TW202226466A - Cover glass with outer frame, semiconductor light-emitting device, and semiconductor light-receiving device - Google Patents

Abstract

The present invention relates to a cover glass with an outer frame, which comprises a flat glass and an outer frame joined to each other, in which: in the outer frame, a glass matrix contains at least one of bismuth oxide and boron oxide and the thermal expansion coefficient of a glass ceramic is equal to or more than 15*10<SP>-7</SP>/DEG C and equal to or less than the thermal expansion coefficient of the flat glass; in the glass ceramic, each of the total volume fraction of negative thermal expansion fillers and the total volume fraction of filler components is 40 to 65%; and the softening point of a glass component in the glass matrix is lower than the glass transition temperature of the flat glass.

Description

Cover glass with outer frame, semiconductor light-emitting device and semiconductor light-receiving device

The present invention relates to a cover glass with an outer frame. Furthermore, the present invention also relates to a semiconductor light-emitting device and a semiconductor light-receiving device that are hermetically sealed by the above-mentioned cover glass with an outer frame.

Components using light emitting diodes (LED: Light Emission Diode) are used in a wide range of applications such as backlighting and lighting for mobile phones or large LCD TVs. For example, in the case of a light-emitting device using a light-emitting diode (visible light LED) that emits visible light, a member in which an LED chip is mounted on a flat substrate such as aluminum nitride and a resin base is often used Make up the seal.

On the other hand, in light-emitting devices using light-emitting diodes (UV-LEDs) that emit ultraviolet light, laser diodes (LDs), vertical resonator-type surface-emitting lasers (VCSELs), etc., airtight sealing is required. sex. In addition, a diffuser plate is also required in VCSELs. Therefore, for these light-emitting devices, a shape in which an outer frame is attached to the cover glass is required. Although the outer frame can also be arranged on a substrate such as aluminum nitride, it is more realistic to arrange the outer frame on the cover glass in terms of cost.

The light-emitting device is not limited to the above-described light-emitting device, and light-receiving devices such as sensors sometimes require airtightness. For example, there is an element called MEMS (Micro Electro Mechanical Systems), which integrates circuits and fine mechanical structures on a substrate. As a substrate for MEMS, for example, a silicon substrate can be exemplified. Similar to the light-emitting device, the light-receiving device is required to have a shape with an outer frame attached to the cover glass. Although the outer frame can also be disposed on a substrate such as silicon, in terms of cost, it is more realistic to provide the outer frame on the cover glass.

When manufacturing the cover glass with the outer frame, the simplest method is to separately manufacture the cover glass and the glass for the outer frame, and then use the resin base member to join them together. However, in the bonding of members using a resin base as an organic substance, hermetic sealing cannot be achieved. As a method for obtaining airtightness, the method of forming an outer frame part by wet-etching glass directly can be mentioned. However, in addition to being unable to obtain the verticality of the flat portion and the portion that becomes the outer frame, it is also difficult to make a deeper frame. Therefore, in order to maintain the verticality and also obtain airtightness, a method of directly bonding the flat glass to the glass serving as the outer frame includes diffusion bonding, room temperature bonding, and the like. On the other hand, direct bonding is very expensive.

In this regard, the inventors have studied and proposed a technique of providing an outer frame on a glass substrate from various angles. For example, in the synthetic silica glass cavity disclosed in Patent Document 1, a plurality of through holes are formed on a raw synthetic silica glass substrate by sandblasting. The synthetic silica glass cavity is obtained by laminating the raw synthetic silica glass substrate with another raw synthetic silica glass substrate, and bonding them at 1000-1200° C., for example. In Patent Document 2, a framed antireflection glass is disclosed which uses borosilicate glass as a flat plate member and a silicon substrate as a frame member. By performing reactive ion etching on a silicon substrate to form through holes, a frame-shaped member is superimposed on a flat-plate member, and the two are joined by anodic bonding, thereby obtaining the framed anti-reflection glass.

In Patent Document 3, there is disclosed a glass sealing material in which a glass plate and a glass sheet are joined by welding by sandwiching a glass plate and a glass sheet with a base mold and a counter mold, and performing heat pressing. . Patent Document 4 discloses an airtight container in which paste such as glass frit having a softening point lower than that of a glass substrate is screen-printed on a glass substrate to form a bonding material, and the bonding material is used as a frame member. Patent Document 5 discloses a method of filling a mold frame with a paste containing a heat-eliminating curable resin composition containing glass powder, or filling a sheet containing a heat-eliminating curable composition containing glass powder with a paste. The material and the mold frame are crimped and heated to obtain a glass substrate with partition walls. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2020-21937 [Patent Document 2] Japanese Patent No. 5646981 [Patent Document 3] Japanese Patent Laid-Open No. 2013-222522 [Patent Document 4] Japanese Patent Laid-Open No. 2011-233479 [Patent Document 5] Japanese Patent Laid-Open No. 2005-243454

[Problems to be Solved by Invention]

However, as in the method described in Patent Document 1 or 3, when heat is applied at a temperature exceeding the glass softening point of the glass material to be used, the glass surface is damaged and reliability is concerned. As in the method described in Patent Document 2, when the thermal expansion coefficients of the plate-shaped member and the frame-shaped member are different, cracks may occur in the glass serving as the plate-shaped member. In addition, the cost of anodic bonding is also high. As in the method described in Patent Document 4, when the paste is applied, there is a possibility that the sealing property may be lowered due to uneven application or uneven film thickness. In the method described in Patent Document 5, the upper limit of the height of the partition wall serving as the outer frame is about 150 μm, and the height is limited.

Therefore, an object of the present invention is to provide a semiconductor light-emitting device that can achieve high verticality even if the height of the outer frame is higher than a certain level, and can satisfy the adhesion with the cover glass, and reduce the damage and cracks on the surface of the flat glass. A cover glass with an outer frame that is hermetically sealed for a device or a semiconductor light-receiving device. [Technical means to solve problems]

As a result of earnest research, the present inventors found that the above-mentioned problems can be solved by using a specific glass ceramic for the outer frame, and completed the present invention.

That is, the present invention and an aspect thereof relate to the following [1] to [10]. [1] A cover glass with an outer frame, which is provided with an outer frame on one main surface of a flat glass, and the outer frame includes a glass ceramic in which a filler component is dispersed in a glass matrix, and the glass matrix includes an oxide At least one of bismuth and boron oxide, the thermal expansion coefficient of the glass ceramic is in the range of 15×10 ^-7 /°C or more and the thermal expansion coefficient of the flat glass or less, and the filler component contains at least one negative thermal expansion filler. In glass ceramics, the total volume fraction of the negative thermal expansion fillers is 40 to 65%, the total volume fraction of the filler components is 40 to 65%, and the softening point of the glass components in the glass matrix is lower than the flat glass. At the glass transition point, the flat glass is directly bonded to the outer frame. [2] The cover glass with an outer frame according to the above [1], wherein at least one of the negative thermal expansion fillers is an inorganic powder containing at least one of zirconium phosphate and β-eucryptite. [3] The cover glass with an outer frame according to the above [1] or [2], wherein the flat glass includes a light diffusing portion on the main surface of the same side as the side on which the outer frame is provided, and the above The light-diffusion part is formed by the direct processing of the said flat glass. [4] The cover glass with an outer frame according to the above [3], wherein the light diffusing portion is formed in an inner region of the region to which the outer frame is directly bonded. [5] The cover glass with an outer frame according to any one of the above [1] to [4], wherein the height of the outer frame is 350 μm or more and 4 mm or less. [6] The cover glass with an outer frame according to any one of the above [1] to [5], wherein an antireflection film is provided on at least one main surface of the flat glass. [7] The cover glass with an outer frame according to any one of the above [1] to [6], wherein a surface of the surface of the outer frame facing the surface directly joined to the flat glass is provided with A sealing material layer, and the said sealing material layer contains a metal film or a glass frit. [8] The cover glass with an outer frame according to any one of the above [1] to [7], wherein the flat glass has electrical conductivity on the main surface of the same side as the side on which the outer frame is provided The film includes, inside the outer frame, a metal conductor that penetrates the outer frame and is provided perpendicular to the flat glass, and the conductive film and the metal conductor are electrically conductive. [9] A semiconductor light-emitting device in which a light-emitting element provided on a substrate is hermetically sealed by the cover glass with an outer frame as described in any one of the above [1] to [8]. [10] A semiconductor light-receiving device in which a light-receiving element provided on a substrate is hermetically sealed by the cover glass with an outer frame according to any one of the above [1] to [8]. [Effect of invention]

According to the cover glass with an outer frame of the present invention, even if the height of the outer frame is above a certain level, the verticality is high, and the adhesiveness with the cover glass can be taken into account, and the UV-LED or LD (lightning) as the light source can be prevented from being damaged. Damage to the cover glass caused by the energy of the emitter diode) or the light energy received by the sensor. In addition, since the surface of the flat glass is not damaged or cracked by heat, the reliability as a cover glass with an outer frame is very high. The reliability is not only from the viewpoint of airtightness, but also from the viewpoints of resistance, chemical resistance, verticality, etc. under the influence of high temperature and high humidity or thermal shock. Therefore, an excellent semiconductor light-emitting device or semiconductor light-receiving device can be obtained.

Hereinafter, although this invention is demonstrated in detail, this invention is not limited to the following embodiment, It can change arbitrarily in the range which does not deviate from the summary of this invention, and can implement. In this specification, the meaning of "-" which shows a numerical range at the time of use includes the numerical value described before and after it as a lower limit and an upper limit. The "thermal expansion coefficient" in this specification refers to a value measured based on the average value of the elongation per 1°C when heated in the range of 50 to 350°C. The content of the glass component in the glass matrix in this specification refers to the content of the component obtained by removing the filler component from the glass ceramic, and is a value expressed in mass % on an oxide basis. In addition, "mass %" and "weight %" have the same meaning.

<Cover Glass with Outer Frame> As shown in FIG. 1 , in the cover glass 10 with an outer frame of the present embodiment, an outer frame 2 is provided on one main surface of a flat glass 1 . The outer frame 2 is formed along the outer edge of the flat glass 1 . The outer frame 2 includes glass ceramics in which a filler component is dispersed in a glass matrix, and the flat glass 1 is directly bonded to the glass ceramics serving as the outer frame 2 . The glass matrix includes at least one of bismuth oxide and boron oxide. The glass softening point of the glass matrix is lower than the glass transition point of the flat glass 1 . The thermal expansion coefficient of the glass ceramic is in the range of not less than 15×10 ⁻⁷ /°C and not more than the thermal expansion coefficient of the flat glass 1 . The filler component constituting the glass ceramic includes at least one negative thermal expansion filler, and the total volume fraction of the negative thermal expansion filler in the glass ceramic is 40-65%. Moreover, the total volume fraction of filler components in the glass ceramics is 40 to 65%.

The flat glass 1 and the outer frame 2 are directly joined. Direct bonding refers to a state in which the flat glass 1 and the outer frame 2 are joined without intervening an adhesive layer of an organic material such as a resin layer other than the flat glass 1 and the outer frame 2 . In addition, when forming the conductive film 4 which is the following inorganic material on the main surface of the flat glass 1, the flat glass 1 and the outer frame 2 are joined via the conductive film 4. In this case, the conductive film 4 is treated as a structure that is integrated with the flat glass 1 and includes an inorganic material, and is regarded as a state in which the flat glass 1 and the outer frame 2 are directly joined. When directly joining the flat glass 1 and the outer frame 2, it is not necessary to apply a voltage as in anodic bonding, and the flat glass 1 and the outer frame 2 can be joined only by overlapping and heating.

The direct bonding eliminates the need for organic materials such as a resin layer, and thus has excellent durability. In addition, the manufacturing process is also simplified in that it is not necessary to form an adhesive layer. In addition, whether it is a direct bonding can be judged based on the presence or absence of the said adhesive layer between the flat glass 1 and the outer frame 2.

Regarding the glass ceramic used as the outer frame 2 , the glass softening point Ts of the glass matrix constituting the glass ceramic is lower than the glass transition point Tg of the flat glass 1 . Thereby, direct bonding is possible without requiring a high temperature that would damage the surface of the flat glass 1 . From the viewpoint of preventing damage to the surface of the flat glass 1, the difference between the glass transition point Tg of the flat glass 1 and the glass softening point Ts of the glass matrix is preferably 50°C or higher, more preferably 65°C or higher, and still more Preferably it is 75 degreeC or more.

The difference between the glass transition point Tg of the flat glass 1 and the glass softening point Ts of the glass matrix is preferably within the above-mentioned range, but from the viewpoint of suppressing the increase of carbon residues during firing, which hinders the insulating properties, and the heat resistance during sealing with the substrate From the viewpoint of properties, specifically, it is preferably 500°C or higher, more preferably 525°C or higher, still more preferably 545°C or higher, and the higher the temperature, the better. Furthermore, the glass transition point Tg of the flat glass 1 is the temperature at the first inflection point of the DTA diagram obtained by differential thermal analysis (DTA).

From the viewpoint of preventing damage to the surface of the flat glass, the glass softening point Ts of the flat glass 1 is preferably 700°C or higher, more preferably 750°C or higher, and more preferably 800°C or higher, and the higher the temperature, the higher the temperature. good. Furthermore, the glass softening point Ts of the flat glass 1 is the temperature at the fourth inflection point of the DTA diagram.

The difference between the glass softening point Ts of the glass matrix and the glass transition point Tg of the flat glass 1 is preferably within the above range, and specifically, preferably 700° C. or lower, more preferably 650° C. or lower, and still more preferably 600° C. ℃ or lower. In addition, the glass softening point Ts of the glass ceramics is preferably 450°C or higher, more preferably 460°C or higher, from the viewpoint of suppressing the increase of carbon residue during firing and inhibiting the insulating properties and the heat resistance at the time of sealing with the substrate. , and more preferably 470°C or higher. Furthermore, the glass softening point Ts of the glass matrix is the temperature at the fourth inflection point of the DTA diagram of the individual components of the glass.

From the viewpoint of being close to the thermal expansion coefficient of the substrate on which the framed cover glass 10 is to be mounted, the thermal expansion coefficient of the glass ceramic is in the range of 15×10 ⁻⁷ /°C or higher and below the thermal expansion coefficient of the flat glass 1 . The thermal expansion coefficient of the glass ceramic is preferably 16×10 ^-7 /°C or higher, more preferably 17×10 ^-7 /°C or higher, and although it varies depending on the thermal expansion coefficient of the flat glass 1, for example, it is preferably 75× 10 ^-7 /°C or less, more preferably 70 × 10 ^-7 /°C or less, still more preferably 65 × 10 ^-7 /°C or less.

In addition, from the viewpoint of preventing the occurrence of cracks in the flat glass 1 when the flat glass 1 and the glass ceramic are directly joined, the difference represented by (the coefficient of thermal expansion of the flat glass - the coefficient of thermal expansion of the glass ceramic) is 0/°C Above, the difference is preferably 4×10 ^-7 /°C or higher, more preferably 6×10 ^-7 /°C or higher, and preferably 24×10 ^-7 /°C or lower, more preferably 22×10 ^-7 /°C or less.

The thermal expansion coefficient of the flat glass 1 is not particularly limited as long as it is greater than or equal to the thermal expansion coefficient of glass ceramics, but is preferably 20×10 ^{− 7} /°C or higher, more preferably 23×10 ^-7 /°C or higher, and preferably 99×10 ^-7 /°C or lower, more preferably 92×10 ^-7 /°C or lower.

The glass matrix constituting the glass-ceramic contains at least one of bismuth oxide and boron oxide in its glass composition. Thereby, the glass softening point Ts is lowered. The content of bismuth oxide is not particularly limited as long as the glass softening point Ts of the glass matrix is lower than the glass transition point Tg of the flat glass 1 , but for example, it is preferably 25 mass % or more, more preferably 30 mass % or more. On the other hand, the content of bismuth oxide is preferably 95 mass % or less, more preferably 90 mass % or less, from the viewpoint of suppressing the deterioration of the weather resistance of the flat glass 1 .

The content of boron oxide is not particularly limited as long as the glass softening point Ts of the glass matrix is lower than the glass transition point Tg of the flat glass 1 , but is preferably 5 mass % or more, more preferably 10 mass % or more. On the other hand, the content of boron oxide is preferably 50 mass % or less, more preferably 30 mass % or less, and still more preferably 20 mass % or less, from the viewpoint of suppressing the deterioration of the weather resistance of the sheet glass 1 .

When both bismuth oxide and boron oxide are contained, it is preferable to make the content of bismuth oxide larger than the content of boron oxide from the viewpoint of suppressing the deterioration of the weather resistance of the flat glass 1 .

As mentioned above, as a glass matrix containing at least one of bismuth oxide and boron oxide, what is generally called a bismuth oxide-based glass or a borosilicate-based glass can be exemplified. As the bismuth oxide-based glass, in addition to Bi ₂ O ₃ , B ₂ O ₃ , CeO ₂ , SiO ₂ , RO, R' ₂ O, R'' ₂ O ₃ , R'''O ₂ and the like may be contained. Furthermore, R means at least one selected from the group consisting of Zn, Ba, Sr, Mg, Ca, Fe, Mn, Cr, Sn and Cu. R' refers to at least one selected from the group consisting of Li, Na, K, Cs, and Cu. R'' means at least one selected from the group consisting of Al, Fe, and La. R''' means at least one selected from the group consisting of Zr, Ti, and Sn. In addition, Al ₂ O ₃ when R″ is Al is clearly distinguished from alumina which is a filler component constituting glass ceramics. That is, the content of Al ₂ O ₃ as the glass composition was removed from the content of the inorganic powder containing alumina as the filler component.

More specifically, as the bismuth oxide-based glass, glass containing, for example, 30 to 90 mass % of Bi ₂ O ₃ and 5 to 20 mass % of B ₂ O ₃ is suitably used. The glass may further contain 0 to 10 mass % of CeO ₂ , 0 to 20 mass % of SiO ₂ , 0 to 55 mass % of RO, 0 to 10 mass % of R' ₂ O, and 0 to 20 mass % of R '' ₂ O ₃ , 0 to 30 mass % of R'''O ₂ .

As the borosilicate glass, CeO ₂ , RO, R' ₂ O, R'' ₂ O ₃ , R''' O ₂ and the like may be contained in addition to SiO ₂ and B ₂ O ₃ , and ZnO is preferably contained , K ₂ O, Na ₂ O. More specifically, for example, those containing 23 to 35 mass % of SiO ₂ , 40 to 55 mass % of B ₂ O ₃ , 10 to 20 mass % of ZnO, and a total of 3 to 15 mass % of K ₂ O and Na are suitably used. ₂ O glass.

Hereinafter, each component other than bismuth oxide (Bi ₂ O ₃ ) and boron oxide (B ₂ O ₃ ) will be described. SiO ₂ is a component constituting glass. On the other hand, if it is added excessively, the glass softening point Ts may become too high. CeO ₂ is a component that stabilizes the color tone of the glass powder after melting and vitrifying the glass raw material, and when bismuth oxide is contained, it is preferable to contain both. On the other hand, when it is excessively added, it becomes easy to crystallize, and there exists a possibility that it may become difficult to obtain a stable glass powder. The component represented by RO containing CaO is a component which contributes to stabilization of glass and suppresses crystallization. On the other hand, if it is added excessively, the glass softening point Ts may become too high. A component represented by R' ₂ O containing K ₂ O and Na ₂ O is a component that lowers the glass softening point Ts. The smaller the atomic number of the element, the greater the effect. However, when the content of an element with a smaller atomic number increases, there is a concern that the insulating property of the glass will decrease and reliability will be impaired. A component represented by R″ ₂ O ₃ containing Al ₂ O ₃ contributes to the stabilization of glass, has an effect of suppressing crystallization, and improves the chemical durability of glass. On the other hand, if it is added excessively, the glass softening point Ts may become too high. The component represented by R'''O ₂ is a component that supplies oxygen during bonding. On the other hand, if it is added excessively, there is a possibility of foaming at the time of joining.

The filler components in the glass ceramic are dispersed in the glass matrix. The filler component contains at least one negative thermal expansion filler. Negative thermal expansion fillers refer to fillers with negative thermal expansion coefficients, that is, less than 0/°C.

By using the negative thermal expansion filler, even if it is a substrate with a small thermal expansion coefficient, when the cover glass 10 with an outer frame is installed, the thermal expansion coefficient of the glass ceramics can be properly controlled. Moreover, by containing the negative thermal expansion filler of a specific amount, the perpendicularity of the outer frame 2 with respect to the flat glass 1 and favorable adhesiveness can be made compatible. If only a low thermal expansion filler is used instead of a negative thermal expansion filler, the controllability of the thermal expansion coefficient is lowered, and it is difficult to achieve both the above-mentioned verticality and good adhesion.

Specific examples of the negative thermal expansion filler include zirconium phosphate with a thermal expansion coefficient of -20×10 ^-7 /°C, and β-eucryptite (Li ₂ O-Al ₂ with a thermal expansion coefficient of -50×10 ^-7 /°C). O ₃ -2SiO ₂ ), zirconium tungstate (ZrW ₂ O ₈ ) with a thermal expansion coefficient of -7×10 ^-7 /°C, and the like. Among them, it is preferable that at least one of the negative thermal expansion fillers is an inorganic powder containing at least one of zirconium phosphate and β-eucryptite from the viewpoint of ease of obtaining a material.

From the viewpoint that the glass ceramic has strength as the outer frame 2 and is perpendicular to the flat glass 1 and prevents cracking of the flat glass 1, the total volume fraction of the negative thermal expansion filler in the glass ceramic is 40. % or more, preferably 43% or more, more preferably 45% or more. In addition, from the viewpoint of obtaining high sealing performance by using glass ceramics as the adhesion when the outer frame 2 and the flat glass 1 are directly bonded, and from the viewpoint of preventing cracks in the flat glass 1, the negative thermal expansion filler is used. The total volume fraction is 65% or less, preferably 63% or less, and more preferably 61% or less.

When the inorganic powder of zirconium phosphate alone is contained as the negative thermal expansion filler, the volume fraction of the zirconium phosphate in the glass ceramic is 40% or more, preferably 43% or more, more preferably 45% or more, and 65% Below, it is preferable that it is 63% or less, and it is more preferable that it is 61% or less. When negative thermal expansion fillers other than zirconium phosphate are contained, it is preferable to make the total amount within the above-mentioned range.

In the case where the inorganic powder of β-eucryptite is solely contained as the negative thermal expansion filler, the volume fraction of β-eucryptite in the glass ceramic is 40% or more, preferably 43% or more, more preferably 45% or more , and is 65% or less, preferably 63% or less, more preferably 61% or less. When a negative thermal expansion filler other than β-eucryptite is contained, it is preferable to make the total amount within the above-mentioned range.

The filler component may also contain other fillers than the above-mentioned negative thermal expansion fillers. In the case of containing other fillers, a filler called a low thermal expansion filler and a thermal expansion coefficient of 0×10 ^-7 /°C or more and 40×10 ^-7 /°C or less is preferable. As the low thermal expansion filler, for example, zirconia, silica, a mixture thereof, and the like can be mentioned. As a mixture, cordierite (2MgO-2Al ₂ O ₃ -5SiO ₂ ), which is a mixture of magnesia, alumina, and silica, may, for example, be mentioned.

From the viewpoint of preventing cracks in the flat glass 1, the total volume fraction of filler components in the glass ceramic is 40% or more, preferably 43% or more, and more preferably 45% or more. Moreover, the said volume fraction is 65 % or less, Preferably it is 63 % or less, More preferably, it is 61 % or less from a viewpoint of obtaining favorable adhesiveness with the sheet glass 1. However, the above-mentioned content may be changed according to the specific gravity of the filler component and the like. In addition, the total of filler components means the total of negative thermal expansion fillers and other fillers when the other fillers mentioned above are included in addition to the negative thermal expansion filler. In addition, from the viewpoint of appropriately obtaining the effect obtained by the negative thermal expansion filler, the total ratio of the negative thermal expansion filler in the entire filler component is preferably 43% or more in terms of volume fraction, more preferably 45% or more, and may be 100%, that is, only negative thermal expansion fillers.

The filler component is an inorganic powder, but the shape is not particularly limited, such as spherical, flat, scaly, fibrous, and the like. The size of the inorganic powder is not particularly limited, but for example, the 50% particle size (D ₅₀ ) is preferably 0.5 μm or more, more preferably 2 μm or more, and more preferably 10 μm or less, more preferably 9 μm or less. The 50% particle size is a value measured using a laser diffraction/scattering particle size distribution analyzer.

The flat glass is not particularly limited as long as the thermal expansion coefficient and the glass transition point Tg, the thermal expansion coefficient of the glass ceramic, and the glass softening point Ts of the glass matrix satisfy the above-mentioned relationships. For example, the flat glass is preferably transparent in the visible light range to the near-infrared range.

Specifically, as the flat glass, soda lime glass, borosilicate glass, aluminosilicate glass, silica glass, or the like can be used. Borosilicate glass is preferred in terms of being easily processable. Moreover, from the viewpoint of durability and permeability, silica glass is preferable.

In addition to the flat glass 1 and the outer frame 2 , the cover glass 10 with an outer frame of the present embodiment also has other structures. As another structure, for example, as shown in FIG. 2, the light-diffusion part shown by the code|symbol 1c and the sealing material layer shown by the code|symbol 3 are mentioned. Moreover, as shown in FIG. 3, the electroconductive film shown by the code|symbol 4 and the metal conductor shown by the code|symbol 5 are mentioned. Furthermore, as shown in (a) or (b) of FIG. 4, the antireflection film shown by the code|symbol 6 can be illustrated. Hereinafter, each configuration will be described in order.

The flat glass 1 may have a light diffusing portion on at least one main surface, and when the main surface on the side directly bonded to the outer frame 2 is the first main surface 1a, the first main surface 1a may be provided with a light diffusing portion. Diffusion part 1c. The light-diffusion part 1c is formed by directly processing the 1st main surface of the plate glass 1. In addition, a light-diffusion layer may be provided separately without a directly processed light-diffusion portion, but in this case, it is preferable that the light-diffusion layer contains an inorganic material from the viewpoint of airtightness.

The light diffusing portion 1c formed by directly processing the flat glass 1 reduces the loss due to interface reflection and prevents interlayers compared to the case where the light diffusing layer is formed on the main surface of the flat glass 1. It is preferable from the viewpoint of peeling. From the viewpoint of the adhesion between the flat glass 1 and the outer frame 2, the light diffusing portion 1c is preferably formed on the first main surface 1a of the flat glass 1 on the inner side of the region to which the outer frame 2 is directly bonded. area. In addition, in the case of performing such direct processing, for example, AN100 (trade name), M100 (trade name), M130 (trade name), and TEMPAX (trade name) manufactured by AGC Co., Ltd., and TEMPAX (trade name) manufactured by SCHOTT Co., Ltd. name) or D263 (registered trademark), etc., but not limited to them.

The light diffusing portion 1c preferably includes a plurality of lenses, and preferably has a sharp boundary between adjacent lenses, and is more preferably disposed in at least an effective area on the first main surface 1a of the flat glass 1 without gaps.

The thickness of the plate glass 1 is not particularly limited, but from the viewpoint of durability, it is preferably 300 μm or more, more preferably 400 μm or more, and still more preferably 500 μm or more. On the other hand, from the viewpoint of permeability and weight, the thickness of the flat glass 1 is preferably 1.5 mm or less, more preferably 1.2 mm or less, and still more preferably 1.1 mm or less.

From the viewpoint of preventing damage to the cover glass by light from the light source, the height of the outer frame 2 including the glass ceramic is preferably 350 μm or more, more preferably 400 μm or more, and still more preferably 500 μm or more. On the other hand, in view of the requirement of lowering the height of the device, the height of the outer frame is preferably 4 mm or less, more preferably 3 mm or less, and still more preferably 2 mm or less.

The outer frame 2 is preferably a fired body of the laminated green sheets, since the height can be adjusted by changing the number of laminated layers, or a taller frame can be formed as required. The details of the green sheet will be described later, and the green sheet refers to a sheet obtained by dispersing a powder as a precursor of glass ceramics, for example, in a binder and casting.

From the viewpoint of airtightness when the cover glass 10 with the outer frame is attached to the substrate having the light-emitting element or the light-receiving element, the outer frame 2 preferably faces the surface directly bonded to the flat glass 1 . The sealing material layer 3 is provided on the surface of the surface. The sealing material layer 3 may be a layer including a metal film, or may be a layer including a glass frit.

When the sealing material layer 3 includes a metal film, the substrate and the cover glass 10 with the frame can be hermetically sealed by bonding using metal solder. From the viewpoint of adhesiveness when metal solder is used, the metal film preferably has a metal film (not shown) containing at least one selected from the group consisting of Au, Ag, Cu, and Au—Sn alloys on the outermost surface of the metal film. shown in the figure), more preferably, it has an Au coating. As the base of the coating, there may be a coating (not shown) such as a Ni coating or a Ti coating. Furthermore, when the outer frame 2 is provided with the following metal conductors 5 , the metal film preferably has a metal film using the same metal as the metal conductor 5 .

When the sealing material layer 3 includes glass frit, the substrate and the cover glass 10 with the outer frame can be hermetically sealed by bonding by heating. The frit is a sealing glass including low-melting glass, and a previously known one can be used. For example, low-melting glass such as tin-phosphoric acid-based glass, bismuth-based glass, vanadium-based glass, lead-based glass, and zinc-borate alkali glass is suitably used. Among them, low-melting glass including tin-phosphoric acid-based glass or bismuth-based glass is more preferable in view of reliability such as adhesiveness, adhesion reliability, airtightness, and other effects on the environment and the human body. The glass frit may further contain inorganic fillers such as electromagnetic wave absorbers or low thermal expansion fillers.

From the viewpoint of the purpose of the cover glass 10 with the outer frame and the effective use of the space, the outer frame 2 is preferably arranged vertically with respect to the flat glass 1 . The fact that the flat glass 1 and the outer frame 2 are perpendicular means that the angle formed by the flat glass 1 and the outer surface of the outer frame 2 is vertical. In addition, the verticality does not need to be strictly 90°, and it only needs to be approximately vertical at 90°±5°.

In addition, the cover glass 10 with an outer frame preferably has a system such as a system capable of detecting the breakage of the flat glass 1 according to its application. As an example of the system, it is preferable that the conductive film 4 is provided on the main surface of the flat glass 1 on the same side as the side on which the outer frame 2 is provided. Moreover, it is preferable to provide the metal conductor 5 which penetrates the outer frame 2 and is perpendicular|vertical with respect to the flat glass 1 inside the outer frame 2, and makes the conductive film 4 and the metal conductor 5 conduct|electrically_connect.

The main surface of the flat glass 1 is directly joined to the outer frame 2, but as shown in FIG. In the case of this region, the flat glass 1 and the outer frame 2 are joined with the conductive film 4 interposed therebetween. In this case, the conductive film 4 including the inorganic material is treated as one integrated with the flat glass 1 , and is regarded as a state in which the flat glass 1 and the outer frame 2 are directly joined.

For the conductive film 4, a conventionally known inorganic material can be used, but from the viewpoint of light transmittance, a transparent conductive film is preferred, for example, ITO (Indium Tin Oxide) film, SnO ₂ film, ZnO film, etc. Among them, an ITO film is preferred in terms of durability and resistance. The film thickness of the conductive film 4 is not particularly limited, but in order to ensure stable conductivity, it is preferably 0.05 μm or more, more preferably 0.1 μm or more, and still more preferably 0.2 μm or more. Moreover, in order to ensure permeability, the film thickness of the conductive film 4 is preferably 1 μm or less, more preferably 0.8 μm or less, and still more preferably 0.7 μm or less.

The conductive film 4 only needs to be formed on at least a part of the main surface of the flat glass 1, but for the purpose of detecting cracks in the flat glass 1, it is preferably formed at least in the effective area, that is, the area irradiated from the light source. The light area is more preferably all areas formed on the main surface of the flat glass 1 . In addition, when a film or layer other than the conductive film 4 is formed on the main surface of the flat glass 1, it is preferable to have a light-emitting element or a light-receiving element on the outside of the other films or layers. A conductive film 4 is formed on the outermost surface of the side where the substrate is located.

The metal conductor 5 is sometimes referred to as a via hole, and means a conductor that electrically connects the upper layer wiring and the lower layer wiring. In the present embodiment, in order to connect the conductive film 4 to a detector for detecting the breakage of the flat glass 1 , the metal conductor 5 and the conductive film 4 are electrically connected.

For the metal conductor 5, a previously known metal conductor can be applied by a previously known method. For example, before or after the glass ceramic constituting the outer frame 2 is fired, a hole penetrating the inside of the outer frame 2 is provided, and the metal conductor 5 is laid in the hole.

The metal conductor 5 only needs to be a metal having conductivity, but from the viewpoint of ease of manufacture, it is preferably at least one metal selected from the group consisting of Ag, Au, and Cu, and more preferably Ag. Ease of manufacture means that the glass ceramics serving as the outer frame 2 can be fired together when firing.

The shape of the metal conductor 5 is not particularly limited, but is preferably a metal wire from the viewpoint of easily penetrating the inside of the outer frame 2 . From the viewpoint of preventing the unevenness of the metal conductor 5 from becoming larger and the glass ceramic serving as the outer frame 2 from cracking during firing, the diameter of the metal wire, that is, the diameter of the through hole is more preferably 0.2 mm or less, and more preferably 0.1 mm. mm or less. The lower limit of the diameter of the through hole is not particularly limited, but is preferably 0.05 mm or more from the viewpoint of preventing breakage of the metal conductor 5 .

In addition, the cover glass 10 with an outer frame of the present embodiment may further include an antireflection film 6 and the like on at least one main surface of the flat glass 1 .

The antireflection film 6 is preferably formed on at least one main surface of the flat glass 1 . That is, the anti-reflection film 6 may be formed on the first main surface 1a on the side where the substrate having the light-emitting element or the light-receiving element is located, or may be formed on the other second main surface 1b, and, as shown in FIG. 4(a) As shown, it can also be formed on both main surfaces. When the cover glass 10 with the outer frame is provided with the light diffusing portion 1c, as shown in FIG. 4(b), it is preferable to form a light diffusing portion 1c on the surface of the light diffusing portion 1c, that is, outside the light diffusing portion 1c. Anti-reflection film 6.

The antireflection film 6 is not particularly limited as long as it has an antireflection function of reducing the reflectance of light of a design wavelength at least. The antireflection film ₆ is preferably a film formed of an inorganic material from the viewpoint of preventing it from disappearing when the outer frame ₂ is fired. A multilayer film such as a dielectric multilayer film formed by laminating _two or more types of dielectrics with different refractive indices.

The flat glass 1 may be provided with a layer, a film, etc. having some functions, in addition to the above-mentioned members, within a range that does not impair the effects of the present invention. Furthermore, in the case where the flat glass 1 is provided with films made of inorganic materials such as the antireflection film 6 or the conductive film 4, and these films are formed to the area where the outer frame 2 is joined, the flat glass 1 and the outer frame are formed. 2 are joined through the film. In this case, it is judged that the film is also integrated with the flat glass 1, and the flat glass 1 and the outer frame 2 are directly joined.

The cover glass 10 with the outer frame can be arbitrarily changed within a range that does not impair the effects of the present invention. For example, the metal conductor 5 can be taken out by cutting a part of the outer frame 2 or chamfering the corners so as to pass through a straight line between the flat glass 1 and the outer frame 2 .

The cover glass 10 with an outer frame of the present embodiment can ensure verticality even if the outer frame height is higher than a certain level, and can take into account the adhesiveness with the cover glass. In addition, damage and cracks on the surface of the flat glass are also reduced. Therefore, the cover glass 10 with an outer frame of this embodiment is suitable for hermetically sealing the substrate in the semiconductor light-emitting device or the substrate in the semiconductor light-receiving device.

That is, the present embodiment also relates to a semiconductor light-emitting device in which a light-emitting element provided on a substrate is hermetically sealed by using the above-described cover glass 10 with an outer frame. As a light emitting element, a light emitting diode (LED), a semiconductor laser (LD), etc. are mentioned, for example. The substrate in this case is preferably an aluminum nitride substrate. In addition, as semiconductor light-emitting devices having these, there can be exemplified the backlights of mobile phones and LCD TVs, the light-emitting parts of the operation buttons of small information terminals, the deep-ultraviolet LEDs for automotive or decorative lighting, and sterilization applications, etc. The laser part of the 3D (three-dimensional, three-dimensional) ranging sensor, other light sources, etc.

In addition, the present embodiment also relates to a semiconductor light-receiving device in which a light-receiving element provided on a substrate is hermetically sealed using the above-described cover glass 10 with an outer frame. As a light receiving element, a MEMS sensor etc. are mentioned, for example. As the substrate in this case, a silicon substrate is preferable.

<Manufacturing method of cover glass with outer frame> One Embodiment of the manufacturing method of the cover glass 10 with an outer frame is demonstrated. The manufacturing method of the glass ceramics of the outer frame 2 in the cover glass 10 with the outer frame is not particularly limited. For example, it can be formed by forming and firing the glass ceramic precursor, which is a mixture of the glass powder and the filler component to be the glass matrix. obtained by sintering. Specifically, the above-mentioned precursor is formed into a sheet shape called a green sheet, and a method of firing it is exemplified.

An example of the manufacturing method of a green sheet is shown below. First, each raw material is prepared and mixed so that a desired glass composition may be obtained to obtain a raw material mixture, which is melted and then cooled and pulverized to obtain glass powder. The glass powder obtained by pulverization is fired to form a glass matrix, and the glass composition of the glass ceramic is determined. Therefore, the glass powder in this embodiment contains at least one of bismuth oxide and boron oxide. In addition, the preferable aspect of the glass powder is the same as the preferable aspect described with respect to the glass substrate in the above-mentioned <cover glass with outer frame>.

The melting temperature of the raw material mixture is preferably, for example, 500 to 800° C. or higher, and the melting time is preferably, for example, 30 to 60 minutes. The pulverization may be a dry pulverization method or a wet pulverization method. In the case of the wet pulverization method, water, ethanol, or the like can be used as a solvent. For the pulverization, for example, a pulverizer such as a roll mill, a ball mill, and a jet mill can be used.

Regarding the size of the glass powder, the 50% particle size (D ₅₀ ) is preferably 0.5 μm or more, more preferably 0.5 μm or more, from the viewpoint of preventing the glass powder from agglomerating and becoming difficult to handle, and preventing the time required for powdering from becoming longer. 1 μm or more. In addition, from the viewpoint of preventing an increase in the softening point Ts of the glass and insufficient sintering, the 50% particle size (D ₅₀ ) is preferably 10 μm or less, more preferably 9 μm or less. The maximum particle size of the glass powder is preferably 20 μm or less, more preferably 10 μm or less, from the viewpoints of obtaining good sinterability and preventing a decrease in reflectance caused by the undissolved components remaining in the sintered body. . The adjustment of the particle size can be achieved by, if necessary, classifying after pulverization.

Next, glass powder and filler components are mixed to obtain a glass ceramic precursor. The filler component uses at least one negative thermal expansion filler. As the negative thermal expansion filler, the same negative thermal expansion filler described in the above-mentioned <Cover Glass with Outer Frame> can be used, and the preferred aspect is also the same. In addition, as for other fillers which can be contained, the other fillers similar to those described in the above-mentioned <cover glass with outer frame> can be used, and the preferred aspects are also the same.

The negative thermal expansion filler is mixed so that the total volume fraction in the obtained glass ceramic is 40 to 65%. Moreover, in the case of containing other fillers, it mixes so that the total volume fraction of filler components may become 40-65% in total in the glass-ceramics obtained.

A slurry or paste is prepared by blending an organic solvent, a plasticizer, a binder, a dispersant, etc. into the glass-ceramic precursor as necessary.

Examples of the organic solvent include alcohols, ketones, aromatic hydrocarbons, and the like. More specifically, toluene, methyl ethyl ketone, methanol, 2-butanol, xylene, and the like can be used, and one of them can be used, or two or more of them can be mixed. The plasticizer may, for example, be adipic acid or phthalic acid. More specifically, bis(2-ethylhexyl) adipate, dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, and the like can be used. The binder may, for example, be a thermally degradable resin or the like. More specifically, acrylic resin, polyvinyl butyral, etc. can be used. The dispersing agent may, for example, be a surfactant-type dispersing agent. More specifically, DISPERBYK180 (trade name, manufactured by BYK-Chemie Corporation) or the like can be used.

A sheet is obtained by casting the obtained slurry or paste, which is called a green sheet. Specifically, for example, a green sheet is obtained by applying a slurry or paste on a film and drying it. The thickness of the green sheet is not particularly limited, and can be adjusted according to the thickness at the time of coating, the concentration of the slurry, and the like.

Next, the method of forming the outer frame 2 from the green sheet obtained above, and the method of directly bonding the outer frame 2 to the flat glass 1 will be described. First, the green sheets are stacked in an appropriate number of sheets according to the required height of the outer frame 2 . Then, the outer frame shape is formed by punching out the inside with a punching machine. At this time, when the cover glass 10 with the outer frame is provided with the metal conductor 5, a through hole for passing the metal conductor 5 through may be formed at the same time. In addition, in forming the glass ceramics, the green sheet may not be used, but a glass ceramic precursor formed by molding a mold or the like may be used, but a green sheet is preferred in that the wiring can easily pass through each layer.

The blanks can be made one by one according to the desired outer frame shape, but larger blanks can also be made and punched at multiple positions with a punching machine, thereby making a multi-piece connection substrate with multiple pieces connected the outer frame. In this case, the green sheet and the flat glass are superimposed and thermocompression bonded, and the resultant is fired to obtain a multi-piece cover glass with an outer frame in which the green sheet is glass ceramics and is connected. By dividing the connected multi-piece frame-attached cover glass, a single frame-attached cover glass 10 can be obtained. Moreover, it is also possible to directly join the laminated body of the green sheet by sintering it separately to make glass ceramics in advance, superimposing it on the flat glass and re-firing.

The shape of the outer frame 2 is determined by the shape of the blank. That is, the shape of the inner side of the outer frame 2 is derived from the shape when the blank is punched. In addition, the shape of the outer side of the outer frame 2 is derived from the outer shape of the green sheet. When the cover glass 10 with an outer frame is obtained by dividing from a multi-piece connection substrate, the shape at the time of dividing after firing is the shape of the outer frame 2 .

The flat glass 1 can be produced by a conventionally known method, and a commercially available one can also be used. For example, glass-making feedstock is prepared so that the glass of a desired composition may be obtained, and it heat-melts. Then, the molten glass is homogenized by bubbling, stirring, addition of a clarifying agent, etc., and it is shape|molded into the glass plate of predetermined thickness by a well-known shaping|molding method, and it cools slowly. After homogenizing molten glass, it can also shape|mold into a flat plate shape by the method of shaping|molding into a block shape, and cutting|disconnecting after slow cooling. As a shaping|molding method of flat glass, a float method, a press method, a fusion method, and a down-draw method are mentioned, for example. In particular, the down-draw method is preferable from the viewpoint of controlling the thickness of the glass.

When forming the conductive film 4 on the main surface of the flat glass 1 and making it electrically conductive with the metal conductor 5, it is preferable to form the conductive film 4 before stacking the flat glass 1 on the green sheet.

The conductive film 4 can be formed on the main surface of the flat glass 1 by a conventionally known method. For example, when the conductive film is an ITO film, it is preferably formed by a sputtering method. When the light diffusing portion 1c or the antireflection film 6 are provided on the same main surface of the flat glass 1, the conductive film 4 is preferably formed on the outermost surface thereof, that is, on the side closest to the substrate.

In the case of directly processing the light diffusing portion 1c or forming the anti-reflection film 6 on the main surface of the flat glass 1, the processing or the formation of the film may be performed before the flat glass 1 is overlapped on the blank, or may be After obtaining the cover glass 10 with the outer frame. However, as described above, when the light diffusing portion 1c is provided or when the conductive film 4 is provided, it is preferable to perform the processing or conductivity of the light diffusing portion 1c before stacking the flat glass 1 on the green sheet. Formation of film 4.

The antireflection film 6 can be formed by a previously known method. For example, it can be formed by sequentially laminating a high refractive index layer and a low refractive index layer on the main surface of the flat glass 1 using a known film-forming method such as sputtering or vapor deposition. Furthermore, when the anti-reflection film 6 is formed on the main surface of the flat glass 1 on the opposite side to the side that is directly bonded to the outer frame 2, that is, when the anti-reflection film 6 is formed on the second main surface 1b, it is also possible to obtain an additional external surface. The cover glass 10 of the frame is then formed.

The conditions are not particularly limited as long as the green sheet and the flat glass 1 are integrated with the direct bonding by thermocompression bonding after overlapping the green sheet and the flat glass 1 . The temperature at the time of crimping is preferably, for example, 60 to 65°C. The pressure at the time of crimping is preferably, for example, 12,400 to 14,000 Pa. The time at the time of crimping is preferably, for example, 5 to 10 minutes.

By degreasing the unsintered cover glass with the outer frame as required, and then firing, the green sheet becomes a glass ceramic with filler components dispersed in the glass matrix, thereby obtaining the glass ceramic as the outer frame 2 and the flat plate. The cover glass 10 with an outer frame is formed by directly bonding the glass 1 .

When the unsintered cover glass with an outer frame is a multi-piece connection substrate, a separate cover glass with an outer frame can be obtained by cutting between adjacent holes with a cutting machine or a laser after firing. 10.

Degreasing may be carried out as needed, but it is preferably, for example, 350 to 450°C. The degreasing time is preferably, for example, 1 to 10 hours.

The temperature at the time of firing is preferably a temperature higher than the glass softening point Ts of the glass matrix in the glass ceramics and less than the glass transition point Tg of the flat glass 1 . Thereby, the surface of the sheet glass 1 can be prevented from being damaged by heat.

The specific firing temperature also varies depending on the glass composition in the glass ceramics, but from the viewpoint of obtaining sufficient sinterability, for example, it is preferably 500°C or higher, more preferably 520°C or higher, and still more preferably 550°C or higher. . In addition, from the viewpoint of preventing melting of the metal constituting the sealing material layer 3 or the metal conductor 5, the firing temperature is preferably 900°C or lower, more preferably 750°C or lower, and still more preferably 680°C or lower. From the viewpoint of obtaining sufficient sinterability, the firing time is preferably 10 minutes or more, more preferably 15 minutes or more, and still more preferably 25 minutes or more. Moreover, from the viewpoint of productivity, the firing time is preferably 120 minutes or less, more preferably 90 minutes or less, and still more preferably 60 minutes or less.

In addition to the above, the green sheet and the flat glass 1 may not be stacked and then thermocompression bonded, but the green sheet may be fired alone to form glass ceramics, and then directly joined to the flat glass. In this case, the outer frame of the glass ceramics is overlapped with the flat glass, and the firing is performed within the range of the above firing temperature in this state. In this case, it is preferable to smooth the surface of glass ceramics by grinding|polishing etc. before performing the baking which directly joins glass ceramics and flat glass from the point of adhesiveness. Regarding the surface of the glass ceramics, the surface roughness Ra is preferably 0.3 μm or less, more preferably 0.1 μm or less.

The sealing material layer 3 is formed on one surface of the green sheet in the shape of the outer frame as necessary. The one surface refers to the surface on the opposite side to the side where the flat glass 1 is joined. In addition, the sealing material layer 3 may be formed on one surface of the outer frame 2 fired into glass ceramics, or the sealing material layer 3 may be formed after the cover glass 10 with the outer frame obtained by directly bonding the flat glass 1 and the outer frame 2 is obtained. .

The sealing material layer 3 is formed of a metal film or a glass frit, and can be formed by a conventionally known method. For example, when the sealing material layer 3 is a metal film, it can be formed by applying a conductive paste using a screen printing method. The conductive paste is made by adding a medium such as ethyl cellulose to the metal powder, and as needed Solvent, etc. and made into paste. In addition, when the sealing material layer 3 is glass frit, it can be formed by applying a paste obtained by mixing glass frit of low-melting glass and a vehicle obtained by dissolving resin as a binder component in a solvent made. In the case where a film serving as a base is formed on the surface of the metal film of the sealing material layer 3 or between the outer frame and the metal film, these films can also be formed by a conventionally known method. For example, it can be formed by electroplating or electroless plating.

When the metal conductor 5 is provided, it can be formed by filling, for example, a metal paste into a pre-formed through hole by a screen printing method. The metal conductor 5 may be filled in the through hole of the green sheet in the shape of the outer frame, or may be filled in the through hole of the outer frame fired into the glass ceramics. The sealing material layer 3 or the metal conductor 5 may be formed by a sputtering method, a vapor deposition method, or the like in addition to the screen printing method. [Example]

Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples. Example 1-2 to Example 1-4, Example 1-8, Example 1-9, Example 2 and Example 3 are examples, Example 1-1, Example 1-5 to Example 1-7 and Example 1-10 to Example 1-14 are comparative examples. Examples 1-1 to 1-14 are obtained by pressing a glass-ceramic precursor to form a pressurized powder by providing one main surface of the flat glass, and firing the glass to make the flat glass. Those obtained by direct bonding with glass ceramics. Therefore, although the glass ceramic is not the cover glass with the outer frame attached to the outer frame, the verification of the adhesion between the flat glass and the glass ceramics, the verticality of the outer frame, and whether there is any damage such as cracks on the surface of the flat glass can be verified with the The case of making a cover glass with an outer frame was treated in the same way, and thus it was treated as an example or a comparative example.

[Examples 1-1 to 1-14] As flat glass, a glass plate of 50 mm×50 mm and a thickness of 0.5 mm and containing alkali-free borosilicate glass (AN100 manufactured by AGC) was prepared. Its glass transition point is 710°C, and the thermal expansion coefficient is 39×10 ^-7 /°C. Glass powder (ASF-1109 manufactured by AGC Corporation) was prepared as a glass ceramic precursor. The 50% particle size of the glass powder was 2.8 μm, and the glass softening point of the glass matrix obtained by firing was 545°C. The filler components described in Table 1 were mixed with the above-mentioned glass powders at the volume fractions described in Table 1 to prepare powders as glass ceramic precursors. The powder as the precursor was press-molded by a hydraulic molding machine to obtain a cylindrical pressurized powder having a diameter of 17 mm and a height of 5 mm. By adjusting the weight of the powder used, the volumes of the pressurized powders in Examples 1-1 to 1-14 were all the same despite the difference in specific gravity of the powders used as precursors. A glass ceramic is obtained by arranging the pressurized powder obtained as described above on one of the main surfaces of the flat glass, firing at the following temperature, and directly bonding the flat glass and the glass ceramic to obtain a glass ceramic. The cover glass of the frame is attached to the glass plate of glass ceramic. The firing temperature was set to 600°C in Examples 1-1 to 1-4, Example 1-7, Example 1-11, and Example 1-12, and was set at 600°C in Examples 1-5, 1-8, and 1-9. 620°C, Example 1-6, Example 1-10, Example 1-13, Example 1-14 were set to 640°C. Furthermore, as the filler component, ULTEA (registered trademark) WH2 manufactured by Toagosei Co., Ltd. was used for zirconium phosphate, FE-200 manufactured by MARUSU GLAZE..Co., Ltd. was used for β-eucryptite, and MARUSU GLAZE..Co., Ltd. was used for cordierite. SS-600 manufactured by ., Ltd.

[Evaluation] The obtained glass-ceramic-attached glass plate was evaluated for the thermal expansion coefficient of the glass-ceramic, the adhesion between the plate glass and the glass-ceramic, the verticality of the glass-ceramic to the plate-shaped glass, and the presence or absence of cracks on the surface of the plate-shaped glass.

The thermal expansion coefficient of glass ceramics was measured using TMA-50 manufactured by SHIMADZU Corporation, and the elongation per 1°C when heated in the range of 50 to 350°C was measured, and the average value was taken as the thermal expansion coefficient. The results are shown in Table 1.

Regarding the adhesion between the flat glass and the glass ceramics, in the glass plate with glass ceramics, the joints between the flat glass and the glass ceramics were observed from the glass surface with a microscope to confirm the presence or absence of bonding. Regarding the microscope, observation was performed using a stereo microscope MVX10 from OLYMPUS. The results are shown in "Adhesion" in Table 1, where "○" indicates that the flat glass and glass ceramics were joined, and "X" indicates that no such joining was observed.

The verticality of the glass ceramics with respect to the flat glass was judged using a stereo microscope MVX10 from OLYMPUS. The results are shown in the "vertical properties" in Table 1, and "○" indicates that the vertical properties of the glass ceramics are high. Specifically, the glass ceramics are obtained by firing a cylindrical pressurized powder, so the glass ceramics are also cylindrical in shape similar to the pressurized powder. However, in practice, it is difficult to obtain a completely similar shape with firing. Therefore, "○" indicates that the horizontal direction in the cross section of the cylindrical glass ceramic, that is, the maximum length in the direction corresponding to the diameter 2r of the circle forming the top surface or bottom of the cylindrical shape is L1. When the lateral direction of the glass-bonded region, that is, the diameter of the circle at the bottom surface of the cylindrical shape is set to L2, the difference represented by (L1-L2) is 1.0 mm or less. In addition, in Table 1, "perpendicularity" as "x" means that the difference represented by the above (L1-L2) exceeds 1.0 mm, which means that the glass ceramics loses the perpendicularity and has a radian in the lateral direction.

The presence or absence of cracks on the surface of the flat glass was judged by observing the surface of the flat glass using a stereo microscope MVX10 from OLYMPUS. The results are shown in "Cracks" in Table 1. "○" means that no cracks were observed on the surface of the flat glass, and "X" means that cracks were observed on the surface of the flat glass. In addition, the cracks on the surface of the flat glass may occur when the flat glass and the glass ceramic are directly bonded to each other well, that is, when the adhesion is good. Therefore, the evaluation of the adhesiveness of the flat glass and the glass ceramics as "X" was not used as an evaluation object, and it represented with "-" in Table 1.

[Table 1] Table 1 example flat glass glass ceramic Evaluation results Glass transition point (℃) Thermal expansion coefficient (×10 ^-7 /℃) glass matrix Filler composition Thermal expansion coefficient (×10 ^-7 /℃) tightness verticality cracked Glass softening point (℃) Type of filler Thermal expansion coefficient (×10 ^-7 /℃) Volume fraction (%) 1-1 710 39 545 Zirconium Phosphate -20 28 45 〇 × × 1-2 46 30 〇 〇 〇 1-3 52 26 〇 〇 〇 1-4 57 twenty one 〇 〇 〇 1-5 71 6 × 〇 - 1-6 beta eucryptite -50 15 56 〇 × × 1-7 35 42 〇 〇 × 1-8 46 33 〇 〇 〇 1-9 52 29 〇 〇 〇 1-10 69 20 × 〇 - 1-11 cordierite 20 46 45 〇 × × 1-12 57 38 × 〇 - 1-13 66 32 × 〇 - 1-14 75 25 × 〇 -

In addition, from the results of Examples 1-1 to 1-5 and Examples 1-6 to 1-10, it was found that by increasing the volume fraction of the filler component in the glass ceramics, the vertical direction with respect to the flat glass was increased. Sex becomes good. The reason for this is considered to be that the shape of the glass ceramics can be maintained by making the amount of the filler component more than a certain level. On the other hand, it is known that when the volume fraction of the filler component is too large, the adhesiveness with respect to the plate glass is lowered. The reason for this is considered to be that the reduction in the volume fraction of the glass matrix reduces the meltability of the glass matrix at the time of firing. From the above, it can be said that it is important to set the total volume fraction of negative thermal expansion fillers in the glass ceramics to 40 to 65%, and to set the total volume fraction of filler components to 40 to 65%.

The case where cracks do not occur on the surface of the flat glass means that the values of the thermal expansion coefficients are the same, that is, close to each other, to such an extent that cracks do not occur. If the thermal expansion coefficient of the glass-ceramic is larger than that of the flat glass and is so inconsistent, as shown in Example 1-1 or Example 1-6, Example 1-7, and Example 1-10, the result is even a flat glass. The adhesion between glass and glass ceramics is good, and cracks may occur on the surface of flat glass. In order to reduce the thermal expansion coefficient of glass ceramics, the method of adding negative thermal expansion fillers or low thermal expansion fillers to the glass matrix is considered, but negative thermal expansion fillers must be used. When a low thermal expansion filler is used to reduce the thermal expansion coefficient of the glass ceramics, it becomes impossible to balance the adhesion between the flat glass and the glass ceramics and the verticality of the glass ceramics, so that it is difficult to maintain the airtightness.

[Example 2] By preparing and mixing glass frit (ASF-1109 manufactured by AGC Co., Ltd.) at 43% by volume and zirconium phosphate (ULTEA (registered trademark) WH2 manufactured by Toagosei Co., Ltd.) at 57% by volume, before preparing glass ceramics Expelling powder. To 1 kg of glass-ceramic precursor, prepare 0.35 kg of a mixture of toluene: methyl ethyl ketone: methanol: 2-butanol = 3: 3: 1: 1 (mass ratio) as an organic solvent, 0.060 kg of hexane Bis(2-ethylhexyl) diacid as a plasticizer, 0.447 kg of acrylic resin as a binder, and 0.015 kg of a dispersant (manufactured by BYK-Chemie, trade name: DISPERBYK180) were mixed to prepare slurry. A green sheet is produced by apply|coating a slurry on a polyethylene terephthalate (PET) film by a doctor blade method, and drying it. The thickness of each green sheet is 200 μm.

6 pieces of green sheets were stacked, and 8×8 square holes of 4.0 mm×4.0 mm were cut out by using a hole punching machine to obtain an unsintered panel with 64 joints and a multi-piece outer frame shape. The panel was fired at 600° C. to obtain a glass ceramic with 8×8 square holes of 3.4 mm×3.4 mm and a thickness of 1 mm. One of the surfaces of the glass ceramics is ground so that the surface roughness Ra is less than 0.1 μm. The glass ceramics were placed on the main surface of the flat glass (AN100 manufactured by AGC Corporation) so that the surface on the side where the above-mentioned processing was in contact with the flat glass, and fired at 620°C to directly bond, using a blade Cut into pieces of 5 mm × 5 mm to obtain 64 cover glasses with outer frames.

[Example 3] A cover glass with an outer frame was obtained in the same manner as in Example 2, except that the light diffusing portion was formed before the flat glass and the glass ceramic were directly bonded. The light diffusing portion is formed by directly processing a plurality of lenses on the main surface of the flat glass on the side directly bonded to the glass ceramic. The light-diffusion part is set as a quadrilateral of 2.5 mm×2.5 mm, and avoids the area where the flat glass and the glass ceramics are directly joined, and the light-diffusion part is formed in the inner side of the outer frame.

The present invention has been described in detail with reference to specific embodiments, but it is obvious to those skilled in the art that various changes and corrections can be added without departing from the spirit and scope of the present invention. This application is based on the Japanese patent application filed on December 23, 2020 (Japanese Patent Application No. 2020-213972) and the Japanese Patent Application filed on December 7, 2021 (Japanese Patent Application No. 2021-198726 ), the contents of which are incorporated herein by reference.

1: Flat glass 1a: The first principal surface 1b: Second main side 1c: Light diffusing part 2: Outer frame 3: sealing material layer 4: Conductive film 5: Metal conductor 6: Anti-reflection film 10: Cover glass with outer frame

FIG. 1 is a schematic cross-sectional view showing an example of a cover glass with an outer frame according to this embodiment. FIG. 2 is a schematic cross-sectional view showing an example of the cover glass with an outer frame according to the present embodiment. FIG. 3 is a schematic cross-sectional view showing an example of the cover glass with an outer frame according to the present embodiment. FIG. 4 is a schematic cross-sectional view showing an example of a cover glass with an outer frame according to this embodiment. FIG. 4( a ) is an example in which antireflection films are provided on both main surfaces of the flat glass, and FIG. 4( b ) It is an example in which an antireflection film is provided on both principal surfaces of a flat glass provided with a light diffusing portion on one principal surface.

1: Flat glass

1a: The first principal surface

1b: Second main side

1c: Light diffusing part

2: Outer frame

3: sealing material layer

10: Cover glass with outer frame

Claims (10)

A cover glass with an outer frame, which is provided with an outer frame on one main surface of a flat glass, and the outer frame includes a glass-ceramic in which a filler component is dispersed in a glass matrix, and the glass matrix includes bismuth oxide and oxide At least one of boron, the thermal expansion coefficient of the glass ceramic is in the range of 15×10 ^-7 /°C or more and the thermal expansion coefficient of the flat glass or less, the filler component includes at least one negative thermal expansion filler, in the glass ceramic , the total volume fraction of the negative thermal expansion fillers is 40-65%, and the total volume fraction of the filler components is 40-65%, the softening point of the glass component in the glass matrix is lower than the glass transition of the flat glass The above-mentioned flat glass is directly joined to the above-mentioned outer frame. The cover glass with an outer frame according to claim 1, wherein at least one of the negative thermal expansion fillers is an inorganic powder comprising at least one of zirconium phosphate and β-eucryptite. The cover glass with an outer frame according to claim 1 or 2, wherein the flat glass has a light diffusing portion on the main surface of the same side as the side on which the outer frame is provided, The said light-diffusion part is formed by the direct processing of the said flat glass. The cover glass with an outer frame according to claim 3, wherein the light diffusing portion is formed in a region further inward than a region to which the outer frame is directly joined. The cover glass with an outer frame according to any one of claims 1 to 4, wherein the height of the outer frame is not less than 350 μm and not more than 4 mm. The cover glass with an outer frame according to any one of claims 1 to 5, wherein an antireflection film is provided on at least one main surface of the flat glass. The cover glass with an outer frame according to any one of Claims 1 to 6, wherein a sealing material layer is provided on the surface of the surface of the outer frame facing the surface directly joined to the flat glass, and The said sealing material layer contains a metal film or glass frit. The cover glass with an outer frame according to any one of claims 1 to 7, wherein the flat glass is provided with a conductive film on the main surface of the same side as the side on which the outer frame is provided, The inside of the outer frame is provided with a metal conductor that penetrates through the outer frame and is vertically arranged with respect to the flat glass, The said conductive film and the said metal conductor are electrically connected. A semiconductor light-emitting device, wherein a light-emitting element disposed on a substrate is hermetically sealed by the cover glass with an outer frame according to any one of claims 1 to 8. A semiconductor light-receiving device, wherein a light-receiving element provided on a substrate is hermetically sealed by the cover glass with an outer frame according to any one of claims 1 to 8.

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