JP7035338B2 - Manufacturing method of bonded body - Google Patents

Description

The present invention relates to a sealing material and a method for manufacturing a bonded body using the same.

Conventionally, an airtight package has been used for mounting and sealing an element such as an LED (Light Emitting Diode). Such an airtight package is configured by joining a container on which an element can be mounted and a cover member for sealing the inside of the container.

Patent Document 1 below discloses an airtight package in which a glass-ceramic substrate and a glass lid are joined via a sealing material. In Patent Document 1, a glass frit made of low melting point glass is used as the sealing material. Further, in Patent Document 1, the glass ceramic substrate and the glass lid are joined by firing and melting the glass frit.

However, when an element having low heat resistance is mounted, if the glass frit is fired and melted as in Patent Document 1, the element characteristics may be thermally deteriorated by the heating at the time of firing. As a method for solving this, a method of melting the glass frit by irradiating the glass frit with a laser and locally heating it (laser seal) can be considered. By adopting the above-mentioned sealing by laser irradiation, it is possible to prevent thermal deterioration of the mounted element.

Japanese Unexamined Patent Publication No. 2014-236202

When sealing by laser irradiation, the laser beam is usually irradiated to the glass frit through a base material such as glass that transmits the laser beam. Conventional sealing materials are sealed using an infrared laser with a wavelength larger than approximately 1000 nm, but when irradiated with laser light in the wavelength range, the base material is heated by the laser light, and the base material is a glass base material due to thermal stress. There is a risk of cracking.

An object of the present invention is to reduce thermal stress generated by irradiation of a laser beam when the sealing material is irradiated with a laser beam through a substrate such as glass to perform sealing, and cracks or the like are generated in the substrate. It is an object of the present invention to provide a sealing material capable of suppressing the above-mentioned conditions, and a method for producing a bonded body using the same.

The sealing material of the present invention is characterized by containing an inorganic powder that softens and flows by heat and a phosphor powder. In the sealing material of the present invention, heat is generated from the fluorescent material powder by irradiating the excitation light of the fluorescent material powder, and the inorganic powder softens and flows by this heat, and functions as a sealing material. Here, the phosphor powder is excited in a relatively low wavelength region of, for example, 1000 nm or less. For example, a base material made of glass has a high transmittance for light in the wavelength range, and the ratio of excitation light absorbed by the base material is small. As a result, even if the sealing material is irradiated with the excitation light via the base material, the base material is not easily heated and the generation of cracks can be suppressed.

In the sealing material of the present invention, it is preferable that the inorganic powder is made of glass. Glass has a relatively low softening point and easily softens and flows, so that it is suitable as a sealing material.

In the sealing material of the present invention, the maximum particle size D _max of the inorganic powder is preferably 200 μm or less. By doing so, it is easy to sinter or melt and solidify, and it is easy to obtain a dense sealing layer.

The sealing material of the present invention preferably contains 0.01% by volume or more of the fluorescent substance powder. By doing so, the amount of heat generated when the excitation light is irradiated becomes large, and the inorganic powder becomes sufficiently softened and flows easily.

In the sealing material of the present invention, the fluorescent substance powder is an oxide fluorescent substance, a nitride fluorescent substance, an oxynitride fluorescent substance, a chloride fluorescent substance, a halide fluorescent substance, a sulfide fluorescent substance, and an acid sulfide fluorescent substance. , At least one selected from a halide fluoresceide, a chalcogenide fluorescein, an aluminate fluorescein, a halophosphate fluorinated phosphor and a garnet compound fluorescee can be used.

The sealing material of the present invention is suitable for laser sealing.

The method for producing a bonded body of the present invention is a method for producing a bonded body in which a first base material and a second base material are bonded via a sealing layer, and is described above on the first base material. The step of forming the sealing material layer made of the sealing material, the step of arranging the second base material in contact with the sealing material layer, and the step of arranging the second base material, and through the first base material or the second base material, The present invention comprises a step of irradiating the sealing material layer with the excitation light of the phosphor powder to sinter or melt and solidify the inorganic powder by utilizing the heat generated from the phosphor powder to form the sealing layer. It is characterized by that.

In the method for producing a bonded body of the present invention, the wavelength of the excitation light is preferably 250 to 1000 nm.

In the method for producing a bonded body of the present invention, it is preferable that the excitation light is laser light.

In the method for producing a bonded body of the present invention, it is preferable to scan and irradiate the sealing material layer with excitation light. In this way, the entire sealing material layer can be irradiated with the excitation light.

In the method for producing a bonded body of the present invention, the inorganic powder and the phosphor powder may be melted and integrated by irradiation with excitation light. By doing so, light scattering at the sealing portion is reduced and transparency is increased.

In the method for producing a bonded body of the present invention, it is preferable that the sealing layer is transparent. By doing so, the sealing layer becomes inconspicuous, and the design of the bonded body can be enhanced.

In the method for producing a bonded body of the present invention, it is preferable that the first base material and / or the second base material is made of glass or ceramic. By doing so, the excitation light is easily transmitted, and the excitation light is sufficiently easily applied to the sealing material layer.

According to the present invention, when the sealing material is irradiated with laser light through a base material such as glass to perform sealing, the thermal stress generated by the irradiation of the laser light is reduced, and cracks or the like are generated in the base material. It becomes possible to provide a sealing material capable of suppressing the above-mentioned factors and a method for producing a bonded body using the same.

It is sectional drawing which shows the manufacturing method of the bonded body which concerns on one Embodiment of this invention.

The sealing material of the present invention is characterized by containing an inorganic powder that softens and flows by heat and a phosphor powder.

As the inorganic powder, one made of glass or ceramic can be used. In particular, glass has a relatively low softening point and easily softens and flows, so that it is suitable as a sealing material. Examples of the glass include silicate glass, silica glass, borosilicate glass, tin phosphate glass, bismuthate glass, zinc borosilicate glass and lead borosilicate glass. These may be used alone or in combination of two or more. Among them, silicate glass and borosilicate glass are preferable because they are excellent in weather resistance and heat resistance.

The softening point of the inorganic powder is preferably 1000 ° C. or lower, 950 ° C. or lower, particularly 900 ° C. or lower, from the viewpoint of enhancing the softening fluidity. If the softening point of the inorganic powder is too low, the mechanical strength, chemical durability, and heat resistance of the sealing layer tend to be inferior. Therefore, the softening point of the inorganic powder is preferably 250 ° C. or higher, 300 ° C. or higher, and particularly preferably 500 ° C. or higher.

The particle size of the inorganic powder is not particularly limited, but for example, the maximum particle size D _max is preferably 200 μm or less, 150 μm or less, and particularly preferably 105 μm or less. Further, the average particle diameter D ₅₀ of the inorganic powder is preferably 50 μm or less, particularly preferably 20 μm or less. If the maximum particle diameter D _max or the average particle diameter D ₅₀ is too large, sintering and melt solidification will be insufficient, and it will be difficult to obtain a dense sealing layer. The lower limit of the average particle diameter D ₅₀ is not particularly limited, but is actually 1 μm or more.

In the present invention, the maximum particle diameter D _max and the average particle diameter D ₅₀ refer to the values measured by the laser diffraction method.

Examples of the fluorescent substance powder include oxide fluorescent substances, nitride fluorescent substances, oxynitride phosphors, chloride fluorescent substances, acidified fluorescent substances, sulfide fluorescent substances, acid sulfide phosphors, and halide fluorescent substances. Examples thereof include an inorganic phosphor powder composed of a chalcogenide fluorescent substance, an aluminate fluorescent substance, a halophosphate-based fluorescent substance, a garnet-based compound fluorescent substance, and the like, and a quantum dot fluorescent substance. These may be used alone or in combination of two or more.

The above fluorescent powder has an excitation band at a wavelength of approximately 250 to 1000 nm. Specific examples include the following.

As a phosphor having an ultraviolet to near-ultraviolet excitation band having a wavelength of 300 to 440 nm, (Sr, Ba) MgAl ₁₀ O ₁₇ : Eu ²⁺ , (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu ²⁺ , SrAl ₂ O ₄ : Eu ²⁺ , SrBaSiO ₄ : Eu ²⁺ , Y ₃ (Al, Gd) ₅ O ₁₂ : Ce ³⁺ , SrSiON: Eu ²⁺ , BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , Mn ²⁺ , Ba ₂ MgSi ₂ O ₇ : Eu ²⁺ Ba ₂ SiO ₄ : Eu ²⁺ , Ba ₂ Li ₂ Si ₂ O ₇ : Eu ²⁺ , BaAl ₂ O ₄ : Eu ²⁺ , La ₃ Si ₆ N ₁₁ : Ce ³⁺ (abbreviation: LSN), MgSr ₃ Si ₂ O ₈ : Eu ²⁺ , Mn ²⁺ , Ca ₂ MgSi ₂ O ₇ : Eu ²⁺ , Mn ²⁺ and the like can be mentioned.

Fluorescent materials having a blue excitation band with a wavelength of 440 to 480 nm include SrAl ₂ O ₄ : Eu ²⁺ , SrBaSiO ₄ : Eu ²⁺ , Y ₃ (Al, Gd) ₅ O ₁₂ : Ce ³⁺ , SrSiO N: Eu ²⁺ , β. -SiAlON: Eu ²⁺ , Y ₃ (Al, Gd) ₅ O ₁₂ : Ce ³⁺ , Sr ₂ SiO ₄ : Eu ²⁺ , CaAlSiN ₃ : Eu ²⁺ (abbreviated as CASN), CaSiN ₃ : Eu ²⁺ , (Ca, Sr) ₂ Examples thereof include Si ₅ N ₈ : Eu ²⁺ and α-SiAlON: Eu ²⁺ .

The average particle size D ₅₀ of the fluorescent powder is preferably 100 μm or less, 50 μm or less, and particularly preferably 30 μm. If the average particle size D ₅₀ of the fluorescent material powder is too large, it becomes difficult to obtain a dense sealing layer. The lower limit of the average particle diameter D ₅₀ is not particularly limited, but is actually 0.1 μm or more, and further 1 μm or more.

The content of the fluorescent powder in the sealing material is preferably 0.01% by volume or more, particularly preferably 0.05% by volume or more. If the content of the phosphor powder is too small, the amount of heat generated when the excitation light is irradiated becomes small, and the inorganic powder becomes difficult to sufficiently soften and flow. On the other hand, if the content of the fluorescent powder is too large, the sintering and melt solidification of the inorganic powder may be insufficient. In addition, the porosity of the obtained sealing layer may increase, which may cause problems such as a tendency for the mechanical strength to decrease. Therefore, the content of the fluorescent substance powder is preferably 30% by volume or less, 20% by volume or less, 10% by volume or less, 5% by volume or less, and particularly preferably 3% by volume or less.

Hereinafter, a method for manufacturing the bonded body of the present invention using the above-mentioned sealing material will be described.

FIG. 1 is a cross-sectional view showing a method for manufacturing a bonded body according to an embodiment of the present invention. First, the first base material 1 and the second base material 2 constituting the bonded body are prepared. Next, the sealing material layer 3 made of the above-mentioned sealing material is formed on the first base material 1. The sealing material layer 3 can be formed, for example, by adding a vehicle containing a resin and a solvent to the sealing material to form a paste, and then applying the obtained paste to the surface of the first base material 1. Further, the second base material 2 is arranged so as to be in contact with the sealing material layer 3 formed on the first base material 1. Subsequently, the excitation light E of the phosphor powder is irradiated from the light source 4 to the sealing material layer 3 via the first base material 1 or the second base material 2, so that the phosphor powder is generated. The heat is used to sintered or melt and solidify the inorganic powder to form a sealing layer 3'. If necessary, the excitation light E is irradiated to the entire sealing material layer 3 by scanning and irradiating the sealing material layer 3. In this way, a bonded body 5 is obtained in which the first base material 1 and the second base material 2 are joined via the sealing layer 3'.

It is preferable to use a laser light source as the light source 4 for irradiating the excitation light E. Since the laser light source has high power, the amount of heat generated from the phosphor powder can be increased, and the inorganic powder can be sintered or melt-solidified in a short time. Further, since the laser beam can reduce the spot diameter and locally irradiate the sealing material layer 3 with the excitation light E, the accuracy is also applied to the sealing material layer 3 having a small line width. It becomes possible to irradiate well. If necessary, the excitation light E may be condensed using a lens or the like and irradiated to the sealing material layer 3. By doing so, the energy of the excitation light E applied to the sealing material layer 3 can be increased, so that the bonded body 5 can be formed in a single time.

The wavelength of the excitation light E may be appropriately selected depending on the phosphor powder to be used, and for example, a wavelength in the range of 250 to 1000 nm (particularly 300 to 440 nm or 440 to 480 nm) can be used.

The scanning speed of the excitation light E may be appropriately selected depending on the output of the excitation light E, the thickness of the sealing material layer 3, and the like, for example, 0.01 to 50 mm / s, and further 0.1 to 10 mm / s. can do.

Examples of the material of the first base material 1 and the second base material 2 include glass and ceramic (transparent ceramic). Since the first base material 1 and / or the second base material 2 is made of glass or ceramic, the excitation light E is easily transmitted, and the excitation light E is easily sufficiently irradiated to the sealing material layer 3. Become. Examples of the glass include SiO ₂ -B ₂ O ₃ -RO (R is Mg, Ca, Sr or Ba) glass, SiO ₂ -B ₂ O ₃ - _R'2 O (R'is Li, Na or K). ) -Based glass or SiO ₂ -B ₂ O ₃ -RO- _R'2 O-based glass. Examples of ceramics include aluminum oxide-based ceramics, aluminum nitride-based ceramics, silicon carbide-based ceramics, boron nitride-based ceramics, magnesium oxide-based ceramics, titanium oxide-based ceramics, niobium-based ceramics, zinc oxide-based ceramics, and yttrium oxide-based ceramics. Can be mentioned.

Inorganic powder and phosphor powder may be melted and integrated by irradiation with excitation light E. By doing so, the homogeneity of the obtained sealing layer 3'is enhanced and it can be made transparent (transparent to the visible region). When the sealing layer 3'becomes transparent, it becomes less noticeable, and the design of the bonded body 5 can be enhanced.

Specific examples of the bonded body 5 include an airtight package in which an element such as an LED is mounted and sealed. Such an airtight package is configured by joining a container on which an element can be mounted and a cover member for sealing the inside of the container with the above-mentioned sealing material.

Hereinafter, the present invention will be described in more detail based on specific examples, but the present invention is not limited to the following examples.

Table 1 shows Examples 1 to 5.

(Example 1)
Borosilicate-based glass powder (softening point 850 ° C., maximum particle size D _max = 10 μm, average particle size D ₅₀ = 3 μm) and YAG phosphor powder (average particle size D ₅₀ = 17 μm) are mixed to form a sealing material. Obtained. The content of the YAG phosphor powder in the sealing material was 0.1% by volume. 1 g of the sealing material was sandwiched between two borosilicate glass substrates, and the sealing material was irradiated with blue laser light (wavelength 445 nm), which is an excitation light, for 0.1 seconds at an output of 1 W. As a result, the sealing material was melted and solidified, and two glass plates were joined by the sealing layer to obtain a bonded body. In the sealing layer, both the glass powder and the phosphor powder were melted and integrated to form a homogeneous transparent layer.

(Example 2)
Borosilicate-based glass powder (softening point 700 ° C., maximum particle size D _max = 15 μm, average particle size D ₅₀ = 5 μm) and YAG phosphor powder (average particle size D ₅₀ = 17 μm) are mixed to form a sealing material. Obtained. The content of the YAG phosphor powder in the sealing material was 0.1% by volume. 1 g of the sealing material is sandwiched between two borosilicate glass substrates, and the sealing material is irradiated with blue laser light (wavelength 445 nm), which is excitation light, for 0.1 seconds at an output of 0.8 W. did. As a result, the sealing material was melted and solidified, and two glass plates were joined by the sealing layer to obtain a bonded body. In the sealing layer, both the glass powder and the phosphor powder were melted and integrated to form a homogeneous transparent layer.

(Example 3)
YAG phosphor powder (average particle size D ₅₀ = 17 μm) is mixed with yttrium phosphate-based glass powder (softening point 330 ° C., maximum particle size D _max = 20 μm, average particle size D ₅₀ = 8 μm) to form a sealing material. Obtained. The content of the YAG phosphor powder in the sealing material was 0.1% by volume. 1 g of the sealing material is sandwiched between two borosilicate glass substrates, and the sealing material is irradiated with blue laser light (wavelength 445 nm), which is excitation light, for 0.1 seconds at an output of 0.4 W. did. As a result, the sealing material was melted and solidified, and two glass plates were joined by the sealing layer to obtain a bonded body. In the sealing layer, both the glass powder and the phosphor powder were melted and integrated to form a homogeneous transparent layer.

(Example 4)
Borosilicate-based glass powder (softening point 850 ° C., maximum particle size D _max = 10 μm, average particle size D ₅₀ = 3 μm) and LSN phosphor powder (average particle size D ₅₀ = 12 μm) are mixed to form a sealing material. Obtained. The content of the LSN fluorescent powder in the sealing material was 0.1% by volume. 1 g of the sealing material was sandwiched between two borosilicate glass substrates, and the sealing material was irradiated with blue laser light (wavelength 445 nm), which is an excitation light, for 0.1 seconds at an output of 1 W. As a result, the sealing material was melted and solidified, and two glass plates were joined by the sealing layer to obtain a bonded body. In the sealing layer, both the glass powder and the phosphor powder were melted and integrated to form a homogeneous transparent layer.

(Example 5)
Borosilicate-based glass powder (softening point 850 ° C., maximum particle size D _max = 10 μm, average particle size D ₅₀ = 3 μm) and CASN phosphor powder (average particle size D ₅₀ = 15 μm) are mixed to form a sealing material. Obtained. The content of the CASN fluorescent powder in the sealing material was 0.1% by volume. 1 g of the sealing material was sandwiched between two borosilicate glass substrates, and the sealing material was irradiated with blue laser light (wavelength 445 nm), which is an excitation light, for 0.1 seconds at an output of 1 W. As a result, the sealing material was melted and solidified, and two glass plates were joined by the sealing layer to obtain a bonded body. In the sealing layer, both the glass powder and the phosphor powder were melted and integrated to form a homogeneous transparent layer.

1 First base material 2 Second base material 3 Sealing material layer 3'Sealing layer 4 Light source 5 Bonded body E Excitation light

Claims (9)

A method for manufacturing a bonded body in which a first base material and a second base material are joined via a sealing layer.
A step of forming a sealing material layer made of a sealing material on the first base material,
The process of arranging the second base material so as to be in contact with the sealing material layer, and
Including the step of sealing the first base material and the second base material,
The sealing material layer is composed of a sealing material containing an inorganic powder that softens and flows by heat and a phosphor powder.
By irradiating the sealing material layer with the excitation light of the phosphor powder via the first substrate or the second substrate, the heat generated from the phosphor powder is utilized to utilize the inorganic powder and the phosphor. A method for producing a bonded body, which comprises melting and integrating the powder to obtain a bonded body in which the first base material and the second base material are bonded by a sealing layer. The method for producing a bonded body according to claim 1, wherein the inorganic powder is made of glass. The method for producing a bonded body according to claim 1 or 2, wherein the maximum particle size Dmax of the inorganic powder is 200 μm or less. The method for producing a bonded body according to any one of claims 1 to 3, wherein the fluorescent substance powder is contained in an amount of 0.01% by volume or more. The phosphor powder is an oxide phosphor, a nitride phosphor, an oxynitride phosphor, a chloride phosphor, a acid compound phosphor, a sulfide phosphor, an acid sulfide phosphor, a halide phosphor, and a chalcogen compound. The preparation of the conjugate according to any one of claims 1 to 4, wherein the conjugate is at least one selected from a phosphor, an aluminate phosphor, a halide-based phosphor, and a garnet-based compound phosphor. Method. The method for producing a bonded body according to any one of claims 1 to 5, wherein the wavelength of the excitation light is 250 to 1000 nm. The method for producing a bonded body according to any one of claims 1 to 6, wherein the excitation light is a laser beam. The method for producing a bonded body according to any one of claims 1 to 7, wherein the excitation light is scanned and irradiated to the sealing material layer. The method for producing a bonded body according to any one of claims 1 to 8, wherein the first base material and / or the second base material is made of glass or ceramic.

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