WO2010002001A1 - 窒化珪素基板及びその製造方法並びにそれを使用した窒化珪素回路基板及び半導体モジュール - Google Patents
窒化珪素基板及びその製造方法並びにそれを使用した窒化珪素回路基板及び半導体モジュール Download PDFInfo
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- WO2010002001A1 WO2010002001A1 PCT/JP2009/062221 JP2009062221W WO2010002001A1 WO 2010002001 A1 WO2010002001 A1 WO 2010002001A1 JP 2009062221 W JP2009062221 W JP 2009062221W WO 2010002001 A1 WO2010002001 A1 WO 2010002001A1
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Definitions
- the present invention relates to a silicon nitride substrate and a manufacturing method thereof.
- the present invention also relates to a silicon nitride circuit board and a semiconductor module using the silicon nitride substrate.
- a substrate used for the power semiconductor module a ceramic circuit substrate in which a metal circuit board is bonded to one surface of an insulating ceramic substrate and a metal heat sink is bonded to the other surface can be used.
- a semiconductor element or the like is mounted on the upper surface of the metal circuit board.
- the amount of heat generated is increased by flowing a large current.
- the insulating ceramic substrate has a lower thermal conductivity than a copper plate, it can be a factor that hinders heat dissipation from the semiconductor element. .
- thermal stress based on the difference in thermal expansion coefficient between the insulating ceramic substrate and the metal circuit board and the metal heat radiating plate is generated.
- the metal circuit board or the metal heat radiating plate is peeled off from the insulating ceramic substrate.
- the insulating ceramic substrate requires high thermal conductivity and mechanical strength in order to improve heat dissipation.
- Examples of the material for the insulating ceramic substrate include aluminum nitride and silicon nitride, but the insulating ceramic substrate using aluminum nitride has high thermal conductivity but low mechanical strength, so that such cracks occur. It is easy to use in a power semiconductor module having a structure in which a great stress is applied to the ceramic substrate.
- Patent Document 1 discloses an example of a silicon nitride substrate. By crystallizing 20% or more of the grain boundary phase, the ratio of the glass phase having a low thermal conductivity is reduced to reduce the silicon nitride substrate. Increases thermal conductivity.
- this technique is referred to as a first conventional example.
- Patent Document 2 discloses an example of a silicon nitride ceramic material. By making the grain boundary phase amorphous, the silicon nitride crystal particles are firmly bonded to the amorphous grain boundary phase. , Has increased strength.
- Patent Document 3 discloses an example of a silicon nitride-based heat radiating member.
- a silicon nitride-based heat radiating member having a high thermal conductivity is obtained by containing a crystal phase made of MgSiO 3 or MgSiN 2 in the grain boundary phase. It has gained.
- this technique is referred to as a third conventional example.
- Patent Document 4 discloses an example of a silicon nitride-based sintered body, which reports a sintered body that includes a crystal phase in the grain boundary phase and is excellent in bending strength, fracture toughness, and thermal shock resistance. ing.
- this technique is referred to as a fourth conventional example.
- the thermal conductivity is increased by crystallizing 20% or more of the grain boundary phase.
- High thermal conductivity contributes to reducing the thermal resistance of the circuit board, but it is particularly high when it is used as a silicon nitride circuit board bonded to a thick copper plate, or when mounting at high temperatures or considering the operation of semiconductor modules at high temperatures.
- Mechanical strength is also required. Although the bending strength is described in the first conventional example, the bending strength can be achieved only when the material is manufactured using a specific raw material powder and a specific manufacturing condition.
- the grain boundary phase is made amorphous to obtain a ceramic material with high bending strength, but thermal conductivity is not taken into consideration.
- the thermal conductivity is improved by including a crystal phase composed of MgSiO 3 or MgSiN 2 in the grain boundary phase, but substantially MgSiO 3 and RE Since it contains the contained crystal phase, its thermal conductivity is not sufficiently high as a heat radiating member of the semiconductor module, and the bending strength is not sufficiently high.
- the thermal shock resistance, the bending strength, and the improvement of the thermal conductivity are described, but a phase including sialon having a low thermal conductivity is formed. It is difficult to apply to the use of heat dissipation board.
- the present invention has been made in view of the above-described conventional problems, and an object of the present invention is to provide a silicon nitride substrate made of a silicon nitride-based sintered body having high strength, high thermal conductivity, and excellent thermal shock resistance, a method for producing the same, and a method therefor It is an object to provide a silicon nitride circuit board and a semiconductor module using the above.
- the invention of a silicon nitride sintered body according to claim 1 is characterized in that ⁇ -type silicon nitride crystal particles, at least one kind of rare earth element (RE), magnesium (Mg), and silicon (Si ) Containing a grain boundary phase, the grain boundary phase consists of an amorphous phase and a MgSiN 2 crystal phase, and X-rays of any crystal plane of the crystal phase containing the rare earth element (RE)
- the diffraction line peak intensities are also the diffraction line peak intensities of (110), (200), (101), (210), (201), (310), (320) and (002) of the ⁇ -type silicon nitride crystal particles.
- the X-ray diffraction peak intensity of (121) of the MgSiN 2 crystal phase is (110), (200), (101), (210) of the ⁇ -type silicon nitride crystal particles. ), (201), (310) (320) and characterized in that it is a 0.0005 to 0.003 times the sum of the X-ray diffraction peak intensity of (002).
- the invention of claim 2 is the silicon nitride sintered body according to claim 1, which has a thermal conductivity of 80 W / m ⁇ K or more.
- the invention of claim 3 is the silicon nitride sintered body according to claim 1 or 2, wherein the magnesium (Mg) contained in the silicon nitride sintered body is converted into magnesium oxide (MgO), and at least contained in the same.
- MgO magnesium oxide
- RE 2 O 3 rare earth element oxide
- the MgO content is 6.7 to 12.8 mol%
- the RE 2 O 3 content is 1.1 to 2.
- 9 mol% the total content of MgO and RE 2 O 3 is 7.9 to 15.1 mol%
- the molar ratio of (RE 2 O 3 ) / (MgO) is 0.09 to 0.3. It is characterized by.
- the invention of the method for producing a silicon nitride sintered body according to claim 4 is directed to at least 6.7 to 12.8 mol% of magnesium oxide (MgO) in a silicon nitride raw material powder having an oxygen content of 2.0 mass% or less.
- MgO magnesium oxide
- a silicon nitride circuit board according to claim 5 is a silicon nitride substrate comprising the silicon nitride sintered body according to any one of claims 1 to 3 and a metal circuit board bonded to one surface of the silicon nitride substrate. And a metal heat radiating plate joined to the other surface of the silicon nitride substrate.
- the invention of a semiconductor module according to claim 6 has the silicon nitride circuit board according to claim 5 and a semiconductor element mounted on the silicon nitride circuit board.
- a silicon nitride substrate having high strength and high thermal conductivity can be realized.
- a method for producing a silicon nitride substrate having high strength and high thermal conductivity can be provided.
- FIG. 2 is a transmission electron microscope (TEM) image of silicon nitride particles and grain boundary phase of the silicon nitride-based sintered body of the present invention. It is a schematic diagram of the TEM image of FIG. The surface analysis result with respect to Si, Mg, Y, O component by TEM-EDX of FIG. 1 is shown.
- 3 is a transmission electron microscope (TEM) image of the silicon nitride sintered body obtained in Example 2.
- FIG. It is a schematic diagram of the TEM image of FIG. The relationship between the MgSiN 2 X-ray ratio and the abundance ratio of the grain boundary crystal phase MgSiN 2 obtained by image analysis of a TEM image is shown.
- One embodiment of the present invention is a silicon nitride substrate as an insulating ceramic substrate used in the above-described power semiconductor module or the like, wherein ⁇ -type silicon nitride crystal particles, at least one rare earth element (RE),
- a silicon nitride substrate comprising a grain boundary phase containing magnesium (Mg) and silicon (Si)
- the grain boundary phase comprises an amorphous phase and a MgSiN 2 crystal phase
- the crystal phase containing the rare earth element (RE) Is substantially not included.
- a silicon nitride sintered body is composed of ⁇ -type silicon nitride crystal grains and a grain boundary phase containing a sintering aid component, and the grain boundary phase is composed of an amorphous phase or a crystal phase.
- the grain boundary phase the diffraction line on the substrate surface is measured by X-ray diffraction method, and the presence of each crystal phase in the grain boundary phase is determined by identifying the detected diffraction line peak other than ⁇ -type Si 3 N 4 did.
- the X-ray peak of the crystal phase containing Mg is not detected, it is determined that Mg exists in the grain boundary phase as an amorphous phase.
- any diffraction line peak intensity of the grain boundary crystal phase is (110), (200), (101), (210), (201), (310), (320) of ⁇ -type Si 3 N 4 . ) And (002) when the sum of the diffraction line peak intensities is less than 0.0005 times, it was determined that the grain boundary phase does not contain a crystal phase.
- X-ray peaks of the case of the MgSiN 2 for the presence of crystalline phase (121), also in the case of Re component Re 2 Si 3 O 3 N 4 , Re 2 SiO 3 N and Re 4 Si 2 O 7 N 3 X-ray peaks of (211), (112) and (-221) are the first peaks, respectively, and these X-ray peaks and (110), (200) of ⁇ -type Si 3 N 4 , (101), (210), (201), (310), (320), and (002) with the sum of the diffraction line peak intensities.
- the presence or absence of crystal phase precipitation in the grain boundary phase was confirmed by observation using a transmission electron microscope (TEM), and in the grain boundary phase (the sum of the amorphous phase and the grain boundary crystal phase).
- TEM transmission electron microscope
- the existence ratio (area ratio) of the crystal phase was calculated by image analysis.
- the silicon nitride substrate is composed of a grain boundary phase mainly composed of silicon nitride particles and components added as a sintering aid.
- the grain boundary phase generated by using the added sintering aid as a main component maintains the bonds between the silicon nitride particles and plays a role of suppressing defects between the particles.
- the bonding force of the grain boundary phase of the silicon nitride substrate is insufficient and there are coarse defects on the surface, when stress is applied to the silicon nitride substrate, the defect becomes the starting point of destruction and easily breaks down.
- the field phase must be uniformly dispersed to bond between the particles and suppress the generation of coarse defects.
- FIG. 1 A transmission electron microscope (TEM) image of the silicon nitride particles and grain boundary phase of the silicon nitride sintered body of the present invention is shown in FIG. 1, and a schematic diagram thereof is shown in FIG. 2 (Example 4 below).
- FIG. 1 A transmission electron microscope (TEM) image of the silicon nitride particles and grain boundary phase of the silicon nitride sintered body of the present invention is shown in FIG. 1, and a schematic diagram thereof is shown in FIG. 2 (Example 4 below).
- FIG. 1 A transmission electron microscope (TEM) image of the silicon nitride particles and grain boundary phase of the silicon nitride sintered body of the present invention is shown in FIG. 1, and a schematic diagram thereof is shown in FIG. 2 (Example 4 below).
- FIG. 1 A transmission electron microscope (TEM) image of the silicon nitride particles and grain boundary phase of the silicon nitride sintered body of the present invention is shown in FIG. 1, and a schematic diagram thereof is shown in FIG.
- the grain boundary phase is an amorphous phase.
- the crystal phase 13 having different contrasts in the grain boundary phase between which the silicon nitride particles 11 are sandwiched in FIG. 1 has a low detected concentration of Y and O, and is mainly composed of Mg and Si. .
- the grain boundary crystal phase 13 is MgSiN 2 .
- the grain boundary phase portion 12 other than the crystal phase 13 has a low Si component concentration and is composed of Mg, Y and O components. Further, no diffraction peaks other than MgSiN 2 were detected from the X-ray diffraction. Therefore, it is an amorphous phase mainly composed of Y, Mg and O.
- the grain boundary phase composed of the amorphous phase 12 and the grain boundary crystal phase 13 bonds the silicon nitride particles 11, and the ratio of both influences the mechanical strength and thermal conductivity of the silicon nitride sintered body. .
- the abundance ratio (area ratio) of the grain boundary crystal phase 13 (MgSiN 2 ) in the grain boundary phase in the silicon nitride-based sintered body is preferably in the range of 0.05% or more and less than 20%.
- the abundance ratio of the grain boundary crystal phase MgSiN 2 phase relative to the grain boundary phase is 0.05% or more.
- the abundance ratio of the grain boundary crystal phase which has a lower bonding strength with the silicon nitride particles than the amorphous phase, increases. There arises a problem that it decreases and the variation becomes large. Therefore, the ratio of the MgSiN 2 phase to the grain boundary phase is preferably less than 20%.
- the grain boundary phase containing Mg is also contained as an amorphous phase to maintain the bond between the silicon nitride particles.
- the MgSiN 2 crystal phase generated when the grain boundary phase containing Mg is crystallized has a higher thermal conductivity than the amorphous phase, and the thermal conductivity of the silicon nitride substrate can be improved.
- the (121) X-ray diffraction peak intensity of the MgSiN 2 crystal phase is (110) of ⁇ -type Si 3 N 4. , (200), (101), (210), (201), (310), (320) and (002) is 0.0005 to 0.003 times the sum of the X-ray diffraction peak intensities.
- the silicon nitride substrate according to the present embodiment is characterized in that the grain boundary phase is composed of an amorphous phase and a MgSiN 2 crystal phase, and does not substantially include a crystal phase containing RE. .
- “Substantially free” means that the X-ray diffraction line peak intensity of any crystal plane of the crystal phase containing the rare earth element (RE) is ⁇ -type Si 3 N 4 (110), (200), It means that it is less than 0.0005 times the sum of diffraction line peak intensities of (101), (210), (201), (310), (320) and (002). Thereby, the bending strength of the silicon nitride substrate can be maintained at a high level, and the thermal conductivity can be improved. The method for adjusting the grain boundary phase will be described later.
- the X-ray diffraction peak intensity of (121) of the MgSiN 2 crystal phase is (110), (200), (101), (210) of ⁇ -type Si 3 N 4.
- (201), (310), (320), and (002) contain the MgSiN 2 crystal phase so as to be 0.0005 to 0.003 times the sum of the X-ray diffraction peak intensities. Effect of increasing the MgSiN 2 crystal phase is less and the thermal conductivity of silicon nitride substrate decreases.
- the amount of the MgSiN 2 crystal phase is in the above range.
- Mg is contained so as to be 6.7 to 12.8 mol% in terms of MgO and RE is 1.1 to 2.9 mol% in terms of RE 2 O 3. Yes. Further, Mg is contained in a range of 7.9 to 15.1 mol% in terms of MgO and RE in terms of RE 2 O 3 . Further, Mg and RE are contained in a range where the molar ratio of (RE 2 O 3 ) / (MgO) is 0.09 to 0.3 in terms of oxide. Mg and RE function as sintering aids in the production of a silicon nitride substrate, and are present mainly as grain boundary phases in the produced silicon nitride substrate.
- MgO, RE 2 O 3 , the total content thereof, and the molar ratio of (RE 2 O 3 ) / (MgO) are preferably in the above ranges.
- the silicon nitride-based sintered body of the present invention has high bending strength and thermal conductivity, and the thermal conductivity is 80 W / m ⁇ K or more, preferably 85 W / m ⁇ K or more, more desirably. , 90 W / m ⁇ K or more.
- the bending strength is 820 MPa or more.
- the coefficient of thermal expansion from room temperature to 600 ° C. is in the range of 2.3 to 4.5 ppm / ° C., and the relative density is 98% or more, desirably more than 99%. If the coefficient of thermal expansion is less than 2.3 ppm / ° C, the difference in thermal expansion from the metal circuit board becomes large.
- the silicon nitride substrate produced from the silicon nitride-based sintered body of the present invention is a high-frequency transistor, various substrates such as a power semiconductor module circuit substrate or a multichip module substrate, a Peltier element heat transfer plate, or various heat generation. It can be used for a member for electronic parts such as an element heat sink.
- the silicon nitride substrate according to the present embodiment is used as, for example, a substrate for mounting a semiconductor element
- the silicon nitride substrate is bonded to the metal circuit board and the metal heat sink, the power semiconductor module is manufactured, or the power semiconductor module is operated. It is possible to suppress the occurrence of cracks when subjected to repeated heat cycles, and to easily transfer heat generated from the semiconductor element to the heat radiating member, and to improve the thermal shock resistance, heat cycle resistance and heat dissipation. Can be realized.
- a metal circuit board and a metal heat sink Cu (copper) circuit board or Al (aluminum) circuit board are attached to one or both sides of the silicon nitride substrate according to the present embodiment by the DBC method (Direct Bonding Cupper copper direct bonding method).
- the silicon nitride circuit board is manufactured by bonding using the active metal brazing material method or the like.
- the DBC method is a method in which a silicon nitride substrate and a Cu circuit board or Al circuit board are heated to a temperature equal to or higher than the eutectic temperature in an inert gas or nitrogen atmosphere, and the resulting Cu—O and Al—O eutectic crystals are produced.
- the circuit board is directly bonded to one or both surfaces of the silicon nitride substrate via a eutectic compound layer using a compound liquid phase as a bonding agent.
- the active metal brazing method is a mixture or alloy of an active metal such as titanium (Ti), zirconium (Zr) or hafnium (Hf) and a metal such as silver (Ag) or copper (Cu) which forms a low melting point alloy.
- a Cu circuit board or an Al circuit board is bonded to one surface or both surfaces of a silicon nitride substrate by hot-press bonding in an inert gas or vacuum atmosphere through a brazing material layer.
- the Cu circuit board or Al circuit board on the silicon nitride substrate is etched to form a circuit pattern, and the Cu circuit board or Al circuit board after the circuit pattern is formed is subjected to Ni-P plating. A silicon nitride circuit board is produced.
- a desired semiconductor module can be manufactured by mounting an appropriate semiconductor element on the silicon nitride circuit board.
- the silicon nitride powder has an average particle size of 1.0 ⁇ m or less and a specific surface area of 15 m 2 / g or less.
- the oxygen content is 1.5 wt% or less, particularly the Fe component and Al component are each 1000 ppm or less.
- the MgO powder and Y 2 O 3 powder added as sintering aids each have an average particle diameter of 1.0 ⁇ m or less and a specific surface area of 30 m 2 / g or less.
- the amount of impurities is set to 1000 ppm or less for each of the Fe component and the Al component as in the case of the silicon nitride powder.
- magnesium oxide MgO
- SiO silicon nitride raw material powder having an oxygen content of 2% by mass or less
- at least one rare earth element oxide (RE 2 O 3 ) Is 1.1 to 2.9 mol% in total, and is mixed so that the total ratio of 7.9 to 15.1 mol% and (RE 2 O 3 ) / (MgO) is 0.09 to 0.3
- MgO, RE 2 O 3 and the total amount and the added amount of (RE 2 O 3 ) / (MgO) are outside the above range, the MgO, RE 2 O 3 and the total content and (RE 2
- the molar ratio of the content of O 3 ) / (MgO) is also outside the above range, and as described above, one or both of the bending strength and the thermal conductivity is lowered. Accordingly, MgO, RE 2 O 3 , the total amount added, and the molar ratio of (RE 2 O 3 ) / (MgO) are preferably in the above ranges.
- the mixed raw material slurry is defoamed and thickened, and then formed into a sheet having a predetermined thickness by a known doctor blade method or the like.
- the plate thickness of the sheet molded body at this time can be appropriately determined according to the application, but can be, for example, about 0.2 to 1.0 mm.
- the size of the sheet compact is appropriately selected in consideration of the amount of shrinkage and the dimensions and capacity of the BN setter and firing container on which the sheet compact is placed. In the present invention, the size of the sheet compact is 170 mm ⁇ 140 mm.
- a sintering step one sheet molded body or a plurality of sheet compacts are stacked via a release agent such as BN, and the inside of the sintering furnace is set to a nitrogen pressure atmosphere of 0.5 to 1.0 MPa from 1600 ° C.
- the temperature is increased at a rate of 300 ° C./h or less, held at a temperature of 1800 to 2000 ° C. for 2 to 10 hours, and then cooled by cooling to 1500 ° C. at a rate of 100 ° C./h or more.
- the sintered silicon nitride substrate may be used as it is, but may be subjected to a heat treatment at a temperature lower than the sintering temperature, a surface treatment such as blasting.
- the sintering temperature is less than 1800 ° C., the sintering is insufficient and the strength and thermal conductivity are reduced. On the other hand, if the sintering temperature is higher than 2000 ° C., abnormal grain growth occurs and the strength is reduced. Therefore, the above range is suitable for the sintering temperature. Furthermore, when the atmosphere in the sintering furnace is less than 0.5 MPa, silicon nitride is easily decomposed during sintering, and strength and thermal conductivity are reduced. In addition, an expensive sintering furnace is required to make the pressure higher than 1.0 MPa, and the cost is increased. Therefore, the above range is preferable for the atmosphere in the sintering furnace. Furthermore, when the rate of temperature increase from 1600 ° C.
- the temperature rise rate is preferably in the above range. Further, when the cooling rate to 1500 ° C. is less than 100 ° C./h, the crystallization of the grain boundary phase is promoted, the crystal phase containing RE is precipitated at the grain boundary, and the bond between the silicon nitride particles is weakened and bent. Strength decreases. Therefore, the above range is preferable for the cooling rate.
- the total thickness of the substrate during sintering is greater than 40 mm, the apparent volume of the sample increases, resulting in Since the cooling rate inside the sample is less than 100 ° C./h, the total thickness of the substrate during sintering is preferably 40 mm or less, and more preferably 30 mm or less. Furthermore, when the sintering time is shorter than 2 hours, the formation of the MgSiN 2 crystal phase is suppressed, the thermal conductivity is lowered, the sintering is insufficient, and the bending strength is also lowered.
- the above range is suitable for the sintering time.
- the grain boundary phase containing Mg component has a high vapor pressure, volatilization and segregation are likely to occur during sintering at high temperature, and density reduction due to pore formation and local color unevenness occur in the sintered body surface layer.
- a closed ceramic firing container preferably a BN firing container, is used, and the gas concentration of the Mg component inside thereof is kept constant.
- the grain boundary phase containing RE has a low vapor pressure and is more likely to exist uniformly and stably between the silicon nitride particles than the grain boundary phase containing Mg. It plays a crucial role in maintaining a strong bond between the particles. Therefore, when a part of the grain boundary phase containing RE is crystallized, the bonding between the silicon nitride particles becomes insufficient, and coarse defects are likely to occur in the grain boundary phase. As a result, the mechanical strength of the silicon nitride substrate is reduced, and nitriding is performed by a bonding process between the silicon nitride substrate and the metal circuit board and the metal heat sink, a power semiconductor module manufacturing process, or a thermal cycle accompanying the operation of the power semiconductor module.
- the thermal conductivity of the grain boundary phase containing RE is slightly improved by crystallization, but is significantly lower than that of silicon nitride particles. Does not contribute. Therefore, it is preferable that the grain boundary phase containing RE exists as an amorphous phase in order to maintain a strong bond between the silicon nitride particles.
- RE oxides of Y, Yb, Er, Dy, Gd, Sm, Nd, and Lu can be selected. However, since the bonding strength between the silicon nitride particles and the grain boundary phase is excellent, the selection of Y oxide is desirable.
- a silicon nitride substrate was manufactured based on the manufacturing method, and its physical properties were measured.
- magnesium oxide (MgO) addition amount rare earth element oxide (RE 2 O 3 ) addition amount, total addition amount of MgO and RE 2 O 3 , (RE 2 O 3 ) / (MgO) molar ratio
- the items shown in Tables 1 and 2 as the manufacturing conditions were adopted for the items of RE type, sintering temperature in the sintering process, heating rate, cooling time, sintering time, and total thickness of the substrate (Examples). 1-16).
- As (RE 2 O 3 ) in Examples 10 to 16, an oxide of Yb, Er, Dy, Gd, Sm, Nd, or Lu was used as RE instead of Y. Sintering was performed in a closed BN-made firing container.
- the measured physical properties include the presence / absence of a crystal phase other than ⁇ -type silicon nitride of the silicon nitride substrate and the amount of MgSiN 2 crystal phase, as well as magnesium oxide (MgO) content, rare earth oxide (RE 2 O 3 ) content, There are (RE 2 O 3 ) / (MgO) molar ratio, total content of MgO and RE 2 O 3 , bending strength, bending strength Weibull coefficient, thermal conductivity and thermal shock test results.
- MgO magnesium oxide
- RE 2 O 3 rare earth oxide
- the bending strength, the Weibull coefficient of bending strength, and the thermal conductivity are within the preset ranges (bending strength: 820 MPa or more, Weibull coefficient: 15 or more, thermal conductivity: 80 W / m ⁇ K or more). It was determined whether or not.
- the amount of presence and MgSiN 2 crystal phase of the crystalline phases other than ⁇ -type silicon nitride by X-ray diffraction line measurement of the substrate surface was determined in the manner described above.
- RINT2500 made by Rigaku Corporation was used for the X-ray diffraction evaluation, and the evaluation conditions were tube: copper, tube voltage: 50 kV, tube current: 200 mA, sampling width: 0.020 °, scanning speed: 2 ° / min, scanning angle 2 ⁇ : performed in the range of 20 ° to 120 °.
- Magnesium oxide (MgO) content and rare earth element oxide (RE 2 O 3 ) content are obtained by making the silicon nitride substrate into a solution by microwave decomposition treatment and acid dissolution treatment, and then determining the Mg amount and RE amount by ICP emission analysis. It was determined by measuring and converting to magnesium oxide (MgO) and rare earth element oxide (RE 2 O 3 ). In addition, the molar ratio of (RE 2 O 3 ) / (MgO) content and the total content of MgO and RE 2 O 3 were the obtained magnesium oxide (MgO) content and rare earth element oxide (RE 2 O 3 ). Calculated from the content. In all the samples of Examples and Comparative Examples, the contents of MgO and RE 2 O 3 were almost equal to the addition amounts.
- the bending strength was measured by a three-point bending test according to JIS-R1601.
- a silicon nitride substrate is processed into a test piece with a width of 4 mm, set on a three-point bending jig with a distance between support rolls of 7 mm, and a load is applied at a crosshead speed of 0.5 mm / min. Calculated from
- Weibull coefficient from the test results of the bending strength, create a Weibull plot for plotting lnln (1-F) -1 against ln ⁇ in conformity with JIS-R1625, it was determined Weibull coefficient of the slope.
- ⁇ is the bending strength
- F is the cumulative failure probability.
- Fracture toughness was measured by an IF (Indentation Fracture) method in which a Vickers indenter was pushed into a side surface of a silicon nitride substrate with a predetermined load (2 kgf (19.6 N) in this example) in accordance with JIS-R1607. At this time, the Vickers indenter was pushed so that one diagonal line of the Vickers indentation was perpendicular to the thickness direction of the silicon nitride substrate.
- IF Index Fracture
- the thermal conductivity was measured by a laser flash method in accordance with JIS-R1611 by cutting a 5 mm square measurement sample from a silicon nitride substrate.
- a silicon nitride circuit board having a Cu circuit board and a Cu heat sink formed on both sides of the silicon nitride board was held at 350 ° C. for 10 minutes, and then rapidly cooled to room temperature, and the occurrence of cracks in the silicon nitride board was examined. This operation was repeated 10 times to determine whether or not a crack occurred.
- the thermal conductivity is less than 80 W / m ⁇ K, it is not suitable for a silicon nitride circuit board, and thus the thermal shock test was not performed.
- thermal expansion coefficient a measurement sample was cut out to 5 mm ⁇ 20 mmL of a silicon nitride substrate, and the linear expansion coefficient in the longitudinal direction from room temperature to 600 ° C. was evaluated according to JIS-R1618.
- the relative density is determined by measuring the density of the silicon nitride substrate by the Archimedes method, and dividing this by dividing the theoretical density calculated from the blending ratio of the Si 3 N 4 powder, MgO powder and RE 2 O 3 powder and the individual densities. It is the multiplied value.
- the MgO addition amount 6.7 ⁇ 12.8 mol%, the RE 2 O 3 added amount 1.1 ⁇ 2.9 mol%, the total amount of MgO and RE 2 O 3 7 .9 to 15.1 mol%, (RE 2 O 3 ) / (MgO) addition molar ratio is 0.09 to 0.3
- the sintering temperature in the sintering process is 1800 to 2000 ° C.
- the heating rate is In a silicon nitride substrate manufactured under conditions of 300 ° C./h or less, a cooling rate of 100 ° C./h or more, and a sintering time of 2 to 10 h, only the MgSiN 2 crystal phase is detected as the crystal phase of the grain boundary, and ⁇ -type Si 3 MgSiN 2 crystal phase content (setting range 0.0005 to 0.003), MgO content (setting range 6.7 to 12.8 mol%), RE 2 O 3 content (setting range 1.1 to 2) with respect to N 4 .9mol%),
- the Weibull coefficient also satisfies the setting range of 15 or more, and it can be seen that the variation in bending strength is small.
- the relative density of the silicon nitride substrate is over 98%, and the thermal expansion coefficient is in the range of 2.3 to 4.5 ppm / ° C. As a result, even in the thermal shock test, the silicon nitride substrate was not broken, and all were judged to be acceptable.
- FIG. 4 is a transmission electron microscope (TEM) image of the silicon nitride sintered body obtained in Example 4, and FIG. 5 is a schematic diagram thereof.
- a focused ion beam (Focused) is used for TEM observation.
- Ion Beam: FIB, FB-2100 manufactured by Hitachi, Ltd.) was used to prepare a thinned sample, and subsequently, a transmission electron microscope (TEM, HF2000 manufactured by Hitachi, Ltd.) was used.
- the TEM observation conditions are an acceleration voltage of 200 kV and a direct observation magnification of 20 k times.
- the abundance ratio of the grain boundary crystal phase is a value obtained by dividing the area of the grain boundary crystal phase by the area of the grain boundary phase (the sum of the grain boundary crystal phase and the amorphous phase) and multiplying by 100.
- Comparative Examples 1 and 2 in which a diffraction peak of a grain boundary crystal phase was detected by X-ray diffraction The same evaluation was carried out for 7, 8, 10, 11 and 14, and in each case, the abundance ratio of the grain boundary crystal phase was determined.
- Example 1 there is a correlation between the abundance ratio of MgSiN 2 in the X-ray ratio and the grain boundary phase of the MgSiN 2 from FIG. 6, 0.05% 0.0005 Example 1, 0 of Example 4. 0017 was 7.62%, 0.003 of Example 6 was 18.54%, and Comparative Example 0.0045 was 32.12%.
- the MgO addition amount was 6.7 mol%
- the Y 2 O 3 addition amount was 1.2 mol%
- the sintering temperature in the sintering process was increased to 1850 ° C.
- the amount of MgSiN 2 crystal phase is ⁇ -type Si 3 N 4 Further, it contains a crystal phase of Y 2 Si 3 O 3 N 4 containing Y, has a bending strength as low as 798 MPa, and a Weibull coefficient as low as 14. This is because the cooling rate in the sintering process is relatively slow, crystallization of the grain boundary is promoted, the bonding of silicon nitride particles by the grain boundary phase is weakened, and the bending strength is lowered.
- Comparative Example 2 in which the amount of Y 2 O 3 added was 1.8 mol%, the sintering temperature was 1900 ° C., the cooling rate was 50 ° C./h, and the sintering time was 4 h is also used. Because the cooling rate is slow, the amount of MgSiN 2 crystal phase is as large as 0.0030 times that of ⁇ -type Si 3 N 4 , and also contains the crystal phase of Y 2 Si 3 O 3 N 4 containing Y The bending strength is as low as 802 MPa, and the Weibull coefficient is also as low as 13. As a result, cracks occurred in the silicon nitride substrate in the thermal shock test.
- the MgO addition amount was 9.8 mol%
- the Y 2 O 3 addition amount was 1.8 mol%
- the sintering temperature in the sintering step was 1900 ° C.
- the temperature increase rate was 150 ° C./h
- cooling In the silicon nitride substrate manufactured under the conditions where the speed is 600 ° C./h, the sintering time is 20 h, and the total thickness of the substrate is 4 mm
- the amount of MgSiN 2 crystal phase is 0.0032 times that of ⁇ -type Si 3 N 4
- it contains a crystal phase of Y 2 Si 3 O 3 N 4 containing Y
- its bending strength is as low as 766 MPa
- its Weibull coefficient is as low as 13.
- the MgO addition amount was 9.8 mol%
- the Y 2 O 3 addition amount was 1.2 mol%
- the sintering temperature in the sintering step was 1850 ° C.
- the temperature increase rate was 300 ° C./h
- the amount of MgSiN 2 crystal phase is 0.0035 times that of ⁇ -type Si 3 N 4
- it contains a crystal phase of Y 2 Si 3 O 3 N 4 containing Y
- its bending strength is as low as 810 MPa
- its Weibull coefficient is as low as 13.
- the total thickness of the substrate set in the sintering process is as thick as 51 mm.
- the cooling rate inside the sample is less than 100 ° C./hr, and the cooling rate is slow, which promotes the crystallization of the grain boundaries.
- the bond of silicon nitride particles by the phase is weakened and the bending strength is reduced. As a result, cracks occurred in the silicon nitride substrate in the thermal shock test.
- the MgO addition amount was 6.7 mol%
- the Y 2 O 3 addition amount was 0.6 mol%
- the sintering temperature in the sintering step was 1900 ° C.
- the heating rate was 150 ° C./h
- sintering time 4h not detected MgSiN 2 crystal phase and total thickness of the substrate in the silicon nitride substrate prepared under the conditions as 4 mm
- the thermal conductivity is lowered and 77W / m ⁇ K
- the bending strength was as low as 766 MPa.
- the MgO addition amount was 6.7 mol%
- the Y 2 O 3 addition amount was 2.4 mol%
- the sintering temperature in the sintering step was 1850 ° C.
- the temperature increase rate was 150 ° C./h
- cooling A silicon nitride substrate manufactured under conditions of a speed of 600 ° C./h, a sintering time of 5 h, and a total thickness of the substrate of 8 mm also contains a Y 2 Si 3 O 3 N 4 crystal phase containing Y, and has bending strength.
- the Weibull coefficient was as low as 14.
- the MgO addition amount was 9.8 mol%
- the Y 2 O 3 addition amount was 0.6 mol%
- the sintering temperature in the sintering step was 1900 ° C.
- the temperature increase rate was 200 ° C./h
- the MgSiN 2 crystal phase is not detected
- the thermal conductivity is as low as 78 W / m ⁇ K. It was.
- Comparative Example 13 produced under the conditions of a heating rate of 150 ° C./h and a cooling rate of 300 ° C./h also has a small amount of Y 2 O 3 added, and a molar ratio of (Y 2 O 3 ) / (MgO) Is as low as 0.04, the generation of MgSiN 2 crystal phase was suppressed, and the thermal conductivity of the silicon nitride substrate was lowered to 78 W / m ⁇ K.
- the MgO addition amount was 15.6 mol%
- the Y 2 O 3 addition amount was 1.7 mol%
- the sintering temperature in the sintering step was 1850 ° C.
- the temperature increase rate was 150 ° C./h
- the amount of MgSiN 2 crystal phase is 0.0045 times that of ⁇ -type Si 3 N 4
- the bending strength was as low as 731 MPa
- the Weibull coefficient was also as low as 12.
- the MgO addition amount was 6.8 mol%
- the Y 2 O 3 addition amount was 3.0 mol%
- the sintering temperature in the sintering step was 1900 ° C.
- the temperature increase rate was 300 ° C./h
- the MgSiN 2 crystal phase is not detected
- the crystal phase was low
- the thermal conductivity was as low as 76 W / m ⁇ K
- the bending strength was as low as 769 MPa
- the Weibull coefficient was as low as 12.
- the MgO addition amount was 6.7 mol%
- the Y 2 O 3 addition amount was 1.2 mol%
- the sintering temperature in the sintering step was 1775 ° C.
- the heating rate was 150 ° C./h
- cooling A silicon nitride substrate manufactured under conditions of a speed of 600 ° C./h, a sintering time of 5 h, and a total substrate thickness of 0.4 mm has a low relative density of 97.1% and a thermal conductivity of 79 W / m ⁇ K.
- the bending strength was as low as 792 MPa and the Weibull coefficient was as low as 13. As a result, the thermal shock test was rejected.
- the grain boundary crystal phase MgSiN 2 is difficult to precipitate because the amount of liquid phase necessary for crystallization cannot be obtained due to the reduction of the sintering temperature, and the ⁇ -type Si having the (121) X-ray diffraction peak intensity of the MgSiN 2 crystal phase. 3 N 4 X-ray diffraction peak intensities of (110), (200), (101), (210), (201), (310), (320) and (002) of the ⁇ -type silicon nitride crystal particles The ratio to the sum remained at 0.0003. This reduced the thermal conductivity of the silicon nitride substrate.
- the MgO addition amount was 4.1 mol%
- the Y 2 O 3 addition amount was 0.5 mol%
- the sintering temperature in the sintering step was 1875 ° C.
- the temperature increase rate was 150 ° C./h
- cooling was performed.
- a silicon nitride substrate manufactured under conditions of a speed of 600 ° C./h, a sintering time of 5 h, and a total substrate thickness of 0.4 mm has a low coefficient of thermal expansion of 2.26 ppm / ° C. The difference in expansion coefficient increases. As a result, the difference in thermal expansion coefficient from the Cu circuit board was increased, and although the bending strength was excellent, the thermal shock test failed.
- the grain boundary crystal phase MgSiN 2 is difficult to precipitate because both MgO and Y 2 O 3 are reduced in the amount of addition, and therefore ⁇ -type Si 3 N 4 having an X-ray diffraction peak intensity of (121) of the MgSiN 2 crystal phase.
- the MgO addition amount was 37.2 mol%
- the Y 2 O 3 addition amount was 4.7 mol%
- the sintering temperature in the sintering step was 1875 ° C.
- the temperature increase rate was 150 ° C./h
- cooling A silicon nitride substrate manufactured under conditions of a speed of 600 ° C./h, a sintering time of 5 h, and a total substrate thickness of 0.4 mm has a high coefficient of thermal expansion of 4.52 ppm / ° C. Although the coefficient difference is reduced, the thermal contraction of the substrate itself is increased. Moreover, since the abundance ratio of the grain boundary phase is increased, the thermal conductivity is 65 W / m. Dropped to K.
- MgO and Y 2 O 3 together amount excess MgSiN 2 crystal phase in the grain boundary phase by the increase tends to precipitate, MgSiN 2 beta type Si 3 N 4 wherein the X-ray diffraction peak intensity of the crystalline phase (121)
- the ratio of ⁇ -type silicon nitride crystal particles to the sum of X-ray diffraction peak intensities of (110), (200), (101), (210), (201), (310), (320), and (002) is The bending strength of the silicon nitride substrate was lowered because the ratio of the grain boundary crystal phase having a low bond strength with ⁇ Si 3 N 4 particles was increased.
- the silicon nitride substrate manufactured in the setting range of the manufacturing conditions shown in Table 1 has a grain boundary phase composed of an amorphous phase and an MgSiN 2 crystal phase, and a crystal phase containing a rare earth element (RE).
- the amount of MgSiN 2 phase and other characteristics are within the set range shown in Table 1 and the silicon nitride substrate does not crack and break down, but any manufacturing conditions are within the above set range. It can be seen that the thermal conductivity of the silicon nitride substrate is lowered or the silicon nitride substrate is destroyed.
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Abstract
Description
また、透過型電子顕微鏡(Transmission Electron Microscope:TEM)を用いた観察により粒界相中における結晶相の析出有無を確認し、粒界相(非晶質相と粒界結晶相の和)中における結晶相の存在比率(面積率)について画像解析により算出した。
また、焼結助剤として添加するMgO粉末およびY2O3粉末は、それぞれ、平均粒子径を1.0μm以下、比表面積を30m2/g以下の範囲とする。また、不純物量は窒化珪素粉末と同様にFe成分およびAl成分は、それぞれ1000ppm以下とする。
まず、原料調整・混合工程として、含有酸素量2質量%以下の窒化珪素原料粉に酸化マグネシウム(MgO)が6.7~12.8mol%、少なくとも1種の希土類元素酸化物(RE2O3)が1.1~2.9mol%を合計7.9~15.1mol%、かつ(RE2O3)/(MgO)のモル比が0.09~0.3となるように混合し、溶剤、有機バインダー、可塑剤等とともにボールミル等で混合する。MgO、RE2O3及び合計の添加量と(RE2O3)/(MgO)の添加量のモル比が上記範囲以外の場合、MgO、RE2O3及び合計の含有量と(RE2O3)/(MgO)の含有量のモル比も上記範囲外となり、上述したように曲げ強度と熱伝導率の一方もしくは両方が低下する。従って、MgO、RE2O3、その合計の添加量及び(RE2O3)/(MgO)のモル比は上記範囲が好適である。
Ion Beam:FIB、日立製作所製 FB-2100)を用いて薄片化試料を作製し、続いて、透過型電子顕微鏡(TEM、日立製作所製 HF2000)を用いて行った。TEM観察条件は加速電圧200kV、直接観察倍率20k倍である。図2のTEM像を画像解析装置(ニレコ社製 ルーゼックスAP)を用いて粒界結晶相の存在比率(面積率)を算定したところ、その値は9.33%であった。粒界結晶相の存在比率は粒界結晶相の面積を粒界相(粒界結晶相と非晶質相の和)の面積で除して100を乗じて得られる値である。これと同様に実施例1~3および実施例5~9さらに表2-1および表2-2のおいて、X線回折により粒界結晶相の回折ピークが検出できた比較例1、2、7、8、10、11および14について同様の評価を行い、いずれの場合も粒界結晶相の存在比率を求めた。なお、比較例1,2,7,8,10および11の試料については、X線回折によりMgSiN2相に加えてY2Si3O3N4の回折ピークが検出されたが、TEM観察とTEM-EDX分析の結果からもMgが主成分である粒界結晶相とYが主成分のものの析出が確認できた。比較例1、2、7、8、10および11についてのMgSiN2相の存在比率は、MgSiN2相の面積を粒界相(これらの場合は、MgSiN2とY2Si3O3N4と非晶質相の和)で除して100を乗じて算出した。表5および図6に、MgSiN2結晶相の(121)のX線回折ピーク強度のβ型Si3N4前記β型窒化珪素の結晶粒子の(110)、(200)、(101)、(210)、(201)、(310)、(320)及び(002)のX線回折ピーク強度の和に対する比率(表3中では、単にMgSiN2X線比率と表記)とTEM像の画像解析により求めた粒界結晶相MgSiN2の存在比率の関係を示す。これらの図表から、実施例1~9の場合、MgSiN2のX線比率は、0.0005~0.003の範囲にあり、粒界相におけるMgSiN2の存在比率は、0.05%以上、20%未満の範囲にあった。また、図6よりMgSiN2のX線比率と粒界相におけるMgSiN2の存在比率との間には相関性があり、実施例1の0.0005で0.05%、実施例4の0.0017で7.62%、実施例6の0.003で18.54%および比較例0.0045で32.12%となった。
MgOおよびY2O3ともに添加量増大により粒界相中に過剰のMgSiN2結晶相が析出しやすくなり、MgSiN2結晶相の(121)のX線回折ピーク強度のβ型Si3N4前記β型窒化珪素の結晶粒子の(110)、(200)、(101)、(210)、(201)、(310)、(320)及び(002)のX線回折ピーク強度の和に対する比率は0.0035と増大し、βSi3N4粒子との結合強度の小さい粒界結晶相の存在比率が増加したため窒化珪素基板の曲げ強度は低下した。
11 窒化珪素粒子
12 非晶質の粒界相
13 結晶質の粒界相
Claims (6)
- β型窒化珪素の結晶粒子と、少なくとも1種類の希土類元素(RE)、マグネシウム(Mg)及び珪素(Si)を含有する粒界相からなる窒化珪素基板において、前記粒界相は非晶質相とMgSiN2結晶相からなり、前記希土類元素(RE)を含んだ結晶相のいずれの結晶面のX線回折線ピーク強度も前記β型窒化珪素の結晶粒子の(110)、(200)、(101)、(210)、(201)、(310)、(320)及び(002)の回折線ピーク強度の和の0.0005倍未満であり、前記MgSiN2結晶相の(121)のX線回折ピーク強度が前記β型窒化珪素の結晶粒子の(110)、(200)、(101)、(210)、(201)、(310)、(320)及び(002)のX線回折ピーク強度の和の0.0005~0.003倍であることを特徴とする窒化珪素質焼結体。
- 熱伝導率が80W/m・K以上である請求項1記載の窒化珪素質焼結体。
- 前記窒化珪素基板が含有するマグネシウム(Mg)を酸化マグネシウム(MgO)に換算し、同じく含有する少なくとも1種類の希土類元素(RE)を希土類元素酸化物(RE2O3)に換算したとき、MgO含有量が6.7~12.8mol%、RE2O3含有量が1.1~2.9mol%、MgOとRE2O3の含有量の合計が7.9~15.1mol%で、かつ(RE2O3)/(MgO)のモル比が0.09~0.3であることを特徴とする請求項1または2に記載の窒化珪素質焼結体。
- 含有酸素量2.0質量%以下の窒化珪素原料粉に、酸化マグネシウム(MgO)を6.7~12.8mol%と少なくとも1種類の希土類元素酸化物(RE2O3)を1.1~2.9mol%とを合計7.9~15.1mol%、かつ(RE2O3)/(MgO)のモル比が0.09~0.3になるように配合して総厚み40mm以下のシート成形体とし、前記シート成形体を1600℃から300℃/h以下の速度で1800~2000℃の温度に昇温し、2~10時間保持した後、100℃/h以上の速度で1500℃まで冷却することで焼結することを特徴とする窒化珪素質焼結体の製造方法。
- 請求項1乃至3の何れかに記載の窒化珪素質焼結体からなる窒化珪素基板と、前記窒化珪素基板の一面に接合された金属回路板と、前記窒化珪素基板の他の面に接合された金属放熱板とからなることを特徴とする窒化珪素回路基板。
- 請求項5に記載の窒化珪素回路基板と、該窒化珪素回路基板上に搭載された半導体素子を有することを特徴とする半導体モジュール。
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US8586493B2 (en) | 2013-11-19 |
JP2014058445A (ja) | 2014-04-03 |
KR20110028375A (ko) | 2011-03-17 |
JP5850031B2 (ja) | 2016-02-03 |
JP5477289B2 (ja) | 2014-04-23 |
EP2301906A4 (en) | 2012-06-27 |
CN102105418A (zh) | 2011-06-22 |
US20110176277A1 (en) | 2011-07-21 |
KR101582704B1 (ko) | 2016-01-05 |
EP2301906B1 (en) | 2019-10-23 |
EP2301906A1 (en) | 2011-03-30 |
JPWO2010002001A1 (ja) | 2011-12-22 |
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