Cover member with sealing undercoat, and semiconductor light-emitting device

Abstract

To provide a cover member with a sealing undercoat that does not impair the function of the light diffusion part and has good plating resistance. [Solution] A cover member with a sealing underlay film comprising: a cover member made of a flat glass material having a light-diffusing portion in at least a portion of at least one of a pair of opposing main surfaces; and a sealing underlay film formed in a frame shape on the outer edge of one of the main surfaces of the cover member, wherein the sealing underlay film comprises, in order from the cover member side, a glass-containing Ag layer containing glass frit and Ag, and a metal layer, wherein the glass transition temperature of the glass frit in the glass-containing Ag layer is less than the glass transition temperature of the glass material constituting the cover member, the weight loss rate of the glass frit in the glass-containing Ag layer when immersed in a 10% by mass sodium hydroxide aqueous solution at 40°C for 24 hours is 5% or less, and the content ratio of the glass frit in the glass-containing Ag layer is 7% by mass or more.

Description

[Technical Field]

[0001] The present invention relates to a cover member with a sealing undercoat. The present invention also relates to a semiconductor light-emitting device hermetically sealed via the sealing undercoat of the above-mentioned cover member with a sealing undercoat. [Background technology]

[0002] In recent years, laser-based distance measurement sensors called LiDAR (Light Detection and Ranging) have been expected to be applied to fields such as autonomous driving and AR / MR glasses.

[0003] One type of semiconductor laser light source is the VCSEL (Vertical-Cavity Surface-Emitting Laser). VCSELs are suitable for mass production and possess high directivity. Therefore, they are well-suited for use in applications such as automotive LiDAR.

[0004] For VCSELs to be applied to applications such as automotive LiDAR, the VCSEL package must be composed entirely of inorganic materials for reliability and weather resistance, and high hermetic sealing is required. Furthermore, in order to enable wide-area and long-range measurements as an in-vehicle LiDAR, it is desirable to use a VCSEL package equipped with a cover member having a light-diffusing section.

[0005] In contrast, Patent Document 1 discloses that when sealing the space between a package substrate containing an optical semiconductor element and a window member, one of the metal layers provided on the package substrate side and the metal layer provided on the window member side is made relatively wider than the other. This increases the area over which the two metal layers overlap, thereby improving the sealing performance. Furthermore, Patent Document 2 discloses a VCSEL package in which relief grooves are provided at the four corners of the diffuser plate housing section of the adapter for housing the diffuser plate. The presence of these relief grooves prevents chipping of the diffuser plate. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2018-37581 [Patent Document 2] Japanese Patent Publication No. 2021-190580 [Overview of the project] [Problems that the invention aims to solve]

[0007] Thus, while VCSEL packages with enhanced sealing properties and VCSEL packages equipped with diffusers are known, VCSEL packages with light diffusion capabilities and high sealing properties, as well as cover members with suitable sealing undercoats, are not known.

[0008] For example, the metal layer in the window member of the optoelectronic device disclosed in Patent Document 1 is formed by vacuum deposition or sputtering. Therefore, if a cover member (window member) having a light-diffusing portion is to be used, it is necessary to mask the light-diffusing portion and then form the metal layer on the cover member. However, it was found that when the above method is used, even if the masking is removed after the metal layer is formed, some of it remains in the light-diffusing area, affecting the physical properties such as the light-diffusing function of the light-diffusing area. Furthermore, even when the light-diffusing area is formed on the side of the cover member opposite to the side where the metal layer is formed, metal seepage occurs when forming the metal layer on the cover member, similarly affecting the desired physical properties of the cover member.

[0009] Furthermore, the VCSEL package disclosed in Patent Document 2 above is equipped with an adapter having a diffuser plate housing section with relief grooves, and therefore cannot be hermetically sealed.

[0010] Therefore, the primary objective of the present invention is to provide a cover member with a sealing undercoat that does not impede the function of the light diffusion section.

[0011] In contrast, as a result of intensive studies to form a metal layer on the covering member by a method other than sputtering, it was found that a metal layer could be formed by plating after providing a glass-containing Ag layer containing glass frit on the covering member by coating or the like. However, it was found that depending on the glass frit, the glass disappeared during plating and the adhesive strength between the covering member and the sealing base film could not be ensured.

[0012] Therefore, a second object of the present invention is to provide a covering member with a sealing base film having good plating resistance. That is, an object of the present invention is to provide a covering member with a sealing base film that does not inhibit the function of the light diffusing portion and has good plating resistance.

Means for Solving the Problems

[0013] Regarding the above first problem, as described above, it was found that it can be solved by forming a metal layer after providing a glass-containing Ag layer containing glass frit on the covering member by coating or the like. And regarding the above second problem, it was found that it can be solved by adopting a glass frit with high alkali resistance in the glass-containing Ag layer. When a glass frit with high alkali resistance is used, the disappearance of the glass during plating is suppressed, and the adhesive strength between the covering member and the sealing base film can be ensured. In this way, the present inventor has completed the present invention.

[0014] That is, the gist of the present invention is as follows.

[0015] [1] A covering member with a sealing base film including a covering member and a sealing base film, The covering member is made of a flat glass material having a pair of opposing main surfaces, The covering member has a light diffusing portion in at least a part of at least one of the pair of main surfaces, The sealing underlayment is formed in a frame shape on the outer edge of one of the main surfaces of the cover member. The sealing underlayer film comprises, in order from the cover member side, a glass-containing Ag layer and a metal layer. The glass-containing Ag layer comprises glass frit and Ag. The glass transition temperature of the glass frit in the glass-containing Ag layer is less than the glass transition temperature of the glass material constituting the cover member. The glass frit in the glass-containing Ag layer, when immersed in a 10% by mass sodium hydroxide aqueous solution at 40°C for 24 hours in a cylindrical shape with a diameter of 5 mm and a height of 20 mm, exhibits a weight loss rate of 5% or less. A cover member with a sealing undercoat, wherein the glass frit content in the glass-containing Ag layer is 7% by mass or more. [2] A cover member with a sealing base film, which includes a cover member and a sealing base film, The cover member is made of a glass material with an inverted concave cross-section having an upper wall portion, a side wall portion, and a lower opening. The upper wall portion has a light-diffusing portion in at least a portion of the main surface on the lower opening side, The sealing underlayment is formed in a frame shape on at least the outer edge of the bottom surface of the side wall portion. The sealing underlayer film comprises, in order from the cover member side, a glass-containing Ag layer and a metal layer. The glass-containing Ag layer comprises glass frit and Ag. The glass transition temperature of the glass frit in the glass-containing Ag layer is less than the glass transition temperature of the glass material constituting the cover member. The glass frit in the glass-containing Ag layer, when immersed in a 10% by mass sodium hydroxide aqueous solution at 40°C for 24 hours in a cylindrical shape with a diameter of 5 mm and a height of 20 mm, exhibits a weight loss rate of 5% or less. A cover member with a sealing undercoat, wherein the glass frit content in the glass-containing Ag layer is 7% by mass or more. [3] The glass frit is a cover member with a sealing undercoat according to [1] or [2], wherein the composition in terms of oxide mass percent is at least one of Na2O+TiO2:20~40 mass%, Na2O>0 mass%, and TiO2>0 mass%, and Bi2O3+TiO2:40~70 mass%, Bi2O3>0 mass%, and TiO2>0 mass%. [4] A cover member with a sealing underlayment according to any one of [1] to [3], wherein the outermost layer of the metal layer is an Au layer. [5] The cover member with sealing underlayment according to any one of [1] to [4], wherein the metal layer is a layer in which a Ni layer, a Pd layer, and an Au layer are laminated in order from the glass-containing Ag layer side. [6] A cover member with a sealing underlay film according to any one of [1] to [5], wherein the maximum thickness of the glass-containing Ag layer is 5 to 20 μm. [7] The light-diffusing portion is patterned with recesses and protrusions, A cover member with a sealing undercoat according to any one of [1] to [6], wherein when parallel light from a light-emitting element is incident on the main surface of the cover member on the glass-containing Ag layer side, passing through the light-diffusing portion and toward the opposing main surface, the divergence angle of the emitted light beam is 1.5 times or more the divergence angle of the light-emitting element. [8] A cover member with a sealing underlayment according to any one of [1] to [7], wherein the cover member has an anti-reflective film on at least one main surface of the cover member. [9] A cover member with a sealing underlayment according to any one of [1] to [8] above, a substrate, and a light-emitting element provided on the substrate, A semiconductor light-emitting device in which the cover member with the sealing underlay film and the substrate are integrated via the sealing underlay film and a metal ring, and the light-emitting element is hermetically sealed. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a cover member with a sealing undercoat having a light-diffusing portion that does not impair the function of the light-diffusing portion and has good plating resistance. Therefore, in a semiconductor light-emitting device having the above-mentioned cover member with sealing undercoat, the light from the light-emitting portion can be suitably diffused by the light-diffusing portion, and the disappearance of glass during plating is suppressed, thereby ensuring the adhesive strength between the cover member and the sealing undercoat. [Brief explanation of the drawing]

[0017] [Figure 1] Figure 1 is a schematic cross-sectional view showing one embodiment of a cover member with a sealing underlayment according to this embodiment. [Figure 2] Figure 2 is a schematic cross-sectional view showing one embodiment of a cover member with a sealing underlayment according to this embodiment. [Figure 3] Figure 3 is a schematic cross-sectional view showing one embodiment of the semiconductor light-emitting device according to this embodiment. [Figure 4] Figure 4 is a schematic cross-sectional view showing one embodiment of the semiconductor light-emitting device according to this embodiment. [Modes for carrying out the invention]

[0018] The present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be modified and implemented as appropriate without departing from the spirit of the invention. In this specification, the "~" symbol indicating a numerical range is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. In this specification, "average thermal expansion coefficient" refers to the value measured using a NETZSCH Japan Dilatometer TD5000SA, where the material is heated at a heating rate of 5°C / min in the range of 50 to 350°C, and the average value of the expansion rate per degree Celsius is used.

[0019] 《Cover material with sealing underlay film》 One embodiment of the cover member 10 with a sealing undercoat according to this embodiment includes a cover member 1 and a sealing undercoat 2, as shown in Figure 1. The cover member 1 is made of a flat glass material having a pair of opposing main surfaces, but when the main surface on the side where the sealing undercoat 2 is provided is designated as the first main surface 1a, for example, the cover member 1 has a light-diffusing portion 1c in at least a portion of the area of ​​the first main surface 1a.

[0020] The sealing underlayment film 2 is formed in a frame shape on the outer edge of the first main surface 1a of the cover member 1. The sealing underlayer 2 comprises, in order from the cover member 1 side, a glass-containing Ag layer 2A and a metal layer 2B, and the glass-containing Ag layer 2A contains glass frit and Ag (not shown).

[0021] Glass transition temperature (Tg) of glass frit in glass-containing Ag layer 2A GF ) is the glass transition temperature (Tg) of the glass material constituting the cover member 1. CG ) is less than. That is, Tg GF <Tg CG It satisfies the relationship. Furthermore, the glass frit in the glass-containing Ag layer 2A preferably has high alkali resistance, specifically, when immersed in a 10% by mass sodium hydroxide aqueous solution at 40°C for 24 hours in a cylindrical shape with a diameter of 5 mm and a height of 20 mm, the weight loss rate is preferably 5% or less.

[0022] Another embodiment of the cover member 10' with sealing underlayment according to this embodiment includes a cover member 1' and a sealing underlayment 2', as shown in Figure 2. The cover member 1' is made of a glass material with an inverted concave cross-section having an upper wall portion 1A', a side wall portion 1B', and a lower opening 1C'. The main surface on the side of the upper wall portion 1A where the side wall portion 1B' is provided, i.e., the side with the lower opening 1C', is designated as the first main surface 1a', and the main surface opposite the first main surface 1a' is designated as the second main surface 1b'. The upper wall portion 1A' of the cover member 1' has a light-diffusing portion 1c' in at least a portion of the first main surface 1a'.

[0023] A sealing undercoat 2' is formed in a frame shape on at least the outer edge of the bottom surface of the side wall portion 1B' of the cover member 1'. The sealing underlayer 2' includes, in order from the cover member 1' side, a glass-containing Ag layer 2A' and a metal layer 2B', and the glass-containing Ag layer 2A' contains glass frit and Ag (not shown).

[0024] Glass transition temperature (Tg) of glass frit in glass-containing Ag layer 2A' GF ) is the glass transition temperature (Tg) of the glass material constituting the cover member 1'. CG ) is less than. That is, Tg GF <Tg CG It satisfies the relationship. Furthermore, the glass frit in the glass-containing Ag layer 2A' preferably has high alkali resistance, specifically, when immersed in a 10% by mass sodium hydroxide aqueous solution at 40°C for 24 hours in a cylindrical shape with a diameter of 5 mm and a height of 20 mm, the weight loss rate is preferably 5% or less.

[0025] As described above, the cover members 10, 10' with sealing undercoat according to this embodiment use sealing undercoat 2, 2' which contains metal as a component. When the cover members 1, 1' are joined and sealed to the substrates 4, 4' constituting the semiconductor light-emitting device, metal is preferred over resin from the viewpoint of high resistance to moisture and ultraviolet rays and achieving excellent airtightness. Furthermore, metal is preferred over glass from the viewpoint of being able to select a relatively low temperature during sealing. In other words, sealing with metal is preferred from the viewpoint of airtightness, heat resistance, etc.

[0026] When sealing cover members 1,1' and substrates 4,4' using metal rings or other metals, it is necessary to pre-form a metal layer on both cover members 1,1' and substrates 4,4' because it involves bonding dissimilar materials. Conventionally, this metal layer was formed using a sputtering method.

[0027] When forming a metal layer on cover members 1,1' using the sputtering method, masking is applied to areas where the metal layer is not to be formed. However, completely removing the masking is extremely difficult. In particular, when light-diffusing sections 1c,1c' are provided on the first main surfaces 1a,1a', complete removal of the masking becomes even more difficult. Consequently, it was found that physical properties such as the light-diffusing function of the light-diffusing sections 1c,1c' are significantly affected by the remaining masking components. Furthermore, it was found that even when light diffusing sections 1c and 1c' are provided on the second main surfaces 1b and 1b', metal penetration and other issues can still occur up to the second main surfaces 1b and 1b'. Furthermore, it was found that the physical properties of the material can be affected by the remaining masking components, even when additional functional films, such as anti-reflective coatings, are applied to the first main surfaces 1a and 1a'.

[0028] In contrast, the cover members 10, 10' with sealing undercoats according to this embodiment are formed by coating or otherwise creating glass-containing Ag layers 2A, 2A' on the first main surfaces 1a, 1a' of the cover members 1, 1', and then forming metal layers 2B, 2B' thereon by plating or other means to create sealing undercoats 2, 2'. By using plating or other methods, cover members 1, 1' with metal layers 2B, 2B' can be obtained without the need for masking, which is necessary during sputtering. As a result, hermetically sealed cover members 10, 10' with sealing undercoats can be obtained without hindering the function of the light diffusion section. Furthermore, by using sealing undercoats 2, 2 consisting of glass-containing Ag layers 2A, 2A' and metal layers 2B, 2B', sputtering is not used, which is superior from the viewpoint of cost and mass production.

[0029] Next, the various components of the cover member with a sealing underlayment according to this embodiment will be described.

[0030] <Cover component> In this embodiment, the shape of the cover member varies depending on the shape of the substrate to be sealed. For example, when the substrate has a reverse concave cross-sectional shape with a bottom surface, side wall portions, and an opening portion, it is preferable to use a flat glass material having a pair of opposing main surfaces as shown in FIG. 1 for the cover member. In this case, a sealing base film is provided in a frame shape on the outer edge portion of the first main surface of the flat glass material.

[0031] Also, when the substrate is flat with a pair of opposing main surfaces, it is preferable to use a glass material having a reverse concave cross-sectional shape with an upper wall portion, side wall portions, and a lower opening portion as shown in FIG. 2 for the cover member. In this case, a sealing base film is provided in a frame shape on at least the outer edge portion of the bottom surface of the side wall portion of the glass material having a reverse concave cross-sectional shape.

[0032] For the glass material having a reverse concave cross-sectional shape, it is preferable that the four side wall portions are perpendicular to the upper wall portion, but it does not have to be exactly 90°, and it may be regarded as perpendicular including manufacturing errors, etc. That is, specifically, it is sufficient if it is substantially perpendicular at 90° ± 5°.

[0033] · Glass material The glass material constituting the cover member in the present embodiment is not particularly limited as long as it has a glass transition temperature (Tg GF ) higher than the glass transition temperature (Tg CG ) of the glass frit contained in the glass-containing Ag layer constituting the sealing base film described later, and glass conventionally used as a window material for a cavity can be used.

[0034] The glass material can be produced by a conventionally known method both in the flat shape and the reverse concave cross-sectional shape, or commercially available products may be used.

[0035] The glass transition temperature (Tg CGThe glass transition temperature is preferably 500°C or higher, more preferably 515°C or higher, even more preferably 520°C or higher, and the higher the temperature, the better, but for example, it is 1200°C or lower. In this specification, the glass transition temperature of the glass material is the temperature at the first inflection point of the DTA chart obtained by differential thermal analysis (DTA).

[0036] The glass softening point (Ts) of the glass material is preferably 700°C or higher, more preferably 715°C or higher, even more preferably 730°C or higher, and the higher the better, but for example, it is 1720°C or lower. In this specification, the glass softening point Ts of the glass material is the temperature at the fourth inflection point of the DTA chart.

[0037] The average thermal expansion coefficient of glass materials is, for example, 4.5 × 10⁻⁶. -7 ~120×10 -7 A temperature of / ℃ is preferred. Here, from the viewpoint of approaching the average thermal expansion coefficient of the substrate of the light-emitting device to be mounted, the average thermal expansion coefficient of the glass material is 4.5 × 10⁻⁶. -7 Preferably above / ℃, 5.0 × 10 -7 / ℃ or higher is more preferable, and 120×10 -7 Preferably below / ℃, 110 × 10 -7 A temperature of / ℃ or lower is more preferable. Note that any combination of preferred upper and lower limits is arbitrary.

[0038] The glass material only needs to be able to transmit light emitted from the light-emitting element and extract it to the outside, but it is particularly preferable that it be transparent in the visible to near-infrared region.

[0039] Examples of glass materials that satisfy the above-mentioned characteristics include soda-lime glass, borosilicate glass, and aluminosilicate glass. From the viewpoint of processability, borosilicate glass and aluminosilicate glass are preferred.

[0040] The thickness of the glass material is not particularly limited, but is preferably 200 μm to 1.5 mm. From the viewpoint of durability, the thickness is preferably 200 μm or more, more preferably 250 μm or more, and even more preferably 300 μm or more. On the other hand, from the viewpoint of transparency and miniaturization, the thickness is preferably 1.5 mm or less, more preferably 1.2 mm or less, and even more preferably 1.1 mm or less. The combination of preferred upper and lower limit values ​​is arbitrary.

[0041] • Light diffusion section The cover member in this embodiment has a light-diffusing portion, which may be provided on a first main surface, on a second main surface, or on both the first and second main surfaces.

[0042] The light-diffusing portion is preferably formed directly on the main surface of the cover member by processing. Alternatively, a separate light-diffusing layer may be provided instead of a directly processed light-diffusing portion; in this case, from the viewpoint of hermetically sealing properties, the light-diffusing layer is preferably made of an inorganic material. A light-diffusing portion formed by directly processing the main surface of the cover member is preferable compared to forming a separate light-diffusing layer, as it reduces losses due to interfacial reflection and prevents delamination between layers.

[0043] When the light-diffusing portion is formed by direct processing, suitable glass materials for the cover member include, but are not limited to, EN-A1 (trade name), M100 (trade name), M130 (trade name) from AGC Inc., and Tempax (registered trademark) and D263 (registered trademark) from Schott Corporation.

[0044] From the viewpoint of diffusion, it is preferable that the light-diffusing portion is patterned with recesses and protrusions to provide a light-diffusing function. When parallel light is incident on the cover member from the first main surface side, passing through the light diffusion section and toward the second main surface side, the divergence angle of the emitted light beam is preferably 1.2 times or more, more preferably 1.3 times or more, and even more preferably 1.5 times or more, of the divergence angle of the optical element used, from the viewpoint of spreading the light over a wide area. There is no particular upper limit to the above magnification, but for example, it may be 7.0 times or less.

[0045] Furthermore, as the magnification increases, the surface irregularities become larger. Therefore, when using the sputtering method, complete removal of the masking becomes more difficult, and the impact on the light diffusion function becomes more pronounced. In contrast, with the cover member with a sealing undercoat according to this embodiment, hermetically sealed metal can be used without employing the sputtering method. This eliminates any impact on the light diffusion function and is advantageous in that it does not hinder the formation of the desired surface irregularities.

[0046] ·Anti-reflective coating In this embodiment, the cover member may undergo other surface treatments in addition to the light-diffusing portion. Other surface treatments include, for example, anti-reflective coatings to efficiently extract light from the light-emitting element to the outside. Conductive layers and bandpass filters are also examples.

[0047] The anti-reflective coating is preferably provided on at least one of the first main surface and the second main surface of the cover member. Furthermore, the anti-reflective coating may be formed on the entire surface of the first main surface and the second main surface of the cover member, or on only a portion of those surfaces.

[0048] Conventional anti-reflective coatings can be used, as long as they can reduce the reflectance of light at least at the design wavelength. In particular, from the viewpoint of maintaining good anti-reflective performance even during heat treatment when manufacturing cover members with sealing undercoats or semiconductor light-emitting devices, etc., it is preferable that the anti-reflective coating be made of an inorganic material.

[0049] Examples of anti-reflective coatings made from inorganic materials include single-layer thin films and dielectric multilayer films in which two or more dielectric layers with different refractive indices, such as SiO2 and Ta2O5, are stacked.

[0050] <Base film for sealing> • Glass-containing Ag layer Glass frit In this embodiment, the glass-containing Ag layer is formed by adding glass frit to Ag paste and sintering it. Since the melting point of Ag is high at approximately 962°C, a high sintering temperature is required to form an Ag layer consisting solely of Ag, but the glass transition temperature (Tg) of the glass material constituting the cover member is high. CG It is necessary to sinter at a lower temperature than ).

[0051] In contrast, by adding glass frit, the sintering of Ag at low temperatures can be promoted. From this viewpoint, the glass frit constituting the glass-containing Ag layer in this embodiment has a glass transition temperature (Tg GF ) is the glass transition temperature (Tg) of the glass material constituting the cover member. CG It is preferable that it be lower than ).

[0052] From the viewpoint of obtaining good sinterability at low temperatures, it is preferable that the glass frit be made of low-melting-point glass, and conventionally known low-melting-point glass can be used. Suitable low-melting-point glasses include, for example, tin-phosphate glass, bismuth glass, vanadium glass, lead glass, zinc-alkali borate glass, and borosilicate glass. Among these, tin-phosphate glass, bismuth glass, vanadium glass, and borosilicate glass are more preferred, considering reliability such as adhesion, adhesive reliability, and airtight sealing, as well as impacts on the environment and human health. The glass frit may further contain inorganic fillers such as electromagnetic wave absorbers or low thermal expansion fillers.

[0053] The glass transition temperature (Tg) of the glass that makes up glass frit GFAs mentioned above, the glass transition temperature (Tg) of the glass material constituting the cover member is... CG It is acceptable if it is less than ), but for example, 350 to 700°C is preferred. Here, the glass transition temperature (Tg GF The glass transition temperature (Tg) is preferably 350°C or higher, more preferably 380°C or higher, and even more preferably 400°C or higher. Furthermore, from the viewpoint of adhesion of the sealing substrate and the cover member, the glass transition temperature (Tg) is also important. GF The temperature is preferably 700°C or lower, more preferably 680°C or lower, and even more preferably 650°C or lower.

[0054] Furthermore, the glass transition temperature (Tg) of the glass material constituting the cover member is also important. CG ) relative to the glass transition temperature (Tg) of the glass constituting the glass frit. GF ) is Tg GF <Tg CG The relationship must be satisfied, but (Tg CG -Tg GF The difference in glass transition temperatures represented by ) is preferably 50 to 2000°C. Here, from the viewpoint of preventing glass frit from lifting off the surface of the sealing substrate, the difference in glass transition temperatures is preferably 200°C or less, more preferably 180°C or less, and even more preferably 160°C or less. Furthermore, from the viewpoint of sinterability, the difference in glass transition temperatures is preferably 50°C or more, more preferably 70°C or more, and even more preferably 100°C or more.

[0055] The glass softening temperature (Ts) of the glass constituting the glass frit is preferably, for example, 400 to 600°C. Here, from the viewpoint of preventing glass from floating, the glass softening temperature (Ts) is preferably 400°C or higher, more preferably 420°C or higher, and even more preferably 450°C or higher. Furthermore, from the viewpoint of the sinterability of the sealing undercoat, the glass softening temperature (Ts) is preferably 600°C or lower, more preferably 580°C or lower, and even more preferably 575°C or lower.

[0056] In this embodiment, the glass frit preferably has high alkali resistance, and more specifically, it is preferable that its weight loss rate when immersed in a 10% by mass aqueous sodium hydroxide solution at 40°C for 24 hours is 5% or less. This ensures that even when a plating method is used to form a metal layer on top of the glass-containing Ag layer, the glass frit does not dissolve, and good bonding between the cover member and the glass-containing Ag layer can be maintained.

[0057] Note that the above weight reduction rate may vary depending on the specific surface area of ​​the glass frit. Therefore, a cylindrical shape with a diameter of 5 mm and a height of 20 mm (surface area ≈ 353.43 mm²) 2 The weight loss rate when using glass frit is adopted, and if necessary, the weight loss rate when using cylindrical glass frit is converted from the surface area of ​​the glass frit used and the measured weight loss rate.

[0058] The above weight reduction rate is preferably 5% or less, preferably 3% or less, more preferably 2% or less, and may also be 1.5% or less. The smaller the rate, the better, but it may also be, for example, 0.01% or more.

[0059] The glass frit in this embodiment has the above glass transition temperature (Tg GF ) and the above weight reduction rate are not particularly limited, but specific examples include those that satisfy the following compositions (1) to (3). (1)Na2O+TiO2: 20~40% by mass, Na2O>0% by mass, and TiO2>0% by mass (2) Bi2O3+TiO2: 40~70% by mass, Bi2O3>0% by mass, and TiO2>0% by mass (3)SiO2+ZnO:20~50% by mass, SiO2>0% by mass, and ZnO>0% by mass

[0060] Examples of glass frit compositions that satisfy the above (1) include the following, but are not limited to these. (1-1) Na2O: 13.0~20.0% by mass, TiO2: 7.0~20.0% by mass, SiO2: 20-40% by mass, The Na2O + TiO2 ratio satisfies 20.0-40.0% by mass.

[0061] Examples of glass frit compositions that satisfy the above (2) include the following, but are not limited to these. (2-1) Bi2O3: 40.0~60.0% by mass, TiO2:2.5~20.0% by mass, SiO2: 20.0~40.0% by mass, and The Bi2O3 + TiO2 ratio satisfies 42.5-70% by mass.

[0062] Examples of glass frit compositions that satisfy the above (3) include the following, but are not limited to these. (3-1) SiO2: 12~40% by mass ZnO: 8-38% by mass, The SiO2 + ZnO ratio must be 20-50% by mass.

[0063] In this embodiment, the glass frit content in the glass-containing Ag layer is 7% by mass or more, preferably 7 to 25% by mass. Here, from the viewpoint of alkali resistance and airtight sealing, the above content is 7% by mass or more, preferably 10% by mass or more, and more preferably 12% by mass or more. Furthermore, from the viewpoint of preventing cracking of the cover glass, the above content is preferably 25% by mass or less, more preferably 23% by mass or less, and even more preferably 21% by mass or less. In this embodiment, the Ag content in the glass-containing Ag layer is preferably 70% by mass or more, and more preferably 70 to 93% by mass. From the viewpoint of plating properties, the above content is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 79% by mass or more. Furthermore, from the viewpoint of adhesion to the cover glass, the above content is preferably 93% by mass or less, more preferably 92% by mass or less, and even more preferably 90% by mass or less.

[0064] The glass-containing Ag layer is formed in a frame shape on the outer edge of the first main surface of the glass material that serves as the cover member, or on at least the outer edge of the bottom surface of the side wall of the glass material that serves as the cover member. The maximum thickness of the formed glass-containing Ag layer is preferably 5 to 24 μm. Here, from the viewpoint of adhesion, the above maximum thickness is preferably 5 μm or more, more preferably 6 μm or more, and even more preferably 7 μm or more. Furthermore, from the viewpoint of suppressing cracking of the glass material, the above maximum thickness is preferably 24 μm or less, more preferably 23 μm or less, and even more preferably 20 μm or less.

[0065] The ratio of the maximum thickness to the width of the glass-containing Ag layer, i.e., the aspect ratio of the glass-containing Ag layers 2A and 2A' in Figure 1 or Figure 2, is preferably 0.02 to 0.05. Here, from the viewpoint of adhesion, the above ratio is preferably 0.02 or higher, more preferably 0.025 or higher, and even more preferably 0.03 or higher. Furthermore, from the viewpoint of suppressing cracking of the glass material, the above ratio is preferably 0.05 or lower, more preferably 0.48 or lower, and even more preferably 0.45 or lower.

[0066] In this embodiment, the glass-containing Ag layer can be formed by applying an Ag paste containing Ag, glass frit, and vehicle to a glass material and sintering it. By applying an Ag paste, which becomes a glass-containing Ag layer upon coating, onto a glass material, it is possible to avoid the glass-containing Ag layer interfering with undesirable areas such as light diffusion regions.

[0067] A vehicle consists of a binder and an organic solvent, and is used to obtain a paste. Examples of binders include resins.

[0068] The resins that make up the vehicle are not particularly limited, but examples include methylcellulose, ethylcellulose, carboxymethylcellulose, oxyethylcellulose, benzylcellulose, propylcellulose, and nitrocellulose. Examples of organic solvents for the above-mentioned resins include terpineol, texanol, butyl carbitol acetate, and ethyl carbitol acetate.

[0069] Furthermore, acrylic resins such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate can also be used as resins to constitute the vehicle. In this case, examples of organic solvents include methyl ethyl ketone, terpineol, texanol, butyl carbitol acetate, and ethyl carbitol acetate. In this specification, (meth)acrylate means at least one of acrylate and methacrylate.

[0070] Furthermore, examples of resins that make up the vehicle include polyalkylene carbonates such as polyethylene carbonate and polypropylene carbonate. In this case, examples of organic solvents include triethyl acetyl citrate, propylene glycol diacetate, diethyl succinate, ethyl carbitol acetate, triacetin, texanol, dimethyl adipate, ethyl benzoate, and a mixed solvent of propylene glycol monophenyl ether and triethylene glycol dimethyl ether.

[0071] The mixing ratio of the resin and organic solvent in the vehicle of this embodiment is not particularly limited, and the mixing ratio can be adjusted according to the viscosity of the desired Ag paste. For example, the mass ratio of resin to organic solvent is preferably around 3:97 to 30:70.

[0072] The vehicle content in the above Ag paste is preferably 2 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass. Here, from the viewpoint of suppressing the increase in viscosity of the metal paste and facilitating the formation of the sealing undercoat, the above content is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. Furthermore, from the viewpoint of obtaining a sufficient coating thickness of the sealing undercoat, the above content is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. Note that the above vehicle content is related to the solid content concentration of the Ag paste. That is, if the Ag paste consists only of metal, glass powder and vehicle, the total content of Ag and glass powder, which are the components other than vehicle, will be the solid content concentration.

[0073] In this embodiment, the Ag paste may further contain other additives, insofar as they do not impair the effects of the present invention. Examples of other additives include dispersants, defoamers, viscosity modifiers, and the like.

[0074] The method for applying the Ag paste onto the glass material is not particularly limited, but examples include printing and dispensing methods. Among these, the printing method is preferred from the viewpoint of process time.

[0075] The sintering temperature of Ag paste applied to a glass material is the glass transition temperature (Tg) of the glass frit. GF The temperature can be appropriately determined depending on the content ratio of the material, but for example, 500 to 650°C is preferred. Here, from the viewpoint of the sinterability of Ag, the above sintering temperature is preferably 500°C or higher, more preferably 510°C or higher, and even more preferably 520°C or higher. Also, from the viewpoint of preventing surface blistering of the glass, the above sintering temperature is preferably 650°C or lower, more preferably 630°C or lower, and even more preferably 600°C or lower.

[0076] The sintering time for the Ag paste is not particularly limited, but is preferably 10 to 180 minutes. From the viewpoint of sinterability, the sintering time is preferably 10 minutes or more, more preferably 15 minutes or more, and even more preferably 20 minutes or more. Also, from the viewpoint of sealing the glass frit, the sintering time is preferably 180 minutes or less, more preferably 150 minutes or less, and even more preferably 130 minutes or less.

[0077] ·Metal layer In this embodiment, the metal layer is provided on the surface of the glass-containing Ag layer, which is provided to adhere to the cover member. That is, the sealing underlayer includes the glass-containing Ag layer and the metal layer in that order, starting from the cover member side. The metal layer only needs to be provided on the surface of the glass-containing Ag layer facing the adhesive portion with the cover member, and may also be provided so as to cover the entire surface of the glass-containing Ag layer other than the portion that is adhered to the cover member, as shown in Figures 1 and 2.

[0078] The outermost layer of the metal layer, that is, the layer in contact with the substrate that is sealed to the cover member, is preferably a metal film layer containing one or more selected from the group consisting of an Au layer, an Ag layer, a Cu layer, a Ni layer, a Cr layer, and an Au-Sn alloy layer. From the viewpoint of sealing performance, an Ag layer or an Au layer is more preferable, and an Au layer is even more preferable.

[0079] The metal layer may further include another metal layer as a base layer for the outermost layer. Examples of other metal layers include one or more selected from the group consisting of Ni layers, Ti layers, Pd layers, Pt layers, and Cu layers. Among these, Ni layers and Pd layers are preferred from the viewpoint of sealing properties.

[0080] Furthermore, from the standpoint of reliability, it is even more preferable that the metal layer consists of layers stacked in the following order, starting from the glass-containing Ag layer: Ni layer, Pd layer, and Au layer.

[0081] The method for forming these metal layers is not particularly limited as long as it does not require masking. For example, wet methods such as electroplating, electroless plating, printing, and dispensing can be used. Among these, electroless plating is preferred from the viewpoint of uniformity of the metal layer.

[0082] Semiconductor light-emitting device The semiconductor light-emitting device according to this embodiment comprises a cover member with a sealing undercoat, a substrate, and a light-emitting element provided on the substrate.

[0083] When a flat glass material having a pair of opposing main surfaces, as shown in Figure 1, is used as the cover member with a sealing undercoat, the semiconductor light-emitting device 20 is formed as shown in Figure 3, with the substrate 4 having side walls and the cover member 1 being integrated via the sealing undercoat 2 and metal ring 6 on the cover member 1, and the light-emitting element 5 provided on the substrate 4 being hermetically sealed. At this time, it is preferable that the substrate 4 is provided with a metal film 3 to improve adhesion with the metal ring 6.

[0084] When a glass material with an inverted concave cross-section having an upper wall portion 1A', a side wall portion 1B', and a lower opening 1C' is used as the cover member with a sealing undercoat, as shown in Figure 2, the semiconductor light-emitting device 20' is formed as shown in Figure 4, with the flat substrate 4' and the cover member 1' integrated via the sealing undercoat 2' and metal ring 6' on the cover member 1', and the light-emitting element 5' provided on the substrate 4' is hermetically sealed. At this time, it is preferable that the substrate 4' is provided with a metal film 3' to improve adhesion with the metal ring 6'.

[0085] The combination of the cover member and the substrate in the semiconductor light-emitting element according to this embodiment is not limited to the above; for example, both the cover member and the substrate may have side walls. Furthermore, the cover member and the substrate may both be flat, for example, by embedding light-emitting elements in the substrate. Also, at least one of the cover member and the substrate may be changed to a shape such as a dome or lens.

[0086] <Cover material with sealing underlay film> The cover member with a sealing undercoat in the semiconductor light-emitting element according to this embodiment can be the one described above in "Cover Member with Sealing Undercoat," and the preferred embodiment is the same. Furthermore, as mentioned above, the shape may be changed to one that is dome-shaped or lens-shaped.

[0087] <substrate> The substrate in this embodiment is not particularly limited as long as it is insulating, but a ceramic substrate is preferred from the viewpoint of heat dissipation. Preferred ceramic substrates include aluminum nitride (AlN) substrates, alumina (Al2O3) substrates, low-temperature co-fired ceramic (LTCC) substrates, and glass ceramic substrates.

[0088] In this embodiment, when a metal film is provided on the substrate, the configuration of the metal film is not particularly limited, but it is preferable, for example, that a metal layer is provided on the outermost layer.

[0089] The outermost layer of the metal layer, that is, the layer in contact with the cover member that seals to the substrate, is preferably a metal film layer containing one or more selected from the group consisting of an Au layer, an Ag layer, a Cu layer, a Ni layer, a Cr layer, and an Au-Sn alloy layer. From the viewpoint of sealing performance, an Ag layer or an Au layer is more preferable, and an Au layer is even more preferable.

[0090] The metal layer may further include another metal layer as a base layer for the outermost layer. Examples of other metal layers include one or more selected from the group consisting of Ni layers, Ti layers, Pd layers, Pt layers, and Cu layers. Among these, Ni layers and Pd layers are preferred from the viewpoint of sealing properties.

[0091] The metal film may further have an Ag layer between the metal layer and the substrate. That is, it is also preferable that the metal film is laminated in the order of Ag layer and metal layer from the substrate side.

[0092] The Ag layer may be a layer consisting solely of Ag, for example, a glass-containing Ag layer in the sealing underlayer of the cover member described above, which does not contain glass frit.

[0093] The method for forming the Ag layer is not particularly limited. It may be formed by applying an Ag paste containing Ag and vehicle using a wet method such as printing and sintering, or by a dry method such as sputtering.

[0094] <Light-emitting element> The light-emitting element according to this embodiment can be used for both top-side emission and end-side emission. When the cover member is made of a flat glass material having a pair of opposing main surfaces as shown in Figure 1, a light-emitting element that emits light from the top surface is preferred. Alternatively, the light emitted from a light-emitting element that emits light from the end surface may be refracted by a prism mirror or the like, and the light may be extracted to the outside through the cover member. If the cover member is made of a glass material with an inverted concave cross-section having an upper wall, side walls, and a lower opening as shown in Figure 2, both top-emitting and end-emitting light-emitting elements can be used as is. Alternatively, the light may be refracted by a prism mirror or the like and then exposed to the outside.

[0095] The light emitted from the light-emitting element is preferably in the horizontal direction, and for example, a laser diode (LD) is a preferred example. Furthermore, from the viewpoint of the straightness of light propagation, an LD is preferred as the light-emitting element, and among these, a VCSEL is more preferred from the viewpoint of directionality.

[0096] <Metal ring> In this embodiment, the cover member with a sealing undercoat is integrated with the substrate via the sealing undercoat and a metal ring. More preferably, in addition to the sealing undercoat and the metal ring, it is also integrated via a metal film on the substrate. This ensures an hermetically sealed environment between the cover component and the substrate.

[0097] Examples of metal rings include gold (Au)-tin (Sn) rings, tin (Sn)-antimony (Sb) rings, and tin (Sn)-silver (Ag)-copper (Cu) rings, but from the viewpoint of sealing performance, gold-tin rings are more preferable.

[0098] From the viewpoint of sealing performance when sealing via a metal ring, the layer made of a metal film preferably has a layer of metal film on its outermost surface containing one or more selected from the group consisting of Au, Ag, Cu, and Au-Sn alloy, and more preferably has an Ag layer or an Au layer. The layer made of a metal film may further have a film of Ni, Ti, Pd, Pt, Cu, etc. as a base for the metal film layer. [Examples]

[0099] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 3 are examples of actual cases, and Examples 4 to 6 are comparative examples. The above example is a cover member made of a flat glass material and does not have a light-diffusing portion. However, although the details will be described later, since masking is not required when forming the sealing undercoat, even if there is a light-diffusing portion, it can be said that there is no effect on the light-diffusing function due to residual material when the masking is removed, and it can be treated as an example or comparative example. Furthermore, the above example is not a test example of a cover member made of a glass material with an inverted concave cross-section having an upper wall, side walls, and a lower opening. However, the hermetic sealing performance with the substrate can be considered equivalent to the results obtained when using a glass material with an inverted concave cross-section. Furthermore, in the evaluation of sealing performance, although the substrate does not have a light-emitting element, the sealing performance between the substrate and the cover member can be considered the same as that of a semiconductor light-emitting device equipped with a light-emitting element, and therefore it can be treated as an example or comparative example.

[0100] [Example Test] <Example 1> As a cover component, a flat glass plate having a pair of opposing main surfaces (manufactured by SCHOTT, product name D263T eco (trademark registered), Tg: 557℃, average thermal expansion coefficient: 7.2 × 10⁻⁶) is used. -6 A glass plate (at / °C) was prepared. A glass-containing Ag layer was applied to the outer edge of one of the main surfaces of this glass plate by screen printing, and sintering was performed at 540°C for 120 minutes. For the glass-containing Ag layer, Ag and glass frit were weighed as solids in a ratio of Ag:glass frit 80:20 (by weight), and an Ag paste was prepared with a solids:vehicle ratio of 70:30 (by weight). Here, the composition of the glass frit in terms of oxide mass percentage is shown in Table 1, and the Tg is 420°C.

[0101] The glass-containing Ag layer obtained by the above sintering had a width of 0.400 mm and a maximum thickness of 18.84 μm, and the aspect ratio, which is the ratio of the maximum thickness to the width of the glass-containing Ag layer, was 0.0471. The glass frit content in the glass-containing Ag layer was 20% by mass. The width of the glass-containing Ag layer was measured using a VERTEX 311HC three-dimensional image measuring instrument (manufactured by Micto Vu), and the height was measured using a Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.).

[0102] Next, the glass-containing Ag layer underwent neutral degreasing using a neutral cleaner, etching using a two-component neutral etching solution, and activator treatment using a Pd catalyst-granting solution, followed by electroless Ni plating. Then, electroless Pd plating was performed, and finally, electroless Au plating was carried out. This resulted in a cover member with a sealing underlayment having a glass-containing Ag layer and a metal layer in which Ni layers, Pd layers, and Au layers are laminated in that order from the glass-containing Ag layer side.

[0103] <Example 2> A cover member with a sealing undercoat was obtained in the same manner as in Example 1, except that the glass frit used in the glass-containing Ag layer had the composition of the oxide-based mass % shown in Table 1 (Tg: 410°C). The glass-containing Ag layer obtained by sintering had a width of 0.400 mm and a maximum thickness of 17.39 μm, and the aspect ratio, which is the ratio of the maximum thickness to the width of the glass-containing Ag layer, was 0.0435.

[0104] <Example 3> A cover member with a sealing undercoat was obtained in the same manner as in Example 2, except that the width of the glass-containing Ag layer obtained by sintering was set to 0.400 mm, the maximum thickness to 25.28 μm, and the aspect ratio, which is the ratio of the maximum thickness to the width of the glass-containing Ag layer, was set to 0.0632.

[0105] <Example 4> A cover member with a sealing undercoat was obtained in the same manner as in Example 2, except that the width of the glass-containing Ag layer obtained by sintering was set to 0.400 mm, the maximum thickness to 15.39 μm, the aspect ratio (the ratio of the maximum thickness to the width of the glass-containing Ag layer) to 0.0385, and the Ag content in the glass-containing Ag layer was set to 95% by mass and the glass frit content to 5% by mass.

[0106] <Example 5> A cover member with a sealing underlayment was obtained in the same manner as in Example 1, except that the glass frit used in the glass-containing Ag layer was glass frit (Tg: 406°C) with the composition expressed in mass percent based on oxides as listed in Table 1, the width of the glass-containing Ag layer obtained by sintering was set to 0.400 mm, the maximum thickness to 15.00 μm, the aspect ratio (the ratio of the maximum thickness to the width of the glass-containing Ag layer) to 0.0375, and the Ag content in the glass-containing Ag layer was set to 90% by mass and the glass frit content to 10% by mass.

[0107] <Example 6> A cover member with a sealing undercoat was obtained in the same manner as in Example 5, except that the glass frit used in the glass-containing Ag layer had the composition of the oxide-based mass % shown in Table 1 (Tg: 474°C).

[0108] "evaluation" <Alkali resistance> The glass frit used in Examples 1 to 6 was shaped into a cylinder with a diameter of 5 mm and a height of 20 mm, and the weight loss rate was determined when it was immersed in a 10% by mass sodium hydroxide aqueous solution at 40°C for 24 hours. The results are shown in Table 1 under "Weight Reduction Rate [%]".

[0109] <Plating resistance> For each of Examples 1 to 6, the cover member was visually observed at each stage of forming the glass-containing Ag layer, namely (1) after neutral degreasing using a neutral cleaner, (2) after etching using a two-component neutral etching solution, (3) after activator treatment using a Pd catalyst-granting solution, (4) after electroless Ni plating, (5) after electroless Pd plating, and (6) after electroless Au plating. The results are shown in Table 1, where "○" indicates that the glass frit remained without disappearing, and "×" indicates that the glass frit had disappeared. Note that if it is difficult to confirm visually due to the color of the cover member and the glass frit, the presence or absence of glass frit disappearance may be confirmed by microscopic observation instead of visual observation.

[0110] <Hermetry and sealing properties 1: Tape test> For the cover members with sealing undercoats from Examples 1 to 4 after electroless Au plating, cellophane tape was applied, and after the tape was firmly attached to the conductor, the tape was peeled off at a sufficiently slow speed while applying a constant force. The results are shown in Table 1 under "Tape Test." When metal adhesion to the cellophane tape was visually confirmed, the sealing undercoat peeled off from the cover member, indicating weak adhesive strength between the cover member and the sealing undercoat, and thus a "×" was indicated as insufficient for proper airtight sealing. On the other hand, when metal adhesion to the cellophane tape was not visually confirmed, the adhesive strength between the cover member and the sealing undercoat was strong, indicating good airtight sealing was possible, and thus a "○" was indicated. Furthermore, the cover members with sealing undercoats in Examples 5 and 6 were marked "-" (not performed) because the glass frit disappeared during the electroless Ni plating or electroless Pd plating process, meaning they could not be considered to have undergone electroless Au plating and therefore could not be evaluated.

[0111] <Hermetry and sealing performance 2: Leak test> The cover members with sealing undercoats obtained in Example 1 and Example 2 were joined to a glass-ceramic substrate with an outer frame. Specifically, an Ag film was formed on the joining area of ​​the glass-ceramic substrate with an outer frame by printing, and then an Au film was formed by plating. Then, the cover members with sealing undercoats obtained in Example 1 and Example 2 were placed on top of each other, and the mixture was bonded by heating at 300°C for 1 minute in a nitrogen atmosphere, followed by heating at 270°C for 1 minute in air, and then cooling to room temperature in air. As a result, a cell was obtained in which the cover member with sealing undercoat and the substrate were integrated. The airtight sealing properties of the joined cells were evaluated using the immersion method (bombing method). Specifically, the above-mentioned cell was placed in a pressurized tank and pressurized with He gas for a certain period of time. After that, the cell was removed and the outside of the cell was evacuated in a vacuum chamber. The presence or absence of leaks at that time was detected using a leak detector. The results are shown in Table 1 under "Leak Test," but the vacuum level in the leak detector was 10 -8 If the reading is less than or equal to atm·cc / sec, it can be considered that there is no leak. In Table 1, "-" indicates that the procedure has not been performed.

[0112] [Table 1]

[0113] The cover members with sealing undercoats in Examples 1 to 4 all exhibit excellent alkali resistance, enabling good plating resistance. Therefore, even after forming a metal layer by electroless plating, the glass frit in the glass-containing Ag layer does not dissolve, or if it does dissolve, it is only a small amount. Furthermore, in the cover members with sealing undercoats in Examples 1 to 3, the glass frit content in the glass-containing Ag layer is above a predetermined value, which allows for suitable adhesion strength between the cover member and the sealing undercoat, resulting in good hertically tight sealing. Furthermore, as described above, the cover member with a sealing undercoat according to this embodiment can form a sealing undercoat without masking. Therefore, even if the cover member has a light-diffusing portion, its function is not hindered. [Explanation of symbols]

[0114] 1,1' Cover member 1a, 1a' First main surface 1b, 1b' Second principal surface 1c,1c' Light Diffusion Section 1A' Upper wall 1B' Side wall part 1C' Lower opening 2,2' Base film for sealing 2A,2A' Glass-containing Ag layer 2B,2B' metal layer 3,3' metal film 4,4' substrate 5,5' Light-emitting element 6.6' Metal Ring 10,10' Cover component with sealing undercoat 20,20' Semiconductor light-emitting device

Claims

1. A cover member with a sealing underlay film, comprising a cover member and a sealing underlay film, The cover member is made of a flat glass material having a pair of opposing main surfaces. The cover member has a light-diffusing portion in at least a portion of at least one of the pair of main surfaces, The sealing underlayment is formed in a frame shape on the outer edge of one of the main surfaces of the cover member. The sealing underlayer film comprises, in order from the cover member side, a glass-containing Ag layer and a metal layer. The glass-containing Ag layer comprises glass frit and Ag. The glass transition temperature of the glass frit in the glass-containing Ag layer is less than the glass transition temperature of the glass material constituting the cover member. The glass frit in the glass-containing Ag layer, when immersed in a 10% by mass sodium hydroxide aqueous solution at 40°C for 24 hours in a cylindrical shape with a diameter of 5 mm and a height of 20 mm, exhibits a weight loss rate of 5% or less. A cover member with a sealing undercoat, wherein the glass frit content in the glass-containing Ag layer is 7% by mass or more.

2. A cover member with a sealing underlay film, comprising a cover member and a sealing underlay film, The cover member is made of a glass material with an inverted concave cross-section having an upper wall portion, a side wall portion, and a lower opening. The upper wall portion has a light-diffusing portion in at least a portion of the main surface on the lower opening side, The sealing underlayment is formed in a frame shape on at least the outer edge of the bottom surface of the side wall portion. The sealing underlayer film comprises, in order from the cover member side, a glass-containing Ag layer and a metal layer. The glass-containing Ag layer comprises glass frit and Ag. The glass transition temperature of the glass frit in the glass-containing Ag layer is less than the glass transition temperature of the glass material constituting the cover member. The glass frit in the glass-containing Ag layer, when immersed in a 10% by mass sodium hydroxide aqueous solution at 40°C for 24 hours in a cylindrical shape with a diameter of 5 mm and a height of 20 mm, exhibits a weight loss rate of 5% or less. A cover member with a sealing undercoat, wherein the glass frit content in the glass-containing Ag layer is 7% by mass or more.

3. The glass frit has a composition expressed in mass % based on oxides, where Na ２ O + TiO ２ : 20 to 40 mass %, Na ２ O > 0 mass %, and TiO ２ > 0 mass %, and, Na ２ O + TiO ２ : 40 to 70 mass %, Bi ２ O ３ > 0 mass %, and TiO ２ > 0 mass %, and satisfies at least one of them. The cover member with a sealing base film according to claim 1 or 2.

4. The cover member with sealing underlayment according to claim 1 or 2, wherein the outermost layer of the metal layer is an Au layer.

5. The cover member with sealing underlayment according to claim 1 or 2, wherein the metal layer is a layer in which a Ni layer, a Pd layer, and an Au layer are laminated in order from the glass-containing Ag layer side.

6. The cover member with sealing underlayment according to claim 1 or 2, wherein the maximum thickness of the glass-containing Ag layer is 5 to 20 μm.

7. The light-diffusing portion is patterned with recesses and protrusions. The cover member with sealing undercoat according to claim 1 or 2, wherein when parallel light from a light-emitting element is incident on the main surface of the cover member on the glass-containing Ag layer side, passing through the light-diffusing portion and toward the opposing main surface, the divergence angle of the emitted light beam is 1.5 times or more the divergence angle of the light-emitting element.

8. The cover member with sealing undercoat according to claim 1 or 2, wherein the cover member has an anti-reflective film on at least one main surface of the cover member.

9. A cover member with a sealing underlayment according to claim 1 or 2, a substrate, and a light-emitting element provided on the substrate, A semiconductor light-emitting device in which the cover member with the sealing underlay film and the substrate are integrated via the sealing underlay film and a metal ring, and the light-emitting element is hermetically sealed.

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