WO2024084631A1 - Corps fritté de nitrure de silicium - Google Patents

Corps fritté de nitrure de silicium Download PDF

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WO2024084631A1
WO2024084631A1 PCT/JP2022/038967 JP2022038967W WO2024084631A1 WO 2024084631 A1 WO2024084631 A1 WO 2024084631A1 JP 2022038967 W JP2022038967 W JP 2022038967W WO 2024084631 A1 WO2024084631 A1 WO 2024084631A1
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silicon nitride
sintered body
nitride sintered
grain boundary
boundary phase
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PCT/JP2022/038967
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Japanese (ja)
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理 松本
光隆 高橋
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株式会社Maruwa
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Priority to PCT/JP2022/038967 priority Critical patent/WO2024084631A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/587—Fine ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/15—Ceramic or glass substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to silicon nitride sintered bodies that are used as circuit boards, heat dissipation components, etc.
  • insulating ceramics used as circuit boards, heat dissipation members, and the like include aluminum nitride (AlN) and silicon nitride (Si 3 N 4 ).
  • Aluminum nitride has a high thermal conductivity of 150 W/m ⁇ K or more, but has low mechanical strength, making it prone to cracks and difficult to use.
  • Silicon nitride has a thermal conductivity of 50 W/m ⁇ K or more, although it is not as high as aluminum nitride, and has high mechanical strength, so it has the advantages of being less susceptible to cracks and being able to be made thinner. For this reason, the development and adoption of silicon nitride sintered bodies has progressed in recent years.
  • Patent Document 1 describes a silicon nitride sintered body in which the crystal phase present in the grain boundary phase of silicon nitride crystal grains has an X-ray diffraction peak intensity ratio of 0.05 to 0.40 (silicon nitride being 1), and a manufacturing method in which a green sheet of this material is sintered at 1600 to 1900°C in a nitrogen atmosphere, and then the residual glass phase is removed at 1100 to 1700°C.
  • Patent Document 2 describes a silicon nitride substrate that has improved bonding of circuit components and has a dielectric breakdown voltage of 36 to 47 kV/mm (Table 6 in the same document) measured on a substrate 3 mm thick, and a manufacturing method in which a green sheet of the material is placed in a firing furnace containing magnesium oxide and erbium oxide co-materials to suppress volatilization of the components, and sintered at 1750°C for 3 to 5 hours.
  • Patent Document 3 describes a silicon nitride substrate with a porosity of 0-1.0%, a maximum pore diameter of 0.2-3 ⁇ m, and a dielectric strength of 17-29 kV/mm (Tables 7 and 8 of the same document) measured on a substrate with a thickness of 0.15-0.635 mm, and a manufacturing method in which a green sheet of the material is sintered at 1800-1900°C in a non-oxidizing atmosphere.
  • Patent Document 4 describes a silicon nitride substrate with a warpage of 2.0 ⁇ m/mm or less, and a manufacturing method in which a green sheet of the material is sintered in a pressurized nitrogen atmosphere at 1800-2000°C for 8-18 hours, and then heat-treated at 1550-1700°C while applying a load to suppress the warpage.
  • Patent Document 5 describes a silicon nitride substrate that has little warping and high strength, and a manufacturing method in which a green sheet of the material is placed in a firing vessel in which packed powder such as magnesium oxide is placed to suppress the volatilization of silicon nitride and magnesia, and sintered at 1,860°C for five hours.
  • Patent document 6 describes a silicon nitride substrate with a void ratio of 0.1-4% and a dielectric breakdown strength of 32-36 kV/mm (Table 3 in the same document) measured on a substrate with a thickness of 0.15-0.25 mm, and a manufacturing method in which a green sheet of the material is sintered in a nitrogen atmosphere at 1850-1900°C for 3-5 hours.
  • Patent Documents 1 to 6 describes a silicon nitride sintered body in which the grain boundary phase formed by the sintering aid has an amorphous structure. Rather, Patent Document 1 describes that if the sintering aid remains in the grain boundary phase as a glass phase, high-temperature properties such as high-temperature strength and creep resistance decrease, and therefore, as described above, the remaining glass phase is removed by crystallizing it at 1100 to 1700°C after sintering.
  • the inventors' research has revealed that if the grain boundary phase formed by the sintering aid is a crystalline phase, the volumetric shrinkage during cooling after sintering becomes large, the number of voids in the silicon nitride sintered body increases, and the warping of the silicon nitride sintered body becomes large. It has also been found that if the grain boundary phase formed by the sintering aid has an amorphous structure, the volumetric shrinkage during cooling after sintering becomes small, the number of voids in the silicon nitride sintered body decreases, and the warping of the silicon nitride sintered body becomes small.
  • the present invention was made as a result of further intensive research into this issue.
  • a material in which 2 to 3 mass% of MgO is added as a sintering aid to silicon nitride powder and 2.7 to 4 mass% of a rare earth oxide having an oxidation number of 3 (however, the amount is greater than the amount of MgO) is added is used and sintered
  • a silicon nitride sintered body comprising silicon nitride and a grain boundary phase formed with a sintering aid, wherein the grain boundary phase has an amorphous structure, and the maximum integrated intensity of peaks of crystalline compounds in the grain boundary phase present in a diffraction angle 2 ⁇ range of 28° to 32° in an X-ray diffraction pattern obtained using an X-ray diffractometer equipped with a semiconductor detector is 2.4% or less of the integrated intensity of the silicon nitride (101) plane.
  • the grain boundary phase preferably contains at least MgO or MgSiN 2 and does not contain SrO.
  • the thermal conductivity is 72 W/mK or more.
  • the silicon nitride sintered body is processed into a test piece measuring 40 mm ⁇ 20 mm ⁇ 0.32 mm, and the three-point bending strength measured at a crosshead speed of 0.5 mm/min, a support distance of 30 mm, and at room temperature (23 ⁇ 2°C) is preferably 625 MPa or more.
  • the surface of the silicon nitride sintered body is polished by 50 ⁇ m or more, and in at least one arbitrary 64 ⁇ m ⁇ 48 ⁇ m area of the polished surface, the plane projection area ratio of voids is 1.0% or less.
  • the thermal conductivity is 80 W/m ⁇ K or more.
  • the grain boundary phase has an amorphous structure, and among the peaks of crystalline compounds in the grain boundary phase that exist in the diffraction angle 2 ⁇ range of 28° to 32° in an X-ray diffraction pattern obtained using an X-ray diffractometer equipped with a semiconductor detector, the maximum integrated intensity is 2.4% or less of the integrated intensity of the silicon nitride (101) plane, so that the volume shrinkage is small during cooling after sintering, and the sintering aid exists as a liquid phase until a lower temperature and penetrates to the narrow portions between the silicon nitride crystal grains, so that the number of voids in the silicon nitride sintered body is reduced, and the internal stress of the silicon nitride sintered body is reduced, resulting in less warping.
  • an alkaline earth metal as a sintering aid has the effect of lowering the melting point of the liquid phase.
  • SrO is less likely to volatilize than MgO or MgSiN2 , so it remains after sintering and becomes a factor that inhibits thermal conduction, so by containing at least MgO or MgSiN2 and not containing SrO, a silicon nitride sintered body with high thermal conductivity can be obtained.
  • the number of voids in the silicon nitride sintered body is reduced, and the warping of the silicon nitride sintered body is reduced.
  • FIG. 1 shows X-ray diffraction patterns of sintered silicon nitride bodies, where (a) is the same pattern for Example 1 and (b) is the same pattern for Comparative Example 1.
  • FIG. 2 shows SEM photographs of the silicon nitride sintered body, where (a) is the same photograph of Example 1 and (b) is the same photograph of Comparative Example 1.
  • FIG. 3 is a diagram for explaining the unevenness of voids.
  • FIG. 4 is a diagram for explaining a method for measuring the warpage of a silicon nitride sintered body.
  • FIG. 5 is a diagram showing examples of applications of the silicon nitride sintered body.
  • the silicon nitride sintered body of the present invention is a silicon nitride sintered body consisting of silicon nitride and a grain boundary phase formed by a sintering aid, characterized in that the grain boundary phase has an amorphous structure.
  • the following preferred forms are exemplified.
  • the sintering step of sintering a mixture of silicon nitride powder and a sintering aid is preferably performed such that 1930 ⁇ sintering temperature (° C.)+sintering time (hr) ⁇ 50 ⁇ 2200, and the grain boundary phase formed by the sintering aid has an amorphous structure. It is preferable that no peaks derived from grain boundary phases are detected in an X-ray diffraction pattern obtained using an X-ray diffractometer equipped with a semiconductor detector.
  • the sintering step it is preferable to place a pre-sintered plate-shaped silicon nitride sintered body separate from the silicon nitride sintered body to be produced in a closed casing for firing. It is preferable that the sintering aid contains at least MgO or MgSiN2 , and does not contain SrO.
  • the temperature (°C) + firing time (hr) x 50 ⁇ 2200 By setting the temperature (°C) + firing time (hr) x 50 ⁇ 2200, sintering is realized, and the volatilization of SiO2 during sintering is suppressed, and the crystallization of the grain boundary phase is suppressed.
  • the grain boundary phase formed by the sintering aid into an amorphous structure By making the grain boundary phase formed by the sintering aid into an amorphous structure, the volume shrinkage during cooling after sintering is reduced, and the sintering aid exists as a liquid phase at lower temperatures and penetrates to the narrow parts between the silicon nitride crystal grains, so that the number of voids in the silicon nitride sintered body is reduced, and the internal stress of the silicon nitride sintered body is reduced, resulting in less warping.
  • a pre-sintered plate-shaped silicon nitride sintered body (hereinafter referred to as a "dummy silicon nitride sintered body") separate from the silicon nitride sintered body to be produced is placed in a closed casing for firing, the SiO 2 of the dummy silicon nitride sintered body will volatilize during firing, suppressing the volatilization of SiO 2 of the silicon nitride sintered body to be produced, which also suppresses crystallization and prevents a decrease in sintering density.
  • the dummy silicon nitride sintered body does not need to have the same composition as the silicon nitride sintered body to be produced, but it is preferable that they use the same auxiliary agent system.
  • an alkaline earth metal as a sintering aid has the effect of lowering the melting point of the liquid phase.
  • SrO is less likely to volatilize than MgO or MgSiN2 , so it remains after sintering and becomes a factor that inhibits thermal conduction, so by containing at least MgO or MgSiN2 and not containing SrO, a silicon nitride sintered body with high thermal conductivity can be obtained.
  • the bending strength and the dielectric breakdown voltage become high.
  • Voids In at least one 64 ⁇ m ⁇ 48 ⁇ m area of a polished surface obtained by polishing the surface of a silicon nitride sintered body by 50 ⁇ m or more, the number of voids having a degree of irregularity of 0.9 or more, calculated by dividing the area within the contour line of the void by the area within the envelope line of the void, preferably accounts for 10% or more of the total number of voids.
  • the number of voids having a degree of irregularity of 0.8 or more calculated by dividing the area within the contour line of the void by the area within the envelope line of the void, accounts for 30% or more of the total number of voids.
  • the plane projected area ratio of voids is 1.0% or less.
  • Warpage A plate-shaped silicon nitride sintered body is preferably maintained at 120°C for 1 hour or more, and then placed on a flat sample stage at 25°C. The warpage is measured within 1 minute of placing the plate-shaped silicon nitride sintered body on a flat sample stage at 25°C, and is calculated as a ratio of the difference between the height of the highest point of the upper surface of the silicon nitride sintered body from the sample stage to the height of the lowest point of the upper surface of the silicon nitride sintered body from the sample stage to the maximum transverse length of the silicon nitride sintered body, and is preferably 0.2% or less.
  • the maximum transverse length of the silicon nitride sintered body refers to the maximum length of a line segment that crosses the plate surface of the silicon nitride sintered body from one point on its edge to another point, and is, for example, the diagonal length when the plate surface is rectangular, and the diameter length when the plate surface is circular.
  • the measured warpage is 0.2% or less, so even if products in which the silicon nitride sintered body is used as a circuit board, heat dissipation component, etc. are exposed to high-temperature environments exceeding 100°C, the small warpage of the silicon nitride sintered body ensures sufficient heat dissipation and is less likely to break,
  • the dielectric breakdown voltage is preferably 5 kV or more.
  • the silicon nitride sintered body can be used in applications where a high dielectric breakdown voltage is required when actually formed to a thickness of about 100 ⁇ m.
  • the "thickness of 100 ⁇ m" is defined only as a condition for measuring the dielectric breakdown voltage, and does not define the thickness of the silicon nitride sintered body product.
  • the silicon nitride sintered body product may have any thickness, and it is preferable that the dielectric breakdown voltage measured after processing the silicon nitride sintered body to a thickness of 100 ⁇ m is 5 kV or more.
  • FIG. 5A a circuit board used in a semiconductor module, an LED package, a Peltier module, a printer, a multifunction machine, a semiconductor laser, optical communication, high frequency, etc.
  • a general-purpose heat dissipation member as shown in FIG. A heat dissipation member (heat sink) for a power semiconductor module as shown in FIG.
  • An insulating plate as shown in FIG. An insulating plate for bonding wafers as shown in FIG. 5(e).
  • a high frequency window is used in gyrotrons, klystrons, etc.
  • Silicon nitride sintered bodies were produced as Examples 1 to 21 shown in Tables 1 and 2, and as Comparative Examples 1 to 8 shown in Table 3.
  • each example refers to each of Examples 1 to 21 and Comparative Examples 1 to 8.
  • Example 21 is a reference example.
  • Silicon nitride powder having an average particle size (D50) of about 1.0 ⁇ m produced by the imide pyrolysis method or the direct nitridation method was used as the main raw material silicon nitride (Si 3 N 4 ) in each example.
  • sintering aid two types selected from the powders of MgO, MgSiN2, Y2O3, La2O3 , Nd2O3 , Sm2O3 , and Dy2O3 were used in each example, as shown in Tables 1 to 3. In Examples 1 to 21, at least MgO or MgSiN2 was used, and SrO was not used.
  • a dissolved binder solution consisting of 10 parts by weight of polyvinyl butyral as a binder, 4 parts by weight of dioctyl adipate as a plasticizer, and approximately 20 parts by weight of a mixed solvent of toluene and ethanol was added to this pulverized mixture, and the dissolved binder solution and the pulverized mixture were stirred and mixed in a ball mill until they were completely mixed, after which a slurry was produced. The slurry was then heated and left in a vacuum to degas and volatilize the solvent, adjusting the viscosity at 25°C to 15,000 cps.
  • a boron nitride (BN) powder slurry was sprayed onto the surface of the die-cut green sheet as a release agent, and the green sheet laminate made by stacking multiple green sheets was placed in a BN case and heated to 500°C in a dry air flow for approximately four hours, performing a degreasing process to remove organic components such as binders.
  • BN boron nitride
  • the green sheet laminate was sintered by heating for the firing time at the firing temperature shown in Tables 1 and 2 for each example, and the sintered laminate was separated into individual silicon nitride sintered bodies.
  • the separated silicon nitride sintered bodies were subjected to honing to remove the BN mold release agent.
  • the silicon nitride sintered bodies after honing were broken on the four outer periphery sides with a diamond scriber, and the shape and dimensions of the silicon nitride sintered bodies finally obtained were rectangular plate-like 139.6 mm x 190.5 mm x 0.32 mm.
  • the firing temperature was in the range of 1830 to 1920° C., and sintering was performed for a relatively short time so as to satisfy the following formula 1. 1930 ⁇ firing temperature (° C.)+firing time (hr) ⁇ 50 ⁇ 2200 (Equation 1)
  • the firing temperature was in the range of 1860 to 1880° C., but sintering was carried out for a relatively long time so as to exceed the upper limit of the above formula 1.
  • the firing temperature was set to 1800° C., and sintering was performed for a short time so that the temperature was below the lower limit of the formula (1).
  • the three-point bending strength was measured by processing the silicon nitride sintered body into a test piece measuring 40 mm ⁇ 20 mm ⁇ 0.32 mm, and using a universal testing machine, model "AG-IS", manufactured by Shimadzu Corporation, at a crosshead speed of 0.5 mm/min, a support distance of 30 mm, and room temperature (23 ⁇ 2°C).
  • thermal conductivity was measured by processing the silicon nitride sintered body into a test piece having a size of 10 mm ⁇ 10 mm ⁇ 0.32 mm, subjecting the test piece to a surface treatment (Ag film deposition + carbon blackening treatment), and then using a thermal conductivity measuring device manufactured by NETZSCH, model "LFA 467 HyperFlash.”
  • the integrated intensity of the (101) plane of ⁇ -Si 3 N 4 (hereinafter referred to as "silicon nitride I") and the integrated intensity of the maximum peak among the peaks of the Si-Y-N-O compound of the grain boundary phase having a diffraction angle 2 ⁇ in the range of 28° to 32° (hereinafter referred to as "grain boundary phase I”) were calculated by the following procedure to determine the integrated intensity ratio (grain boundary phase I/silicon nitride I).
  • Preprocessing is performed by removing background, removing K ⁇ 2 and smoothing, and then a peak search is performed.
  • the background profile is calculated by subtracting the peak profile from the measured data, and the calculated data is fitted with a B-spline function.
  • the peak shape is represented by a split pseudo-Voight function, and the integrated intensity is calculated.
  • Example 1(a) shows the X-ray diffraction pattern of Example 1.
  • No peak derived from the grain boundary phase formed by the sintering aid was detected, and the integrated intensity ratio was 0 as shown in Table 1. This indicates that no grain boundary crystalline phase exists, and the grain boundary phase has a substantially amorphous structure.
  • Examples 2 to 19 were similar to Example 1.
  • Example 20 a peak derived from the grain boundary phase formed by the sintering aid was detected, but as shown in Table 1, the integrated intensity ratio was only 2.4%, which is also an amorphous structure.
  • Comparative Example 1(b) shows the X-ray diffraction pattern of Comparative Example 1.
  • a peak derived from the grain boundary phase formed by the sintering aid was detected, and as shown in Table 3, the integrated intensity ratio was 24.6%. This indicates that not only was the grain boundary crystalline phase present, but that the grain boundary phase was substantially composed of a crystalline phase.
  • Comparative Examples 2 to 7 were basically similar to Comparative Example 1 (although the integrated intensity ratios were different).
  • no peak derived from the grain boundary phase formed by the sintering aid was detected, and the integrated intensity ratio was 0, as shown in Table 1. This indicates that no grain boundary crystal phase exists, and the grain boundary phase is substantially an amorphous structure.
  • Comparative Example 8 has a low relative density and few voids with an irregularity degree of 0.8 or more.
  • Voids The silicon nitride sintered body was subjected to a surface treatment as follows. The silicon nitride sintered body was processed into a test piece of 8 mm x 8 mm x 0.32 mm, and fixed to a ⁇ 40 aluminum sample stage using Alcowax "5402SL” manufactured by Nikka Seiko Co., Ltd.
  • the sample stage was set on a sample rotator (model "SP-L1") manufactured by IMT Corporation, and the silicon nitride sintered body was surface-polished (polishing load: 15N, polishing plate rotation speed: 150 rpm, sample rotation speed: 150 rpm) using diamond polishing pads (manufactured by the same company) of #80, #600, and #1200 in that order using a tabletop polishing machine (model "IM-P2”) manufactured by the same company, and the flatness was adjusted. The final polishing amount with the diamond polishing pad was adjusted to about 50 ⁇ m.
  • the specimen was subjected to plasma etching in CF4 gas for 4 minutes using a plasma etching device (model: SEDE-PHL) manufactured by Meiwa Force Systems Co., Ltd., to prepare a surface for microstructure observation.
  • a plasma etching device model: SEDE-PHL
  • SEDE-PHL plasma etching device manufactured by Meiwa Force Systems Co., Ltd.
  • an Au film was formed using an ion sputter, model "E-1010" manufactured by Hitachi High-Technologies Corporation.
  • the sputtering time was 120 seconds, and according to the operation manual, the thickness of the formed Au film was about 15 to 20 nm.
  • the SEM photographs taken were subjected to image analysis using software "A-zo-kun Ver. 2.58" manufactured by Asahi Kasei Engineering Co., Ltd., and the unevenness of the voids present in any one 64 ⁇ m ⁇ 48 ⁇ m area of the polished surface was measured.
  • the unevenness was divided into six categories (0.9 or more, 0.8 to less than 0.9, 0.7 to less than 0.8, 0.6 to less than 0.7, 0.5 to less than 0.6, and less than 0.5), and the number of voids in each category and the percentage of the number of voids in each category to the total number of voids were calculated.
  • the unevenness is calculated by the following formula 2 based on the contour line and envelope line of the void as shown in Fig. 3.
  • Examples 1 to 21 voids with a degree of unevenness of 0.9 or more accounted for 10% or more, and voids with a degree of unevenness of 0.8 or more accounted for 30% or more.
  • the percentage of voids with a degree of unevenness of 0.9 or more was less than 10%, and the percentage of voids with a degree of unevenness of 0.8 or more was less than 30%.
  • Plane projection area ratio (total plane projection area of voids / area area) x 100 ... (Equation 3)
  • Planar projected area ratio was 1.0% or less.
  • the planar projected area ratio exceeded 1.0%.
  • the difference ( ⁇ m) between the height of the highest point of the silicon nitride sintered body from the sample stage and the height of the lowest point of the silicon nitride sintered body from the sample stage was measured using the same measuring device, and the average value of the three differences was calculated.
  • the ratio (%) of the average value to the maximum transverse length (diagonal length in this example) of the plate surface of the silicon nitride sintered body was taken as the value of warpage.
  • Example 1 the holding time at 120°C was increased to 2 hours, 4 hours, and 8 hours, and the warpage was measured in the same manner as above. However, since the measurement result when held for 1 hour was within ⁇ 1%, no significant difference due to the holding time was observed.
  • the time elapsed from removal from the heating furnace to placing the sample on a flat sample stand at 25°C for measurement was changed to 20 seconds and 40 seconds, and the warpage was measured in the same manner as above, but the results were within ⁇ 3% of the measurement results after 1 minute, so there was no significant difference due to the time elapsed from removal from the heating furnace within 1 minute. Note that within ⁇ 3% means a variation of 0.194% to 0.206% for a silicon nitride sintered body with a warpage of 0.2%, and it can be said that there is no significant difference.
  • the second silicon nitride sintered body for which warpage was measured was divided into four pieces to reduce the size (69.8 mm x 95.3 mm x 0.32 mm, diagonal length 118 mm), further divided into two pieces to reduce the size (69.8 mm x 47.6 mm x 0.32 mm, diagonal length 85 mm), and further divided into two pieces to reduce the size (34.9 mm x 47.6 mm x 0.32 mm, diagonal length 59 mm).
  • the warpage was measured after holding at 120°C in the same manner as above.
  • the warpage before division (diagonal length 236 mm) was 0.14%, while the warpage after division (diagonal lengths 118 mm, 85 mm, 59 mm) was 0.12%, 0.13%, and 0.15%, respectively. This shows that even when dividing into smaller sizes, the warpage remains almost the same as before division.
  • Conductive copper foil adhesive tape of ⁇ 10.4 mm was attached to both sides of the sample as a measurement electrode, and an AC voltage (sine wave) was applied in a fluorine-based inert liquid (Fluorinert FC-43 manufactured by 3M Japan Ltd.) using a withstand voltage tester: model "TOS5101" manufactured by Kikusui Electronics Co., Ltd.
  • the AC voltage was increased at a rate of 500 V/s, and the average breakdown voltage in the measurements of three samples was measured.
  • the dielectric breakdown voltage was 5 kV or more. In Comparative Examples 1 to 7, the dielectric breakdown voltage was less than 5 kV.
  • the breakdown voltage is often measured on sintered bodies that are thicker than 100 ⁇ m (e.g., 300 ⁇ m), but the value obtained by converting the measurement results of such a sintered body to a value per 100 ⁇ m is merely a theoretical value. Therefore, it is not possible to guarantee that the breakdown voltage of the sintered body when actually formed to a thickness of about 100 ⁇ m will be the converted value.
  • the present invention makes it possible to guarantee this.

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Abstract

Le problème décrit par la présente invention est de réduire le retrait volumique pendant le refroidissement après frittage de façon à réduire les vides dans un corps fritté de nitrure de silicium et à réduire le gauchissement du corps fritté de nitrure de silicium. La solution selon l'invention porte sur un corps fritté de nitrure de silicium dans lequel est utilisé un matériau obtenu par ajout, à une poudre de nitrure de silicium, de 2 à 3 % en masse de MgO en tant qu'auxiliaire de frittage et de 2,7 à 4 % en masse d'un oxyde de terre rare (sa quantité étant supérieure à celle du MgO) présentant un nombre d'oxydation de 3, le matériau étant fritté et le corps fritté de nitrure de silicium comprenant un nitrure de silicium et une phase de limite de grain formée à partir de l'auxiliaire de frittage, la phase de limite de grain présentant une structure amorphe. Au niveau du pic d'un composé cristallin dans la phase de limite de grain, dans lequel l'angle de diffraction 2θ est situé dans une plage de 28° à 32° dans un diagramme de diffraction de rayons X obtenu à l'aide d'un dispositif de diffraction de rayons X pourvu d'un détecteur semi-conducteur, l'intensité intégrale la plus grande est inférieure ou égale à 2,4 % par rapport à l'intensité intégrale du plan de nitrure de silicium (101).
PCT/JP2022/038967 2022-10-19 2022-10-19 Corps fritté de nitrure de silicium WO2024084631A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018024548A (ja) * 2016-08-09 2018-02-15 住友電気工業株式会社 窒化ケイ素焼結体およびその製造方法
JP2019052072A (ja) * 2017-09-19 2019-04-04 株式会社Maruwa 窒化ケイ素焼結体基板、電子装置、及び、窒化ケイ素焼結体基板の製造方法
WO2020203787A1 (fr) * 2019-03-29 2020-10-08 デンカ株式会社 Substrat de nitrure de silicium, complexe nitrure de silicium-métal, carte de circuit imprimé en nitrure de silicium et boîtier semi-conducteur
WO2021117829A1 (fr) * 2019-12-11 2021-06-17 宇部興産株式会社 Corps fritté à base de nitrure de silicium de type plaque et son procédé de fabrication

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018024548A (ja) * 2016-08-09 2018-02-15 住友電気工業株式会社 窒化ケイ素焼結体およびその製造方法
JP2019052072A (ja) * 2017-09-19 2019-04-04 株式会社Maruwa 窒化ケイ素焼結体基板、電子装置、及び、窒化ケイ素焼結体基板の製造方法
WO2020203787A1 (fr) * 2019-03-29 2020-10-08 デンカ株式会社 Substrat de nitrure de silicium, complexe nitrure de silicium-métal, carte de circuit imprimé en nitrure de silicium et boîtier semi-conducteur
WO2021117829A1 (fr) * 2019-12-11 2021-06-17 宇部興産株式会社 Corps fritté à base de nitrure de silicium de type plaque et son procédé de fabrication

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