealing material layer are bonded without causing thermal degradation of the element even when the element substrate is a metal or ceramic. The idea is to improve the reliability of the electrical device package by creating a method that can increase the strength.

  As a result of intensive studies, the inventors have formed a reaction film on the element substrate in advance, and then reacting the reaction film with the sealing material layer at the time of laser sealing, the element substrate and the sealing material layer It is found that the sealing strength is improved and is proposed as the present invention.

  That is, the electrical element package manufacturing method of the present invention provides a glass substrate, a step of forming a sealing material layer on the glass substrate, an element substrate made of metal or ceramic, and an element substrate. The step of forming the reaction film, the step of arranging the glass substrate and the element substrate so that the sealing material layer and the reaction film are in contact, and irradiating the sealing material layer with laser light from the glass substrate side And a step of reacting the adhesion material layer and the reaction film to seal the glass substrate and the element substrate. Here, both the steps of preparing a glass substrate, forming a sealing material layer on the glass substrate, and preparing an element substrate made of metal or ceramic, and forming a reaction film on the element substrate, The process order does not matter. That is, while preparing a glass substrate, the process of forming a sealing material layer on a glass substrate may be performed first, and an element substrate made of metal or ceramic is prepared, and a reaction film is formed on the element substrate. The step of performing may be performed first.

  In the method for manufacturing an electric element package of the present invention, the reaction film is preferably an oxide film or a nitride film. These films have good reactivity with the sealing material layer, and can increase the adhesive strength between the element substrate and the sealing material layer after laser sealing.

In the method for manufacturing an electric element package of the present invention, the reaction film is preferably any one of SiO ₂ , SiN, and glass. These films have good reactivity with the sealing material layer, and can increase the adhesive strength between the element substrate and the sealing material layer after laser sealing.

  In the manufacturing method of the electric element package of the present invention, the thickness of the reaction film is preferably less than 10 μm.

  In the method for manufacturing an electrical element package of the present invention, the sealing material layer is preferably a sintered body of a sealing material. As a result, the mechanical strength of the sealing material layer is improved, and the sealing material layer can be appropriately formed even when the thickness of the sealing material layer is thin.

  In the electrical element package manufacturing method of the present invention, the electrical element package is preferably a piezoelectric vibrator package or organic EL lighting.

  An electrical element package of the present invention includes an element substrate, a glass substrate facing the surface of the element substrate on the electrical element side with a space therebetween, and a sealing material layer that seals a gap between the element substrate and the glass substrate. The electric element package includes a reaction film disposed between the element substrate and the sealing material layer.

  In the electric element package of the present invention, the element substrate and the glass substrate are preferably sealed by a sealing process using a laser beam.

  In the electric element package of the present invention, the reaction film is preferably an oxide film or a nitride film.

In the electric element package of the present invention, the reaction film is preferably any one of SiO ₂ , SiN, and glass.

  In the electric element package of the present invention, the thickness of the reaction film is preferably less than 10 μm.

  In the electric element package of the present invention, the heat resistance temperature of the reaction film is preferably higher than (softening point of sealing material + 50) ° C. Here, “heat-resistant temperature” refers to the maximum temperature at which softening deformation does not occur. The “softening point” refers to a value measured with a macro-type differential thermal analysis (DTA) apparatus in an air atmosphere. DTA starts measurement from room temperature, and the rate of temperature rise is 10 ° C./min. In addition, the softening point measured with the macro type | mold DTA apparatus points out the temperature (Ts) of the 4th bending point shown in FIG.

  In the electrical element package of the present invention, the average thickness of the sealing material layer is preferably less than 20 μm. The smaller the average thickness of the sealing material layer, the lower the stress remaining on the sealed portion and the glass substrate after laser sealing. As a result, even if the difference in thermal expansion coefficient between the glass substrate and the sealing material layer or the difference in thermal expansion coefficient between the element substrate and the sealing material layer is large, the accuracy of laser sealing can be improved. Here, the “average thickness of the sealing material layer” can be measured by, for example, a non-contact type laser film thickness meter.

  In the electric element package of the present invention, the sealing material layer is preferably a sintered body of a sealing material.

In the electric element package of the present invention, the sealing material preferably contains 55 to 95% by volume of bismuth glass and 5 to 45% by volume of a refractory filler. Bismuth glass generally has good reactivity with an object to be sealed. Thereby, sealing strength can be raised. Furthermore, bismuth-based glass has a low melting point but high thermal stability (devitrification resistance). Thereby, it can soften and flow well at the time of laser sealing, and the accuracy of laser sealing can be increased. The “bismuth-based glass” refers to glass containing Bi ₂ O ₃ as a main component, and specifically refers to glass containing 50% by mass or more of Bi ₂ O ₃ in the glass composition.

  The electrical element package of the present invention is preferably either a piezoelectric vibrator package or organic EL lighting.

It is a longitudinal cross-sectional view for demonstrating the structural example of the electric element package of this invention. It is a schematic diagram which shows the softening point of the sealing material when it measures with a macro type | mold DTA apparatus.

  In the manufacturing method of the electrical element package of this invention, it has the process of forming a sealing material layer on a glass substrate while preparing a glass substrate. As a method for forming a sealing material layer on a glass substrate, a sealing material paste is applied on the glass substrate to form a sealing material film, and then the sealing material film is dried and the solvent is volatilized. Further, a method of firing at a temperature higher than the softening point of the sealing material to incinerate the resin component in the sealing material paste (debinding treatment) and sinter (fixing) the sealing material is preferable. If it does in this way, while being able to form a sealing material layer easily, the adhesive strength of a glass substrate and a sealing material layer can be raised.

  The sealing material paste is preferably applied in a frame shape along the outer peripheral edge region of the glass substrate. In this way, the effective area that functions as a device can be expanded.

  The sealing material paste generally includes a sealing material and a vehicle. Although various materials can be used as the sealing material, a composite powder containing glass and a refractory filler is preferable. Thereby, the low melting point characteristics and the mechanical strength are compatible, and the thermal expansion coefficient of the sealing material easily matches the thermal expansion coefficient of the glass substrate.

  The sealing material preferably contains 55 to 95 volume% glass (especially bismuth glass) and 5 to 45 volume% refractory filler, 60 to 90 volume% glass and 10 to 40 volume% refractory. It is more preferable to contain a flammable filler, and it is particularly preferable to contain 60 to 85% by volume of glass and 15 to 40% by volume of a refractory filler. If a predetermined amount of refractory filler is added to the glass, the thermal expansion coefficient of the sealing material can easily match the thermal expansion coefficient of the glass substrate. As a result, it becomes easy to prevent a situation in which undue stress remains on the sealed portion or the glass substrate after laser sealing. On the other hand, when the content of the refractory filler is too large, the glass content is relatively decreased, so that the surface smoothness of the sealing material layer is lowered, and the accuracy of laser sealing is easily lowered.

Various glasses can be used as the glass. Among them, tin phosphate glass, vanadium glass, and bismuth glass are preferable from the viewpoint of water resistance and thermal stability, and bismuth glass is particularly preferable. is there. Here, the “tin phosphate glass” refers to a glass mainly composed of SnO and P ₂ O ₅ , specifically, SnO and P ₂ O ₅ in a total amount of 40% by mass or more in the glass composition. Refers to glass containing. “Vanadium-based glass” refers to glass mainly composed of V ₂ O ₅ , and specifically refers to glass containing 25% by mass or more of V ₂ O ₅ in the total amount in the glass composition.

  The bismuth-based glass has a transition metal oxide content of 0.5% by mass or more (preferably 2 to 18% by mass, more preferably 3 to 15% by mass, still more preferably 4 to 12% by mass, particularly preferably glass composition). 5-10% by mass) is desirable. If it does in this way, light absorption characteristics can be improved, suppressing a fall of thermal stability.

Bismuth glass contains, as a glass composition, mass%, Bi ₂ O ₃ 67 to 90%, B ₂ O ₃ 2 to 12%, ZnO 1 to 20%, CuO + Fe ₂ O ₃ 0.5 to 18%. It is preferable. The reason for limiting the content of each component as described above will be described below.

Bi ₂ O ₃ is a main component for forming the reaction layer and a main component for lowering the softening point, and its content is 67 to 87%, preferably 70 to 85%, more preferably 72 to 83. %. When the content of Bi ₂ O ₃ is less than 67%, the reaction layer is difficult to be generated, and the softening point becomes too high, and the glass is difficult to soften even when irradiated with laser light. On the other hand, when the content of Bi ₂ O ₃ is more than 90%, the glass becomes thermally unstable, and the glass tends to devitrify when melted, sintered (fixed), or sealed with laser.

B ₂ O ₃ is a component that forms a glass network of bismuth-based glass, and its content is 2 to 12%, preferably 3 to 10%, more preferably 4 to 10%, still more preferably 5 to 9%. It is. When the content of B ₂ O ₃ is less than 2%, the glass becomes thermally unstable, and the glass tends to be devitrified during melting, sintering (adhering), or laser sealing. On the other hand, if the content of B ₂ O ₃ is more than 12%, the softening point becomes too high and the glass is difficult to soften even when irradiated with laser light.

  ZnO is a component that suppresses devitrification at the time of melting, sintering (adhering), or laser sealing, and lowers the thermal expansion coefficient, and its content is 1 to 20%, preferably 2 to 15 %, More preferably 3 to 11%, still more preferably 3 to 9%. If the ZnO content is less than 1%, it is difficult to obtain the above effect. On the other hand, if the ZnO content is more than 20%, the component balance in the glass composition is impaired, and conversely, the glass tends to devitrify.

CuO and Fe ₂ O ₃ are components having light absorption characteristics, and when irradiated with laser light having a predetermined emission center wavelength, CuO and Fe ₂ O ₃ are components that make the glass easy to soften. CuO and Fe ₂ O ₃ are components that suppress devitrification at the time of melting, sintering (adhering), or laser sealing. The content of CuO + Fe ₂ O ₃ is 0.5 to 18%, preferably 3 to 15%, more preferably 3.5 to 15%, still more preferably 4 to 12%, and particularly preferably 5 to 10%. If the content of CuO + Fe ₂ O ₃ is less than 0.5%, the light absorption characteristics are poor, and the glass is difficult to soften even when irradiated with laser light. On the other hand, when the content of CuO + Fe ₂ O ₃ is more than 18 percent, is impaired balance of components in the glass composition, the glass is liable to devitrify reversed. “CuO + Fe ₂ O ₃ ” is the total amount of CuO and Fe ₂ O ₃ .

  CuO is a component having light absorption characteristics. When irradiated with a laser beam having a predetermined emission center wavelength, CuO is a component that absorbs the laser beam and softens the glass. ) Or a component that suppresses devitrification at the time of laser sealing. The content of CuO is preferably 0 to 15%, 1 to 15%, 2 to 12%, 3 to 10%, particularly 4.5 to 10%. When there is more content of CuO than 15%, the component balance in a glass composition will be impaired and it will become easy to devitrify glass conversely. If the CuO content is restricted to 1% or more, the light absorption characteristics are improved, and the glass is easily softened during laser sealing.

Fe ₂ O _{3 is} also a component having light absorption characteristics. When irradiated with laser light having a predetermined emission center wavelength, it is a component that absorbs laser light and softens the glass easily. It is a component that suppresses devitrification at the time of bonding (fixing) or laser sealing. The content of Fe ₂ O ₃ is preferably 0 to 7%, 0.05 to 7%, 0.1 to 4%, particularly 0.2 to 3%. When the content of Fe ₂ O ₃ is more than 7%, 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 0.05% 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%, 0 to 3%, especially 0 to less than 1%. 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 laser light.

Al ₂ O ₃ is a component that improves water resistance. The content of Al ₂ O ₃ is preferably 0 to 5%, 0 to 2%, particularly 0 to less than 0.5%. 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 laser light.

  MgO, CaO, SrO and BaO are components that suppress devitrification at the time of melting, sintering (adhering), or laser sealing, and the content of MgO + CaO + SrO + BaO (total amount of MgO, CaO, SrO and BaO) Is preferably 0 to 15%, in particular 0 to 10%. If the content of MgO + CaO + SrO + BaO is more than 15%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with laser light.

  MgO, CaO, and SrO are components that suppress devitrification during melting, sintering (adhering), or laser sealing. The content of each component is preferably 0 to 5%, particularly 0 to 2%. When 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 laser light.

  BaO is a component that suppresses devitrification during melting, sintering (adhering), or laser sealing. The content of BaO is preferably 0 to 10%, in particular 0 to 8%. When the content of BaO is more than 10%, the softening point becomes too high and the glass is difficult to soften even when irradiated with laser light.

CeO ₂ and Sb ₂ O ₃ are components that suppress devitrification during melting, sintering (adhering), 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, sintering (adhering), 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 and Ga ₂ O ₃ are components that suppress devitrification during melting, sintering (adhering), or laser sealing. The content of In ₂ O ₃ + Ga ₂ O ₃ (total amount of In ₂ O ₃ and 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} is a component to suppress phase separation during melting, when these total amount is more than 3%, the softening point becomes too high, the laser beam Even when irradiated, the glass becomes difficult to soften.

NiO, V ₂ O ₅ , CoO, MoO ₃ , TiO _2, and MnO ₂ are components having light absorption characteristics. When irradiated with laser light having a predetermined emission center wavelength, the laser light is absorbed and glass is absorbed. It is a component that facilitates softening. 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.

  PbO is a component that lowers the softening point, but it is a component that is concerned about environmental effects. Therefore, the content of PbO is preferably less than 0.1%.

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

  As the refractory filler, it is preferable to use one or more selected from cordierite, zircon, tin oxide, niobium oxide, zirconium phosphate ceramic, and willemite. These refractory fillers have a low thermal expansion coefficient, a high mechanical strength, and a good compatibility with bismuth glass. Of the above refractory fillers, cordierite is most preferred. Cordierite has a property that it is difficult to devitrify the bismuth glass even when the particle size is small, even when laser sealing. In addition to the above refractory filler, β-eucryptite, quartz glass and the like may be added.

The average particle size D ₅₀ of the refractory filler is preferably less than 2 μm, in particular less than 1.8 μm. When the average particle diameter D ₅₀ of the refractory filler is less than 2 μm, the surface smoothness of the sealing material layer is improved and the average thickness of the sealing material layer is easily regulated to less than 10 μm. The accuracy of wearing can be increased.

Maximum particle diameter _{D 99} of the refractory filler is preferably less than 5 [mu] m, 4 [mu] m or less, particularly 3μm or less. When the maximum particle diameter D ₉₉ of the refractory filler is less than 5 [mu] m, together with the surface smoothness of the sealing material layer is improved, easily regulate the average thickness of the sealing material layer less than 10 [mu] m, as a result, the laser sealing The accuracy of wearing can be increased.

The thermal expansion coefficient of the sealing material is preferably 60 × 10 ^{−7 to} 95 × 10 ⁻⁷ / ° C., 66 × 10 ^{−7 to} 90 × 10 ⁻⁷ / ° C., particularly 70 × 10 ^{−7 to} 88 × 10 ^{− 7} / ° C. In this way, the thermal expansion coefficient of the sealing material layer can be easily matched with the thermal expansion coefficient of the element substrate, and the content of the refractory filler can be reduced, so that the sealing material layer softens and flows during laser sealing. It becomes easy to do.

  The softening point of the sealing material is preferably 460 ° C. or lower, 450 ° C. or lower, particularly 430 ° C. or lower. When the softening point is higher than 460 ° C., the sealing material is softened and hardly flows during laser sealing. The lower limit of the softening point is not particularly set, but considering the thermal stability of the glass, the softening point is preferably 350 ° C. or higher.

  The sealing material may further contain a laser absorbing material in order to enhance the light absorption property, but the laser absorbing material has an action of promoting devitrification of the bismuth-based glass. Therefore, the content of the laser absorber is preferably 0 to 10% by volume, 0 to 5% by volume, particularly 0 to 3% by volume. When the content of the laser absorbing material is more than 10% by volume, the glass tends to be devitrified at the time of laser sealing. Cu-based oxides, Fe-based oxides, Cr-based oxides, Mn-based oxides and spinel complex oxides thereof can be used as the laser absorber, and in particular, from the viewpoint of compatibility with bismuth-based glass. Therefore, a Mn-based oxide (for example, 42-343B manufactured by Toago Material Co., Ltd.) is preferable. In addition, when adding a laser absorber, the content is 0.1 volume% or more, 0.5 volume% or more, 1 volume% or more, 1.5 volume% or more, and especially 2 volume% or more is preferable.

  A vehicle usually includes a resin and a solvent. 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 used in the vehicle include N, N′-dimethylformamide (DMF), α-terpineol, higher alcohol, γ-butyllactone (γ-BL), tetralin, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol mono Ethyl ether, diethylene glycol monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl Ether, tripropylene glycol monobutyl ether, propylene carbonate, dimethyl sulfoxide (D SO), N-methyl-2-pyrrolidone and the like can be used. In particular, α-terpineol is preferable because it is highly viscous and has good solubility in resins and the like.

  It is preferable to regulate the average thickness of the sealing material layer after forming the sealing material layer on the glass substrate to be less than 20 μm, less than 15 μm, less than 12 μm, less than 10 μm, and particularly less than 8 μm. Similarly, the average thickness of the sealing material layer after laser sealing is preferably regulated to less than 20 μm, less than 15 μm, less than 12 μm, less than 10 μm, and particularly less than 8 μm. The smaller the average thickness of the sealing material layer, the lower the stress remaining on the sealed portion and the glass substrate after laser sealing. As a result, even if the thermal expansion coefficient of the glass substrate is high, the accuracy of laser sealing can be increased.

  The surface roughness Ra of the sealing material layer after forming the sealing material layer on the glass substrate is regulated to less than 0.5 μm, 0.3 μm or less, 0.2 μm or less, particularly 0.01 to 0.15 μm. Is preferred. In this way, the adhesion between the glass substrate and the element substrate is improved, and the accuracy of laser sealing is improved. “Surface roughness Ra” can be measured by, for example, a non-contact type laser film thickness meter or a surface roughness meter.

  The surface roughness RMS of the sealing material layer after forming the sealing material layer on the glass substrate is restricted to less than 1.0 μm, 0.7 μm or less, 0.5 μm or less, particularly 0.05 to 0.3 μm. Is preferred. In this way, the adhesion between the glass substrate and the element substrate is improved, and the accuracy of laser sealing is improved. Here, the “surface roughness RMS” can be measured by, for example, a non-contact type laser film thickness meter or a surface roughness meter.

  The electrical element package of the present invention includes a step of preparing an element substrate made of metal or ceramic and forming a reaction film on the element substrate.

  The element substrate is made of metal or ceramic. Examples of the metal include kovar and aluminum. As the ceramic, zirconia, alumina, mullite and the like are preferable from the viewpoints of cost and sinterability.

  The reaction film is preferably formed before mounting the element on the element substrate. Thereby, the thermal degradation of the element can be prevented when forming the reaction film.

  The reaction film may be formed over the entire surface of the element substrate, but is preferably formed partially from the viewpoint of manufacturing efficiency, and is preferably formed in a part corresponding to the sealing material layer. Therefore, when the sealing material layer is formed in a frame shape in the outer peripheral edge region of the glass substrate, the reaction film is also preferably formed in a frame shape in the outer peripheral edge region of the element substrate.

  Although various materials can be used as the reaction film, an oxide film or a nitride film is preferable, and an oxide film is particularly preferable. These films have good reactivity with the sealing material layer, and can increase the adhesive strength between the element substrate and the sealing material layer after laser sealing.

As the oxide film, SiO ₂ and glass are suitable, and as the nitride film, SiN is suitable. These films can be easily formed, have good reactivity with the sealing material layer, and can increase the adhesive strength between the element substrate and the sealing material layer after laser sealing.

  Various methods can be used as a method for forming the reaction film, and from the viewpoint of film formation efficiency and thinning, a CVD method, a sputtering method, a vacuum evaporation method and the like are preferable. In the case where the reaction film is glass, it is also preferable that the glass paste containing glass powder and a vehicle is applied to an element substrate (element substrate before element formation) and then fired at a temperature equal to or higher than the softening point of the glass powder. . In this case, the above-mentioned vehicle is preferable.

  The thickness of the reaction film is preferably less than 10 μm, less than 5 μm, less than 3 μm, particularly preferably 1 μm or less. In particular, when the reaction film is glass, the thickness of the reaction film is preferably less than 10 μm, less than 7 μm, and particularly preferably less than 4 μm. If the thickness of the reaction film is too large, it takes time to produce the reaction film, and the manufacturing efficiency of the electric element package tends to be lowered.

  The heat resistant temperature of the reaction film is higher than (softening point of sealing material + 50) ° C., and particularly preferably higher than (softening point of sealing material + 70) ° C. By doing so, it is possible to prevent the reaction film from eroding the electrode or the like during laser sealing.

  In the method for manufacturing an electrical element package of the present invention, a step of sealing the glass substrate and the element substrate by irradiating the sealing material layer with laser light from the glass substrate side, causing the sealing material layer and the reaction film to react with each other. Have

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.

  An electrical element package of the present invention includes an element substrate, a glass substrate facing the surface of the element substrate on the electrical element side with a space therebetween, and a sealing material layer that seals a gap between the element substrate and the glass substrate. The electric element package includes a reaction film disposed between the element substrate and the sealing material layer. The technical features (preferable configuration, effects, etc.) of the electric element package of the present invention have already been described in the explanation column of the method of manufacturing the electric element package of the present invention, and the description of the overlapping parts is omitted here.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

  FIG. 1 is a longitudinal sectional view for explaining a configuration example of an electric element package of the present invention. The electric element package 1 has an element substrate 4 in which an element 2 is formed in a central region and a reaction film 3 is formed in an outer peripheral edge region, and a surface of the element substrate 4 on the element 2 side with a space therebetween. The glass substrate 5 which opposes and the sealing material layer 6 which airtightly seals the clearance gap between the element substrate 4 and the glass substrate 5 are provided as a basic structure, surrounding the element 2 in the shape of a frame.

  The element substrate 4 is made of, for example, 0.05 to 2 mm of alumina or metal. An electrode film (not shown) that is guided to the outside is formed on the element substrate.

  The glass substrate 5 is made of, for example, 0.05 to 2 mm glass. In addition, in order to avoid contact with the element 2 or to install a hygroscopic material, the glass substrate 4 may be formed with a certain thickness of digging.

  And as shown in FIG. 1, the laser beam radiate | emitted from the laser L is irradiated to the sealing material layer 5 from the glass substrate 4 side, the sealing material layer 5 is made to react with the reaction film 3, and the glass substrate 4 and By sealing the element substrate 5, the hermetic sealing structure of the electric element package 1 is formed. As the laser L, for example, a near infrared semiconductor laser (wavelength 800 to 1100 nm) is used.

  Hereinafter, based on an Example, this invention is demonstrated in detail. The following examples are merely illustrative. The present invention is not limited to the following examples.

Table 1 shows the material structure of the sealing material. Bismuth-based glass has a glass composition of mol%, Bi ₂ O ₃ 76.5%, B ₂ O ₃ 8.0%, ZnO 6.0%, CuO 5.0%, Fe ₂ O ₃ 0.5. %, BaO 4.0%, and have the particle sizes listed in Table 1.

  The above-mentioned bismuth-based glass powder and refractory filler were mixed at a ratio shown in Table 1 to prepare a sealing material. Cordierite having the particle size shown in Table 1 was used as the refractory filler. About this sealing material, the glass transition point, the softening point, and the thermal expansion coefficient were measured. The results are shown in Table 1.

  The glass transition point is a value measured with a push rod TMA apparatus.

  The softening point is a value measured with a macro DTA apparatus. The measurement was performed in an air atmosphere at a temperature rising rate of 10 ° C./min, and the measurement was performed from room temperature to 600 ° C.

  The thermal expansion coefficient is a value measured by a push rod type TMA apparatus. The measurement temperature range is 30 to 300 ° C.

  A sealing material layer was formed on the glass substrate as follows. First, the sealing material shown in Table 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. Turned into. As the vehicle, α-terpineol containing ethyl cellulose was used. Next, along the outer peripheral edge region of a non-alkali glass substrate (OA-10G manufactured by Nippon Electric Glass Co., Ltd.) or alkali borosilicate glass (BDA manufactured by Nippon Electric Glass Co., Ltd.) having a length of 50 mm × width of 50 mm × thickness of 1.0 mm. The sealing material paste was printed in a frame shape with a screen printer so that the thickness was about 5 μm and the width was about 0.6 mm, and then dried at 125 ° C. for 10 minutes in an air atmosphere. Then, it is baked at 500 ° C. for 10 minutes in an air atmosphere to incinerate the resin component in the sealing material paste (debinder treatment) and sinter (fix) the sealing material, and seal it on the glass substrate. A dressing material layer was formed.

  The average thickness of the sealing material layer is a value measured with a non-contact type laser film thickness meter.

After forming the reaction film shown in Table 2 on the element substrate (alumina or kovar) having a length of 50 mm, a width of 50 mm, and a thickness of 1.0 mm so that the outer peripheral edge region has a frame shape, the central region of the element substrate An element was formed. Sample No. 1 is an alkali borosilicate glass (softening point 560 ° C.), and is formed by firing and sintering a glass powder paste in the same manner as the method described in paragraph [0098] of the present specification. . This glass powder has a glass composition of mol%, B ₂ O ₃ 45.0%, ZnO 30.0%, SiO ₂ 12.0%, Al ₂ O ₃ 0.7%, Li ₂ O 4.7. %, Na ₂ O 7.6%.

  Subsequently, after placing the element substrate on the glass substrate in an air atmosphere so that the sealing material layer and the reaction film are in contact with each other, the output described in Table 2 along the sealing material layer from the glass substrate side, By irradiating a laser beam having a wavelength of 808 nm at a scanning speed, the sealing material layer is softened and fluidized to seal the glass substrate and the element substrate. 1 to 5 electrical element packages were obtained.

  Each sample was subjected to a high temperature, high humidity, and high pressure test: HAST test (Highly Accelerated Temperature and Humidity Stress test), and then the presence or absence of peeling was observed for the glass substrate and the element substrate. The peel resistance was evaluated with “x” indicating that peeling was observed. The conditions of the HAST test are 121 ° C., humidity 100%, 2 atm, 24 hours.

  As apparent from Table 2, the sample No. Since 1-4 had a reaction film on the element substrate, the peel resistance was good. This means that the reaction layer is sufficiently formed at the interface between the sealing material layer and the reaction film. On the other hand, sample No. No. 5 did not have a reaction film on the element substrate, so the peel resistance was poor.

  The electric element package of the present invention is suitable as a piezoelectric vibration package such as an organic EL illumination or a crystal resonator package.

DESCRIPTION OF SYMBOLS 1 Electric element package 2 Element 3 Element substrate 4 Reaction film 5 Glass substrate 6 Sealing material layer L Laser

Claims (16)

Preparing a glass substrate and forming a sealing material layer on the glass substrate;
Preparing an element substrate made of metal or ceramic and forming a reaction film on the element substrate;
Placing the glass substrate and the element substrate so that the sealing material layer and the reaction film are in contact with each other;
An electric element comprising: a step of irradiating a sealing material layer with a laser beam from the glass substrate side, causing the sealing material layer and the reaction film to react, and sealing the glass substrate and the element substrate. Package manufacturing method.   2. The method of manufacturing an electric element package according to claim 1, wherein the reaction film is an oxide film or a nitride film. The method for manufacturing an electric element package according to claim 1, wherein the reaction film is any one of SiO ₂ , SiN, and glass.   The method of manufacturing an electric element package according to any one of claims 1 to 3, wherein the thickness of the reaction film is less than 10 µm.   The method for manufacturing an electrical element package according to claim 1, wherein the sealing material layer is a sintered body of a sealing material.   The method of manufacturing an electric element package according to claim 1, wherein the electric element package is any one of a piezoelectric vibrator package and organic EL lighting. In an electric element package having an element substrate, a glass substrate facing the surface on the electric element side of the element substrate with a gap, and a sealing material layer that seals a gap between the element substrate and the glass substrate,
An electric element package, wherein a reaction film is disposed between an element substrate and a sealing material layer.   8. The electric element package according to claim 7, wherein the element substrate and the glass substrate are sealed by a sealing process using a laser beam.   9. The electric element package according to claim 7, wherein the reaction film is an oxide film or a nitride film. Electrical device package according to claim 7 or 8 reaction film is characterized in that SiO 2, _SiN, is any of glass.   The electric element package according to claim 7, wherein a thickness of the reaction film is less than 10 μm.   The electric element package according to claim 7, wherein the heat resistant temperature of the reaction film is higher than (softening point of sealing material + 50) ° C.   The electrical element package according to any one of claims 7 to 12, wherein an average thickness of the sealing material layer is less than 20 µm.   The electrical element package according to claim 7, wherein the sealing material layer is a sintered body of a sealing material.   The electrical element package according to claim 14, wherein the sealing material contains 55 to 95% by volume of bismuth glass and 5 to 45% by volume of a refractory filler.   16. The electric element package according to claim 7, wherein the electric element package is any one of a piezoelectric vibrator package and organic EL lighting.