WO2013146789A1

WO2013146789A1 - Sintered silicon nitride substrate and process for producing same

Info

Publication number: WO2013146789A1
Application number: PCT/JP2013/058813
Authority: WO
Inventors: 徳善李; 加賀　洋一郎; 渡辺　純一
Original assignee: 日立金属株式会社
Priority date: 2012-03-26
Filing date: 2013-03-26
Publication date: 2013-10-03
Also published as: JPWO2013146789A1; JP5729519B2

Abstract

A process for producing a sintered silicon nitride substrate which comprises 80-98.3 mass% Si₃N₄, 0.7-10 mass% (in terms of oxide amount) Mg, and 1-10 mass% (in terms of oxide amount) at least one rare-earth element and which has length and width dimensions of 100 mm or larger each and a thickness of 0.7 mm or less, characterized by comprising a step in which a silicon nitride powder is mixed with a sintering aid powder comprising both Mg and at least one rare-earth element, a step in which the obtained mixed powder is molded, and a step in which the obtained green sheet is fired in a nitrogen atmosphere, the firing step being conducted while a weight plate is kept being placed on the green sheet so that a load of 10-600 Pa is imposed on the green sheet.

Description

Sintered silicon nitride substrate and manufacturing method thereof

The present invention relates to a silicon nitride sintered body substrate having high thermal conductivity and less warpage and undulation, and an efficient manufacturing method thereof.

Circuit boards used for power semiconductor modules, etc. are made of metal bonded to a silicon nitride sintered body substrate with high insulation, mechanical strength, thermal conductivity, etc. by brazing or direct bonding (DBC). Circuit board or heat sink. In the case of a semiconductor module, a semiconductor chip is bonded to a circuit board. In order to efficiently dissipate heat from the operating semiconductor chip, the silicon nitride sintered substrate is required to have high thermal conductivity. Of course, the silicon nitride sintered body substrate is also required to have high insulation (electrical resistivity).

In general, a silicon nitride sintered substrate is formed by mixing a silicon nitride powder with a sintering aid such as MgO, a binder, a plasticizer, etc. to form a slurry, and molding and drying the slurry to form a green sheet. It is formed through a process of degreasing and baking the sheet. Since the thermal conductivity of the silicon nitride sintered substrate is greatly influenced by the porosity and the state of the grain boundary phase, various manufacturing methods for improving these have been proposed.

For example, in Japanese Patent Laid-Open No. 2003-313079, fine particles having a particle size of 100 nm or less containing at least one element selected from the group consisting of Mg or Y and rare earth elements and O are present in silicon nitride particles. As a method for producing a silicon nitride sintered body with high thermal conductivity, at least one step of holding at a temperature of 1400 to 1600 ° C. for 1 to 10 hours is performed at the time of raising the temperature of the sintering step, and the sintering temperature is determined from this holding temperature. We have proposed a method to keep the temperature rise rate up to 5.0 ℃ / min. In this method, MgO and rare earth oxide are used as sintering aids in order to obtain a silicon nitride sintered body substrate having high thermal conductivity. However, because MgO is easily segregated, the distribution of grain boundary phases is not uniform. In addition, large warpage and undulation occur in the silicon nitride sintered body substrate. In particular, it has been found that when the silicon nitride sintered body substrate is as large as 100 mm × 100 mm and is as thin as 0.7 mm or less, warping and waviness increase.

If the silicon nitride sintered substrate is warped or wavy, voids are generated at the bonding interface when the circuit board or the heat sink is bonded, and the thermal conductivity is lowered. Therefore, it is very important to suppress warpage and undulation of the silicon nitride sintered body substrate.

Japanese Patent Laid-Open No. 2009-215142 discloses that 3-4 mass% magnesium oxide powder and 2-5 mass% rare earth oxide powder are mixed with silicon nitride powder, and a solvent, an organic binder and A plasticizer is mixed to produce a slurry, the slurry is formed into a green sheet, the green sheet is sintered once, and a plurality of the obtained sintered bodies are stacked, and 1550 while applying a load of 0.5 to 6.0 kPa A method of heat treatment at ~ 1700 ° C is proposed. The silicon nitride sintered substrate obtained by this method has a Mg distribution variation coefficient of 0.20 or less, a warpage suppressed to 2.0 μm / mm or less, and high mechanical strength and thermal conductivity. However, since the heat treatment process of the sintered body must be performed after the firing process, there is a problem that the manufacturing cost is inevitably increased.

Therefore, an object of the present invention is to provide a silicon nitride sintered substrate having a sufficient mechanical strength and thermal conductivity with little warpage and undulation, and an efficient manufacturing method thereof.

As a result of diligent research in view of the above-mentioned object, the present inventors, (a) When a moderate uniform load is vertically applied to the silicon nitride green sheet during firing, the sintering shrinkage is substantially prevented without being hindered. Since the sintering of the silicon nitride green sheet proceeds while holding the surface, a silicon nitride sintered body substrate with less warpage and waviness is formed, and (b) 第二 after the first sintering temperature range When the temperature holding region was provided, it was discovered that the silicon nitride particles were rearranged and densified in the sintering aid liquidized in the sintering process, and the present invention was completed.

That is, the method for producing a silicon nitride sintered substrate of the present invention comprises 80-98.3 mass% Si ₃ N ₄ , 0.7-10 mass% (oxide conversion) Mg, and 1-10 mass% (oxide conversion). ) Containing at least one rare earth element, each of which is 100 mm or more in length and breadth and has a thickness of 0.7 mm or less.
Mixing a silicon nitride powder and a sintering aid powder containing Mg and at least one rare earth element;
A step of molding the obtained mixed powder;
And baking the obtained green sheet in a nitrogen atmosphere,
The firing step is performed in a state where a weight plate is placed on the green sheet so that a load of 10 to 600 Pa is applied to the green sheet.

The temperature profile in the baking step is 0.5 to a temperature lower than the first temperature holding range in the range of 1400 to 1700 ° C. after the first temperature holding range in which the temperature is in the range of 1600 to 2000 ° C. It is preferred to have a second temperature holding region that holds for ˜45 hours.

It is preferable that the temperature profile in the firing step has a cooling region for cooling at a rate of 100 ° C./hour or more after the second temperature holding region.

The temperature profile in the firing step is, before the first temperature holding region, (a) a gradually heating region where heating is performed at a rate of 300 ° C./hour or less in a temperature range of 1400 to 1600 ° C., or (b) 1400 to 1400 to It is preferable to have a temperature holding range for holding for 0.5 to 40 hours in a temperature range of 1600 ° C.

The firing step is performed in a state where a weight plate is disposed on a laminate composed of a plurality of green sheets, and the weight of the weight plate is set so that a load of 10 to 600 Pa is applied to each green sheet in the laminate. It is preferable to set it to work.

Each of the laminates is placed on a mounting plate, a plurality of mounting plates are stacked via a vertical frame member to form a mounting plate assembly, and the crucible in which the mounting plate assembly is disposed is placed in a firing furnace. The firing step is preferably performed.

It is preferable that the firing step is performed after a stuffing powder made of a mixed powder of magnesia powder, boron nitride powder and silicon nitride powder is placed in the crucible together with the laminate. The packing powder is preferably arranged on the upper surface of the uppermost mounting plate of the mounting plate assembly.

The crucible preferably has a double structure of an inner crucible and an outer crucible. The inner crucible is preferably made of BN, and the outer crucible is preferably made of carbon coated with BN.

The silicon nitride sintered substrate of the present invention produced by the above method preferably has a warpage of 2.5 μm / mm or less and a surface area of 2.0 μm or more in an area ratio of 15% or less.

The silicon nitride sintered substrate of the present invention preferably has a variation coefficient of Mg distribution in the thickness direction of 0.3 or less.

The voids in the silicon nitride sintered body substrate of the present invention preferably have an area ratio of 2.0% or less and a diameter of 10.0 μm or less.

When the copper plate is brazed to the silicon nitride sintered body substrate, it is preferable that the area ratio of voids having a diameter of 100 μm or more generated at the bonding interface is 3.0% or less.

In the method for producing a silicon nitride sintered substrate according to the present invention, since the weight plate is disposed on the green sheet laminate, warping and undulation are suppressed by one firing, and high mechanical strength and heat conduction are achieved. A silicon nitride sintered body substrate having a high rate can be obtained. Furthermore, since the temperature profile of the firing process has the second temperature holding region after the first temperature holding region, the distribution of the grain boundary phase is uniform and Mg segregation is suppressed, and the warp of the silicon nitride sintered body substrate is more It is suppressed. In addition, a double structure crucible consisting of a BN inner crucible and a carbon outer crucible coated with BN is used, and a mounting plate assembly in which a plurality of mounting plates on which a laminate is placed is stacked on the inner side. When the filling powder made of mixed powder of magnesia powder, boron nitride powder and silicon nitride powder is placed on the upper surface of the uppermost mounting plate of the mounting plate assembly, warpage and undulation are further suppressed and high. A silicon nitride sintered substrate having mechanical strength and thermal conductivity is obtained.

It is a flowchart which shows the manufacturing method of the silicon nitride sintered compact board | substrate of this invention. It is sectional drawing which shows the laminated body which consists of several green sheets. It is sectional drawing which shows a mode that a weight board is arrange | positioned on the upper surface of a laminated body. It is sectional drawing which shows a mode that the laminated body which mounted the weight board on the multistage frame in the crucible of a double structure has been arrange | positioned. It is sectional drawing which shows the state which mounted the one laminated body through the mounting board on the lower board of an inner side crucible and an outer side crucible. FIG. 6 is a cross-sectional view illustrating a state in which another mounting plate is disposed on the mounting plate illustrated in FIG. 5 via a vertical frame member and a second stacked body is mounted thereon. It is a graph which shows the temperature profile of the baking process in the manufacturing method of the silicon nitride sintered compact board | substrate of this invention. 6 is a SEM photograph showing a cross-sectional structure of an upper surface portion, a center portion, and a lower surface portion of a silicon nitride sintered body substrate of Example 5. 6 is an SEM photograph showing a cross-sectional structure of an upper surface portion, a central portion, and a lower surface portion of a silicon nitride sintered body substrate of Comparative Example 6. It is sectional drawing which shows a mode that a laser beam is irradiated to the surface of the silicon nitride sintered compact substrate mounted in the surface plate, and a curvature and a wave | undulation are measured. FIG. 3 is a plan view showing a state in which laser light is irradiated along the three scanning lines on the surface of a silicon nitride sintered body substrate placed on a surface plate. It is a top view which shows the method of calculating | requiring the curvature of a silicon nitride sintered compact board | substrate. It is the schematic which shows the method of calculating | requiring the area ratio of the area | region where surface waviness is 2.0 micrometers or more in a silicon nitride sintered compact substrate.

Embodiments of the present invention will be described below in detail with reference to the accompanying drawings, but the present invention is not limited to them, and can be appropriately changed within the scope of the technical idea of the present invention. The description of each embodiment is applicable to other embodiments unless otherwise specified.

[1] Raw material powder The raw material powder for producing the silicon nitride sintered body substrate of the present invention contains 80 to 98.3% by mass of silicon nitride (Si ₃ N ₄ ) as a main component, and 0.7 to It contains 10% by mass (as oxide) Mg and 1-10% by mass (as oxide) at least one rare earth element. From the viewpoint of the density, bending strength, and thermal conductivity of the silicon nitride sintered body, the alpha conversion rate of the silicon nitride powder is preferably 20 to 100%.

When Si ₃ N ₄ is less than 80% by mass, the resulting silicon nitride sintered substrate has too low bending strength and thermal conductivity. On the other hand, if Si ₃ N ₄ exceeds 98.3% by mass, the sintering aid is insufficient and a dense silicon nitride sintered body substrate cannot be obtained. Moreover, the liquid phase produced | generated at low temperature is inadequate that Mg is less than 0.7 mass% in conversion of an oxide. On the other hand, when Mg exceeds 10% by mass in terms of oxide, the volatilization amount of Mg increases, and voids are easily generated in the silicon nitride sintered substrate. Further, if the rare earth element is less than 1% by mass in terms of oxide, the bond between the silicon nitride particles becomes weak, and the cracks easily extend the grain boundary, so the bending strength becomes low. On the other hand, when the rare earth element exceeds 10% by mass in terms of oxide, the ratio of the grain boundary phase increases and the thermal conductivity decreases.

The Mg content (as oxide) is preferably 0.7 to 7% by mass, more preferably 1 to 5% by mass, and most preferably 2 to 5% by mass. The rare earth element content (as oxide) is preferably 2 to 10% by mass, more preferably 2 to 5% by mass. Accordingly, the content of Si ₃ N ₄ is preferably 83 to 97.3% by mass, and more preferably 90 to 97% by mass. As rare earth elements, Y, La, Ce, Nd, Pm, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, etc. can be used, among which Y is a silicon nitride sintered body It is effective and preferable for increasing the density of the substrate. Mg and rare earth elements are preferably used in the form of oxide powders. Accordingly, a preferred sintering aid is a combination of MgO powder and Y ₂ O ₃ powder.

[2] Method for Producing Silicon Nitride Sintered Substrate The case of producing a silicon nitride sintered substrate using a laminate of green sheets will be described in detail below, but the method of the present invention is limited to the use of the laminate. It is not something.

FIG. 1 is a flowchart showing a preferred example of the method of the present invention for producing a silicon nitride sintered body substrate. For simplification of explanation, the silicon nitride raw material powder is Si ₃ N ₄ powder, the Mg raw material powder is MgO powder, and the rare earth element raw material powder is Y ₂ O ₃ powder. It is not limited to the case of using raw material powder.

(1) Raw material powder mixing process S1
A plasticizer, an organic binder, and an organic solvent (for example, ethyl alcohol) are mixed with a Si ₃ N ₄ powder, MgO powder, and Y ₂ O ₃ powder blended so as to obtain the above sintered composition with a ball mill or the like to produce a slurry. To do. The solid content concentration of the slurry is preferably 30 to 70% by mass.

(2) Molding process S2
After defoaming and thickening the slurry, a green sheet is formed by, for example, a doctor blade method. The thickness of the green sheet is appropriately set in consideration of the thickness of the silicon nitride sintered substrate to be formed and the sintering shrinkage rate. Since the green sheet formed by the doctor blade method is usually a long strip, it is punched or cut into a predetermined shape and size. When forming a plurality of silicon nitride sintered body substrates from one green sheet, the substrate is cut after sintering.

(3) Lamination process S3
In order to efficiently manufacture the silicon nitride sintered body substrate, it is preferable to stack a plurality of green sheets. As shown in FIG. 2, a plurality of green sheets 1 are laminated through a boron nitride (BN) powder layer 12 having a thickness of about 1 to 20 μm to form a laminated body 10. The BN powder layer 12 is for facilitating separation of the sintered silicon nitride sintered substrate, and a slurry of BN powder is applied to one surface of each green sheet 1 by, for example, spraying, brush coating or screen printing. Can be formed. The BN powder preferably has a purity of 95% or more and an average particle diameter of 1 to 20 μm.

As shown in FIG. 3, in order to suppress warpage and undulation of the obtained silicon nitride sintered body substrate, a weight plate 11 is placed on the upper surface of each laminate 10, and a load is applied to each green sheet 1. . The load acting on each green sheet 1 is within the range of 10 to 600 Pa. When the load is less than 10 Pa, the sintered silicon nitride sintered substrate is likely to warp. On the other hand, when the load exceeds 600 Pa, each green sheet 1 is constrained by the load and smooth shrinkage during sintering is inhibited, so that it is difficult to obtain a dense silicon nitride sintered body substrate. The load acting on each green sheet 1 is preferably 20 to 300 Pa, more preferably 20 to 200 Pa, and most preferably 30 to 150 Pa.

If the weight of the weight plate 11 is W ₁ g, the weight and area of each green sheet 1 are W ₂ g and S cm ² respectively, and the number of green sheets 1 in the laminate 10 is n, the uppermost layer The load applied to the green sheet 1a is 98 × (W ₁ / S) Pa, and the load applied to the lowermost green sheet 1b is 98 × [W ₁ + W ₂ × (n−1)] / S Pa. For example, if a BN plate having a thickness of 2 mm is used as the weight plate 11 and the laminate 10 is composed of 20 green sheets 1, the load applied to the lowermost green sheet 1b is applied to the uppermost green sheet 1a. About 3 to 4 times the load. Taking this point into consideration, the weight of the weight plate 11 and the number of green sheets 1 in the laminate 10 are set. Weight W ₁ of the weigh plate 11, as well as receives a load in the range of the lowermost green sheet 1b even 10 ~ 600 Pa, shrinkage to set so as to be sintered without warpage and undulation unconstrained Is preferred.

(4) Degreasing process S4
Since the green sheet 1 contains an organic binder and a plasticizer, the laminate 10 is heated to 400 to 800 ° C. and degreased before the firing step S5. Since the green sheet 1 after degreasing is brittle, it is preferable to degrease in the state of the laminate 10.

(5) Sintering step S5
(a) Firing crucible FIG. 4 shows an example of a crucible for firing a plurality of laminated bodies 10 simultaneously. The crucible 20 includes a mounting plate assembly 30 in which mounting plates 21 that store the stacked bodies 10 are stacked in multiple stages, an inner crucible 40 that stores the mounting plate assembly 30, and an outer crucible that stores the inner crucible 40. It consists of 50. The interval between the mounting plates 21 adjacent in the vertical direction is held by the vertical frame member 22.

By making the crucible 20 having a double structure of the inner crucible 40 and the outer crucible 50, the decomposition of Si ₃ N ₄ and the volatilization of MgO in the green sheet 1 can be suppressed, and the silicon nitride firing is more dense and less warped. A bonded substrate can be obtained. Both the inner crucible 40 and the outer crucible 50 are preferably made of BN, but the outer crucible 50 can also be made of carbon coated with p-BN by CVD. In the case of the carbon outer crucible 50 coated with p-BN, the temperature distribution at the time of temperature rise can be easily made uniform by the carbon base material having good thermal conductivity, and the warp and undulation of the silicon nitride sintered body substrate can be suppressed. -Generation of reducing atmosphere by carbon substrate can be prevented by BN coating. The inner crucible 40 includes a lower plate 40a, a side plate 40b, and an upper plate 40c, and the outer crucible 50 includes a lower plate 50a, a side plate 50b, and an upper plate 50c.

When the upper surface of the mounting plate 21 is warped or undulated, the lowermost green sheet 1b in contact with the mounting plate 21 has a portion that is in contact with the upper surface of the mounting plate 21 and a portion that is not in contact therewith. Then, the non-contact part of the green sheet 1b is easily contracted during sintering, and the contact part is difficult to contract. Therefore, non-uniform contraction occurs in the green sheet 1b, and warping and undulation occur. Further, the warpage and undulation of the lowermost green sheet 1b also affect the upper green sheet 1, and as a result, warpage and undulation occur in all the silicon nitride sintered substrates. Therefore, the upper surface of the mounting plate 21 needs to be as flat as possible. Specifically, it is preferable that the warpage is within 2.0 μm / mm and the undulation is within 2.0 μm. The warping and waviness of the mounting plate 21 can be measured by the same method as the warping and waviness of the silicon nitride sintered substrate.

As shown in FIG. 4, it is preferable to place the filling powder 24 in the inner crucible 40. The filling powder 24 is made of, for example, 0.1 to 50% by mass of magnesia (MgO) powder, 25 to 99% by mass of silicon nitride (Si ₃ N ₄ ) powder, and 0.1 to 70% by mass of boron nitride (BN) powder. It is a mixed powder. Silicon nitride powder and magnesia powder in padding powder 24 volatilize at a high temperature of 1400 ° C or higher, and adjust the partial pressure of Mg and Si in the firing atmosphere to suppress silicon nitride and magnesia from volatilizing from green sheet 1 To do. The BN powder prevents adhesion of silicon nitride powder and magnesi powder in the filling powder 24. By using the filling powder 24, it is possible to obtain a silicon nitride sintered body substrate that is dense and has little warpage. In order to facilitate handling of the filling powder 24 and to prevent it from coming into contact with the green sheet 1, it is preferable to place the filling powder 24 on the uppermost mounting plate 21a.

As shown in FIG. 5, the lower plate 40a of the inner crucible 40 is placed on the upper surface of the lower plate 50a of the outer crucible 50, the placing plate 21 is placed on the upper surface of the lower plate 40a of the inner crucible 40, and a plurality of pieces are placed thereon. The laminated body 10 made of the green sheet 1 and the weight plate 11 are placed. As shown in FIG. 6, the vertical frame member 22 is installed on the outer peripheral portion of the mounting plate 21, the next stage mounting plate 21 is placed, and the stacked body 10 and the weight plate 11 are mounted thereon. . In this way, after forming the mounting plate assembly 30 on which the desired-stage laminated body 10 and the weight plate 11 are placed, the filling powder 24 is disposed on the upper surface of the uppermost mounting plate 21a. Next, the side plate 40b and the upper plate 40c of the inner crucible 40 are assembled, and further, the side plate 50b and the upper plate 50c of the outer crucible 50 are assembled to complete the crucible 20 containing the laminate 10. A desired number of such crucibles 20 are arranged in a firing furnace (not shown).

(b) Temperature profile The green sheet 1 is fired according to the temperature profile P shown in FIG. The temperature profile P includes a temperature rising area having a gradual heating area P ₀ , a temperature holding area having a first temperature holding area P ₁ and a second temperature holding area P ₂ , and a cooling area. In FIG. 7, the temperature shown on the vertical axis is the heating temperature of the firing furnace.

(c) Slow heating zone The slow heating zone P ₀ is a temperature zone where the sintering aid contained in the green sheet 1 reacts with the oxide layer on the surface of the silicon nitride particles to generate a liquid phase. In the slow heating region P ₀ , the growth of α-type silicon nitride grains is suppressed, and the silicon nitride grains are rearranged and densified in the liquid phase sintering aid. As a result, through the first and second temperature holding regions P ₁ and P ₂ , a silicon nitride sintered substrate having a small pore diameter and porosity, a high bending strength and a high thermal conductivity can be obtained. The temperature T ₀ of Jonetsuiki P _0, then the first temperature holding zone in the range of 1400 ~ 1600 ° C. lower than the temperature T ₁ of the P _1, the heating rate in Jonetsuiki P ₀ and less 300 ° C. / time, The heating time t ₀ is preferably 0.5 to 30 hours. The heating rate may include 0 ° C./hour, that is, a temperature holding region where the slow heating region P ₀ is held at a constant temperature. The heating rate in the slow heating region P ₀ is more preferably 1 to 150 ° C./hour, and most preferably 1 to 100 ° C./hour. The heating time t ₀ is more preferably 1 to 25 hours, and most preferably 5 to 20 hours.

(d) First temperature holding region The first temperature holding region P ₁ is the rearrangement of silicon nitride particles, the formation of β-type silicon nitride crystal, and the silicon nitride crystal by the liquid phase generated in the slow heating region P ₀ This is a temperature range in which the grain growth of the sintered body is increased, and the sintered body is further densified. Considering the size and aspect ratio of the β-type silicon nitride particles (ratio of major axis to minor axis) and the formation of vacancies due to volatilization of the sintering aid, the temperature T in the first temperature holding region P ₁ ₁ was in the range of 1600 ~ 2000 ° C., preferably the holding time t ₁ and about 1 to 30 hours. When the temperature T _{1 of} the first temperature holding region P ₁ is less than 1600 ° C., it is difficult to densify the silicon nitride sintered body. On the other hand, when the temperature T ₁ exceeds 2000 ° C., volatilization of the sintering aid and decomposition of the silicon nitride become intense, and it becomes difficult to obtain a dense silicon nitride sintered body. If the temperature is in the range of 1600 to 2000 ° C., the heating temperature T ₁ may change (for example, gradually increase in temperature) within the first temperature holding region P ₁ .

The temperature T _{1 in} the first temperature holding region P ₁ is more preferably in the range of 1750 to 1950 ° C., and most preferably in the range of 1800 to 1900 ° C. Further, the first temperature T ₁ of the temperature holding zone P ₁ is preferably greater 50 ° C. or higher than the upper limit of the temperature T ₀ of Jonetsuiki P _0, more preferably higher 100 ~ 300 ° C. or higher. The holding time t ₁ is more preferably 2 to 20 hours, and most preferably 3 to 10 hours.

(e) a second second temperature holding zone P ₂ that follows the temperature holding zone first temperature holding zone P ₁ is slightly lower than the temperature T ₁ of the sintered body first temperature holding zone P ₁ by holding the T _2, the temperature range to maintain a state of directly or solid-liquid coexisting a first temperature holding zone P ₁ a through the liquid phase. The temperature T ₂ of the second temperature holding region P ₂ is preferably in the range of 1400 to 1700 ° C. and lower than the temperature T _{1 of} the first temperature holding region P ₁ . The holding time t ₂ of the second temperature holding zone P ₂ is 0.5 to 45 hours. By providing the second temperature holding area P ₂ after the first temperature holding area P ₁ , the warp of the silicon nitride sintered substrate can be made within 2.5 μm / mm.

When the temperature T _{2 of} the second temperature holding region P ₂ is less than 1400 ° C., the grain boundary phase is easily crystallized, and the resulting silicon nitride sintered substrate has low bending strength. On the other hand, when the temperature T ₂ exceeds 1700 ° C., the fluidity of the liquid phase is too high and the above effect cannot be obtained. The temperature T ₂ is more preferably 1500-1650 ° C., and most preferably 1550-1650 ° C. The holding time t _{2 in} the second temperature holding region P ₂ is preferably 0.5 to 45 hours, more preferably 0.5 to 10 hours, and most preferably 1 to 5 hours. The holding time t ₂ of the second temperature holding zone P ₂ is less than 0.5 hours, sufficient uniformity of the grain boundary phase. By suppressing the volatilization of the sintering aids, in order to prevent the deterioration of mechanical properties and thermal conductivity of the sintered silicon nitride substrate, the second holding time t ₂ of the temperature holding zone P ₂ for 45 hours The following is preferable.

In order to confirm the effect of providing the second temperature holding region P ₂ after the first temperature holding region P ₁ , the cross-sectional structures of the silicon nitride sintered body substrates of Example 5 and Comparative Example 6 are compared. Fig. 8 (a) shows the first temperature holding region P ₁ (T ₁ : 1850 ° C, t ₁ : 5 hours) followed by the second temperature holding region P ₂ (T ₂ : 1600 ° C, t ₂ : 2 hours). upper surface portion of the silicon nitride sintered body substrate of example 5 in which a is a SEM photograph showing a sectional structure in the middle portion and the lower surface portion, FIG. 8 (b) a first temperature holding zone P _₁ (T _1: (1850 ° C., t ₁ : 5 hours) SEM photograph showing a cross-sectional structure of the upper surface portion, the central portion and the lower surface portion of the silicon nitride sintered body substrate of Comparative Example 6 in which the second temperature holding region P ₂ was not provided is there.

In the cross-sectional structure of the silicon nitride sintered body substrate of Comparative Example 6 shown in FIG. 8 (b), the distribution of the grain boundary phase (appears as white spots due to the heavy element Y) is uneven in the thickness direction, An area without white spots (encircled by circle O) is observed. The region without white spots is a grain boundary phase with a high Mg / Y concentration ratio (low Y) and can be said to be a Mg segregation portion. Therefore, the cross-sectional structure of the silicon nitride sintered body substrate of Comparative Example 6 in which the second temperature holding region P ₂ is not provided after the first temperature holding region P ₁ has an Mg segregation portion, and has a grain in the thickness direction. It can be said that the field phase distribution is non-uniform. An excessively large Mg segregation part serves as a starting point of fracture, which decreases mechanical strength (bending strength and fracture toughness) and causes excessive warpage.

On the other hand, in the cross-sectional structure of the silicon nitride sintered body substrate of Example 5 shown in FIG. 8 (a), the grain boundary phase (which looks like white spots due to heavy element Y) is uniform in the thickness direction. It is distributed and no Mg segregation part is observed. Therefore, the silicon nitride sintered body substrate of Example 5 in which the second temperature holding region P ₂ is provided after the first temperature holding region P ₁ has high mechanical strength (bending strength and fracture toughness), Warpage is suppressed.

cooling zone P ₃ that follows the (f) cooling zone second temperature holding zone P ₂ is a second liquid phase which is maintained at a temperature holding zone P ₂ of solidified by cooling, the position of the resulting grain boundary phase This is the temperature range for fixing The solidification of the liquid phase carried out quickly in order to maintain the uniformity of the grain boundary phase distribution, the cooling rate of the cooling zone P ₃ is preferably at least 100 ° C. / hour, more preferably at least 300 ° C. / time, 500 ° C. / Most preferred is more than hours. Practically, the cooling rate is preferably 500 to 600 ° C./hour. By cooling at such a cooling rate, crystallization of the solidifying sintering aid can be suppressed and a grain boundary phase mainly composed of the glass phase can be formed, so that the bending strength of the silicon nitride sintered substrate can be increased. it can. If the cooling rate of the cooling zone P ₃ is maintained up to 1200 ° C., the cooling rate at a lower temperature is not particularly limited.

[3] Silicon Nitride Sintered Substrate The silicon nitride sintered substrate obtained by the above method has a warpage reduced to 2.5 μm / mm or less. Since the warpage is within 2.5 μm / mm, a metal circuit board or a heat radiating plate (sometimes collectively referred to as a “metal plate”) is joined to the silicon nitride sintered substrate via a brazing material, etc. When the substrate is formed, the generation of voids (portions where the silicon nitride sintered substrate is not bonded to the metal plate) at the bonding interface between the silicon nitride sintered substrate and the metal plate via the brazing material is suppressed. As a result, the thermal conductivity and electrical pressure resistance of the entire circuit board are improved, and the bonding reliability between the metal plate and the silicon nitride sintered body substrate in the cooling / heating cycle is increased. The warp is preferably within 2.0 μm / mm, more preferably within 1.5 μm / mm. The warp is preferably as small as possible, but practically, the lower limit is about 0.1 μm / mm.

The warpage of the silicon nitride sintered body substrate 60 is measured as follows using a three-dimensional laser measuring instrument (LT-8100 manufactured by Keyence Corporation). As shown in FIG. 9 (a) and FIG. 9 (b), the three scanning lines L1 are applied to the surface of the silicon nitride sintered substrate 60 placed on the surface plate by the three-dimensional laser measuring instrument 80. The laser beam 81 is scanned along L2, L3. As shown in FIG. 9 (b), the scanning lines L1 and L3 are along the inner line by 10 mm from each side end of the silicon nitride sintered body substrate 60, and the scanning line L2 is the silicon nitride sintered body substrate 60. Along the center line. As shown in FIG. 9 (c), for each of the scanning lines L1 to L3, a straight line C connecting both ends A and B in the scanning direction of the surface of the silicon nitride sintered body substrate 60 is horizontal, and is separated from the straight line C to the uppermost position. The height G of the point E and the height H of the point F that is farthest downward are obtained. The vertical distance (G + H) between point E and point F is divided by the length I of each scanning line L1 to L3, and the value of (G + H) / I obtained for each scanning line L1 to L3 is averaged. To do. 9A and 9C, the warp of the silicon nitride sintered body substrate 60 is exaggerated for the sake of explanation.

Since the silicon nitride sintered substrate of the present invention has a uniform grain boundary phase distribution, it is preferable that the variation coefficient of the Mg amount in the thickness direction (simply referred to as “Mg variation coefficient”) is 0.3 or less. By controlling the Mg coefficient of variation to 0.3 or less, warpage of the silicon nitride sintered substrate can be effectively reduced. The Mg variation coefficient is obtained by scanning an electron beam with a beam diameter of 0.1 μm at an interval of 2 μm with an EPMA in an arbitrary range of 0.2 mm in the cross section in the thickness direction of the silicon nitride sintered body substrate, and obtaining an X-ray of Mg Determined by dividing the standard deviation of intensity by its average.

The area ratio of the pores of the silicon nitride sintered body substrate of the present invention is 2.0% or less, and the maximum diameter of the pores is about 10 μm. The maximum diameter and area ratio of the holes are obtained from a scanning electron microscope (SEM) photograph. For example, when the hole has a shape having a major axis and a minor axis, the maximum diameter of the hole is the length of the major axis.

In the silicon nitride sintered substrate 60 of the present invention, the area ratio of the region having a surface waviness of 2.0 μm or more is preferably 15% or less. As exaggeratedly shown in FIG. 10, the area ratio (%) of the region where the surface waviness is 2.0 μm or more is the center line (straight line obtained by averaging the waviness) of the surface 60a of the silicon nitride sintered body substrate 60. Divided into a plurality of

undulations

1, 2, 3, 4, 5... According to the intersecting points, the area S ₂ of the

undulations

2, 5... , S ₅ ..., And the total area obtained is divided by the area S of the entire surface and multiplied by 100. Specifically, the area ratio of the area where the surface waviness is 2.0 μm or more is determined based on the surface of the silicon nitride sintered substrate 60 using an optical interference type non-contact surface shape measuring machine (MikroCAD Premium 80 × 60 manufactured by GFM). Is calculated from the processed image with the pre-filter set as follows.
Preset filter set value polynomial filter: 8,
Bandpass filter: Filter Size 1 X: 11, Y: 11
Filter Size 2 X: 51, Y: 51
Averaging filter: X: 15, Y: 15
Median filter: X: 7, Y: 27

When a silicon nitride sintered body substrate in which warpage and undulation are suppressed is joined to a copper plate via a brazing material, the area ratio of voids having a diameter of 100 μm or more at the joining interface is 3.0% or less. Examples of the brazing material include an Ag—In—Cu based brazing material, an Ag—Cu based brazing material mainly composed of eutectic Ag and Cu, and added with an active metal such as Ti, Zr, and Hf.

Since the individual substrates are produced by cutting the silicon nitride sintered body substrate of the present invention, the larger the silicon nitride sintered body substrate is, the better the efficiency is. However, the problem of warpage and waviness also increases accordingly. From the viewpoint of the balance between manufacturing efficiency, warpage, and undulation, the size of the silicon nitride sintered body substrate of the present invention is set to 100 mm or more in both vertical and horizontal directions. A preferable size is 120 mm × 120 mm, and a more preferable size is 140 mm × 140 mm. A thinner silicon nitride sintered substrate used as a heat transfer substrate for a circuit element such as a semiconductor is better, but the thinner it is, the more difficult it is to manufacture. Taking into consideration the performance as a heat transfer substrate and the difficulty of manufacturing, the thickness of the silicon nitride sintered substrate of the present invention is set to 0.7 mm or less. The thickness of the silicon nitride sintered body substrate is preferably 0.5 mm or less, more preferably 0.4 mm or less.

Examples 1-6
Green sheet by a doctor blade method from a slurry of solid powder (solid content concentration: 60% by mass) with 3.0% by mass of MgO powder, 2.0% by mass of Y ₂ O ₃ powder and the balance being Si ₃ N ₄ powder and unavoidable impurities (Dry size: 200 mm × 200 mm) 1 was formed, and 20 laminates were formed via BN powder to form a laminate 10. A weight plate 11 was placed on each laminate 10, placed on the placement plate 21, and placed in the crucible 20 shown in FIG. The load on the uppermost green sheet 1a by the weight plate 11 was 40 Pa. In the crucible 20, a plurality of mounting plates 21 on which the laminates 10 of Examples 1 to 6 are stacked in multiple stages to form a mounting

plate assembly

30, and 15% by mass on the upper surface of the uppermost mounting plate 21 a. A stuffing powder made of magnesia powder, 55 mass% silicon nitride powder, and 30 mass% boron nitride powder was placed. Each mounting plate 21 had a warp of 0.5 μm / mm and a waviness of 0.3 μm.

The crucible 20 is put into a firing furnace, a heating range P ₀ for 10 hours at a temperature rising rate of 1 to 100 ° C./hour, a first temperature holding range P _{1 for 14} hours at a temperature T ₁ of 1850 ° C., 1420 to 1650 second temperature holding zone P ₂ of temperature T ₂ at 1.5 hours in the range of ° C., and the temperature profile having a cooling zone P ₃ of the cooling rate of 600 ° C. / time, the green sheets 1 in each stack 10 Sintering produced a 0.32 mm thick silicon nitride sintered substrate.

Examples 7-13
Example ₂ was repeated except that the temperature T ₂ of the second temperature holding region P ₂ was changed within the range of 1420 to 1650 ° C., and the holding time t ₂ was also changed between 0.6 and 29.0 hours. A silicon nitride sintered substrate having a thickness of 0.32 mm was manufactured.

Examples 14-16
A silicon nitride sintered substrate having a thickness of 0.32 mm was manufactured in the same manner as in Example 5 except that the amount of MgO powder in the raw material powder was 1.0 to 5.0 mass%.

Examples 17-20
A silicon nitride sintered substrate was produced in the same manner as in Example 5 except that the cooling rate in the cooling zone P ₃ was changed within the range of 50 to 500 ° C./hour.

Examples 21-23
The thickness was changed in the same manner as in Example 5 except that the rate of temperature increase in the slow heating region P ₀ was changed within the range of 50 to 300 ° C./hour and the temperature increase time was changed within the range of 1 to 20 hours. A 0.32 mm silicon nitride sintered substrate was produced.

Examples 24-27
A silicon nitride sintered substrate having a thickness of 0.32 mm was manufactured in the same manner as in Example 5 except that the load applied to the uppermost green sheet 1a by the weight plate 11 was changed within the range of 10 to 100 Pa.

Examples 28-30
A silicon nitride sintered substrate having a thickness of 0.12 to 0.60 mm was manufactured in the same manner as in Example 5 except that the thickness of the green sheet 1 was changed.

Example 31
In the same manner as in Example 5 except that the second holding time t ₂ of the temperature holding zone P ₂ were 45 hours to produce a sintered silicon nitride substrate having a thickness of 0.32 mm.

Comparative Example 1
A silicon nitride sintered body substrate having a thickness of 0.32 mm was manufactured in the same manner as in Example 5 except that the firing step was performed without placing the overlapping plate 11 on the laminate 10 of the green sheet 1.

Comparative Example 2
A silicon nitride sintered substrate having a thickness of 0.32 mm was manufactured in the same manner as in Example 5 except that the load applied to the uppermost green sheet 1a by the weight plate 11 was 5 Pa.

Comparative Example 3
Silicon nitride having a thickness of 0.32 mm, in the same manner as in Example 5, except that the temperature T ₂ of the second temperature holding region P ₂ was 1300 ° C., less than the lower limit of the present invention, and the holding time t ₂ was 5.0 hours. A sintered substrate was produced.

Comparative Example 4
Silicon nitride having a thickness of 0.32 mm in the same manner as in Example 5 except that the temperature T ₂ of the second temperature holding region P ₂ was 1800 ° C., exceeding the upper limit of the present invention, and the holding time t ₂ was 2.0 hours. A sintered substrate was produced.

Comparative Example 5
Second holding time t ₂ of the temperature holding zone P ₂ in the same manner as in Example 5 except that as short as 0.1 hours to produce a sintered silicon nitride substrate having a thickness of 0.32 mm.

Comparative Example 6
A silicon nitride sintered substrate having a thickness of 0.32 mm was manufactured in the same manner as in Example 5 except that the temperature profile having no _second temperature holding region P ₂ was used.

Comparative Example 7
A silicon nitride sintered substrate having a thickness of 0.32 mm was manufactured in the same manner as in Example 5 except that the load applied to the uppermost green sheet 1a by the weight plate 11 was 700 Pa.

The thicknesses and structures of the silicon nitride sintered substrates of Examples 1 to 31 and Comparative Examples 1 to 7 are shown in Table 1-1 and Table 1-2, and the manufacturing conditions are shown in Table 2-1 and Table 2-2. .

The silicon nitride sintered substrates of Examples 1 to 31 and Comparative Examples 1 to 7 have a bending strength, thermal conductivity, relative density, Mg coefficient of variation, warpage, waviness, voids, and a diameter of 100 μm or more at the bonding interface. The void area ratio was measured by the following method. The bending strength, thermal conductivity, relative density, and Mg variation coefficient of each silicon nitride sintered substrate are shown in Table 3-1 and Table 3-2, and warp, undulation, pores, and a diameter of 100 μm or more at the bonding interface are shown. Table 4-1 and Table 4-2 show the void area ratios.

(1) Bending strength In accordance with JIS R1601, each silicon nitride sintered substrate is cut to a width of 4 mm, set in a three-point bending jig with a distance between support rolls of 7 mm, and a crosshead speed of 0.5 mm / min. A load was applied to measure the load at break, and the bending strength of each silicon nitride sintered substrate was calculated therefrom.

(2) Thermal conductivity Each silicon nitride sintered substrate is cut to 5 mm x 5 mm size, and the front and back surfaces are blackened with carbon spray, and then the thermal conductivity is measured by the laser flash method according to JIS R1611. Was measured.

(3) Relative density Based on JIS R1634, the density of each silicon nitride sintered body substrate was measured, and the relative density with respect to the theoretical density was calculated. The theoretical density of the sintered silicon nitride is as follows: the density of silicon nitride is 3.20 g / cm ³ , the density of MgO is 3.58 g / cm ³ and the density of Y ₂ O ₃ is 5.03 g / cm ^3. It calculated based on the mixture ratio.

(4) Mg variation coefficient It was measured by the method described in [3] above.

(5) Warpage and undulation Measurement was performed by the method described in [3] above.

(6) Maximum pore diameter and area ratio of pores Obtained from SEM photographs by the method described in [3] above.

(7) Oxygen-free copper plate of 14 mm x 28 mm x 0.5 mm (JIS H3100 C1020H) on each silicon nitride sintered body substrate with an area ratio of 18 mm x 32 mm of voids with a diameter of 100 µm or more at the joint interface Joined with the following brazing material, the test specimen obtained is immersed in an aqueous solvent, and is generated at the joining interface between the sintered silicon nitride substrate and the copper plate by an ultrasonic flaw detector (Mi-scope manufactured by Hitachi Construction Machinery Co., Ltd.) The area ratio of voids having a diameter of 100 μm or more was measured. The brazing material is Ag-In-Cu alloy powder having an average particle size of 20 μm (Ag: 70% by mass, In: 5% by mass, balance: Cu, oxygen: 0.1% by mass or less) 76.5% by mass, Ag having an average particle size of 10 μm Contains 7.6% by weight of powder and 0.8% by weight of titanium hydride powder (particle size of 85% or more, 45 μm or less), 5% by weight of acrylic resin binder, 10% by weight of α-terpineol solvent, and 0.1% by weight % Dispersant, having a melting point of 770 ° C. and a viscosity of 55 Pa · s.

Note: (1) Thickness of the obtained silicon nitride sintered substrate.
(2) Load applied to the uppermost green sheet 1a.
(3) The unit is μm / mm.

Note: (1) Thickness of sintered silicon nitride substrate.
(2) Load applied to the uppermost green sheet 1a.
(3) The unit is μm / mm.

Note: (1) Area ratio (%) of the area where surface waviness is 2.0μm or more.
(2) Area ratio (%) of voids having a diameter of 100 μm or more generated at the bonding interface.

As is apparent from Tables 1 to 4, 80 to 98.3% by mass of Si ₃ N ₄ , 0.7 to 10% by mass (as oxide) Mg, and 1 to 10% by mass (as oxide) It was found that a silicon nitride sintered body substrate having small warpage and undulation can be obtained by firing while applying a load to a laminate of green sheets containing the rare earth element. In particular, the silicon nitride sintered body substrate of Comparative Example 1 fired without applying a load to the laminate had large warpage and waviness. Further, in Comparative Example 2 in which the load applied to the laminate was small, the warpage and the undulation were relatively large.

Further, the temperature T ₁ of the first temperature holding region P ₁ is in the range of 1600 to 2000 ° C., and the temperature T ₂ of the second temperature holding region P ₂ is in the range of 1400 to 1700 ° C. Bending strength of 600 MPa or more, 65 W / m /, depending on the conditions of Examples 1-31, which is lower than the holding zone P ₁ and the holding time t ₂ of the second temperature holding zone P ₂ is 0.5 to 45 hours It has been found that a silicon nitride sintered substrate having a thermal conductivity of K or higher and a relative density of 95% or higher can be obtained. The warp of the silicon nitride sintered body substrate of the example was in the range of 2.5 μm / mm, and the area ratio of the region of 2 μm or more was as small as 15% or less even though there was undulation. Moreover, in the test piece in which the silicon nitride sintered body substrate of each example was bonded to a copper plate, the area ratio of voids having a diameter of 100 μm or more was as small as 3% or less.

As is clear from Table 3-1 and Table 3-2, the Mg coefficient of variation of the silicon nitride sintered substrates of Examples 1 to 31 was small. This means that Mg segregation in the thickness direction is small.

In Comparative Examples 3 to 5 in which the condition of the second temperature holding region P ₂ is outside the range of the present invention, at least one of bending strength, thermal conductivity, and relative density is inferior to that of Examples 1 to 31 and warpage occurs. It was larger than the example.

Claims

Contains 80 to 98.3 mass% Si 3 N 4 , 0.7 to 10 mass% (oxide equivalent) Mg, and 1 to 10 mass% (oxide equivalent) at least one rare earth element. A method for producing a silicon nitride sintered body substrate having a thickness of at least mm and a thickness of at most 0.7 mm,
Mixing a silicon nitride powder and a sintering aid powder containing Mg and at least one rare earth element;
A step of molding the obtained mixed powder;
And baking the obtained green sheet in a nitrogen atmosphere,
A method comprising performing the firing step in a state in which a weight plate is disposed on the green sheet so that a load of 10 to 600 Pa is applied to the green sheet.
2. The method of manufacturing a silicon nitride sintered body substrate according to claim 1, wherein the temperature profile in the firing step is 1400 to 1700 ° C. after the first temperature holding region where the temperature profile is set to a temperature within the range of 1600 to 2000 ° C. The method further comprises a second temperature holding range for holding for 0.5 to 45 hours at a temperature lower than the first temperature holding range.
3. The method of manufacturing a silicon nitride sintered body substrate according to claim 1 or 2, wherein the temperature profile in the firing step is a cooling zone for cooling at a rate of 100 ° C./hour or more after the second temperature holding zone. A method characterized by comprising.
4. The method of manufacturing a silicon nitride sintered body substrate according to claim 1, wherein a temperature profile in the firing step is 300 in a temperature range of 1400 to 1600 ° C. before the first temperature holding region. A method comprising a gradual heating range in which the temperature is increased at a rate of not more than ° C / hour.
4. The method of manufacturing a silicon nitride sintered body substrate according to claim 1, wherein the temperature profile in the baking step is 0.5 to 1400 to 1600 ° C. before the first temperature holding region. A method having a temperature holding range for holding for ˜40 hours.
The method for producing a silicon nitride sintered body substrate according to any one of claims 1 to 5, wherein the firing step is performed in a state where a weight plate is disposed on a laminate composed of a plurality of the green sheets, A method wherein the weight of the weight plate is set so that a load of 10 to 600 Pa acts on each green sheet in the laminate.
In the method for manufacturing a silicon nitride sintered body substrate according to claim 6, each of the laminates is placed on a mounting plate, and a plurality of mounting plates are stacked via a vertical frame member to form a mounting plate assembly, A method, wherein the crucible having the mounting plate assembly is placed in a firing furnace and the firing step is performed.
8. The method of manufacturing a silicon nitride sintered body substrate according to claim 7, wherein a packing powder made of a mixed powder of magnesia powder, boron nitride powder and silicon nitride powder is placed in a crucible together with the laminate, and then the firing step. The method characterized by performing.
9. The method of manufacturing a silicon nitride sintered body substrate according to claim 8, wherein the filling powder is disposed on the upper surface of the uppermost mounting plate of the mounting plate assembly.
10. The method for producing a sintered silicon nitride substrate according to claim 7, wherein the crucible has a double structure of an inner crucible and an outer crucible.
11. The method of manufacturing a silicon nitride sintered body substrate according to claim 10, wherein the inner crucible is made of BN, and the outer crucible is made of carbon coated with BN.
A silicon nitride sintered substrate produced by the method according to any one of claims 1 to 11, wherein the area ratio of a region having a warp of 2.5 μm / mm or less and a surface waviness of 2.0 μm or more is 15 % Of silicon nitride sintered body substrate.
13. The silicon nitride sintered substrate according to claim 12, wherein a variation coefficient of Mg distribution in the thickness direction is 0.3 or less.
14. The silicon nitride sintered substrate according to claim 12, wherein the area ratio of pores is 2.0% or less, and the maximum diameter of the pores is 10.0 μm. Bonded substrate.
15. The silicon nitride sintered body substrate according to claim 14, wherein when a copper plate is brazed to the silicon nitride sintered body substrate, an area ratio of voids having a diameter of 100 μm or more generated at a bonding interface is 3.0% or less. There is provided a silicon nitride sintered substrate.