JP2013115122A - Glass ceramic sintered compact, reflection member and light-emitting element mounting substrate using the same, and light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass ceramic sintered compact which is less susceptible to occurrence of defects due to cracking or shedding on the surface in the external machining or cutting step, and to provide a reflection member using the same, and a light-emitting element mounting substrate and a light-emitting device.SOLUTION: A glass ceramic sintered compact 1 has an anorthite phase, a quartz phase, a calcium/zirconium/silicate phase, and a zirconia phase in the glass phase. The light-emitting element mounting substrate includes an insulating substrate 13 having a mounting part 11 on which a light-emitting element is mounted, and a reflection member 19 provided on the upper surface of the insulating substrate 13 so as to surround the mounting part 11. At least one of the insulating substrate 13 and the reflection member 19 consists of the glass ceramic sintered compact.

Description

  The present invention relates to a glass-ceramic sintered body excellent in external formability, a reflecting member and a light-emitting element mounting substrate using the same, and a light-emitting device.

  In recent years, light-emitting devices equipped with light-emitting elements have been improved for high brightness and whitening, and are used as backlights for mobile phones, large liquid crystal televisions, and the like. Among them, it has not only high reflectivity but also excellent heat resistance and durability compared to the synthetic resin that has been used for conventional light emitting element mounting substrates, and it does not deteriorate even when exposed to ultraviolet rays for a long time. For this reason, glass ceramic sintered bodies have attracted attention.

  For example, Patent Document 1 discloses a glass-ceramic sintered material that exhibits high reflectance in the visible light region by using borosilicate glass, alumina, a Group 2 element such as calcium, and niobium metal or niobium oxide as ceramic materials. The body is disclosed.

JP 2009-64842 A

  However, since the glass-ceramic sintered body disclosed in Patent Document 1 contains alumina particles with high hardness in the glass-ceramic sintered body, in the outer shape processing or cutting processing step using a dicing saw or the like. There has been a problem that defects caused by cracks or degranulation are likely to occur on the surface of the glass ceramic sintered body.

  Accordingly, the present invention provides a glass-ceramic sintered body that is less prone to defects caused by cracks or grain separation on the surface in a processing step of outer shape processing or cutting, a reflecting member using the same, a light-emitting element mounting substrate, and a light-emitting device. The purpose is to provide.

  The glass-ceramic sintered body of the present invention is characterized by having an anorthite phase, a quartz phase, a calcium-zirconium silicate phase, and a zirconia phase in the glass phase.

  The reflecting member of the present invention is characterized by comprising the above glass ceramic sintered body.

  The light emitting element mounting substrate according to the present invention includes an insulating base having a mounting portion for mounting the light emitting element, and a reflective member provided on the mounting portion side of the insulating base so as to surround the mounting portion. And at least one of the insulating base and the reflecting member is made of the glass ceramic sintered body.

  The light emitting device of the present invention is characterized in that a light emitting element is provided in the mounting portion of the light emitting element mounting substrate.

According to the present invention, a glass-ceramic sintered body in which defects due to cracks or degranulation are hardly generated in a processing step of outer shape processing or cutting, a reflecting member, a light-emitting element mounting substrate, and a light-emitting device using the same Can be obtained.

(A) shows the glass-ceramic sintered compact of this embodiment, and is a perspective view which shows the state after cut | disconnecting a mother board | substrate, (b) is the sectional view on the AA line of (a). is there. It is sectional drawing which shows an example of the light emitting element mounting substrate of this embodiment.

  An example of the glass ceramic sintered body of the present embodiment will be described with reference to FIG. Fig.1 (a) shows the glass ceramic sintered compact of this embodiment, and is a perspective view which shows the state after cut | disconnecting a mother board | substrate, (b) is the sectional view on the AA line of (a). FIG.

  The glass-ceramic sintered body 1 of the present embodiment has an anorthite phase, a quartz phase, a calcium-zirconium silicate phase, and a zirconia phase in a glass phase. In the glass-ceramic sintered body 1 of the present embodiment, the glass phase matrix has a structure in which crystal phases such as anorthite phase, quartz phase, calcium-zirconium-silicate phase, and zirconia phase exist. The surface of the glass ceramic sintered body 1 is covered with a glass phase. For this reason, defects such as chipping due to crystal phase and filler degranulation in the vicinity of the surface of the glass ceramic sintered body 1 can be reduced.

  In the glass-ceramic sintered body 1, even the quartz (α-quartz) having the highest hardness among the crystal phases contained in the glass phase has a Mohs hardness of about 7, so alumina (Mohs hardness 9) or the like. Compared to the glass ceramic sintered body 1 containing a crystalline phase having a Mohs hardness higher than 7, in the outer shape processing and cutting processing steps, not only on the surface of the glass ceramic sintered body 1 but also on the inside thereof, cracks, grain breakage, etc. The size of the resulting defect 3 can be reduced. In this case, for example, the chipping width (maximum value) in a cutting process using a dicing saw can be set to 70 μm or less.

Further, as described above, the sintered glass ceramic body 1 of the present embodiment includes an anosite (CaAl ₂ Si ₂ O ₈ , refraction) together with a quartz phase (α-quartz, refractive index 1.45) in the glass phase. And a calcium-zirconium-silicate phase (for example, Ca ₂ ZrSi ₄ O ₁₂ , refractive index 1.7 to 2.1) and a zirconia phase (refractive index 2.4). have. As a result, the reflectance of light in the visible light wavelength region (wavelength 400 to 700 nm) can be made 90% or more, and the light in the near ultraviolet wavelength region (380 nm or less) shorter than the visible light wavelength region. It is possible to make the reflectivity of 69% or more.

  This is because the surface of the glass-ceramic sintered body is covered with a glass phase, and in the glass phase on the surface and on the lower layer side of this glass phase, around the quartz phase, the anorthite phase and calcium / zirconium having different refractive indexes are provided.・ Since the silicate phase and zirconia phase are mixed and uniformly dispersed, each crystal phase can be reflected in response to light having a short wavelength, It is thought that this is because diffused reflection of light is likely to occur near the surface of the bonded body.

Moreover, in the glass ceramic sintered body of the present embodiment, the content of the glass phase is 26 to 44% by mass, the content of the anorthite phase is 5 to 35% by mass, the content of the quartz phase is 1 to 9% by mass, When the content of the calcium / zirconium / silicate phase is 6 to 14% by mass and the content of the zirconia phase is 17 to 41% by mass, the reflectance of light in a wavelength region of 380 nm or less may be 90% or more. it can. Among these, when the contents of the glass phase, the anorthite phase, the quartz phase, and the calcium / zirconium / silicate phase are within the above ranges and the content of the zirconia phase is 18 to 41% by mass, the wavelength of 380 nm or less The light reflectance in the region can be 91% or more.

  Further, the glass phase content is 32 to 44% by mass, the anorthite phase content is 22 to 26% by mass, the quartz phase content is 5 to 9% by mass, and the calcium / zirconium silicate phase content is 6%. When the content of -10% by mass and the content of the zirconia phase is 18-30% by mass, and the average particle size of the quartz phase is 0.9-5.5 μm, the reflectance of light in the wavelength region of 380 nm or less is With the state maintained at 91% or more, the chipping width in the cutting process using the dicing saw can be made 55 μm or less.

  Further, the contents of the anorthite phase, the quartz phase and the calcium / zirconium / silicate phase are 22 to 26 mass%, 5 to 9 mass% and 6 to 10 mass%, respectively, and the glass phase content is 32 to 42 mass%. When the content of the zirconia phase is 22 to 30% by mass and the average particle size of the quartz phase is 1.9 to 5.5 μm, the chipping width in cutting using a dicing saw is maintained at 55 μm or less. The reflectance of light in a wavelength region of 380 nm or less can be increased to 92% or more.

  Further, the content of the anorthite phase and the quartz phase is in the range of 22 to 26% by mass and 5 to 9% by mass, the average particle size of the quartz phase is 1.9 to 5.5 μm, and the content of the glass phase When the content of the calcium / zirconium silicate phase is 6 to 9% by mass and the content of the zirconia phase is 22 to 27% by mass, the chipping width in the cutting process using a dicing saw is 45 μm. The following can be reduced.

  Furthermore, in the above composition, when the average particle size of the quartz phase is 1.9 to 3.8 μm, the chipping width in the cutting process using a dicing saw can be further reduced to 40 μm or less.

  Next, an example in which the glass ceramic sintered body 1 of the present embodiment is applied to a light emitting element mounting substrate will be described. FIG. 2 is a cross-sectional view illustrating an example of the light emitting element mounting substrate of the present embodiment.

  The light emitting element mounting substrate of this embodiment includes an insulating base 13 provided with a mounting portion 11 for mounting a light emitting element (not shown), a conductor layer 15 provided on the upper and lower surfaces of the insulating base 13, and A through conductor 17 for connecting the conductor layers 15 provided on the upper and lower surfaces of the insulating base 13, and a reflecting member 19 provided so as to surround the mounting portion 11 on the upper surface of the insulating base 13; And at least one of the insulating base 13 and the reflecting member 19 is made of the glass ceramic sintered body 1 of the present embodiment.

  As described above, the glass ceramic sintered body 1 of the present embodiment is excellent in external formability such as cutting and polishing, and the size of the defect 3 generated on the surface of the glass ceramic sintered body 1 can be reduced. Therefore, when such a glass ceramic sintered body 1 is applied to at least one of the insulating base 13 and the reflecting member 19 of the light emitting element mounting substrate, the defect 3 is small and not only in the visible light region, It is possible to obtain a light-emitting element mounting substrate that exhibits high reflectance even in the near-ultraviolet wavelength region where the wavelength is shorter than 400 nm. In this case, it is desirable that the maximum size of the defect 3 (width w shown in FIG. 1B) is 70 μm or less in that the defect rate in the appearance inspection as the light emitting element mounting substrate can be reduced.

Further, in the light emitting device in which the light emitting element is attached to the mounting portion 11 of the light emitting element mounting substrate, at least one of the insulating base 13 and the reflecting member 19 constituting the light emitting element mounting substrate is not only in the visible light region, Since it exhibits high reflectance even in the near ultraviolet wavelength region where the wavelength is shorter than 400 nm, it exhibits high light emission characteristics over a wide wavelength range.

Next, the manufacturing method of the glass ceramic sintered compact 1 of this embodiment is demonstrated. First, glass powder, quartz powder, and zirconia (ZrO ₂ ) powder are prepared as raw material powders. In this case, borosilicate glass powder containing Si, B, Al, Ca, Mg, and Zn, respectively, is used for the glass powder because the anorthite phase (CaAl ₂ Si ₂ O ₈ ) phase is likely to precipitate. preferable. Further, when zirconia powder is included in the raw material powder, a high refractive index calcium / zirconium / silicate phase (for example, between the oxide of an alkaline earth element such as Ca and silicon dioxide constituting the glass powder (for example, Coexisting system of Ca ₂ ZrSi ₄ O ₁₂ ) and zirconia phase is likely to be formed, and this makes it possible to obtain a glass ceramic sintered body 1 having a high light reflectance. In this case, the content of the quartz powder contained in the raw material powder is preferably 2 to 15% by mass, particularly 3 to 7% by mass, but the average particle size of the quartz powder is 1 to 6 μm, particularly 1 to It is preferable to use one having a thickness of 4 μm.

  The content of the zirconia powder contained in the raw material powder is preferably 5 to 55% by mass, 15 to 40% by mass, and particularly preferably 20 to 25% by mass. However, the zirconia powder has an average particle size larger than that of the quartz powder. It is desirable to use a powder having a small average particle diameter of 0.3 to 1.0 [mu] m, particularly 0.3 to 0.8 [mu] m. When a zirconia powder having an average particle size of 1 μm or less is used as a raw material powder, a fine calcium / zirconium / silicate phase can be formed around the quartz phase, and the anorthite phase can be atomized. Furthermore, the zirconia phase remaining without being introduced into the calcium / zirconium / silicate phase can coexist with the anorthite phase and the calcium / zirconium / silicate phase as described above. It becomes possible to obtain the glass ceramic sintered body 1 having a higher light reflectance.

  Next, a glass powder, quartz powder, and zirconia powder are mixed with an organic vehicle to prepare a molding mixture using a stirring mixer such as a ball mill.

  Next, after the prepared molding mixture is molded into a predetermined shape, it is fired at a temperature of 800 to 1000 ° C. to thereby make the glass ceramic sintered body of the present embodiment or the reflecting member made of this glass ceramic sintered body. Can be obtained.

  Further, when manufacturing the insulating base 13 of the light emitting element mounting substrate, after forming a molding mixture into a slurry, a sheet-like molded body is formed by a molding method such as a doctor blade method, After forming a through-hole by punching the sheet-shaped molded body, a conductor mainly composed of Ag or Cu is formed on the sheet-shaped molded body that is a portion having the conductor layer 15 and the through conductor 17 in the manufactured sheet-shaped molded body. A conductor pattern is formed using a paste. Next, a sheet-like molded body on which a conductor pattern is formed and a sheet-like molded body on which a conductor pattern is not formed as necessary are combined and laminated so as to have a desired number of layers. Then, a mother substrate to be a light emitting element mounting substrate is manufactured by firing under predetermined conditions.

  Next, the mother substrate is cut to a predetermined size to obtain the insulating base 13 of the light emitting element mounting substrate of the present embodiment. When the mother substrate is formed of the glass ceramic sintered body of the present embodiment, it is possible to suppress the occurrence of defects due to cracks and degranulation on the surface in the processing step of cutting or outline processing, and the appearance is good In addition, a light-emitting element mounting substrate having excellent light reflection characteristics can be obtained.

First, as a raw material powder, SiO ₂ : B ₂ O ₃ : Al ₂ O ₃ : CaO: MgO in a weight ratio.
: ZnO = Borosilicate glass powder (average particle diameter: 2.5 μm), quartz (α-quartz) powder, and zirconia (ZrO ₂ ) powder having a composition ratio of 49: 8: 18: 21: 1: 3 (Average particle size: 0.5 μm) is weighed in the ratio shown in Table 1, and then 100 parts by mass of the raw material powder is 14 parts by mass of acrylic binder, 5 parts by mass of DOP as a plasticizer, An organic vehicle containing 30 parts by mass of toluene was added and mixed using a ball mill for about 40 hours to prepare a slurry. Next, this slurry was molded using a doctor blade method to produce a sheet-like molded body having an average thickness of 0.2 mm.

  Next, three sheets of this sheet-like molded body were bonded and pressure-laminated to produce a raw laminate, and then fired at the maximum temperature shown in Table 1 for 1 hour. Mother substrates of 60 mm, 50 mm, and 0.4 mm were produced.

  Next, the mother substrate was cut with a dicing saw (DAD3350 manufactured by DISCO) to prepare 10 sample pieces having lengths, widths, and thicknesses of about 50 mm, about 5 mm, and about 0.4 mm, respectively. Next, 10 cut sample pieces were observed using a stereomicroscope, and defects such as chips generated in the sample pieces were observed. Table 1 shows the maximum width in the direction perpendicular to the ridgeline. In each of the cut sample pieces, minute chipping (chipping) occurred only in the vicinity of the ridgeline.

  Next, two sheet-like molded bodies are bonded together and pressure-laminated to produce a raw laminate, which is then cut and fired under the same conditions as the substrate used for evaluation of chipping, and reflected. A substrate for rate measurement was prepared. The size of the substrate for reflectance measurement was 30 mm, 30 mm, and 0.25 mm in length, width, and thickness, respectively. The reflectance of the produced reflectance measurement substrate was measured in the wavelength range of 360 to 720 nm using a spectrocolorimeter (CM-3700d manufactured by Konica Minolta), and the reflectances at 360 nm, 430 nm, 540 nm, and 700 nm were all measured. Obtained from reflectance.

  The ratio of each crystal phase and glass phase present in the glass ceramic sintered body is determined by crushing the glass ceramic sintered body and identifying the main peak position obtained by X-ray diffraction in light of JCPDS. It was determined by performing an analysis.

  The average particle size of the quartz phase contained in the glass ceramic sintered body is determined by scanning a portion of the glass ceramic sintered body cut out from the mother substrate in a resin, polishing the cross section, and then polishing the sample. Take a picture of the internal structure using an electron microscope, draw about 50 circles on the picture, select the crystal particles that fall within and around the circle, and then image-process the outline of each crystal particle Then, the area of each crystal particle was obtained, the diameter when replaced with a circle having the same area was calculated, and the average value was obtained. At this time, an element of a main component contained in the crystal phase was identified by an X-ray microanalyzer provided in the scanning electron microscope, and a crystal phase in which only oxygen other than Si was detected was identified as a quartz phase.

  As a comparative example, a sample using alumina powder instead of quartz (α-quartz) powder was prepared by the same method as described above, and the same evaluation was performed (sample No. 15 in Table 1).

  As is clear from the results in Table 1, sample No. In 1-7, 9-14, and 16-27, the chipping width in cutting using a dicing saw was 70 μm or less. Further, these samples all had a reflectance of 69% or more at a wavelength of 360 to 700 nm.

  Further, the glass phase content contained in the glass ceramic sintered body is 26 to 44% by mass, the anorthite phase content is 5 to 35% by mass, the quartz phase content is 1 to 9% by mass, calcium. Sample No. 2 having a zirconium silicate phase content of 6 to 14% by mass and a zirconia phase content of 17 to 41% by mass. In 3-7, 9-14, 16, 18, 20, 21, 26 and 27, the reflectance at 360 nm was 90% or more, and the chipping width in the cutting process using the dicing saw was 70 μm or less.

  Further, the glass phase content contained in the glass ceramic sintered body is 32 to 44% by mass, the anorthite phase content is 22 to 26% by mass, the quartz phase content is 5 to 9% by mass, calcium. Sample No. 2 having a zirconium silicate phase content of 6 to 14% by mass and a zirconia phase content of 18 to 41% by mass. In 3-7, 10-14, 16, 18, 20, 21, 26 and 27, the reflectance at 360 nm was 91% or more, and the chipping width in the cutting process using a dicing saw was 70 μm or less.

  Further, the glass phase content is 32 to 44% by mass, the anorthite phase content is 22 to 26% by mass, the quartz phase content is 5 to 9% by mass, and the calcium / zirconium silicate phase content is 6%. No. 10 mass% and the content of the zirconia phase is 18-30 mass%, and the average particle size of the quartz phase is 0.9-5.5 μm. In 3-5, 10-13, 18, 20, 26, and 27, the reflectance at 360 nm was 91% or more, and the chipping width in cutting using a dicing saw was 55 μm or less.

  Further, the contents of the anorthite phase, the quartz phase and the calcium / zirconium / silicate phase are 22 to 26 mass%, 5 to 9 mass% and 6 to 10 mass%, respectively, and the glass phase content is 32 to 42 mass%. Sample No. 2 having a zirconia phase content of 22 to 30% by mass and an average particle size of the quartz phase of 1.9 to 5.5 μm. In 4, 5, 10-12, 18, 20, 26 and 27, the light reflectance in the wavelength region of 380 nm or less is 92% in a state where the chipping width in the cutting process using the dicing saw is maintained at 55 μm or less. That was all.

  Furthermore, the contents of the anorthite phase and the quartz phase are in the range of 22 to 26% by mass and 5 to 9% by mass, respectively, and the average particle size of the quartz phase is 1.9 to 5.5 μm. Sample No. 2 having a content of 34 to 42% by mass, a calcium / zirconium / silicate phase content of 6 to 9% by mass, and a zirconia phase content of 22 to 27% by mass. In 4, 5, 10-12, 26, and 27, the reflectance of light in a wavelength region of 380 nm or less was 92% or more, and the chipping width in cutting using a dicing saw was 45 μm or less.

  Furthermore, in the above composition, the sample No. 1 in which the average particle size of the quartz phase was 1.9 to 3.8 μm. In 4, 5, 10-12 and 26, the chipping width in cutting using a dicing saw could be reduced to 40 μm or less while maintaining the reflectance of light in a wavelength region of 380 nm or less at 92% or more.

On the other hand, the sample (sample No. 15) using alumina powder instead of quartz (α-quartz) powder had a chipping width of 100 μm in a cutting process using a dicing saw.
In addition, a sample (sample No. 8) produced only by glass powder without mixing both quartz powder and zirconia powder also had a large chipping width of 80 μm in cutting using a dicing saw.

DESCRIPTION OF SYMBOLS 1 ... Glass ceramic sintered compact 3 ... Defect 11 ... Mounting part 13 ... Insulating base | substrate 15 ... Conductor layer 17 ... Through-conductor 19 ...・ Reflective member

Claims (9)

  A glass-ceramic sintered body comprising an anorthite phase, a quartz phase, a calcium-zirconium-silicate phase, and a zirconia phase in a glass phase.   The content of the glass phase is 26 to 44% by mass, the content of the anorthite phase is 5 to 35% by mass, the content of the quartz phase is 1 to 9% by mass, and the content of the calcium / zirconium silicate phase The glass-ceramic sintered body according to claim 1, wherein the content of the zirconia phase is 17 to 41% by mass.   The glass phase content is 32 to 44% by mass, the anorthite phase content is 22 to 26% by mass, the quartz phase content is 5 to 9% by mass, and the calcium / zirconium silicate phase content is The content of the zirconia phase is 18 to 30% by mass, and the average particle size of the quartz phase is 0.9 to 5.5 μm. The glass-ceramic sintered body described in 1.   The glass phase content is 32-42% by mass, the zirconia phase content is 22-30% by mass, and the quartz phase has an average particle size of 1.9-5.5 μm. The glass ceramic sintered body according to claim 3.   The glass phase content is 34 to 42% by mass, the calcium / zirconium / silicate phase content is 6 to 9% by mass, and the zirconia phase content is 22 to 27% by mass. Item 5. A glass ceramic sintered body according to Item 4.   6. The glass ceramic sintered body according to claim 5, wherein an average particle diameter of the quartz phase is 1.9 to 3.8 μm.   A reflecting member comprising the glass ceramic sintered body according to claim 1.   An insulating base having a mounting portion for mounting a light emitting element, and a reflecting member provided on the mounting portion side of the insulating base so as to surround the mounting portion, the insulating base and the reflecting member A substrate for mounting a light emitting element, wherein at least one of the glass ceramic sintered bodies according to any one of claims 1 to 6 is formed.   A light emitting device comprising a light emitting element in the mounting portion of the light emitting element mounting substrate according to claim 8.

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