TW202240940A - Silica member and led device - Google Patents

Abstract

The present invention relates to a silica member characterized in that the silica member is equipped with a body section comprising a silica glass, the body section is equipped with an other member joining section for another member, the other member joining section is provided with, in order from the body section side, an underlayer, an intermediate layer, and a surface layer formed from Au, the porosity of the underlayer is within the range of 5-10%, the porosity of the intermediate layer is within the range of 4-5%, the thickness of the underlayer is within the range of 20-100 nm, and the thickness of the intermediate layer is within the range of 100-200 nm.

Description

Silicon oxide components and LED devices

The present invention relates to a silicon oxide component and an LED device, in particular to a silicon oxide component suitable for a top cover or a lens of an ultraviolet LED (Light Emitting Diode, light emitting diode) and an LED device using the silicon oxide component.

Mercury lamps have been widely used in ultraviolet sterilization for a long time, but due to the entry into force of the "Minamata Treaty on Mercury", since 2020, the manufacture, import and export of mercury products will be restricted. Therefore, ultraviolet LEDs, especially deep ultraviolet LEDs with a wavelength below 280 nm, have attracted much attention as an alternative light source after the life of the mercury lamps currently used is over. For example, the LED is placed in a housing and sealed with a glass lens before use.

For example, a light-emitting module is described in Patent Document 1, which uses a sealing part containing a low-melting-point metal material such as AuSn (gold tin) or AgSn (silver tin), and a package substrate containing ceramics such as aluminum nitride and the like. Window components containing quartz glass are bonded. A multilayer film of Ti (titanium), Cu (copper), Ni (nickel), and Au (gold) is formed by laminating layers of Ti (titanium), Cu (copper), Ni (nickel), and Au (gold) sequentially from the joint side on the junction of the window member and the packaging substrate, and the bonding The joints of the window components are metallized.

Also, for example, Patent Document 2 discloses an LED device in which a main body made of vitreous silica having a lens part and a flange part and a case made of aluminum nitride are welded with AuSn solder. On the junction with the housing, that is, the flange, a Cu layer with a thickness of 0.5 μm is formed by wet plating as the base layer, and an Au layer with a thickness of 0.5 μm is formed on the surface by wet plating, and on the housing At the junction with the main body, a shell metallization layer formed by sequentially forming a Ni layer and an Au layer is formed. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-59716 [Patent Document 2] Japanese Patent Laid-Open No. 2019-46826

[Problem to be solved by the invention]

However, in the prior art, there is a problem that metals such as Ti, Cu, Ni, and Au are densely deposited on the surface of the glass-silicon member at the joint between the glass-silicon-silicon member and the ceramic-made member. Therefore, when bonding with ceramic components, thermal stress will be generated due to the difference in thermal expansion rate between silicon oxide glass and metal. Therefore, there is a possibility that a load is applied to the vitreous silica and the member may be damaged.

The present invention was made based on such a problem, and an object of the present invention is to provide a silicon oxide member capable of suppressing breakage and performing good bonding, and an LED device using the silicon oxide member. [Technical means to solve the problem]

The silicon oxide member of the present invention has a body portion containing vitreous silica, the body portion has another member joining portion with another member, and at the other member joining portion, a base layer, an intermediate layer, and And the surface layer containing Au, and the porosity of the base layer is in the range of 5% to 10%, the porosity of the intermediate layer is in the range of 4% to 5%, and the thickness of the base layer is in the range of 20 nm to 100 nm In the range of not more than 100 nm, the thickness of the intermediate layer is in the range of not less than 100 nm and not more than 200 nm.

The LED device of the present invention includes: an LED; a base member that supports the LED; and a silicon oxide member of the present invention that is bonded to the base member in such a way as to cover the LED; The metallized layer having a first layer containing Au on the surface of the silicon oxide component junction is formed, and the silicon oxide component junction of the basic component and other component junctions of the silicon oxide component are formed by solder containing AuSn. The solder layer is bonded. [Effect of Invention]

According to the silicon oxide member of the present invention, a base layer, an intermediate layer, and a surface layer containing Au are provided on the joint portion of the main body containing vitreous silica, and the porosity of the base layer is set to 5% to 10% , the porosity of the intermediate layer is set at 4% to 5%, so by controlling the porosity, the stress generated when the main body part is joined to other components can be eased, the damage of the main body part can be suppressed, and the main body part can be bonded to other components. Securely joined for air tightness. Moreover, if the thickness of the base layer is set to 20 nm or more and 100 nm or less, it is possible to ensure adhesion and relax internal stress. Furthermore, if the thickness of the intermediate layer is set to 100 nm or more and 200 nm or less, the effect as a barrier layer preventing the diffusion of Sn atoms of the solder can be maintained and internal stress can be relaxed.

Also, if the porosity of the base layer is greater than that of the middle layer, the stress load can be reduced and the adhesion between the base layer and the middle layer can be improved, thereby more effectively relieving stress and ensuring airtightness.

Furthermore, if the porosity of the surface layer is set to 0.1% to 0.5%, and the thickness of the surface layer is set to 150 nm to 500 nm, the increase in internal stress can be suppressed, and the main body and other members can be connected by solder. Follow it firmly.

In addition, if the base layer includes at least one of a Cr (chromium) layer and a Ti layer, the adhesion to the body portion containing vitreous silica can be improved. In addition, if the intermediate layer includes at least one of the Ni layer and the Ti layer, the infiltration of Sn atoms contained in the solder into the base layer can be suppressed, thereby suppressing the deterioration of the adhesion between the junction of other members and the base layer.

In addition, by setting the average particle diameter of the above-mentioned base layer obtained by the intercept method within the range of preferably 40 nm to 80 nm, the average particle diameter of the above-mentioned intermediate layer obtained by the intercept method is set to be relatively small. It is preferably in the range of 50 nm to 70 nm, and the average particle size of the above-mentioned surface layer obtained by the intercept method is preferably set in the range of 50 nm to 70 nm, so that moderate voids can appear and the Young's modulus Dropped to a specific range, so each layer is easy to deform, which can ease the internal stress generated during film formation.

According to the LED device of the present invention, the silicon oxide member of the present invention is used, and a metallization layer is formed on the joint portion of the silicon oxide member of the basic member, the metallization layer has a first layer containing Au on the surface, and by containing AuSn solder The solder layer joins the silicon oxide component joints of the base component to other component joints of the silicon oxide component, so good bonding can be performed.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

(first embodiment) FIG. 1 shows the structure of a lens 10 for LED as a silicon oxide member of the first embodiment, (A) shows a cross-sectional structure, and (B) shows a structure seen from the lower side. FIG. 2 shows a cross-sectional structure of an LED device 20 using the lens 10 for LEDs. (A) shows the overall structure, and (B) shows an enlarged portion of the dotted line in (A).

This LED lens 10 has a body part 11 made of silica glass. The main body part 11 has, for example, a hemispherical lens part 11A and a flange part 11B provided on the plane-side peripheral edge part of the lens part 11A. This LED lens 10 is used for the LED device 20, for example.

The LED device 20 includes, for example, a lens 10 for LED, an LED 21 , and a base member 22 supporting the LED 21 , and the lens 10 for an LED is arranged on the base member 22 so as to cover the LED 21 . The base member 22 is provided with, for example, a concave portion 23 for arranging the LED 21 , and a stepped portion 24 for arranging the LED lens 10 is provided, for example, on the top of the concave portion 23 . The lens 10 for LEDs, for example, is disposed so that the flange portion 11B abuts against the step portion 24 so that the bottom surface of the flange portion 11B and the upper surface of the step portion 24 are bonded together. That is, the bottom surface of the flange portion 11B in the lens 10 for LEDs is the joint portion 11C of the other member of the basic member 22 as other members, and the upper surface of the step portion 24 in the basic member 22 becomes the surface of the LED that is a silicon oxide member. The bonding part of the silicon oxide member of the lens 10 is used.

The bottom surface of the flange portion 11B of the LED lens 10 and the upper surface of the step portion 24 of the base member 22 are bonded by soldering, for example, with a solder layer 25 . Its purpose is to seal with high airtightness. The material of the solder layer 25 is preferably AuSn solder. Moreover, a metallization layer 26 is preferably formed on the upper surface of the step portion 24 to improve wettability with solder. For example, the metallization layer 26 preferably has a first layer containing Au on the surface, and preferably has a Ni layer between the first layer and the step portion 24 .

On the bottom surface of the flange portion 11B of the LED lens 10 , that is, the other member joint portion 11C, a base layer 12 , an intermediate layer 13 , and a surface layer 14 containing Au are provided in order from the side of the body portion 11 . Since silica glass is not easily wetted by solder, its purpose is to metallize the surface to improve compatibility with solder. In particular, Au reacts with AuSn solder and alloys to form intermetallic compounds such as Au ₅ Sn, AuSn, AuSn ₂ , and AuSn ₄ . Therefore, adding Au to the surface layer 14 improves compatibility with solder. In addition, in FIG. 1(B), the area|region where the base layer 12, the intermediate|middle layer 13, and the surface layer 14 are provided is marked and shown with dots.

The base layer 12 is used to improve the adhesion with the silica glass and suppress peeling. The base layer 12 contains, for example, metal, and may consist of one layer or a plurality of laminated layers. The base layer 12 preferably includes at least one of a Cr layer and a Ti layer, for example, it is preferably composed of a Cr layer, a Ti layer, or a plurality of layers in which a Cr layer and a Ti layer are laminated. The reason for this is that Cr and Ti can obtain good adhesion to silica glass.

The intermediate layer 13 is used to prevent the Sn atoms contained in the solder layer 25 from penetrating into the base layer 12 , thereby suppressing deterioration of the adhesive force between the joint portion 11C of other members and the base layer 12 . The intermediate layer 13 contains metal, for example, and may consist of one layer, or may consist of plural layers laminated|stacked. The intermediate layer 13 preferably includes at least one of a Ni layer and a Ti layer, and is preferably composed of a Ni layer, a Ti layer, or a plurality of layers in which a Ni layer and a Ti layer are laminated, for example. The reason for this is that Ni and Ti have a remarkable effect of suppressing penetration of Sn atoms into the base layer 12 .

The porosity of the base layer 12 is preferably in the range of 5% to 10%, and the porosity of the intermediate layer 13 is preferably in the range of 4% to 5%. The purpose is to reduce the internal stress generated when the body part 11 and the base member 22 are bonded due to the difference in thermal expansion coefficient between vitreous silica and metal by controlling the porosity (film density). If the porosity of the base layer 12 is less than 5%, the stress cannot be sufficiently relaxed, and the surface of the main body portion 11 is easily damaged. On the other hand, if the porosity of the base layer 12 exceeds 10%, the adhesion between the main body 11 and the base member 22 will be insufficient, and peeling will occur during bonding. Therefore, airtightness cannot be ensured, and good adhesion cannot be obtained.

In addition, if the porosity of the intermediate layer 13 is less than 4%, the stress cannot be sufficiently relaxed, which may affect the breakage of the main body portion 11 . If the void ratio of the intermediate layer 13 exceeds 5%, the interface between the base layer 12 and the intermediate layer 13 may peel off when the main body 11 and the base member 22 are bonded due to insufficient adhesion between the base layer 12 and the intermediate layer 13. Furthermore, it is considered that during soldering, the Sn atoms of the solder tend to diffuse to the intermediate layer 13 and the base layer 12 , which promotes the deterioration of the joint interface between the joint portion 11C of other components and the base layer 12 , and shortens the life of the LED device 20 .

The thickness of the base layer 12 is preferably in the range of not less than 20 nm and not more than 100 nm. The reason for this is that if the thickness of the base layer 12 is less than 20 nm, the porosity is high, and thus the adhesiveness with the joint portion 11C of other members is insufficient, resulting in easy peeling when joining with the base member 22 . Also, the reason is that when the thickness of the base layer 12 exceeds 100 nm, the internal stress becomes large, and the main body portion 11 is easily damaged. The thickness of the intermediate layer 13 is preferably in the range of not less than 100 nm and not more than 200 nm. The reason is that if the thickness of the intermediate layer 13 is less than 100 nm, the effect of the barrier layer for preventing the diffusion of Sn atoms of the solder is reduced, and if it exceeds 200 nm, the internal stress becomes large, and the main body 11 is easily damaged. The reason for this is that if the thickness of the intermediate layer 13 exceeds 200 nm, the intermediate layer 13 tends to shrink and crack when cooled after film formation.

The porosity of the base layer 12 is preferably greater than that of the middle layer 13 . The reason is that by increasing the porosity of the base layer 12, the effect of reducing the stress load on the body portion 11 can be obtained, and by making the porosity of the intermediate layer 13 smaller than that of the base layer 12, the stress load can be reduced and The adhesive force between the base layer 12 and the intermediate layer 13 is improved, so that the stress can be more effectively relieved and the airtightness can be ensured.

The porosity of the surface layer 14 is preferably in the range of not less than 0.1% and not more than 0.5%. The reason is that the metallization layer 26 formed on the step portion 24 and the surface layer 14 can be more firmly bonded by the solder layer 25 . Furthermore, the porosity of the base layer 12 , the intermediate layer 13 , and the surface layer 14 can be controlled by adjusting pressure or input power when forming a film by vacuum evaporation or sputtering, for example.

The thickness of the surface layer 14 is preferably in the range of not less than 150 nm and not more than 500 nm. By setting the thickness of the surface layer 14 to 150 nm or more, the Sn atoms of the solder diffuse into the surface layer 14 during soldering to alloy the surface layer 14 as a whole, thereby preventing the bonding strength of the surface layer 14 from decreasing. As a result, the bonding strength between the main body 11 and the base member 22 can be improved, peeling can be prevented, and the life of the LED device 20 can be extended. By setting the thickness of the surface layer 14 to 500 nm or less, internal stress can be reduced and cracks can be prevented. Thereby, it is possible to prevent the solder from being difficult to melt due to the progress of the diffusion of Sn atoms caused by the fractured portion and the increase of the melting point due to the decrease in the concentration of the solder, making it difficult to join. Furthermore, the thickness of each layer can be obtained, for example, by observing and measuring the cross-sectional structure of each layer with a FE-SEM (Field Emission Scanning Electron Microscopy, Field Emission Scanning Electron Microscopy) device.

Also, the porosity in the present invention refers to the two-dimensional void obtained by dividing the total area of the void portion by the overall area based on photographing the upper surface of the base layer 12, the intermediate layer 13, or the surface layer 14. Rate. Specifically, for example, the porosity can be calculated by using a FE-SEM device (S-4800) manufactured by Hitachi High-Tech Co., Ltd. to examine the gap between the base layer 12, the intermediate layer 13, or the surface layer 14. The upper surface is photographed, and the program language Python is used, and the image processing module OpenCV is used to binarize the gap part of the captured image. At this time, the portion in the image where the contrast greatly changes is judged as a blowhole. The upper surface of the base layer 12 or the intermediate layer 13 is etched to remove the surface layer 14 and the intermediate layer 13 or the surface layer 14, and the base layer 12 and the intermediate layer 13 are exposed on the surface, and then photographed.

The average particle diameter of the base layer 12 obtained by the intercept method is preferably in the range of 40 nm to 80 nm, and the average particle diameter of the intermediate layer 13 obtained by the intercept method is preferably in the range of 50 nm to 70 nm Within the range of , the average particle size of the surface layer 14 obtained by the intercept method is preferably in the range of not less than 50 nm and not more than 70 nm. By setting the average particle size within this range, appropriate voids can appear in each layer, and the Young's modulus can be reduced to a specific range, so that each layer is easily deformed, and the internal stress generated during film formation can be eased. Also, the Young's modulus of the base layer 12 is preferably in the range of 30% to 70% of the Young's modulus of the material block constituting the base layer 12, and the Young's modulus of the intermediate layer 13 is preferably in the range of The Young's modulus of the material block constituting the intermediate layer 13 is within the range of 40% to 80% of the Young's modulus, and the Young's modulus of the surface layer 14 is preferably within the range of 20 GPa to 60 GPa.

Furthermore, in the present invention, the average particle diameter obtained by the intercept method means the average particle diameter observed on the surface of the base layer 12, the intermediate layer 13, or the surface layer 14 using the intercept method according to ISO13383-1:2012. Measured average particle size. Specifically, for example, use the FE-SEM device (S-4800) manufactured by Hitachi High-Tech Co., Ltd. to photograph the upper surface of the base layer 12, the middle layer 13, or the surface layer 14, and draw 10 in the image taken. Count the particles on the straight line, and divide the length of the straight line by the number to calculate the particle size. The upper surface of the base layer 12 or the intermediate layer 13 is observed after removing the surface layer 14 and the intermediate layer 13 or the surface layer 14 by etching to expose the base layer 12 and the intermediate layer 13 on the surface.

The Young's modulus of the base layer 12, the intermediate layer 13, or the surface layer 14, for example, uses a surface acoustic wave method (according to DIN (German Standards Institute) standard 50992-1), and the surface acoustic wave method uses a piezoelectric element to measure the direction of the sample. Surface acoustic waves excited by irradiating pulsed laser (wavelength 337 nm), and calculate Young's modulus according to the dispersion curve. The base layer 12 or the intermediate layer 13 is measured by removing the surface layer 14 and the intermediate layer 13 or the surface layer 14 by etching etc., and exposing the base layer 12 and the intermediate layer 13 on the surface.

Furthermore, when the base layer 12 or the intermediate layer 13 is composed of plural layers, the Young's modulus of the base layer 12 or the intermediate layer 13 is judged for each layer constituting the base layer 12 or the intermediate layer 13 . That is, regarding the base layer 12, it is preferable that the Young's modulus of each layer constituting the base layer 12 is in the range of 30% to 70% of the Young's modulus of the material block constituting the layer, and the intermediate layer 13 Preferably, the Young's modulus of each layer constituting the intermediate layer 13 is in the range of 40% to 80% of the Young's modulus of the material block constituting the layer.

This LED lens 10 can be manufactured by the following method, for example. First, the body part 11 is formed by silicon oxide glass. For example, silicon oxide powder is molded by gel injection molding and sintered to form the main body 11 . Next, base layer 12 , intermediate layer 13 , and surface layer 14 are sequentially laminated on at least a part of the bottom surface of flange portion 11B, that is, other member joint portion 11C. In the film formation of the base layer 12, the intermediate layer 13, and the surface layer 14, for example, use a vacuum evaporation method or a sputtering method, and properly adjust the pressure in the range of, for example, 0.5 Pa to 3.0 Pa, and properly adjust the input power at For example, within the range of 50 W to 200 W, the porosity of each layer can be adjusted accordingly.

Moreover, the lens 10 for LEDs is bonded to the base member 22 via, for example, a solder layer 25 . For example, a ribbon-shaped solder is placed on the stepped part 24 of the base member 22 on which the metallization layer 26 is formed, and other parts on which the base layer 12, the intermediate layer 13, and the surface layer 14 are formed abut the flange part 11B. The LED lens 10 is disposed in the member joining portion 11C, and is heated and melted in an oxygen-free environment to be welded.

Thus, according to this embodiment, the base layer 12, the intermediate layer 13, and the surface layer 14 containing Au are provided on the other member joint portion 11C of the body portion 11 containing vitreous silica, and the porosity of the base layer 12 is set to 5. % to 10%, the void ratio of the intermediate layer 13 is set to 4% to 5%, so the stress generated when the main body part 11 and the basic member 22 are joined can be eased, the damage of the main body part 11 can be suppressed, and the main body part 11 is firmly joined with the basic component 22 to ensure airtightness. Moreover, if the thickness of the base layer 12 is set to 20 nm or more and 100 nm or less, the internal stress can be relaxed while ensuring adhesion. Furthermore, if the thickness of the intermediate layer 13 is set to 100 nm or more and 200 nm or less, the effect as a barrier layer preventing the diffusion of Sn atoms of the solder can be maintained and internal stress can be relaxed.

In addition, if the porosity of the base layer 12 is greater than that of the intermediate layer 13, the stress burden can be reduced and the adhesion between the base layer 12 and the intermediate layer 13 can be improved, thereby more effectively relieving stress and ensuring airtightness.

Furthermore, if the porosity of the surface layer 14 is set to 0.1% to 0.5%, and the thickness of the surface layer 14 is set to be 150 nm to 500 nm, the increase in internal stress can be suppressed, and the main body 11 can be bonded by solder. It is firmly bonded to the base member 22.

In addition, if the base layer 12 includes at least one of the Cr layer and the Ti layer, the adhesion to the main body portion 11 containing vitreous silica can be improved. In addition, if the intermediate layer 13 includes at least one layer of the Ni layer and the Ti layer, the infiltration of Sn atoms contained in the solder into the base layer 12 can be suppressed, thereby suppressing the deterioration of the adhesion between the joint portion 11C of other members and the base layer 12. .

In addition, by setting the average particle diameter of the above-mentioned base layer 12 obtained by the intercept method within a range of preferably 40 nm to 80 nm, the average particle diameter of the above-mentioned intermediate layer 13 obtained by the intercept method is set to For being preferably in the range of not less than 50 nm and not more than 70 nm, the average particle diameter of the above-mentioned surface layer 14 obtained by the intercept method is set to be preferably in the range of not less than 50 nm and not more than 70 nm, so that moderate voids can appear, so that poplar Since the modulus of the film falls within a specific range, each layer is easily deformed, and the internal stress generated during film formation can be eased.

(second embodiment) FIG. 3 shows the structure of the LED top cover 30 which is a silicon oxide member of the second embodiment, (A) shows a cross-sectional structure, and (B) shows a structure seen from the lower side. This LED top cover 30 has the same configuration as that of the LED lens 10 described in the first embodiment except for the shape of the main body 31 . Therefore, the same symbols are attached to the same constituent elements, and symbols in which the tens digit is changed to ''3'' are assigned to the corresponding constituent elements, and detailed descriptions thereof are omitted.

The main body part 31 is made of silica glass, and has, for example, a cylindrical top cover part 31A with one end sealed, and a flange part 31B provided at the opening end part of the top cover part 31A. The flange portion 31B corresponds to the flange portion 11B in the first embodiment, and is disposed on the step portion 24 of the base member 22 similarly to the first embodiment, and the bottom surface of the flange portion 31B is in contact with the step portion 24. The upper surface is joined (see Figure 2). That is, in this top cover 30 for LEDs, the bottom surface of the flange part 31B becomes the other member joining part 31C of the basic member 22 which is another member. On the bottom surface of the flange portion 31B of the LED top cover 30 , that is, the other member joint portion 31C, the base layer 12 , the intermediate layer 13 , and the Au-containing layer are sequentially provided from the side of the main body portion 31 in the same manner as in the first embodiment. surface layer14. In FIG. 3(B), the area where the base layer 12 , the intermediate layer 13 , and the surface layer 14 are provided is indicated by marking dots.

This LED top cover 30 can be manufactured in the same manner as the LED lens 10 described in the first embodiment, and can be used in the same manner. Also, the same effect can be obtained. [Example]

(Example 1) A lens 10 for LEDs as shown in FIG. 1 was fabricated. First, silicon oxide powder was molded by gel injection molding, and fired to produce a hemispherical lens part 11A with a lens diameter of ϕ3 mm and a lens height of 1.5 mm, and a flange diameter of 3.5×3.5 mm and a flange thickness The body part 11 made of silica glass with a square flange part 11B of 0.5 mm. Then, a Cr layer with a thickness of 50 nm as the base layer 12 , a Ni layer with a thickness of 150 nm as the middle layer 13 , and an Au layer with a thickness of 300 nm as the surface layer 14 were sequentially formed on the bottom surface of the flange portion 11B. The base layer 12, the middle layer 13, and the surface layer 14 are formed by using a sputtering device, and the pressure conditions are appropriately set in the range of 1 Pa to 3 Pa, and the input power is appropriately set in the range of 120 W to 160 W. conduct. Next, a photosensitive resist is coated on the base layer 12, the intermediate layer 13, and the surface layer 14 formed on the bottom surface of the flange portion 11B, and formed into an outer diameter of 3.3 mm×3.3 mm by photolithography. mm, frame pattern with an inner diameter of 2.7 mm×2.7 mm.

The porosity of the base layer 12 , the intermediate layer 13 , and the surface layer 14 were measured for the fabricated lens 10 for LED. During the measurement, the FE-SEM device (S-4800) manufactured by Hitachi High-Tech Co., Ltd. was used to take the surface image of each layer with an applied voltage of 5 kV and a magnification of 100,000 times. The porosity (%) is calculated by using the programming language Python, using OpenCV of the image processing module to binarize the voids in the captured image, dividing the total area of the voids by the overall area and multiplying by 100. At this time, the portion where the contrast greatly changed was determined to be a blow hole. Also, when photographing the surface of the intermediate layer 13, the surface layer 14 was etched under the condition that the chemical solution was AURUM-314 (manufactured by Kanto Chemical Co., Ltd.), the temperature was normal temperature, and the time was 5 minutes, so that the intermediate layer 13 became the outermost surface. Shoot later. When photographing the surface of the base layer 12, after removing the surface layer 14 by etching in the above-mentioned manner, the middle layer was etched under the condition that the chemical solution was a mixed acid Cu-02 (manufactured by Kanto Chemical Co., Ltd.), the temperature was normal temperature, and the time was 10 minutes. Layer 13, make the base layer 12 the outermost surface before shooting.

FIG. 4 shows (A) SEM image, (B) processed image, and (C) image of void portion of base layer 12 . FIG. 5 shows (A) SEM image, (B) processed image, and (C) image of void portion of intermediate layer 13 . FIG. 6 shows (A) SEM image, (B) processed image, and (C) image of void portion of surface layer 14 . As shown in FIGS. 4 to 6 , it was confirmed that voids existed in the base layer 12 , the intermediate layer 13 , and the surface layer 14 . Also, the void ratio was 9.5% for the base layer 12 , 4.6% for the intermediate layer 13 , and 0.2% for the surface layer 14 .

Also, the average particle diameters of the base layer 12, the intermediate layer 13, and the surface layer 14 obtained by the intercept method were measured. When measuring, use the FE-SEM device (S-4800) manufactured by Hitachi High-Tech Co., Ltd. to photograph the upper surface of each layer, and calculate according to ISO13383-1:2012. As a result, the average particle diameter obtained by the intercept method was 63 nm for the base layer 12 , 58 nm for the intermediate layer 13 , and 62 nm for the surface layer 14 .

Furthermore, the Young's modulus of the base layer 12, the intermediate layer 13, and the surface layer 14 were measured. The measurement is carried out by the surface acoustic wave method (according to DIN (German Standards Institute) standard 50992-1). The surface acoustic wave method uses a piezoelectric element to measure the excitation by irradiating pulsed laser (wavelength 337 nm) to the upper surface of each layer. surface acoustic waves, and calculate Young's modulus from the dispersion curve. As a result, the Young's modulus of the base layer 12 is 50% of the Young's modulus of the bulk Cr which is the material constituting the base layer 12, and the Young's modulus of the intermediate layer 13 is the bulk Ni which is the material constituting the intermediate layer 13. 60% of the Young's modulus, the Young's modulus of the surface layer 14 is 40 GPa.

Next, a base member 22 made of aluminum nitride as shown in FIG. 2 is prepared. A metallization layer 26 having a first layer containing Au on the surface and a Ni layer between the first layer and the step portion 24 is formed on the step portion 24 of the base member 22 . Thereafter, a frame-shaped AuSn solder with an outer diameter of 3.2 mm×3.2 mm, an inner diameter of 2.8 mm×2.8 mm, and a thickness of 20 μm was inserted between the flange portion 11B of the main body portion 11 and the step portion 24 of the basic member 22, And bonding was carried out under pressure conditions of a temperature of 300° C., a pressure of 0.5 MPa, and 30 seconds to obtain an LED device 20 . As a result of producing ten LED devices 20 , the lens 10 for LEDs was not damaged in all ten LED devices 20 . In addition, in order to confirm the airtightness of the LED device 20, that is, the tightness of the main body 11 and the basic member 22, a FLORINERT test (usually a gross leak test) was performed, and it was confirmed that no leakage was found for all 10 LED devices 20, and the airtightness Sex is preserved. Furthermore, the above-mentioned FLORINERT test is in accordance with the airtightness test method stipulated in the MIL (military, US military) standard (MIL-STD-883), and the above-mentioned airtightness is evaluated by the following method, that is, in the container Store a chlorofluorocarbon liquid called FLORINERT (trademark of 3M Company in the United States) with a high boiling point and low viscosity. Immerse the sample in FLORINERT heated to 125°C for 1 minute, and observe whether there are bubbles leaking from the sample. produce.

(comparative example 1) After the body part 11 was produced in the same manner as in Example 1, a Cr layer with a porosity of 0.1% was sequentially formed on the bottom surface of the flange part 11B using a vacuum evaporation device as the base layer 12, and a Ni layer with a porosity of 0.1% as the base layer 12. The middle layer 13 and the Au layer with a porosity of 0.05% were used as the surface layer 14 and formed into a frame pattern in the same manner as in Example 1. The thickness of each layer was set to be the same as in Example 1, and the porosity of each layer was measured in the same manner as in Example 1. Next, the manufactured LED lens 10 was bonded to the base member 22 made of aluminum nitride in the same manner as in Example 1 to manufacture the LED device 20 . Ten LED devices 20 were manufactured, and cracks appeared in 8 out of 10 from the outer diameter of the flange part 11B, and damage was found.

(comparative example 2) After producing the main body 11 in the same manner as in Example 1, use a sputtering device to sequentially form a Cr layer as the base layer 12 and a Ni layer as the intermediate layer with the same thickness as in Example 1 on the bottom surface of the flange 11B. 13. The Au layer is used as the surface layer 14, and is formed into a frame pattern in the same manner as in Example 1. At this time, by increasing the pressure of the sputtering device and reducing the output, the porosity of each layer is increased. The porosity of each layer was measured in the same manner as in Example 1. As a result, the base layer 12 was 25%, the middle layer 13 was 25%, and the surface layer 14 was 5%. Next, the manufactured LED lens 10 was bonded to the base member 22 made of aluminum nitride in the same manner as in Example 1 to manufacture the LED device 20 . As a result of producing ten LED devices 20 , the lens 10 for LEDs was not damaged in all ten LED devices 20 . In addition, the airtightness of the LED device 20, that is, the adhesion between the main body 11 and the base member 22 was confirmed by the FLORINERT test, and leakage was found in 6 out of 10. The leaked LED device 20 was pulled by hand, and as a result, the LED lens 10 and the basic member 22 were easily peeled off. Moreover, the use test was also performed on the remaining four LED devices 20 , and as a result, the lens 10 for LEDs was peeled off from the base member 22 during use. That is, it can be seen that the joint state is poor.

(Comparison between Example 1 and Comparative Examples 1 and 2) According to the results of Example 1, Comparative Example 1, and Comparative Example 2, it can be seen that if the porosity of the base layer 12 and the intermediate layer 13 is small, the stress cannot be sufficiently relieved, and the LED lens 10 may be damaged. It can also be seen that if the porosity of the base layer 12 and the intermediate layer 13 is large, the LED lens 10 and the base member 22 cannot be bonded well with high airtightness.

(comparative example 3) The body part 11 was produced in the same manner as in Example 1, and the base layer 12, the intermediate layer 13, and the surface layer 14 were formed on the bottom surface of the flange part 11B, and formed into a frame pattern. At this time, the thickness of the base layer 12 was set to 300 nm, the thickness of the intermediate layer 13 was set to 500 nm, and the thickness of the surface layer 14 was set to 800 nm. The porosity of each layer is the same as in Example 1. Next, the manufactured LED lens 10 was bonded to the base member 22 made of aluminum nitride in the same manner as in Example 1 to manufacture the LED device 20 . Ten LED devices 20 were manufactured, and cracks were found in seven of the ten LED devices from the outer diameter of the flange portion 11B, and damage was found.

(comparative example 4) The body part 11 was produced in the same manner as in Example 1, and the base layer 12, the intermediate layer 13, and the surface layer 14 were formed on the bottom surface of the flange part 11B, and formed into a frame pattern. At this time, the thickness of the base layer 12 was set to 10 nm, the thickness of the intermediate layer 13 was set to 50 nm, and the thickness of the surface layer 14 was set to 100 nm. The porosity of each layer is the same as in Example 1. Next, the manufactured LED lens 10 was bonded to the base member 22 made of aluminum nitride in the same manner as in Example 1 to manufacture the LED device 20 . As a result of producing ten LED devices 20 , the lens 10 for LEDs was not damaged in all ten LED devices 20 . In addition, the airtightness of the LED device 20, that is, the adhesion between the main body 11 and the base member 22 was confirmed by the FLORINERT test, and leaks were found in 10 out of 10 units. The leaked LED device 20 was pulled by hand, and as a result, the LED lens 10 and the base member 22 were easily peeled off, and it was found that the bonding state was poor.

(Comparison between Example 1 and Comparative Examples 3 and 4) According to the results of Example 1, Comparative Example 3, and Comparative Example 4, it can be known that if the base layer 12, the intermediate layer 13, and the surface layer 14 are thicker, the stress cannot be sufficiently relieved, and the LED lens 10 will be damaged. It can also be seen that if the base layer 12 , the intermediate layer 13 , and the surface layer 14 are thin, the LED lens 10 and the base member 22 cannot be bonded well with high airtightness.

As mentioned above, although embodiment was mentioned and this invention was demonstrated, this invention is not limited to the said embodiment, Various changes are possible. For example, in the above-mentioned embodiment, as the silicon oxide member, the lens 10 for LED and the top cover 30 for LED as the member for the light source were cited and described, but it can also be applied to other members for the light source. In addition, it can also be applied to other silicon oxide members such as optical windows for optical equipment and covers of crystal resonators, not limited to members for light sources.

Furthermore, in the said embodiment, although the structure of the lens 10 for LEDs and the top cover 30 for LEDs was demonstrated concretely, it may have other structures. For example, in the above-mentioned embodiments and examples, the case where the outer peripheral shape of the flange portions 11B, 31B is a square has been described, but it may be a circle or a polygon other than a square. In addition, the flange parts 11B and 31B may not be provided. In this case, for example, the peripheral portion of the plane portion of the lens portion 11A or the opening end portion of the top cover portion 31A can be used as the other member joint portions 11C, 31C. Furthermore, in the above-mentioned embodiments and examples, the case where the shape of the lens portion 11A was hemispherical was described, but a shape other than a hemispherical (spherical) shape such as an aspherical surface or a semiellipse may be used.

In addition, in the said embodiment and the Example, although the structure of the basic member 22 was demonstrated concretely, it may have other structures. For example, in the above-mentioned embodiments and examples, the case where the recessed portion 23 for disposing the LED 21 is provided on one side of the flat plate has been described, but the LED 21 may also be disposed on a flat plate without the recessed portion 23, and, It can also be made into a shell shape.

The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments, and various design changes can be made within the scope described in the claims. This application is based on Japanese Patent Application No. 2020-217879 filed on December 25, 2020 and Japanese Patent Application No. 2021-172818 filed on October 22, 2021, and the contents thereof are incorporated herein by reference. [Industrial availability]

The present invention is particularly applicable to members for light sources and the like.

10: Lens for LED 11: Main body 11A: Lens part 11B: flange part 11C: Joints of other components 12: Base layer 13: middle layer 14: Surface layer 20: LED device 21:LED 22: Basic components 23: Concave 24: Step Department 25: Solder layer 26: metallization layer 30: LED top cover 31: Body Department 31A: top cover 31B: Flange 31C: Joints of other components

1(A) and (B) are diagrams showing the configuration of a lens for LED which is a silicon oxide member according to the first embodiment of the present invention. 2(A) and (B) are cross-sectional views showing the structure of an LED device using the LED lens shown in FIG. 1 . 3(A) and (B) are diagrams showing the structure of a top cover for LED which is a silicon oxide member according to a second embodiment of the present invention. 4(A)-(C) are image diagrams showing the particle state of the base layer in Example 1. FIG. 5(A)-(C) are images showing the particle state of the intermediate layer in Example 1. FIG. 6(A)-(C) are images showing the particle state of the surface layer in Example 1. FIG.

10: Lens for LED

11: Main body

11A: Lens part

11B: flange part

11C: Joints of other components

12: Base layer

13: middle layer

14: Surface layer

Claims (7)

A silicon oxide member, characterized in that: it has a body part containing silicon oxide glass, The above-mentioned main body part has other component joining parts with other components, A base layer, an intermediate layer, and a surface layer containing Au are provided in order from the side of the above-mentioned main body at the joint portion of the above-mentioned other member, and The porosity of the base layer is in the range of 5% to 10%, the porosity of the intermediate layer is in the range of 4% to 5%, and the thickness of the base layer is in the range of 20 nm to 100 nm , the thickness of the above-mentioned intermediate layer is in the range of not less than 100 nm and not more than 200 nm. The silicon oxide member according to claim 1, wherein the porosity of the base layer is greater than the porosity of the intermediate layer. The silicon oxide member according to claim 1 or 2, wherein the porosity of the above-mentioned surface layer is in the range of 0.1% to 0.5%, and the thickness of the above-mentioned surface layer is in the range of 150 nm to 500 nm. The silicon oxide member according to any one of claims 1 to 3, wherein the base layer includes at least one layer of a Cr layer and a Ti layer, and the intermediate layer includes at least one layer of a Ni layer and a Ti layer. The silicon oxide member according to any one of claims 1 to 4, wherein the average particle diameter of the above-mentioned base layer obtained by the intercept method is in the range of 40 nm to 80 nm, and the average particle size of the above-mentioned intermediate layer obtained by the intercept method The average particle diameter is in the range of 50 nm to 70 nm, and the average particle diameter of the surface layer obtained by the intercept method is in the range of 50 nm to 70 nm. The silicon oxide component according to any one of claims 1 to 5, which is a lens for LED or a top cover for LED. An LED device, characterized in that it has: LED; a basic building block supporting the above-mentioned LEDs; and The silicon oxide member according to any one of claims 1 to 6, which is bonded to the above-mentioned basic member in such a way as to cover the above-mentioned LED; The above basic member has a silicon oxide member joining portion with the silicon oxide member, A metallization layer having a first layer containing Au on the surface is formed at the joint portion of the silicon oxide member, and The silicon oxide member joining portion of the basic member and the other member joining portion of the silicon oxide member are joined by a solder layer containing AuSn solder.

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