Joined body

Abstract

Provided is a bonded body of a ceramic plate and an MMC plate having high bonding strength. This joined body is provided with: a ceramic plate; an MMC plate which is provided so as to face one side of the ceramic plate, and which is composed of a metal-based composite material (MMC); and a bonding layer that is provided between the ceramic plate and the MMC plate and bonds the ceramic plate and the MMC plate, the bonding layer containing Al as a main component and containing Si and Mg as auxiliary components, and the bonding interface between the ceramic plate and the bonding layer including an Mg-containing layer.

Description

Technical Field

[0001] This invention relates to a joint. Background Technology

[0002] Circuit formation in semiconductor device manufacturing is typically performed using plasma etching. Plasma etching is performed as follows: an inert gas is introduced into a vacuum chamber within a plasma etching apparatus, resulting in plasmaification. An electrostatic chuck assembly, which functions as a base for holding the wafer to be etched, is provided within the plasma etching apparatus. A typical electrostatic chuck assembly includes: a ceramic plate with embedded electrodes that functions as an electrostatic chuck, and a cooling plate that supports the bottom surface of the ceramic plate with embedded electrodes. Plasma etching is performed by electrostatically adsorbing the wafer onto the ceramic plate with embedded electrodes, thus fixing it to the electrostatic chuck assembly. On the other hand, the cooling plate is configured to dissipate heat generated on the wafer during plasma etching by being located on the bottom surface of the ceramic plate with embedded electrodes. The ceramic plate with embedded electrodes typically has the following configuration: internal electrodes such as electrostatic chuck (ESC) electrodes, RF electrodes, and heater electrodes are embedded within a ceramic substrate made of alumina or aluminum nitride, which have excellent heat resistance and corrosion resistance.

[0003] As an example of an electrostatic chuck assembly, Patent Document 1 (Japanese Patent Application Publication No. 2009-141204) discloses a substrate holder, which is obtained by bonding a first substrate made of a first ceramic sintered body and a second substrate made of a second ceramic sintered body using a bonding film containing an Al metal. This document discloses that by sandwiching the Al-containing metal bonding film between the first and second substrates, and simultaneously heating the metal while performing hot pressing at a pressure of 4 to 20 MPa, the first and second substrates are bonded together using the bonding film. Preferably, the Al-containing metal is an Al alloy containing Mg in the range of 0.5 to 5% by weight.

[0004] However, in recent years, metal matrix composites (MMCs) have attracted much attention. Metal matrix composites are materials obtained by incorporating ceramic reinforcing materials such as SiC and TiC into a metal matrix composed of metals such as Al and Si. They are known to possess advantages such as lightweight, high rigidity, high thermal conductivity, and low thermal expansion. Methods for bonding metal matrix composites (MMCs) and ceramic materials have been proposed. Patent Document 2 (Japanese Patent No. 4373538) discloses a joint in which MMC containing an aluminum alloy as a matrix and a ceramic material are bonded together using a solder composed of an Al alloy containing Mg.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2009-141204

[0008] Patent Document 2: Japanese Patent No. 4373538

[0009] Patent Document 3: Japanese Patent Application Publication No. 2006-196864 Summary of the Invention

[0010] As a cooling plate for electrostatic chuck assemblies, MMC (Metallic Ceramic) plates are preferred due to their advantages such as high thermal conductivity and low thermal expansion. Therefore, it is necessary to improve the bonding strength between the MMC plate and the ceramic plate.

[0011] The inventors of this invention have recently discovered that by (1) providing a specified bonding layer between the MMC plate and the ceramic plate, and (2a) making the bonding interface between the ceramic plate and the bonding layer include a Mg layer, and / or (2b) making the MMC plate have an Al diffusion layer at a specified depth (thickness) from the bonding interface between the bonding layer and the MMC plate, it is possible to provide a ceramic plate and MMC plate joint with high bonding strength.

[0012] Therefore, the object of the present invention is to provide a joint between a ceramic plate and an MMC plate with high bonding strength.

[0013] According to the present invention, the following solution is provided.

[0014] [Option 1]

[0015] A joint comprising:

[0016] Ceramic slab;

[0017] An MMC plate, which is disposed opposite to one side of the ceramic plate and is made of metal matrix composite (MMC); and

[0018] A bonding layer is disposed between the ceramic plate and the MMC plate to bond the ceramic plate and the MMC plate. The bonding layer contains Al as the main component and Si and Mg as secondary components.

[0019] The bonding interface between the ceramic plate and the bonding layer includes a Mg-containing layer.

[0020] [Option 2]

[0021] According to the conjugate of Scheme 1, the Mg-containing layer further comprises Al and O.

[0022] [Option 3]

[0023] According to the conjugate of Scheme 2, the weight ratio of Al:Mg:O in the Mg-containing layer is 1:0.01~0.50:0.001~0.100.

[0024] [Option 4]

[0025] According to Scheme 1 or 2, the thickness of the Mg-containing layer is 1 to 10 μm.

[0026] [Option 5]

[0027] According to any one of Schemes 1 to 3, the bonding of the ceramic plate, the bonding layer and the MMC plate is a thermoforming process.

[0028] [Option 6]

[0029] The conjugate according to any one of Schemes 1 to 3, wherein the MMC comprises Si, C and Ti.

[0030] [Option 7]

[0031] According to any one of Schemes 1 to 4, the MMC board has an Al originating from the bonding layer at the bonding interface between the bonding layer and the MMC board at a predetermined depth D. Al Al diffusion layer obtained by diffusion.

[0032] [Option 8]

[0033] According to the joint of embodiment 7, wherein the MMC plate has Mg originating from the joint layer from the joint interface between the joint layer and the MMC plate at a specified depth D. Mg The Mg diffusion layer obtained by diffusion.

[0034] [Option 9]

[0035] According to the conjugate described in Scheme 8, the depth D of the Al diffusion layer is... Al The depth D of the Mg diffusion layer is greater than Mg That is, satisfying D Al >D Mg .

[0036] [Option 10]

[0037] According to any one of Schemes 1 to 9, the surface of the MMC plate on the interface side has an arithmetic mean roughness Ra of 0.01 to 1.0 μm.

[0038] [Option 11]

[0039] The joint according to any one of Schemes 1 to 10 exhibits a joint strength of more than 200 MPa in a 4-point bending test.

[0040] [Option 12]

[0041] The conjugate according to any one of claims 1 to 11, wherein the ceramic plate comprises alumina and / or aluminum nitride and has an internal electrode embedded therein.

[0042] [Option 13]

[0043] A joint comprising:

[0044] Ceramic slab;

[0045] An MMC plate, which is disposed opposite to one side of the ceramic plate, and is composed of a metal matrix composite (MMC) containing Si, C, and Ti; and

[0046] A bonding layer is disposed between the ceramic plate and the MMC plate to bond the ceramic plate and the MMC plate. The bonding layer contains Al as the main component and Si and Mg as secondary components.

[0047] The MMC board has an Al originating from the bonding layer at the bonding interface between the bonding layer and the MMC board at a specified depth D. Al The Al diffusion layer obtained by diffusion, wherein the depth D of the Al diffusion layer is... Al It is above 40μm.

[0048] [Option 14]

[0049] According to the joint of embodiment 13, wherein the MMC plate has Mg originating from the joint layer from the joint interface between the joint layer and the MMC plate at a specified depth D. Mg The Mg diffusion layer obtained by diffusion.

[0050] [Option 15]

[0051] According to the conjugate of scheme 14, the depth D of the Al diffusion layer is... Al The depth D of the Mg diffusion layer is greater than Mg That is, satisfying D Al >D Mg .

[0052] [Option 16]

[0053] The conjugate according to any one of claims 13 to 15, wherein the ceramic plate comprises alumina and / or aluminum nitride and has an internal electrode embedded therein.

[0054] [Option 17]

[0055] According to any one of Schemes 13 to 16, the bonding of the ceramic plate, the bonding layer and the MMC plate is a thermoforming process.

[0056] [Option 18]

[0057] According to any one of Schemes 13 to 17, the surface of the MMC plate on the interface side has an arithmetic mean roughness Ra of 0.01 to 1.0 μm.

[0058] [Option 19]

[0059] The joint according to any one of Schemes 13 to 18 exhibits a joint strength of more than 200 MPa in a 4-point bending test. Attached Figure Description

[0060] Figure 1 This is a simplified cross-sectional view illustrating an example of the joint of the present invention.

[0061] Figure 2 This is a simplified cross-sectional view illustrating another example of the assembly of the present invention.

[0062] Figure 3A The image shows a SEM image (Compo image) of a cross section of the joint including the ceramic plate 12, the joint interface 20 and the joint layer 16 in Example 7, as well as Si, C and Ti mapping images of the corresponding regions.

[0063] Figure 3B The image shows a SEM image (Compo image) of a cross section of the joint including the ceramic plate 12, the joint interface 20 and the joint layer 16 in Example 7, as well as O, Mg and Al mapping images of the corresponding regions.

[0064] Figure 4A The image shows a SEM image (Compo image) of a cross section of the joint including the bonding layer 16, the bonding interface 22 and the MMC plate 14 in Example 7, as well as Si, C and Ti mapping images of the corresponding regions.

[0065] Figure 4B The image shows a SEM image (Compo image) of a cross section of the joint including the joint layer 16, the joint interface 22 and the MMC plate 14 in Example 7, as well as O, Mg and Al mapping images of the corresponding regions.

[0066] Figure 5AThe SEM image (Compo image) of the cross section of the joint including the bonding layer 16, the bonding interface 22 and the MMC plate 14 in Example 7, and the Si, C and Ti mapping images of the corresponding regions are shown in a reduced concentration scale form.

[0067] Figure 5B The SEM image (Compo image) of the cross section of the joint including the bonding layer 16, the bonding interface 22 and the MMC plate 14 in Example 7, and the O, Mg and Al mapping images of the corresponding regions are shown in a reduced concentration scale form. Detailed Implementation

[0068] joint

[0069] Figure 1 An example of the assembly of the present invention is shown in the figure. Figure 1 The shown bonding body 10 includes a ceramic plate 12, an MMC plate 14, and a bonding layer 16. Preferably, the ceramic plate 12 comprises alumina and / or aluminum nitride and has an internal electrode 18 embedded therein. The MMC plate 14 is a plate made of metal matrix composite (MMC) and is disposed opposite to one side of the ceramic plate 12. The metal matrix composite (MMC) preferably comprises Si, C, and Ti. The bonding layer 16 is a layer that bonds the ceramic plate 12 and the MMC plate 14 and is disposed between the ceramic plate 12 and the MMC plate 14. The bonding layer 16 contains Al as the main component and Si and Mg as secondary components. In the first embodiment of the present invention, the bonding interface 20 between the ceramic plate 12 and the bonding layer 16 includes a Mg-containing layer 24. On the other hand, in the second embodiment of the present invention, as Figure 2 More specifically, the MMC board 14 has an Al originating from the bonding layer 16, which forms a bonding interface 22 between the bonding layer 16 and the MMC board 14 at a specified depth D. Al The Al diffusion layer 26 was obtained. The depth D of the Al diffusion layer. Al Preferably, the thickness is 40 μm or more. The first solution may include features of the second solution, and vice versa. In this way, by (1) providing a predetermined bonding layer 16 between the MMC plate 14 and the ceramic plate 12, and (2a) making the bonding interface 20 between the ceramic plate 12 and the bonding layer 16 include a Mg-containing layer 24, and / or (2b) making the MMC plate 14 have an Al diffusion layer 26 at a predetermined depth (thickness) from the bonding interface 22 between the bonding layer 16 and the MMC plate 14, a joint 10 of ceramic plate 12 and MMC plate 14 with high bonding strength can be provided. That is, by employing a predetermined bonding layer 16 and providing a Mg-containing layer 24 and / or an Al diffusion layer 26, high bonding strength can be achieved between the MMC plate 14 and the ceramic plate 12.

[0070] The ceramic plate 12 is a plate-shaped component comprising a ceramic sintered body, and may have the same configuration as ceramic plates used in known ceramic substrates (e.g., electrostatic chuck assemblies, ceramic heaters, etc.). Typically, an internal electrode 18 is embedded in the ceramic plate 12. From the viewpoints of excellent thermal conductivity, high electrical insulation, and thermal expansion characteristics close to those of silicon, the ceramic sintered body constituting the main part of the ceramic plate 12 (i.e., the ceramic matrix), excluding the internal electrode 18, preferably contains alumina and / or aluminum nitride, more preferably aluminum nitride. In addition to alumina and / or aluminum nitride, the ceramic sintered body constituting the ceramic plate 12 may also contain additives such as MgO. In this case, the content of alumina and / or aluminum nitride in the ceramic sintered body constituting the ceramic plate 12 is typically 50 to 100% by mass, with the balance being additives such as MgO. The thickness of the ceramic plate 12 can be the thickness of a typical ceramic plate, without particular limitation, typically 2 to 10 mm, more typically 2 to 5 mm.

[0071] Examples of internal electrodes 18 implanted in the ceramic plate 12 include: ESC electrodes, heater electrodes, and RF electrodes. Two types of internal electrodes 18 can be provided within the ceramic plate 12. An ESC electrode is short for Electrostatic Chuck (ESC) electrode, also known as an electrostatic electrode. The ESC electrode is preferably a thin, circular electrode with a diameter slightly smaller than the ceramic plate 12; for example, it can be a mesh electrode obtained by braiding fine metal wires into a mesh and forming it into a sheet. The ESC electrode can be used as a plasma electrode. That is, by applying a high frequency to the ESC electrode, it can also be used as a plasma electrode, and film deposition based on plasma CVD processes can be performed. Regarding the ESC electrode, when an external power supply is applied, the wafer placed on the surface of the ceramic plate 12 is held by the Johnson-Label force. The heater electrode is not particularly limited; for example, it can be a component obtained by wiring a conductive coil across the entire surface of the ceramic plate 12 in a single stroke. Regarding the heater electrode, when powered by a heater power supply, it heats up, heating the wafer placed on the surface of the ceramic plate 12. The heater electrode is not limited to a coil; for example, it can be a strip (a thin, elongated plate) or a mesh. A strip-shaped heater electrode can be a component formed by printing.

[0072] MMC plate 14 is composed of a metal matrix composite (MMC). The MMC can be any known material obtained by incorporating a ceramic reinforcing material into a metal matrix, and is not particularly limited. Examples of metal matrices include aluminum and metallic silicon. Examples of ceramic reinforcing materials include SiC and TiC. Preferably, the MMC contains Si, C, and Ti. Examples of MMCs containing Si, C, and Ti include composite materials containing 37–60% by mass of silicon carbide and titanium silicon carbide and titanium carbide in amounts less than the silicon carbide content (by mass%). The thickness of the MMC plate 14 is not particularly limited, but is typically 5–35 mm.

[0073] The arithmetic mean roughness Ra of the surface on the bonding interface 22 side of the MMC plate 14 is preferably 0.01 to 1.0 μm, more preferably 0.05 to 0.70 μm. If the arithmetic mean roughness Ra is within the above range, the bonding strength can be improved more effectively. This is believed to be because: by ensuring Ra is not too high, the adhesion between the MMC plate 14 and the bonding layer 16 is improved; furthermore, by ensuring Ra is not too low, an anchoring effect is obtained from the surface roughness or unevenness of the MMC plate 14.

[0074] The bonding layer 16 is a metal layer containing Al as the main component and Si and Mg as secondary components. Here, "main component" refers to the component that occupies 80% or more by weight of the bonding layer 16. "Secondary component" refers to the component included in a lower content than the main component (excluding unavoidable impurities). Therefore, the bonding material constituting the bonding layer 16 is preferably an Al alloy containing Si and Mg. The Si content in this Al alloy is preferably 5 to 15% by weight. In addition, the Mg content in this aluminum alloy is preferably 0.1 to 5.0% by weight. That is, the bonding layer 16 is preferably composed of an Al alloy containing Si: 5 to 15% by weight, Mg: 0.5 to 5.0% by weight, with the balance being Al and unavoidable impurities.

[0075] The bonding interface 20 between the ceramic plate 12 and the bonding layer 16 preferably includes a Mg-containing layer 24. It is believed that the presence of the Mg-containing layer 24 at the bonding interface 20 improves the bonding strength between the ceramic plate 12 and the bonding layer 16, resulting in high bonding strength between the ceramic plate 12 and the MMC plate 14. The Mg-containing layer 24 is defined as a layer containing a high concentration of Mg at the bonding interface 20 compared to its surroundings, as shown in an elemental mapping image obtained using an EPMA (electron probe microanalyzer). The Mg-containing layer 24 preferably also contains Al and O. In this case, the Al:Mg:O weight ratio in the Mg-containing layer 24 is preferably in the range of 1:0.01 to 0.50:0.001 to 0.100, more preferably in the range of 1:0.05 to 0.30:0.005 to 0.050. The Al:Mg:O weight ratio can be determined using EPMA. From the viewpoint of improving bonding strength, the thickness of the Mg layer 24 is preferably 1 to 10 μm, more preferably 1 to 7 μm.

[0076] The bonding of the ceramic plate 12, the bonding layer 16, and the MMC plate 14 is preferably hot-pressed. Hot-pressing refers to a method of bonding the two components by sandwiching the metal bonding film (equivalent to the bonding layer 16) between them and applying pressure while heating the film to a temperature below the liquidus temperature of the metal bonding film (see Patent Document 1).

[0077] MMC board 14 is preferred. Figure 2 The bonding interface 22 between the bonding layer 16 and the MMC board 14 is shown at a specified depth D. Al An Al diffusion layer 26 is provided, derived from Al diffusion originating from the bonding layer 16. As described above, by providing the Al diffusion layer 26, high bonding strength can be achieved between the MMC plate 14 and the ceramic plate 12. The Al diffusion layer 26 is defined as follows: as described later. Figure 5B As illustrated, in the Al elemental mapping image obtained using EPMA, a layer containing a high concentration of Al was observed in the region of the MMC plate 14 adjacent to the bonding interface 22 (compared to other regions of the MMC plate 14). That is, in the Al elemental mapping image, where pixels representing high Al concentration are continuously distributed from the bonding layer 16 throughout the entire region of the MMC plate 14 adjacent to the bonding interface 22, the high Al concentration observed in this adjacent region of the MMC plate 14 can be attributed to Al originating from the bonding layer 16. Thus, the Al diffusion layer 26 is determined. The depth D of the Al diffusion layer 26... Al Preferably, it is 40 μm or more, more preferably 40 to 600 μm, even more preferably 50 to 500 μm, and particularly preferably 250 to 500 μm.

[0078] MMC board 14 Figure 2In addition to the Al diffusion layer 26, the diagram shows an interface 22 between the bonding layer 16 and the MMC plate 14, with Mg originating from the bonding layer 16 at a specified depth D. Mg A Mg diffusion layer 28 is obtained through diffusion. In this case, the Al diffusion layer 26 and the Mg diffusion layer 28 at least partially overlap (i.e., there are portions belonging to both the Al diffusion layer 26 and the Mg diffusion layer 28 in the MMC plate 14). It is believed that the Mg diffusion layer 28, together with the Al diffusion layer 26, can contribute to the achievement of high bonding strength. The Mg diffusion layer 28 is defined as follows: as described later. Figure 5B As illustrated, in the Mg elemental mapping image obtained using EPMA, a layer containing a high concentration of Mg was observed in the region of MMC plate 14 adjacent to the bonding interface 22 (compared to other regions of MMC plate 14). That is, in the Mg elemental mapping image, where pixels representing high Mg concentration are continuously distributed from the bonding layer 16 throughout the entire region of MMC plate 14 adjacent to the bonding interface 22, the high concentration of Mg observed in the aforementioned adjacent region of MMC plate 14 can be said to originate from the Mg in the bonding layer 16. This is how the Mg diffusion layer 28 is determined. The depth D of the Mg diffusion layer 28... Mg Preferably, the depth is 10–300 μm, more preferably 20–200 μm, and even more preferably 90–180 μm. Typically, the depth D of the Al diffusion layer 26 is… Al Depth D greater than Mg diffusion layer 28 Mg (that is, satisfying D) Al >D Mg ).

[0079] The MMC plate 14 may have internal spaces such as flow paths for refrigerant circulation. Accordingly, the MMC plate 14 becomes a suitable configuration for a cooling plate in an electrostatic chuck assembly.

[0080] The joint 10 exhibits a joint strength of preferably 200 MPa or more, more preferably 250 MPa or more, and even more preferably 300 MPa or more in a 4-point bending test. The 4-point bending test is performed in the order and conditions disclosed in the embodiments described later, and the maximum bending stress obtained therefrom is used as the joint strength. A high joint strength is desirable; therefore, the upper limit is not particularly limited, typically 500 MPa or less, and more typically 450 MPa or less.

[0081] Method for manufacturing the joint

[0082] Regarding the joint of the present invention, it can be manufactured by any method as long as a joint with a specified layer structure is obtained. The preferred manufacturing method is described below.

[0083] First, a ceramic plate, an MMC plate, and a bonding layer with internal electrodes implanted are prepared. Details of each component are as described above. The ceramic plate, MMC plate, and bonding layer can all use known components; however, they can also be appropriately manufactured based on known methods.

[0084] Next, the ceramic plate, MMC plate, and bonding layer are ultrasonically cleaned using organic solvents. Ultrasonic cleaning removes contaminants adhering to the surfaces of each component, thereby improving the adhesion between the components and the bonding layer, resulting in high bonding strength. Preferred examples of organic solvents include acetone or isopropanol (IPA). By increasing the ultrasonic cleaning time, contaminants can be removed more thoroughly, promoting the movement and diffusion of elements such as Mg and Al during hot pressing. Therefore, by controlling the ultrasonic cleaning time, the formation / non-formation of a Mg-containing layer can be controlled during subsequent hot pressing, and the depth (thickness) of the Al diffusion layer and the Mg-containing layer can be varied. For example, by increasing the ultrasonic cleaning time, a Mg-containing layer can be formed, and the depth of the Al diffusion layer and the Mg-containing layer can be increased. From the viewpoint of more effectively removing contaminants adhering to the surfaces of each component, ultrasonic cleaning using acetone and ultrasonic cleaning using isopropanol (IPA) are preferred. For ceramic and MMC plates that have undergone ultrasonic cleaning, it is preferable to use pure water for running water rinsing, purge with N2 gas, wipe with a wiping sheet impregnated with an organic solvent (IPA, etc.), and then dry to further clean them. Additionally, for the bonding layers that have undergone ultrasonic cleaning, it is preferable to purge with N2 gas to further clean them.

[0085] Using the aforementioned purified ceramic plate, MMC plate, and bonding layer, a bonded body is fabricated by hot pressing. For example, the bonding layer is sandwiched between the ceramic plate and the MMC plate, and hot pressing is performed at a pressure of 4 MPa to 30 MPa while heating to a temperature below the liquidus temperature of the bonding material film, thus bonding the ceramic plate and the MMC plate together via the bonding layer. The hot pressing temperature is preferably lower than the liquidus temperature of the bonding layer and at least about 30°C lower than the solidus temperature. For example, the liquidus temperature of an aluminum alloy containing 10 wt% Si and 1 wt% Mg is about 590°C, and its solidus temperature is about 560°C. Therefore, the preferred hot pressing temperature is in the range of about 520°C or higher and lower than about 540°C. This allows for the formation of the bonded body of the present invention, in which the ceramic plate and the MMC plate are bonded together via the bonding layer.

[0086] Example

[0087] The invention will be further illustrated by the following examples. However, the invention is not limited to these examples.

[0088] Examples 1 to 9

[0089] (1) Production of ceramic slabs

[0090] As a ceramic plate, a circular alumina sintered body (thickness: 5 mm, diameter: 300 mm) with embedded ESC electrodes is manufactured as follows. First, first and second green sheets of alumina in the shape of discs are prepared. An ESC electrode is formed on one surface of the first green sheet by screen printing, and a heater electrode is formed on one surface of the second green sheet by screen printing. Next, another green sheet of alumina (hereinafter referred to as a third green sheet) is stacked on the surface of the first green sheet where the ESC electrode is formed, and the second green sheet is stacked on the third green sheet with the heater electrode in contact with the third green sheet. The resulting laminate is fired by hot pressing, thereby obtaining a ceramic sintered body with embedded ESC electrodes and heater electrodes. The two sides of the obtained ceramic sintered body are ground and sandblasted, and the shape and thickness are adjusted to obtain a flat electrostatic chuck as a ceramic plate. The specific manufacturing conditions of this electrostatic chuck are set with reference to the conditions described in Japanese Patent Application Publication No. 2006-196864.

[0091] (2) Fabrication of MMC board

[0092] As an MMC board, a board containing Si, C, and Ti (SiSiCTi board) is fabricated as follows. First, as raw materials, commercially available SiC raw material (purity ≥ 97%, average particle size 15.5 μm), commercially available metallic Si raw material (purity ≥ 97%, average particle size 9.0 μm), and commercially available metallic Ti raw material (purity ≥ 99.5%, average particle size 31.1 μm) are prepared. The SiC, metallic Si, and metallic Ti raw materials are weighed according to the following ratio: SiC: 49.5% by mass, Si: 20.0% by mass, Ti: 30.5% by mass. These are then placed in a nylon container along with isopropanol as a solvent and wet-mixed for 4 hours using 10 mm diameter iron-core nylon balls. The resulting slurry is removed and dried at 110°C in a nitrogen atmosphere, then passed through a 30-mesh sieve to form a blended powder. The blended powder is then subjected to a 200 kgf / cm³ pressure... 2 The pressure is applied uniaxially to form a disc-shaped molded body with a diameter of approximately 50 mm and a thickness of approximately 17 mm, which is then placed in a graphite mold for firing. The disc-shaped molded body is then hot-pressed and fired to obtain the MMC board. This hot-pressing and firing process is performed as follows: under a vacuum atmosphere, 200 kgf / cm² is applied... 2 The pressure is applied, and the mixture is kept at the firing temperature (maximum temperature) of 1400℃ for 4 hours.

[0093] The arithmetic mean roughness Ra of the surface of the bonding layer to be bonded in the prepared MMC board was measured using a stylus-type surface roughness measuring machine according to JIS B 0601-2001. The results are shown in Table 1.

[0094] (3) Preparation of the bonding layer

[0095] To create the bonding layer, an Al alloy sheet containing Si and Mg with a thickness of 0.12 mm was prepared (alloy composition: Si: 10 wt%, Mg: 1 wt%, balance: Al and unavoidable impurities).

[0096] (4) Cleaning process

[0097] For ceramic plates and MMC plates, the following purification processes (i) to (vi) are performed in sequence. On the other hand, for Al alloy sheets containing Si and Mg, the following purification processes (i), (ii) and (iv) are performed in sequence only.

[0098] <Cleanroom Process>

[0099] (i) Ultrasonic cleaning with acetone (not performed in Example 9)

[0100] (ii) Ultrasonic cleaning using isopropyl alcohol (IPA) (not performed in Example 9)

[0101] (iii) Cleaning with pure water

[0102] (iv) Purging with N2 gas

[0103] (v) Dry at 120°C for 10 minutes.

[0104] At this point, in each experimental example, as shown in Table 1, the total cleaning time (i) for ultrasonic cleaning using acetone and (ii) for ultrasonic cleaning using isopropanol (IPA), i.e., the ultrasonic cleaning time in the organic solvent, changed. Therefore, as described above, Example 9 did not perform the ultrasonic cleaning described in (i) and (ii).

[0105] (5) Hot pressing

[0106] Using a cleaned ceramic plate, an MMC plate, and a bonding sheet, hot pressing is performed as follows: The bonding sheet is sandwiched between the ceramic plate and the MMC plate as a bonding layer. The plate is heated to 530°C (a temperature lower than the liquidus temperature of the Al alloy containing Si and Mg but approximately 30°C lower than the solidus temperature) and then hot-pressed under a vacuum at a pressure of 20 MPa to bond the ceramic plate, bonding sheet (bonding layer), and MMC plate together. This results in a composite body where the ceramic plate and MMC plate are bonded together by means of the bonding layer.

[0107] (6) Evaluation of the joint

[0108] The following evaluation is given to the assembled joint.

[0109] <Obtaining Element Mapping Images Using EPMA>

[0110] After cutting out the cross-section of the obtained joint and performing mirror polishing, Ar ion-based planar ion milling was performed to obtain the observation section. A 75μm × 75μm region, including the ceramic plate 12, the joint interface 20, and the joint layer 16, in the obtained observation section was observed using SEM (scanning electron microscope). Furthermore, elemental analysis based on EPMA (manufactured by Nippon Electron Ltd.) was performed on this region under a measurement condition with an accelerating voltage of 15kV to obtain elemental mapping images of Si, C, Ti, O, Mg, and Al. Figure 3A and Figure 3B The table shows SEM images (Compo images) of cross-sections of the joint including ceramic plate 12, joint interface 20, and joint layer 16 in Example 7, as well as element-mapped images of the corresponding regions. The results are shown in Table 1. Figure 3A and Figure 3B As shown, in the joints of Examples 1 to 7, a Mg-containing layer 24 with a high concentration of Mg compared to its surroundings was observed at the joint interface 20, and it was also confirmed that the Mg-containing layer 24 also contained Al and O. On the other hand, no such Mg-containing layer was observed in the joints of Examples 8 and 9 (comparative examples).

[0111] In addition, for the 75μm×75μm region in the obtained observation section, including the bonding layer 16, the bonding interface 22 and the MMC plate 14, SEM observation and EPMA elemental analysis were performed in the same manner as above. Figure 4A and Figure 4B The image shows a SEM image (Compo image) of a cross-section of the joint including the bonding layer 16, the bonding interface 22, and the MMC plate 14 in Example 7, as well as element-mapping images of the corresponding regions. As a result, in the joints of Examples 1 to 9, the following microstructure was observed in all of them, namely, as shown... Figure 4A and Figure 4B As shown, the MMC plate 14 (SiSiCTi plate) contains TiC particles (black particles in the figure), TiSi2 matrix phase (gray portion in the figure), and SiC particles (white particles in the figure). Furthermore, in the joints of Examples 1-7, Mg and Al were also found to diffuse within the SiSiCTi constituting the MMC plate 14.

[0112] In addition, for the wider 300μm×300μm cross-sectional area including the bonding layer 16, the bonding interface 22 and the MMC plate 14, the magnification was reduced and the concentration scale was narrowed. Otherwise, SEM observation and EPMA elemental analysis were performed in the same manner as above. Figure 5A and Figure 5B The diagram shows a SEM image (Compo image) of a cross-section of the joint including the bonding layer 16, the bonding interface 22, and the MMC plate 14 in Example 7, along with elemental mapping images of the corresponding regions, scaled down to the concentration scale. As a result, in the joints of Examples 1-9, the presence of an Al diffusion layer 26 and a Mg diffusion layer 28, considered to originate from the bonding layer 16 and diffused from the bonding interface 22 along the entire depth direction of the MMC plate 14, was confirmed. The depth D of the Al diffusion layer 26 from the bonding interface 22 is shown. Al and the depth D of the Mg diffusion layer 28, measured from the interface 22. Mg The measurements were performed, and the results are shown in Table 1.

[0113] <Weight ratio of Al:Mg:O in the Mg-containing layer>

[0114] Based on the EPMA measurement results, the semi-quantitative values ​​of each element in a 0.24μm×0.24μm pixel were calculated. The weight ratio of Al:Mg:O was calculated by using the average value of 300 pixels.

[0115] <Joint strength>

[0116] From the obtained joint, a strip-shaped specimen was cut with the joint layer located at the center along its length. The surface of the specimen was ground to produce a test piece with dimensions of 1.5 mm × 2.0 mm × 20 mm. For this test piece, a four-point bending test was conducted with the joint interface as the center, under conditions of a lower span of 15 mm, an upper span of 5 mm, and a crosshead speed of 0.5 mm / min. The maximum bending stress (MPa) obtained was set as the joint strength. The results are shown in Table 1.

[0117] Table 1

[0118]

Claims

1. A joint, wherein, have: Ceramic slab; An MMC plate, which is disposed opposite to one side of the ceramic plate and is made of metal matrix composite (MMC); and A bonding layer is disposed between the ceramic plate and the MMC plate to bond the ceramic plate and the MMC plate. The bonding layer contains Al as the main component and Si and Mg as secondary components. The bonding interface between the ceramic plate and the bonding layer includes a Mg-containing layer.

2. The joint according to claim 1, wherein, The Mg-containing layer also contains Al and O.

3. The joint according to claim 2, wherein, The weight ratio of Al:Mg:O in the Mg-containing layer is 1:0.01-0.50:0.001-0.

100.

4. The joint according to claim 1 or 2, wherein, The thickness of the Mg-containing layer is 1–10 μm.

5. The joint according to any one of claims 1 to 3, wherein, The ceramic plate, the bonding layer, and the MMC plate are joined by thermoforming.

6. The joint according to any one of claims 1 to 3, wherein, The MMC contains Si, C, and Ti.

7. The joint according to any one of claims 1 to 3, wherein, The MMC board has an Al originating from the bonding layer, extending from the bonding interface between the bonding layer and the MMC board at a specified depth D. Al Al diffusion layer obtained by diffusion.

8. The joint according to claim 7, wherein, The MMC board has Mg originating from the bonding layer at the bonding interface between the bonding layer and the MMC board at a specified depth D. Mg The Mg diffusion layer obtained by diffusion.

9. The joint according to claim 8, wherein, The depth D of the Al diffusion layer Al The depth D of the Mg diffusion layer is greater than that of the Mg diffusion layer. Mg That is, satisfying D Al >D Mg .

10. The joint according to any one of claims 1 to 3, wherein, The surface of the MMC plate on the interface side has an arithmetic mean roughness Ra of 0.01 to 1.0 μm.

11. The joint according to any one of claims 1 to 3, wherein, In the 4-point bending test, it exhibited a joint strength of over 200 MPa.

12. The joint according to any one of claims 1 to 3, wherein, The ceramic plate comprises aluminum oxide and / or aluminum nitride and has internal electrodes embedded therein.

13. A joint, wherein, have: Ceramic slab; An MMC plate, which is disposed opposite to one side of the ceramic plate, and is composed of a metal matrix composite (MMC) containing Si, C, and Ti; and A bonding layer is disposed between the ceramic plate and the MMC plate to bond the ceramic plate and the MMC plate. The bonding layer contains Al as the main component and Si and Mg as secondary components. The MMC board has an Al originating from the bonding layer at the bonding interface between the bonding layer and the MMC board at a specified depth D. Al The Al diffusion layer obtained by diffusion, wherein the depth D of the Al diffusion layer is... Al It is above 40μm.

14. The joint according to claim 13, wherein, The MMC board has Mg originating from the bonding layer at the bonding interface between the bonding layer and the MMC board at a specified depth D. Mg The Mg diffusion layer obtained by diffusion.

15. The joint according to claim 14, wherein, The depth D of the Al diffusion layer Al The depth D of the Mg diffusion layer is greater than that of the Mg diffusion layer. Mg That is, satisfying D Al >D Mg .

16. The joint according to any one of claims 13 to 15, wherein, The ceramic plate comprises aluminum oxide and / or aluminum nitride and has internal electrodes embedded therein.

17. The joint according to any one of claims 13 to 15, wherein, The ceramic plate, the bonding layer, and the MMC plate are joined by thermoforming.

18. The joint according to any one of claims 13 to 15, wherein, The surface of the MMC plate on the interface side has an arithmetic mean roughness Ra of 0.01 to 1.0 μm.

19. The joint according to any one of claims 13 to 15, wherein, In the 4-point bending test, it exhibited a joint strength of over 200 MPa.

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