Hermetic packaging

Abstract

The glass substrate with a sealing material layer of the present invention is a glass substrate with a sealing material layer formed thereon, characterized in that the average transmittance at 250 nm or more and less than 300 nm when the thickness of the glass substrate is 0.2 mm is 85% or more, and the difference in the coefficient of thermal expansion between the sealing material layer and the glass substrate in the temperature range of 30°C to 300°C is 5 ppm / °C or less.

Description

Technical Field

[0001] This invention relates to a glass substrate with a sealing material layer, an hermetically sealed device, and a method for manufacturing the hermetically sealed device. Prior Technology

[0002] Hermetic packaging of electronic components, including light-emitting diodes (LEDs), is used in various fields such as lighting and communications due to its long lifespan or energy efficiency.

[0003] In this type of hermetically sealed packaging, there are cases where, in order to protect the electronic components, a glass substrate (glass cover) is placed over the packaging substrate containing the electronic components in such a way that the electronic components are housed inside.

[0004] For example, Patent Document 1 discloses a hermetically sealed package comprising: a package substrate on which electronic components are mounted; a frame portion surrounding the electronic components; and a cover portion comprising a glass substrate covering an opening at one end of the frame portion. Additionally, Patent Document 2 discloses a hermetically sealed package having a recess in the package substrate for housing electronic components, and including a cover portion comprising a glass substrate covering the recess. [Existing technical documents] [Patent Literature]

[0005] [Patent Document 1] International Publication No. 2015 / 190242 [Patent Document 2] Japanese Patent Application Publication No. 2016-027610 Summary of the Invention

[0006] [The problem that the invention aims to solve]

[0007] Furthermore, quartz has the characteristic of being difficult to absorb wavelengths of light in the ultraviolet region. Therefore, in cases such as hermetically sealed ultraviolet LED packages, from the viewpoint of improving ultraviolet transmittance, there are situations where a quartz substrate is used for the cover.

[0008] However, if conventional metal solder (such as gold-tin solder) is used to bond the quartz substrate to the frame or package substrate, the matching of the coefficients of thermal expansion between the materials becomes problematic. Specifically, the coefficient of thermal expansion of the quartz substrate (approximately 0.6 ppm) is very low compared to that of conventional metal solder (approximately 12.0 ppm), resulting in a large difference in the coefficients of thermal expansion between the materials. Consequently, residual stress is generated at or near the joint, making the quartz substrate prone to damage (e.g., cracks or breakage). If the quartz substrate breaks as described above, the hermeticity of the hermetic package's containment space cannot be maintained.

[0009] The objective of this invention is to provide a glass substrate that can maintain high airtightness and a method for manufacturing airtight packaging. [Methods for solving problems]

[0010] The inventors conducted extensive research and discovered that the aforementioned problem can be solved by forming a sealing material layer on a glass substrate with high ultraviolet transmittance and reducing the difference in the coefficients of thermal expansion between the glass substrate and the sealing material layer. Therefore, this invention is proposed. Specifically, the glass substrate with a sealing material layer of this invention is a glass substrate with a sealing material layer formed thereon, characterized in that, when the thickness of the glass substrate is 0.2 mm, the average transmittance at 250 nm or more and less than 300 nm is 85% or more, and the difference in the coefficients of thermal expansion between the sealing material layer and the glass substrate within a temperature range of 30°C to 300°C is 5 ppm / °C or less. Furthermore, "average transmittance at 250 nm or more and less than 300 nm when the thickness is 0.2 mm" refers to the average transmittance calculated after converting a glass substrate thickness other than 0.2 mm to a thickness of 0.2 mm.

[0011] In addition, the glass substrate with a sealing material layer of the present invention is preferably such that the area of ​​the sealing material layer formed on the side of the glass substrate on which the sealing material layer is formed is 1% to 50%.

[0012] Furthermore, the glass substrate with a sealing material layer of the present invention preferably has a sealing material layer having multiple sealing patterns, and the sealing patterns are in a closed-loop shape. If so, an hermetically sealed device can be formed for each sealing pattern, thus a hermetically sealed device group (an assembly of multiple hermetically sealed devices) can be fabricated using a single glass substrate with a sealing material layer through a series of laser seals. Moreover, by dividing or cutting the hermetically sealed device group, a large number of hermetically sealed devices can be easily fabricated. Furthermore, the term "closed-loop shape" includes not only shapes composed solely of curves, but also shapes composed of a combination of curves and straight lines, and shapes composed solely of straight lines (e.g., quadrilateral shapes and other polygonal shapes).

[0013] In addition, the glass substrate with a sealing material layer of the present invention is preferably a sintered body of a composite powder containing at least bismuth-based glass powder and ceramic powder, wherein the content of bismuth-based glass in the sealing material layer is 65% to 95% by volume, and the content of ceramic is 5% to 35% by volume.

[0014] Furthermore, the glass substrate with a sealing material layer of the present invention is preferably one in which the sealing material layer substantially does not contain a laser absorber. Here, "the sealing material layer substantially does not contain a laser absorber" means that the content of the laser absorbing material in the sealing material layer is less than 1% by volume.

[0015] In addition, the glass substrate with a sealing material layer of the present invention preferably has an average thickness of 15 μm or less for the sealing material layer, and the value obtained by dividing the average thickness of the sealing material layer by the thickness of the glass substrate is 0.005 to 0.5.

[0016] In addition, the glass substrate with a sealing material layer of the present invention preferably has an average width of 1000 μm or less for the sealing material layer, and the average thickness of the sealing material layer divided by the average width of the sealing material layer is 0.005 to 0.1.

[0017] In addition, the glass substrate with a sealing material layer of the present invention is preferably a rectangular, circular, or circular substrate with an oriented plane.

[0018] Preferably, an anti-reflective film is formed on any surface of the glass substrate. If so, reflection loss is reduced and the light extraction efficiency of the LED device is improved.

[0019] Furthermore, the glass substrate with a sealing material layer of the present invention is preferably used for sealing by laser light. In this case, it is easy to prevent thermal degradation of electronic components during sealing.

[0020] The method for manufacturing hermetic devices according to the present invention is characterized by comprising: a step of preparing a packaging substrate; a step of preparing a glass substrate having a sealing material layer including a plurality of sealing patterns; a step of separating the sealing material layer and stacking the packaging substrate and the glass substrate having the sealing material layer; a step of irradiating the glass substrate side with laser light to soften and deform the sealing material layer, thereby hermetically sealing the glass substrate and the packaging substrate to obtain a hermetic device group; and a step of dividing the hermetic device group to obtain a plurality of hermetic devices, wherein the glass substrate having the sealing material layer is the glass substrate having the sealing material layer.

[0021] The hermetic packaging of the present invention is a hermetic packaging formed by the glass substrate and the packaging substrate through a sealing material layer. It is characterized in that the average transmittance at 250 nm or more and less than 300 nm is 85% or more when the thickness of the glass substrate is 0.2 mm, and the difference in the coefficient of thermal expansion between the sealing material layer and the glass substrate in the temperature range of 30°C to 300°C is less than 5 ppm / °C. [The effects of the invention]

[0022] According to the present invention, a glass substrate with a sealing material layer that can maintain high airtightness and a method for manufacturing hermetically sealed packaging can be provided. Simple Explanation of the Diagram

[0023] Figure 1 is a schematic cross-sectional view showing an example of the hermetically sealed device of the present invention. Figure 2 is a photograph of a glass substrate with a sealing material layer in Example 2. Implementation

[0024] In the glass substrate with a sealing material layer of the present invention, when the thickness of the glass substrate is 0.2 mm, the average transmittance at 250 nm or more and less than 300 nm is 85% or more, preferably 86% or more, 87% or more, 88% or more, 89% or more, 90% or more, 91% or more, and particularly 92% or more. If the average transmittance at 250 nm or more and less than 300 nm when the thickness of the glass substrate is 0.2 mm is too low, ultraviolet light is difficult to pass through, making it unsuitable for hermetic packaging such as ultraviolet LED packaging.

[0025] When the thickness of the glass substrate is 0.2 mm, the preferred average transmittance at wavelengths above 300 nm and below 1000 nm is 89% or higher, 90% or higher, 91% or higher, 92% or higher, 93% or higher, 94% or higher, and especially 95% or higher. If the average transmittance at wavelengths above 300 nm and below 1000 nm is too low when the thickness of the glass substrate is 0.2 mm, visible light cannot pass through easily, making it unsuitable for hermetic packaging such as LED packaging.

[0026] The difference in the coefficients of thermal expansion between the sealing material layer and the glass substrate within a temperature range of 30°C to 300°C is less than 5 ppm / °C, preferably less than 4 ppm / °C, less than 3.5 ppm / °C, less than 3.2 ppm / °C, and particularly less than 3 ppm / °C. If the difference in the coefficients of thermal expansion between the sealing material layer and the glass substrate within a temperature range of 30°C to 300°C is too large, residual stress will be generated at or near the joint after sealing, which can easily cause damage to the glass substrate (e.g., cracks). Moreover, if the glass substrate is damaged, there is a risk of a decrease in the airtightness of the hermetically sealed containment space.

[0027] The coefficient of thermal expansion of the glass substrate in the temperature range of 30°C to 300°C is preferably below 11 ppm / °C, below 10 ppm / °C, below 9 ppm / °C, below 8 ppm / °C, below 7 ppm / °C, below 6 ppm / °C, and particularly below 3 ppm / °C to 5 ppm / °C. Especially when the encapsulation substrate is silicon, the coefficient of thermal expansion of the glass substrate in the temperature range of 30°C to 300°C is preferably below 10 ppm / °C, below 9 ppm / °C, below 8 ppm / °C, below 7 ppm / °C, below 6 ppm / °C, and particularly below 3 ppm / °C to 5 ppm / °C. If the coefficient of thermal expansion of the glass substrate is too low, residual stress will be generated at or near the joint after sealing, which can easily lead to damage to the glass substrate (e.g., cracks or other breakage). Moreover, if the glass substrate breaks, there is a risk of a decrease in the airtightness of the hermetically sealed enclosure space.

[0028] Regarding the glass substrate, the preferred glass composition, by mass%, is as follows: SiO₂ 50%~80%, Al₂O₃ + B₂O₃ (total amount of Al₂O₃ and B₂O₃) 1%~45%, Li₂O + Na₂O + K₂O (total amount of Li₂O, Na₂O, and K₂O) 0%~25%, and MgO + CaO + SrO + BaO (total amount of MgO, CaO, SrO, and BaO) 0%~25%. The reasons for limiting the content of each component as described above are explained below. Furthermore, in the description of the content of each component, the % designation indicates mass unless otherwise specified.

[0029] SiO₂ is the main component forming the glass framework. The preferred SiO₂ content is 50%–80%, 55%–75%, 58%–70%, and especially 60%–68%. If the SiO₂ content is too low, Young's modulus and acid resistance tend to decrease. On the other hand, if the SiO₂ content is too high, in addition to increased viscosity at high temperatures and decreased solubility, devitrifying crystals such as siliceous silica tend to precipitate, and the liquidus temperature tends to rise.

[0030] Al₂O₃ and B₂O₃ are components that improve resistance to devitrification. The preferred Al₂O₃ + B₂O₃ content is 1%~40%, 5%~35%, 10%~30%, and especially 15%~25%. If the Al₂O₃ + B₂O₃ content is too low, the glass is prone to devitrification. Conversely, if the Al₂O₃ + B₂O₃ content is too high, the compositional balance of the glass breaks down, making the glass more prone to devitrification.

[0031] Al₂O₃ is a component that improves Young's modulus and inhibits phase separation and devitrification. The preferred Al₂O₃ content is 0%–20%, 1%–20%, 3%–18%, and especially 5%–16%. If the Al₂O₃ content is too low, the Young's modulus tends to decrease, and the glass composition is prone to phase separation and devitrification. On the other hand, if the Al₂O₃ content is too high, the high-temperature viscosity increases, and the melt flowability tends to decrease.

[0032] B₂O₃ is a component that improves melt flow and resistance to devitrification, and also improves scratch resistance and strength. The preferred B₂O₃ content is 0%~25%, 1%~25%, 2%~25%, 3%~25%, 5%~22%, 7%~19%, and especially 9%~16%. If the B₂O₃ content is too low, melt flow and resistance to devitrification tend to decrease, and resistance to hydrofluoric acid solutions also tends to decrease. On the other hand, if the B₂O₃ content is too high, Young's modulus and acid resistance tend to decrease.

[0033] Li₂O, Na₂O, and K₂O are components that reduce high-temperature viscosity, significantly improve meltability, and facilitate the initial melting of glass raw materials. The preferred contents of Li₂O, Na₂O, and K₂O are 0%–25%, 1%–20%, 4%–15%, and especially 7%–13%. If the contents of Li₂O, Na₂O, and K₂O are too low, meltability tends to decrease. On the other hand, if the contents of Li₂O, Na₂O, and K₂O are too high, the coefficient of thermal expansion may become unreasonably high.

[0034] Li₂O is a component that reduces high-temperature viscosity, significantly improves meltability, and facilitates the initial melting of glass raw materials. The preferred Li₂O content is 0%–5%, 0%–3%, 0%–1%, and especially 0%–0.1%. If the Li₂O content is too low, in addition to a decrease in meltability, there is also a risk of an inappropriately low coefficient of thermal expansion. On the other hand, if the Li₂O content is too high, the glass is prone to phase separation.

[0035] Na₂O is a component that reduces high-temperature viscosity, significantly improves meltability, and facilitates the initial melting of glass raw materials. It is also used to adjust the coefficient of thermal expansion. The preferred Na₂O content is 0%–25%, 1%–20%, 3%–18%, 5%–15%, and especially 7%–13%. If the Na₂O content is too low, in addition to a decrease in meltability, there is a risk of an unduly low coefficient of thermal expansion. On the other hand, if the Na₂O content is too high, there is a risk of an unduly high coefficient of thermal expansion.

[0036] K₂O is a component that reduces viscosity at high temperatures, significantly improves meltability, and facilitates the initial melting of glass raw materials. It is also used to adjust the coefficient of thermal expansion. The preferred K₂O content is 0%–15%, 0.1%–10%, 1%–10%, and especially 3%–5%. Excessive K₂O content may lead to an unduly high coefficient of thermal expansion.

[0037] MgO, CaO, SrO, and BaO are components that reduce viscosity at high temperatures and improve melt flow. The preferred contents of MgO, CaO, SrO, and BaO are 0%~25%, 0%~15%, 0.1%~12%, and 1%~5%, respectively. If the contents of MgO, CaO, SrO, and BaO are too high, the glass is prone to devitrification.

[0038] MgO is a component that reduces high-temperature viscosity and improves meltability, and it is also a component that significantly improves Young's modulus among alkaline earth metal oxides. The preferred MgO content is 0%~10%, 0%~8%, 0%~5%, and especially 0%~1%. If the MgO content is too high, the devitrification resistance is likely to decrease.

[0039] CaO is a component that reduces viscosity at high temperatures and significantly improves melt flow. Furthermore, among alkaline earth metal oxides, it is a component that reduces raw material costs due to its relatively low cost. The preferred CaO content is 0%–15%, 0.1%–12%, 0.5%–10%, and especially 1%–5%. If the CaO content is too high, the glass is prone to devitrification. Conversely, if the CaO content is too low, the aforementioned effects are difficult to achieve.

[0040] SrO is a component that improves resistance to devitrification. The preferred SrO content is 0%~7%, 0%~5%, 0%~3%, and especially 0%~less than 1%. If the SrO content is too high, the compositional balance of the glass will be disrupted, and the glass will be more prone to devitrification.

[0041] BaO is a component that improves resistance to devitrification. The optimal BaO content is 0%~10%, 0%~7%, 0%~5%, 0%~3%, or 0%~less than 1%. If the BaO content is too high, the compositional balance of the glass will be disrupted, and the glass will be more prone to devitrification.

[0042] In addition to the aforementioned ingredients, other ingredients may be introduced as arbitrary ingredients. Furthermore, from the viewpoint of truly enjoying the effects of the present invention, the content of other ingredients besides the aforementioned ingredients is preferably 10% or less, 5% or less, and particularly 3% or less in total.

[0043] ZnO is a component that improves melt flow, but if it is present in large quantities in the glass composition, the glass is prone to devitrification. Therefore, the preferred ZnO content is 0%~5%, 0%~3%, 0%~1%, 0%~less than 1%, and especially 0%~0.1%.

[0044] ZrO₂ is a component that improves acid resistance, but if it is present in large quantities in the glass composition, the glass is prone to devitrification. Therefore, the preferred ZrO₂ content is 0%~5%, 0%~3%, 0%~1%, 0%~0.5%, and especially 0.001%~0.2%.

[0045] Fe₂O₃ and TiO₂ are components that reduce transmittance in the deep ultraviolet region. The preferred content of Fe₂O₃ + TiO₂ (the combined amount of Fe₂O₃ and TiO₂) is below 100 ppm, below 80 ppm, 0.1 ppm to 60 ppm, 0.3 ppm to 40 ppm, 0.5 ppm to 30 ppm, 0.8 ppm to 20 ppm, 1 ppm to 10 ppm, and especially 2 ppm to 5 ppm. If the content of Fe₂O₃ + TiO₂ is too high, the glass will become colored, and the transmittance in the deep ultraviolet region will easily decrease. Furthermore, if the content of Fe₂O₃ + TiO₂ is too low, high-purity glass raw materials must be used, leading to a higher cost of masterbatch.

[0046] Fe₂O₃ is a component that reduces transmittance in the deep ultraviolet region. The preferred Fe₂O₃ content is below 100 ppm, below 80 ppm, 0.05 ppm to 60 ppm, 0.1 ppm to 40 ppm, 0.5 ppm to 20 ppm, 1 ppm to 10 ppm, and especially 2 ppm to 8 ppm. If the Fe₂O₃ content is too high, the glass will become colored, and the transmittance in the deep ultraviolet region will easily decrease. Furthermore, if the Fe₂O₃ content is too low, high-purity glass raw materials must be used, leading to a higher cost of masterbatch.

[0047] Fe ions in iron oxide exist in the form of Fe²⁺ or Fe³⁺. If the proportion of Fe²⁺ is too low, the transmittance under deep ultraviolet light tends to decrease. Therefore, the preferred mass ratio of Fe²⁺ / (Fe²⁺++Fe³⁺) in iron oxide is 0.1 or higher, 0.2 or higher, 0.3 or higher, 0.4 or higher, and especially 0.5 or higher.

[0048] TiO2 is a component that reduces transmittance in the deep ultraviolet region. The preferred TiO2 content is below 100 ppm, below 80 ppm, below 60 ppm, below 40 ppm, 0.05 ppm to 20 ppm, 0.1 ppm to 10 ppm, and especially 0.5 ppm to 5 ppm. If the TiO2 content is too high, the glass will become colored, and the transmittance in the deep ultraviolet region will easily decrease. Furthermore, if the TiO2 content is too low, high-purity glass raw materials must be used, leading to a higher cost of masterbatch.

[0049] Sb₂O₃ is the component that functions as a clarifying agent. The preferred Sb₂O₃ content is below 1000 ppm, below 800 ppm, below 600 ppm, below 400 ppm, below 200 ppm, below 100 ppm, and especially below 50 ppm. If the Sb₂O₃ content is too high, the transmittance in the deep ultraviolet region tends to decrease.

[0050] SnO2 acts as a clarifying agent. The preferred SnO2 content is below 2000 ppm, 1700 ppm, 1400 ppm, 1100 ppm, 800 ppm, 500 ppm, 200 ppm, and especially below 100 ppm. Excessive SnO2 content can easily lead to a decrease in transmittance in the deep ultraviolet region.

[0051] F₂, Cl₂, and SO₃ are the components that function as clarifying agents. The preferred concentration of F₂ + Cl₂ + SO₃ is 10 ppm to 10,000 ppm. The suitable lower limits for F₂ + Cl₂ + SO₃ are 10 ppm and above, 20 ppm and above, 50 ppm and above, 100 ppm and above, 300 ppm and above, especially 500 ppm and above; the suitable upper limits are below 3,000 ppm, below 2,000 ppm, below 1,000 ppm and above, especially below 800 ppm. Furthermore, the suitable lower limits for F₂, Cl₂, and SO₃ are each 10 ppm and above, 20 ppm and above, 50 ppm and above, 100 ppm and above, 300 ppm and above, especially 500 ppm and above; the suitable upper limits are below 3,000 ppm, below 2,000 ppm, below 1,000 ppm and below, especially below 800 ppm. If the content of these components is too low, it will be difficult to achieve a clarifying effect. On the other hand, if the content of these components is too high, there is a risk that clarifying gases may remain in the glass in the form of bubbles.

[0052] The preferred dimensions of the glass substrate are 600 mm² or more, 5000 mm² or more, and especially 15000 mm² or more. The larger the size, the more hermetic packages can be obtained from a single glass substrate, thus making it easier to reduce the manufacturing cost of hermetic packages.

[0053] The thickness of the glass substrate is preferably 2.0 mm or less, 1.5 mm or less, 1.0 mm or less, and especially 0.1 mm to 0.5 mm. If the thickness is too large, the mass of the glass substrate increases, making it difficult to handle, and the transmittance in the deep ultraviolet region tends to decrease. On the other hand, if the thickness is too small, it is difficult to maintain the rigidity of the glass substrate on the transport line, and deformation, warping, and breakage of the glass substrate are likely to occur.

[0054] The surface roughness Ra of the glass substrate is preferably below 10 nm, 9 nm, 8 nm, 7 nm, 6 nm, 5 nm, 4 nm, 3 nm, 2 nm, and especially below 1 nm. If the surface roughness Ra is too large, there is a tendency for the transmittance under deep ultraviolet light to decrease. Here, "Ra" refers to the arithmetic mean roughness as defined in Japanese Industrial Standards (JIS) B0601-1994.

[0055] The glass substrate is preferably any of the following shapes: rectangular, circular, or circular with an oriented plane. With this shape, multiple sealing patterns can be easily formed on the surface of the glass substrate. In particular, if it is circular or circular with an oriented plane, laser sealing can be performed using semiconductor manufacturing equipment, which is therefore preferable.

[0056] A functional film can be formed on the surface of a glass substrate, preferably an anti-reflective film. This reduces the amount of light reflected from the surface of the glass substrate.

[0057] In the glass substrate with a sealing material layer of the present invention, the sealing material layer is formed by sintering a sealing material. The sealing material is generally a composite powder comprising glass powder and ceramic powder. Various glass powders can be used as the glass powder. For example, in terms of low melting point characteristics, Bi₂O₃-based glasses, V₂O₅-based glasses, and SnO-based glasses are suitable; in terms of thermal stability and water resistance, Bi₂O₃-based glasses are particularly preferred. Here, "bi₂O₃-based glass" refers to glass containing the stated components as essential components, and the total amount of the stated components is 25 mol% or more, preferably 30 mol% or more, and more preferably 35 mol% or more. Furthermore, from an environmental point of view, the glass powder preferably does not substantially contain PbO (less than 0.1 mol%) in the glass composition.

[0058] Regarding Bi₂O₃-based glasses, the preferred glass composition is 28%–60% Bi₂O₃, 15%–37% B₂O₃, and 1%–30% ZnO, expressed in moles. The reasons for limiting the content ranges of each component as described above are explained below. Furthermore, in the description of the glass composition range, % refers to moles.

[0059] Bi₂O₃ is the main component used to lower the softening point, and its content is preferably 28%~60%, 33%~55%, and especially 35%~45%. If the content of Bi₂O₃ is too low, the softening point becomes too high, and the fluidity tends to decrease. On the other hand, if the content of Bi₂O₃ is too high, the glass tends to devitrify during firing, and due to this devitrification, the fluidity tends to decrease.

[0060] B₂O₃ is an essential component for glass formation, with a preferred content of 15%–37%, 20%–33%, and particularly 25%–30%. If the B₂O₃ content is too low, it is difficult to form a glass network, thus the glass is prone to devitrification during firing. On the other hand, if the B₂O₃ content is too high, the viscosity of the glass increases, and its fluidity tends to decrease.

[0061] ZnO is a component that improves devitrification resistance, and its optimal content is 1%~30%, 3%~25%, 5%~22%, and especially 9%~20%. If its content is less than 1% or more than 30%, the compositional balance of the glass will be disrupted, and the devitrification resistance will easily decrease.

[0062] In addition to the ingredients mentioned above, the following ingredients may also be added, for example.

[0063] SiO2 is a component that improves water resistance, but it also raises the softening point. Therefore, the preferred SiO2 content is 0%~5%, 0%~3%, 0%~2%, and especially 0%~1%. Furthermore, if the SiO2 content is too high, the glass is prone to devitrification during firing.

[0064] Al₂O₃ is a component that improves water resistance, and its content is preferably 0%~10%, 0%~5%, and especially 0.1%~2%. If the content of Al₂O₃ is too high, there is a risk that the softening point will rise inappropriately.

[0065] Li₂O, Na₂O, and K₂O are components that reduce devitrification resistance. Therefore, the contents of Li₂O, Na₂O, and K₂O are 0%~5%, 0%~3%, and especially 0%~less than 1%.

[0066] MgO, CaO, SrO, and BaO are components that improve devitrification resistance, but they also increase the softening point. Therefore, the contents of MgO, CaO, SrO, and BaO are 0%~20%, 0%~10%, and especially 0%~5%, respectively.

[0067] To lower the softening point of Bi₂O₃-based glasses, a large amount of Bi₂O₃ must be introduced into the glass composition. However, if the Bi₂O₃ content increases, the glass is prone to devitrification during firing, which reduces its fluidity. This tendency becomes particularly pronounced when the Bi₂O₃ content is 30% or higher. As a countermeasure, adding CuO or MnO₂ can effectively suppress devitrification even when the Bi₂O₃ content is 30% or higher. Furthermore, adding CuO can improve the laser absorption characteristics during laser sealing. The preferred individual contents of CuO and MnO₂ are 0%–40%, 5%–35%, 10%–30%, and especially 15%–25%. If the contents of CuO and MnO₂ are too high, the compositional balance of the glass composition will be disrupted, and the resistance to devitrification will actually decrease.

[0068] Fe₂O₃ is a component that improves devitrification resistance and laser absorption properties, and its content is preferably 0%~10%, 0.1%~5%, and especially 0.5%~3%. If the content of Fe₂O₃ is too high, the compositional balance of the glass will be disrupted, and the devitrification resistance will easily decrease.

[0069] Sb₂O₃ is a component that improves devitrification resistance, and its content is preferably 0%~5%, especially 0%~2%. If the content of Sb₂O₃ is too high, the compositional balance of the glass will be disrupted, and the devitrification resistance will easily decrease.

[0070] The average particle size D50 of the glass powder is preferably less than 15 μm, 0.5 μm to 10 μm, and especially 1 μm to 5 μm. The smaller the average particle size D50 of the glass powder, the lower the softening point of the glass powder.

[0071] The preferred content of ceramic powder in the sealing material is 5% to 35% by volume, 10% to 33% by volume, 15% to 30% by volume, and especially 20% to 30% by volume. The preferred content of glass powder in the sealing material is 65% to 95% by volume, 67% to 90% by volume, 70% to 85% by volume, and especially 70% to 80% by volume. If the content of ceramic powder is too high, the content of glass powder will be relatively low, making it difficult to ensure the desired flowability and thermal stability. Furthermore, if the content of ceramic powder is too low, the effect of adding ceramic powder will be insufficient.

[0072] As a ceramic powder, it is preferably selected from one or more of β-nepheline, cordierite, zircon, alumina, mullite, zinc silicate, zirconium phosphate, zirconium tungstate phosphate, zirconium tungstate, etc., especially β-nepheline, which has a high effect on reducing the coefficient of thermal expansion.

[0073] In addition to glass powder and ceramic powder, other powder materials can also be incorporated into the sealing material. Furthermore, glass beads, spacers, etc., can also be incorporated. Here, the glass beads or spacers contain components and materials with high heat resistance so that they can maintain their shape even after sealing. Additionally, to improve laser absorption characteristics, 1% to 15% by volume of laser absorbers such as Mn-Fe-Al oxides, carbon, and Mn-Fe-Cr oxides can be included; however, considering the thermal stability of the sealing material, it is preferable to substantially exclude laser absorbers.

[0074] Sealing materials can be used in powder form, but they are easier to handle and better if they are uniformly mixed and gelled with a medium. The medium typically contains a solvent and a resin. The resin is added to adjust the viscosity of the paste. Additionally, surfactants, thickeners, etc., may be added as needed. The prepared paste is applied to the surface of a glass substrate using a distributor or a screen printing press.

[0075] As resins, acrylates (acrylic resins), ethyl cellulose, polyethylene glycol derivatives, nitrocellulose, polymethyl styrene, polyethyl carbonate, methacrylates, etc., can be used. In particular, acrylates and nitrocellulose are preferred due to their good thermal decomposition properties.

[0076] As solvents, N,N'-dimethylformamide (DMF), α-terpineol, higher alcohols, γ-butyl lactone (γ-BL), tetrahydronaphthalene, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, water, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, propyl carbonate, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone, etc., can be used. α-terpineol, in particular, is preferred due to its high viscosity and good solubility in resins.

[0077] The coefficient of thermal expansion of the sealing material layer is preferably 50 ppm / ℃ to 90 ppm / ℃, 55 ppm / ℃ to 80 ppm / ℃, and particularly 60 ppm / ℃ to 75 ppm / ℃, within a temperature range of 30℃ to 300℃. Especially when the encapsulation substrate is silicon, the coefficient of thermal expansion of the sealing material layer is preferably 60 ppm / ℃ to 80 ppm / ℃, 65 ppm / ℃ to 75 ppm / ℃, and particularly 68 ppm / ℃ to 73 ppm / ℃, within the same temperature range. If the coefficient of thermal expansion of the sealing material layer is too high, residual stress will be generated at or near the joint after sealing, which can easily lead to damage to the glass substrate (e.g., cracks). Furthermore, if the glass substrate breaks, the airtightness of the hermetically sealed enclosure may decrease. On the other hand, if the coefficient of thermal expansion of the sealing material layer is too low, the proportion of refractory filler increases, thus reducing the softening and fluidity of the sealing material and easily leading to poor airtightness in the hermetically sealed enclosure.

[0078] The coefficient of thermal expansion of the encapsulation substrate is preferably above 10 ppm / ℃, above 20 ppm / ℃, and especially 30 ppm / ℃ to 60 ppm / ℃ in the temperature range of 30℃ to 300℃. If the coefficient of thermal expansion of the encapsulation substrate is too low, residual stress will be generated at or near the joint after sealing, which can easily lead to poor airtightness in hermetic packaging.

[0079] When the average thickness of the sealing material layer is 15 μm or less, the difference in the coefficients of thermal expansion between the glass substrate and the encapsulation substrate within a temperature range of 30°C to 300°C is preferably 6.5 ppm / °C or less, 4.5 ppm / °C or less, 3.5 ppm / °C or less, 2.0 ppm / °C or less, and particularly 1.0 ppm / °C or less. When the average thickness of the sealing material layer is 15 μm or less, if the difference in the coefficients of thermal expansion between the glass substrate and the encapsulation substrate within a temperature range of 30°C to 300°C is too large, residual stress will be generated at or near the joint after sealing, which can easily cause damage to the glass substrate (e.g., cracks or other breakage). Furthermore, if the glass substrate breaks, there is a risk of a decrease in the airtightness of the hermetically sealed enclosure space.

[0080] The difference in the coefficients of thermal expansion between the sealing material layer and the encapsulation substrate within the temperature range of 30℃ to 300℃ is preferably below 5.5 ppm / ℃, below 4.0 ppm / ℃, and especially below 3.5 ppm / ℃. If the difference in the coefficients of thermal expansion between the sealing material layer and the encapsulation substrate within the temperature range of 30℃ to 300℃ is too large, residual stress will be generated at or near the joint after sealing, which can easily lead to poor airtightness of the hermetically sealed package.

[0081] The package substrate preferably has a recess for accommodating electronic components. This facilitates the housing of electronic components such as sensors within the recess of the package substrate. The recess of the package substrate is preferably formed as a border along the outer edge region of the package substrate. This expands the effective area for functioning as a device. Furthermore, it facilitates the housing of electronic components within the package substrate and also facilitates wiring connections.

[0082] The encapsulation substrate is preferably any one of metals such as silicon, glass ceramics, aluminum nitride, aluminum oxide, or a composite material thereof (e.g., a material formed by integrating aluminum nitride with glass ceramics). Silicon is particularly preferred due to its good heat dissipation and the ease with which recesses can be formed using etching or other methods.

[0083] The average thickness of the sealing material layer is preferably 15 μm or less and less than 8.0 μm, particularly 1.0 μm or more and less than 7.0 μm. The value obtained by dividing the average thickness of the sealing material layer by the average width of the sealing material layer is preferably 0.005 to 0.1, particularly 0.01 to 0.05. The value obtained by dividing the average thickness of the sealing material layer by the thickness of the glass substrate is preferably 0.005 to 0.5, particularly 0.01 to 0.1. If the average thickness of the sealing material layer, the value obtained by dividing the average thickness of the sealing material layer by the average width of the sealing material layer, and the value obtained by dividing the average thickness of the sealing material layer by the thickness of the glass substrate are outside the aforementioned ranges, the accuracy of the laser seal is prone to decrease. On the other hand, if these values ​​are within the relevant ranges, the stress remaining in the sealed portion after laser sealing can be reduced when the coefficients of thermal expansion of the sealing material layer and the glass substrate do not match. Furthermore, as a method for limiting the average thickness of the sealing material layer as described above, methods such as thinly applying a sealing material paste and grinding the surface of the sealing material layer can be listed.

[0084] The average width of the sealing material layer is preferably 1 μm or more and 1000 μm or less, particularly 100 μm or more and 800 μm or less. A narrower average width of the sealing material layer reduces the stress remaining in the sealed area after laser sealing. Conversely, if the maximum width of the sealing material layer is too narrow, the entire sealing material layer is prone to damage when subjected to large shear stresses, leading to a decrease in the accuracy of the laser seal.

[0085] On the surface of the glass substrate on which the sealing material layer is formed, the area of ​​the sealing material layer is preferably 1% to 50%, 10% to 48%, 20% to 45%, 23% to 43%, and particularly 25% to 40%. If the area of ​​the surface on which the sealing material layer is formed is large, residual stress will be generated at or near the joint after sealing, which can easily cause damage to the glass substrate (e.g., cracks). On the other hand, if the area of ​​the sealing material layer is large, a large number of sealing patterns can be formed, and a large number of hermetically sealed packages can be manufactured from a single substrate. Because the glass substrate with the sealing material layer of the present invention strictly specifies the difference in thermal expansion coefficients between the sealing material layer and the glass substrate, even if the area of ​​the sealing material layer is large, the residual stress generated at or near the joint after sealing can be reduced.

[0086] In the glass substrate with a sealing material layer of the present invention, it is preferable that the sealing material layer has a plurality of sealing patterns, and the sealing patterns are in a closed-loop shape. This allows for the formation of a hermetically sealed group, and if the hermetically sealed group is divided, hermetically sealed packages corresponding to the number of sealing patterns can be efficiently manufactured. The number of sealing patterns is preferably 50 to 5000, 80 to 3000, and particularly 200 to 2500.

[0087] The method for manufacturing hermetic packages of the present invention is characterized by comprising: a step of preparing a packaging substrate; a step of preparing a glass substrate having a sealing material layer including a plurality of sealing patterns; a step of separating the sealing material layer and stacking the substrate and the glass substrate having the sealing material layer; a step of irradiating the glass substrate side with laser light to soften and deform the sealing material layer, thereby hermetically sealing the glass substrate and the packaging substrate to obtain a hermetic package group; and a step of dividing the hermetic package group to obtain a plurality of hermetic packages, wherein the glass substrate having the sealing material layer is the glass substrate having the sealing material layer.

[0088] In the step of setting up the stacked encapsulation substrate and the glass substrate, the glass substrate can be placed below the encapsulation substrate. From the viewpoint of laser sealing efficiency, it is preferable to place the glass substrate above the encapsulation substrate.

[0089] Various lasers can be used as lasers that irradiate from the glass substrate side. In terms of ease of operation, semiconductor lasers, yttrium aluminum garnet (YAG) lasers, CO2 lasers, excimer lasers, and infrared lasers are particularly preferred.

[0090] There are no particular limitations on the shape of the laser beam used for laser sealing. Generally, the beam shape is circular, elliptical, or rectangular, but other shapes are also possible. In addition, the laser beam diameter during laser sealing is preferably 100 mm to 1000 mm.

[0091] There are no particular limitations on the environment for laser sealing; it can be an atmospheric environment or an inert environment such as a nitrogen environment.

[0092] Preferably, the package substrate is preheated at a temperature above 100°C and below the heat resistance temperature of the electrical component before laser sealing. This prevents heat conduction to the package substrate during laser sealing, thus enabling efficient laser sealing.

[0093] It is preferable to perform laser sealing while pressing the glass substrate. This promotes the softening and deformation of the sealing material layer during laser sealing.

[0094] Preferably, before stacking the encapsulation substrate and the glass substrate, the step of accommodating electrical components within a recess in the encapsulation substrate is included.

[0095] The hermetic package of the present invention is a hermetic package in which a glass substrate and a packaging substrate are hermeticly integrated through a sealing material layer. Its characteristic is that, when the thickness of the glass substrate is 0.2 mm, the average transmittance at a range of 250 nm to 300 nm is 85% or higher, and the difference in the coefficients of thermal expansion between the sealing material layer and the glass substrate within a temperature range of 30°C to 300°C is 5 ppm / °C or lower. Since the technical features of the packaging of the present invention have been described above, detailed descriptions are omitted here.

[0096] Hereinafter, the features of the present invention will be described with reference to the drawings. FIG1 is a schematic cross-sectional view showing an example of the hermetically sealed device of the present invention. The hermetically sealed device 1 includes a glass substrate 10 and a packaging substrate 11. The packaging substrate 11 has a base 12, and a frame portion is formed on the outer periphery of the base 12, thereby forming a recess 13. In addition, an electrical component 14 is housed in the recess 13 of the packaging substrate 11. Furthermore, an electrical wiring (not shown) for electrically connecting the electrical component 14 to the outside is formed in the packaging substrate 11.

[0097] A border-shaped sealing material layer 15 is formed on the surface of the glass substrate 10. The width of the sealing material layer 15 is smaller than the width of the top 16 of the frame portion of the encapsulation substrate 11.

[0098] The glass substrate 10 and the encapsulation substrate 11 are laminated such that the sealing material layer 15 of the glass substrate 10 and the centerline of the top 16 of the frame portion of the encapsulation substrate 11 are aligned in the width direction. Then, laser light L emitted from the laser irradiation device 17 is irradiated from the glass substrate 10 side along the sealing material layer 15. This softens and flows the sealing material layer 15, thereby hermetically sealing the glass substrate 10 and the encapsulation substrate 11, thus forming a hermetically sealed structure of the hermetically sealed package 1. [Example 1]

[0099] The present invention will now be described in detail based on embodiments. However, the following embodiments are merely illustrative and are not intended to limit the invention in any way.

[0100] (Sample No. 1) First, prepare a silicon substrate (3.8 ppm / ℃, □4 mm, thermal expansion coefficient at 30℃~300℃).

[0101] Next, a glass substrate comprising alkali borosilicate glass (coefficient of thermal expansion of 4.2 ppm / ℃ at 30℃~300℃, □4 mm, 0.2 mm thickness) was prepared. Regarding the glass substrate, as a glass composition, it contains, by mass%, 70% SiO₂, 5.9% Al₂O₃, 18% B₂O₃, 1% Li₂O, 2% Na₂O, 3% K₂O, 0.1% Cl, 0.0001% TiO₂, and 0.0001% Fe₂O₃. The average transmittance at 250 nm to 300 nm is 91% at a thickness of 0.2 mm, and the average transmittance at 300 nm to 1000 nm is 92% at a thickness of 0.2 mm.

[0102] In addition, a sealing material was prepared by mixing bismuth-based glass powder in a 73 vol% ratio and ceramic powder in a 27 vol% ratio. Here, the average particle size D50 of the bismuth-based glass powder was set to 1.0 μm, and the 99% particle size D99 was set to 2.8 μm. Similarly, the average particle size D50 of the ceramic powder was set to 1.0 μm, and the 99% particle size D99 was set to 2.8 μm. Furthermore, regarding the bismuth-based glass, as a glass composition, it contained, in molar percentages, 36.5% Bi₂O₃, 28.5% B₂O₃, 9.5% ZnO, 1.5% Al₂O₃, 9.5% MnO₂, 13.6% CuO, and 0.9% Fe₂O₃. The ceramic powder was β-nepheline.

[0103] The coefficient of thermal expansion of the obtained sealing material was measured, and the result was 7.1 ppm / ℃. Furthermore, the coefficient of thermal expansion was determined using a pushrod thermomechanical analysis (TMA) device, with a measurement temperature range of 30℃ to 300℃.

[0104] Next, the sealing material is coated onto a glass substrate and dried, debonded, and sintered to form a closed-loop sealing material layer. Specifically, the sealing material, medium, and solvent are first mixed to a viscosity within the range of 90 ± 20 Pa·s (25°C, shear rate: 4), and then further mixed using a three-roll mill until the powder is uniformly dispersed, followed by gelatinization to obtain a sealing material paste. The medium used is an organic resin containing ethyl cellulose dissolved in a glycol ether solvent. Next, the sealing material paste is printed in a border pattern onto the outer periphery of the glass substrate using a screen printing machine. Then, under atmospheric conditions, it is dried at 110°C for 10 minutes to obtain a dried film, followed by heat treatment in an electric furnace at 350°C for 15 minutes ⇒ 500°C for 10 minutes to debond and sinter the dried film, thereby forming a sealing material layer with an average width of approximately 400 μm and an average thickness of approximately 5 μm.

[0105] Finally, the glass substrate and silicon substrate after the sealing material layer has been sintered are laminated. Laser light is then irradiated from the glass substrate side to soften and flow the sealing material layer, thereby achieving hermetic integration of the glass substrate and silicon substrate and obtaining hermetic packaging. Furthermore, the laser output is 10 W, the scanning speed is 15 mm / s, and the beam diameter is ϕ 500 μm.

[0106] (Sample No. 2) Except that a glass substrate containing alkali borosilicate glass (coefficient of thermal expansion of 9.9 ppm / ℃ at 30℃ to 300℃, □4 mm, 0.2 mm thickness) was used instead of the glass substrate of Sample No. 1, hermetically sealed packaging was obtained in the same manner as Sample No. 1. Regarding the glass substrate, as a glass composition, it contains, by mass%, 70.2% SiO₂, 1.6% Al₂O₃, 2.3% B₂O₃, 9.6% Na₂O, 9.1% K₂O, 7.0% BaO, 0.4% Cl, 0.1% SrO, 0.0001% TiO₂, and 0.0001% Fe₂O₃. The average transmittance at 250 nm to less than 300 nm is 89% when the thickness is 0.2 mm, and the average transmittance at 300 nm to less than 1000 nm is 92% when the thickness is 0.2 mm.

[0107] (Sample No. 3) Except that a quartz substrate (with a coefficient of thermal expansion of 0.6 ppm / ℃ at 30℃ to 300℃, □4 mm, and 0.5 mm thickness) was used instead of the glass substrate of sample No. 1, hermetic packaging was obtained in the same manner as sample No. 1.

[0108] (evaluate) For the hermetically sealed packages obtained from samples No.1 to No.3, observe for cracks and conduct temperature cycling tests and high-temperature, high-humidity, and high-pressure tests. The results are shown in Table 1.

[0109] [Table 1] Sample No. 1 Sample No. 2 Sample No. 3 Are there any cracks? none none have Temperature cycling test ○ ○ × High temperature, high humidity and high pressure test ○ ○ ×

[0110] Regarding the presence or absence of cracks, the area near the sealing material layer of the obtained hermetically sealed package was observed and evaluated using an optical microscope.

[0111] Regarding the temperature cycling test, for the obtained hermetically sealed package, after repeated temperature cycling at 125℃⇔-55℃ for 1000 cycles, the vicinity of the sealing material layer is observed and evaluated. Those without confirmed deterioration, cracks, peeling, etc. are evaluated as "○", and those with confirmed deterioration, cracks, peeling, etc. are evaluated as "×".

[0112] Regarding the high temperature, high humidity, and high pressure test: PCT (Pressure Cooker Test), for the obtained airtight packaging, it is maintained at 121°C, 100% humidity, 2 atm, and 24 hours. After being kept in the high temperature, high humidity, and high pressure environment, the vicinity of the sealing material layer is observed and evaluated. Those without confirmed deterioration, cracks, or peeling are evaluated as "○", and those with confirmed deterioration, cracks, or peeling are evaluated as "×".

[0113] As shown in Table 1, the hermetic seals obtained from Sample No. 1 and Sample No. 2 were rated as good in terms of the presence or absence of cracks, temperature cycling test, and high temperature, high humidity, and high pressure test. On the other hand, the hermetic seals obtained from Sample No. 3 were rated as poor in terms of the presence or absence of cracks, temperature cycling test, and high temperature, high humidity, and high pressure test. [Example 2]

[0114] A glass substrate comprising alkali borosilicate glass (coefficient of thermal expansion of 4.2 ppm / ℃ at 30℃~300℃, 0.2 mm thickness, □44 mm) was prepared. Regarding the glass substrate, as a glass composition, it contains, by mass%, 70% SiO₂, 5.9% Al₂O₃, 18% B₂O₃, 1% Li₂O, 2% Na₂O, 3% K₂O, 0.1% Cl, 0.0001% TiO₂, and 0.0001% Fe₂O₃. The average transmittance at 250 nm to 300 nm is 91% at a thickness of 0.2 mm, and the average transmittance at 300 nm to 1000 nm is 92% at a thickness of 0.2 mm. On one surface of the glass substrate, using the same method as in Example 1, 100 closed-loop sealing patterns of □3.3 mm were formed (the average thickness of the sealing material layer was 5 μm and the average width of the sealing material layer was 400 μm), to obtain a glass substrate with a sealing material layer. Figure 2 is a photograph showing the glass substrate with the sealing material layer.

[0115] Additionally, a silicon substrate (with a coefficient of thermal expansion of 3.8 ppm / ℃ at 30℃ to 300℃) is prepared. Here, on the surface of the glass substrate on the side where the sealing material layer is formed, the area where the sealing material layer is formed accounts for 27%.

[0116] Next, a silicon substrate and a glass substrate with the sealing material layer are laminated together, separated by a sealing material layer. Then, using the same method as in Example 1, laser light is irradiated from the glass substrate side to soften and deform the sealing material layer, thereby hermetically sealing the glass substrate and the silicon substrate to obtain a hermetically sealed assembly group. Finally, the hermetically sealed assembly group is divided by dicing without breaking the sealing pattern to obtain 100 hermetically sealed assemblies. [Example 3]

[0117] Except that a glass substrate containing alkali borosilicate glass (with a coefficient of thermal expansion of 9.9 ppm / ℃ at 30℃ to 300℃, □4 mm, and a thickness of 0.2 mm) was used instead of the glass substrate of Example 2, a glass substrate with a sealing material layer and an hermetically sealed package were obtained in the same manner as in Example 2. Regarding the glass substrate, as a glass composition, it contains, by mass%, 70.2% SiO₂, 1.6% Al₂O₃, 2.3% B₂O₃, 9.6% Na₂O, 9.1% K₂O, 7.0% BaO, 0.4% Cl, 0.1% SrO, 0.0001% TiO₂, and 0.0001% Fe₂O₃. The average transmittance at 250 nm to less than 300 nm is 89% when the thickness is 0.2 mm, and the average transmittance at 300 nm to less than 1000 nm is 92%. [Industry availability]

[0118] The hermetic enclosure of the present invention is suitable for hermetic enclosures that house electrical components such as sensor chips and ultraviolet LEDs. In addition, it is also suitable for hermetic enclosures that house piezoelectric vibration elements or wavelength conversion elements in which quantum dots are dispersed in organic resin.

[0119] 1: Hermetically sealed packaging 10: Glass substrate 11: Encapsulation substrate 12: Base 13: concave part 14: Electrical components 15: Sealing material layer 16:The top of the concave part 17: Laser Irradiation Device L: Laser light

Claims

1. A hermetically sealed package, comprising a glass substrate and a packaging substrate integrally formed by a sealing material layer, characterized in that, when the thickness of the glass substrate is 0.2 mm, the average transmittance at 250 nm or more and less than 300 nm is 85% or more, the difference in the coefficient of thermal expansion between the sealing material layer and the glass substrate in the temperature range of 30°C to 300°C is less than 5 ppm / °C, the average thickness of the sealing material layer is less than 15 μm, and the difference in the coefficient of thermal expansion between the glass substrate and the packaging substrate in the temperature range of 30°C to 300°C is less than 6.5 ppm / °C.

2. The hermetically sealed device as described in claim 1, wherein, On the surface of the glass substrate on the side where the sealing material layer is formed, the area of ​​the sealing material layer is 1% to 50%.

3. The hermetically sealed device as described in claim 1 or claim 2, wherein, The sealing material layer has multiple sealing patterns, and the sealing patterns are closed-loop shapes.

4. The hermetically sealed device as described in claim 1 or claim 2, wherein, The sealing material layer is a sintered body of a composite powder containing at least bismuth-based glass powder and refractory filler powder. The bismuth-based glass content in the sealing material layer is 65% to 95% by volume, and the refractory filler content is 5% to 35% by volume.

5. The hermetically sealed device as described in claim 1 or claim 2, wherein, The sealing material layer does not actually contain laser-absorbing material.

6. The hermetically sealed device as described in claim 1 or claim 2, wherein, The average thickness of the sealing material layer is less than 15 μm, and the value obtained by dividing the average thickness of the sealing material layer by the thickness of the glass substrate is 0.005 to 0.

5.

7. The hermetically sealed device as described in claim 1 or claim 2, wherein, The average width of the sealing material layer is less than 1000 μm, and the average thickness of the sealing material layer divided by the average width of the sealing material layer is 0.005 to 0.

1.

8. The hermetically sealed device as described in claim 1 or claim 2, wherein, The glass substrate can be any shape, including rectangular, circular, or circular with an oriented plane.

9. The hermetically sealed device as described in claim 1 or claim 2, wherein, An anti-reflective film is formed on any surface of the glass substrate.

10. The hermetically sealed device as described in claim 1 or claim 2, sealed by laser light.

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