JP2004162147A - Aluminum nitride sintered body having thermal-sprayed coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aluminum nitride sintered body consisting of metal, metal nitride, metal carbide, metal boride, metal silicate or metal oxide and having a thermal-sprayed coating excellent in adhesion strength. <P>SOLUTION: The aluminum nitride sintered body has a thermal-sprayed coating in which at least one kind of thermal-sprayed coating selected from metal, metal nitride, metal carbide, metal boride, metal silicate and metal oxide with the melting point of ≥ 1,800°C, and the coefficient of thermal expansion of ≤ 10x10<SP>-6</SP>[1/°C] on an oxidized layer formed on a surface of the aluminum nitride sintered body is formed. If the oxidized layer is formed on a roughened surface of the aluminum nitride sintered body, the adhesion strength of the thermal-sprayed coating is more enhanced. <P>COPYRIGHT: (C)2004,JPO

Description

【００５０】
【表２】

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【表３】

【００５２】
【表４】

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【００５４】
【発明の効果】
本発明によれば、金属、金属窒化物、金属炭化物、金属ホウ化物、金属ケイ化物あるいは金属酸化物からなり密着強度の優れた溶射被膜が形成されてなる窒化アルミニウム焼結体が容易に得られるので、半導体素子基板、電子回路基板、ヒートシンク等として或いは半導体製造装置内で用いる部材として有用である。
【図面の簡単な説明】
【図１】酸化処理層を形成した窒化アルミニウム焼結体基板の説明図
【図２】酸化処理層上にアンダーコート溶射被膜を形成した窒化アルミニウム焼結体基板の説明図
【図３】酸化処理層上にアンダーコート溶射被膜とトップコートＣｕ溶射被膜を形成した窒化アルミニウム焼結体基板の説明図
【図４】引っ張り試験の模式図
【図５】粗面化処理された表面上の酸化処理層の上にアンダーコート溶射被膜とトップコートＣｕ溶射被膜を形成した窒化アルミニウム焼結体基板の説明図
【符号の説明】
１・・・窒化アルミニウム焼結体研磨成形基板
２・・・酸化処理層
３・・・アンダーコート溶射被膜
４・・・トップコートＣｕ溶射被膜
５・・・Ｓｎハンダ層
６・・・引っ張り試験用端子
７・・・引っ張り試験用端子クランプ部材
８・・・引っ張り試験用端子チャック治具
９・・・片側表面を粗面化処理した窒化アルミニウム焼結体研磨成形基板
１０・・・酸化処理層
１１・・・アンダーコート溶射被膜
１２・・・トップコートＣｕ溶射被膜[0001]
TECHNICAL FIELD OF THE INVENTION
[0002]
The present invention relates to an aluminum nitride sintered body having a thermal spray coating suitable for use as a member such as a semiconductor element substrate, an electronic circuit substrate, a heat sink, or a heater or a stage for mounting a wafer in a semiconductor manufacturing apparatus.
[0003]
[Prior art]
2. Description of the Related Art In recent years, as electronic devices have become smaller, denser, and faster, the output of semiconductor components has also been rapidly increasing. For this reason, heat generated from these electronic devices also increases, and measures to dissipate this heat are important technical issues.
[0004]
The aluminum nitride sintered body has excellent mechanical properties such as excellent oxidation resistance, hardly wet by molten metal, and higher bending strength than alumina sintered body. Further, it has about 10 times the thermal conductivity of alumina and has a thermal expansion coefficient close to that of silicon, so that it has an excellent function as a peripheral substrate of a semiconductor device. For this reason, a substrate of a sintered body of aluminum nitride is increasingly used instead of a sintered body of alumina or beryllia as a substrate for mounting semiconductor components.
[0005]
In order to use a substrate of aluminum nitride sintered body as a substrate for mounting semiconductor components, a metallized layer of conductive metal is formed on the surface of the sintered body for mounting by soldering electronic parts and forming circuits etc. There is a need to. However, the aluminum nitride sintered body has poor wettability to various kinds of molten substances, and it is difficult to form a metallized layer having a stronger adhesive force than an alumina sintered body.
[0006]
Therefore, heat treatment is performed at a temperature of 1000 ° C. to 1500 ° C. in an atmosphere containing oxygen or water vapor to form an Al—O-based oxide layer in which nitrogen of aluminum nitride is replaced with oxygen on the surface of aluminum nitride. It has been proposed that a metallization method used for an alumina sintered body can be applied. In addition, some measures have been taken to improve the degree of adhesion by adding an active metal or oxide to a conductive metal paste used for printing and firing on the surface of the aluminum nitride sintered body.
[0007]
However, in the conventional metallization method on the surface of the aluminum nitride sintered body, a conductive metal paste or a copper plate is applied or brought into contact with the surface of the aluminum nitride sintered body, and is heated at a high temperature of, for example, 1500 ° C. or more in a heating furnace in a nitrogen atmosphere. Baking. For this reason, the sintered body itself may be deformed due to thermal distortion during firing, and there are problems such as difficulty in maintaining dimensional accuracy in the metallizing process for a sintered body having a large dimension.
[0008]
[Problems to be solved by the invention]
The present inventors have studied the use of a thermal spraying method to form a metallized layer on the surface of an aluminum nitride sintered body in order to solve the above problem. The thermal spraying method does not require stepwise steps such as application and drying of paste and subsequent heating and baking at a high temperature, and since the processing step is at about room temperature of 25 to 300 ° C, the aluminum nitride sintered body Since there is no possibility that thermal distortion occurs in the sintered body, it is possible to form a metallized layer on a large-sized sintered body. Furthermore, it is possible to form a solderable or brazable metal layer on the metallized layer by the same spraying process.
[0009]
In addition, if an oxide layer such as Al ₂ O ₃ or Y ₂ O ₃ can be formed on the surface of the aluminum nitride sintered body by thermal spraying, it is difficult to form a multilayer wiring on the aluminum nitride sintered body. An insulating layer can be formed. In addition, since these metal oxides are resistant to highly corrosive halide gas and plasma, it is possible to provide members such as heaters and stages used inside the semiconductor manufacturing apparatus.
[0010]
However, since the aluminum nitride sintered body has poor wettability to various molten substances, even if a metal, nitride, carbide, boride, silicide, oxide or the like is sprayed on the surface of the aluminum nitride sintered body, the sprayed coating is formed. Adhesion is poor. Even after roughening treatment such as sandblasting that is often used in the normal spraying process, the sprayed coating does not adhere and does not form a film, or even if a film is formed, the adhesion is weak, and subsequent soldering There is a problem such as peeling off in the step of.
[0011]
Research to solve this problem and to provide an aluminum nitride sintered body made of metal, metal nitride, metal carbide, metal boride, metal silicide or metal oxide and forming a thermal sprayed coating with excellent adhesion strength As a result, it was discovered that, when an oxidation treatment layer was previously formed on the surface of the aluminum nitride sintered body and a thermal spray coating was formed thereon, a thermal spray coating having practical adhesion strength could be obtained. It has been reached.
[0012]
[Means for Solving the Problems]
The present invention provides a metal, a metal nitride, and a metal carbide having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less on an oxidation treatment layer formed on the surface of an aluminum nitride sintered body. The present invention relates to an aluminum nitride sintered body having a thermal spray coating, wherein at least one thermal spray coating selected from a metal boride, a metal silicide, and a metal oxide is formed.
[0013]
The present invention also provides a method for forming a metal having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less on an oxidized layer formed on a roughened surface of an aluminum nitride sintered body. And a metal nitride, a metal carbide, a metal boride, a metal silicide, and a metal oxide.
[0014]
In the present invention, the thermal spray coating of a metal having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less means, for example, thermal spraying of a metal selected from Mo, W, Nb, Ta and Ti. It is a film to be formed.
[0015]
In the present invention, the thermal spray coating of a metal nitride having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less refers to, for example, a metal nitride selected from TiN, ZrN, TaN and NbN. This is a coating formed by thermal spraying.
[0016]
In the present invention, a thermal sprayed coating of a metal carbide having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less includes, for example, TiC, WC, NbC, TaC, Mo ₂ C, NbC and VC. It is a film formed by thermal spraying of a metal carbide selected from the group consisting of:
[0017]
In the present invention, the thermal sprayed coating of a metal boride having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less includes, for example, TiBr ₂ , ZrB ₂ , TaB ₂ , NbB ₂ , CrB, This is a coating formed by spraying a metal boride selected from MoB and WB.
[0018]
In the present invention, the thermal spray coating of a metal silicide having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less is, for example, a metal selected from TaSi ₂ , NbSi ₂ , MoSi ₂ and WSi. This is a film formed by thermal spraying of silicide.
[0019]
In the present invention, the thermal spray coating of a metal oxide having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less means, for example, a metal oxide selected from Al ₂ O ₃ and Y ₂ O _3. This is a coating formed by spraying an object.
[0020]
The present invention also provides a metal, metal nitride, metal carbide, metal boride or metal silicide having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less on the aluminum nitride sintered body. The present invention relates to an aluminum nitride sintered body characterized in that a metal sprayed coating having solderability and electrical conductivity is further formed on a sprayed coating of a nitride. Here, the metal having solderability and electric conductivity includes Cu, Cu-based alloy, Ni, Ni-based alloy, Co, Co-based alloy, Sn, Sn-based alloy and the like.
[0021]
According to the study of the present inventor, it has been discovered that when a thermal spray coating is formed on an oxidized layer formed by oxidizing the surface of an aluminum nitride sintered body, the adhesion of the thermal spray coating is improved. Furthermore, it has been found that, prior to forming such an oxidation-treated layer, if the surface of the aluminum nitride sintered body is subjected to a roughening treatment, the adhesion of the thermal sprayed coating is further improved.
[0022]
Further, a thermal spray coating having practical adhesion can be formed on the oxidized layer formed on the surface of the aluminum nitride sintered body because the melting point is 1800 ° C. or more and the thermal expansion coefficient is 10 × 10 ⁻⁶ [1 / ° C.] or less. Therefore, using a metal, metal nitride, metal carbide, metal boride, metal silicide, or the like that satisfies this requirement as a thermal spray material, forms a thermal spray coating on the oxidized layer formed on the surface of the aluminum nitride sintered body. Then, an electrically conductive sprayed coating having excellent adhesion is formed. Further, a metal spray coating or plating layer having higher electric conductivity can be formed on the spray coating.
[0023]
A sprayed coating of a metal, metal nitride, metal carbide, metal boride, metal silicide, etc. having a melting point of 1800 ° C. or more and a coefficient of thermal expansion of 10 × 10 ⁻⁶ [1 / ° C.] or less is used as an undercoat on the undercoat. By forming a thermal spray coating such as Cu, Cu-based alloy, Ni, Ni-based alloy, Co, Co-based alloy, Sn or Sn-based alloy having excellent solderability and electric conductivity, excellent solder wettability. An aluminum nitride sintered body having a metallized layer can be easily obtained.
[0024]
Further, using a metal oxide having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less as a thermal spray material, thermal spraying is performed on the oxidized layer formed on the surface of the aluminum nitride sintered body. By forming the coating, an insulating metal oxide layer can be easily formed on the surface of the aluminum nitride sintered body. If a metal oxide having excellent corrosiveness and durability, such as Al ₂ O ₃ and Y ₂ O ₃ , is used as a protective film on the surface of the aluminum nitride sintered body, the semiconductor is exposed to corrosive gas or plasma. An aluminum nitride sintered body useful as a part of a manufacturing apparatus can be obtained.
[0025]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, the oxidized layer formed on the surface of the aluminum nitride sintered body is obtained by converting the surface layer of the aluminum nitride sintered body to an Al-O-based oxide with a thickness of 0.1 to 10 μm by an oxidation treatment. This is a layer that is changed. The method of forming the oxidized layer is not particularly limited. For example, a method of heating aluminum nitride to 1000 to 1500 ° C. in the air or steam (for example, JP-A-61-84037, JP-A-64-24083). Can be formed. If a similar oxidized layer is formed, it may be formed by a method using a chemical treatment with an oxidizing agent or another method.
[0026]
The desirable range of the thickness of the oxidized layer is 0.1 to 10 μm, particularly preferably 2 to 4 μm, which is close to the particle size of the primary aluminum nitride particles constituting the aluminum nitride sintered body. If the thickness is less than 0.1 μm, there is a possibility that an unoxidized portion may partially occur. If the thickness is more than 10 μm, cracks, cracks, peeling, and the like may occur in the oxidized layer.
[0027]
If the surface of the aluminum nitride sintered body is subjected to a surface roughening treatment before forming the oxidation treatment layer, the adhesion of the thermal spray coating is further improved. As a method of the surface roughening treatment, a corrosion treatment with a NaOH solution, a sand blast treatment, a polishing treatment with a diamond grindstone, or the like can be used.
[0028]
In the case of the treatment with the NaOH solution, the grain boundaries of the aluminum nitride primary particles are selectively corroded to form a network-like groove of the aluminum nitride sintered body. Is preferably about half of the particle diameter of Ra, that is, about Ra1 to 2 μm. If it is coarser, primary particles of aluminum nitride will fall off. Further, in the case of the treatment by sandblasting or the treatment by diamond grinding stone, if the roughness is more than Ra 5 μm, the problem of damage or deformation of the whole aluminum nitride sintered body occurs, which is not desirable.
[0029]
In the present invention, the thermal spray coating formed on the oxidized layer formed on the surface of the aluminum nitride sintered body is a metal or ceramic particle which has been brought into a molten state or a semi-molten state by heating and accelerating with a high-temperature and high-speed gas. Is a coating formed by causing metal or ceramic particles to solidify and adhere to the surface of the substrate at high speed.
[0030]
The thermal spraying method used to form the thermal spray coating includes atmospheric plasma spraying, reduced pressure plasma spraying performed in a reduced-pressure atmosphere, electric arc spraying, explosive spraying, high-speed flame spraying, and gas-fired spraying. Depending on the material to be sprayed, it can be selected and used, but air plasma spraying or reduced pressure plasma spraying is most suitable because it can be used for all materials for forming a sprayed coating in the present invention.
[0031]
【Example】
[Examples 1 to 5]
A 1 mm-thick, 55 mm × 38 mm-thick, polished substrate with a surface roughness Ra of 0.8 μm (Rz 3.8 μm) formed by polishing and molding from an aluminum nitride sintered body was heated in air at 1000 ° C. for 10 hours to perform oxidation treatment. went. As a result of observing a cut surface of the substrate of the aluminum nitride sintered body subjected to the heat oxidation treatment with a scanning electron microscope, as shown in FIG. The oxidation treatment layer 2 generated by replacing nitrogen with oxygen was formed. The thickness of the oxidized layer 2 was 3 μm, and the surface roughness Ra was 0.7 to 0.8.
[0032]
Using a plasma spraying apparatus (Model 3600 40KW SG100 system manufactured by Plax Square Co., Ltd.), five kinds of metal powders of Mo, W, Nb, Ta, and Ti were formed on the oxidation treatment layer 2 on one side of the aluminum nitride polished molded substrate 1. (The particle size is 10 to 45 μm) by plasma spraying in the air to prepare three test pieces for each metal having the thermal spray coating 3 as shown in FIG. The thickness of the thermal spray coating 3 was 30 to 60 μm as shown in Table 1. In addition, as a gas for thermal spraying, argon was used as a main gas, and helium was used as an auxiliary gas.
[0033]
Next, Cu powder (particle size: 45 to 74 μm) was plasma-sprayed in the air using the same plasma spraying apparatus as above, using the sprayed coating 3 of each test piece as an undercoat. As shown in Table 2, a test piece formed by using a 110 μm-thick Cu sprayed coating 4 as a top coat was prepared.
[0034]
The adhesion strength of the thermal spray coating to the substrate 1 in each of these test pieces was measured using a tensile tester (Model SV2 manufactured by Imada Seisakusho). FIG. 4 is a schematic diagram of a tensile test, in which a 100% Sn solder layer 5 is interposed on the surface of the Cu sprayed coating 4 to form a joint surface having a diameter of 5 mm and an upper bar portion having a diameter of 2.6 mm. Terminal 6 was joined at 270 ° C. The tensile test terminal 6 is a copper pin plated with silver. Reference numeral 7 denotes a tensile test terminal clamp component, and reference numeral 8 denotes a tensile test terminal chuck jig. The tensile test terminal 6 was pulled upward at a pulling speed of 1 mm / min, and the tensile strength when the bond between the aluminum nitride sintered surface and the sprayed coating was separated was measured as the adhesion strength of the sprayed coating, and the results are shown in Table 1. . The adhesion strength in Table 1 is an average value of three test pieces.
[0035]
[Comparative Examples 1 to 6]
The oxidized layer 2 was formed on the surface of the polished molded substrate 1 of the aluminum nitride sintered body in the same manner as in the above-described embodiment. When the Cu powder was directly plasma-sprayed without forming an undercoat thereon, Immediately after thermal spraying, the thermal spray coating peeled off, and a test piece could not be prepared. Also, the metal (Mo, W, Nb) used for the undercoat in Examples 1 to 5 was the same as in Examples 1 to 5 except that the oxidation treatment layer 2 was not formed on the polished molded substrate 1 of the aluminum nitride sintered body. , Ta, and Ti) were plasma-sprayed, and the coatings peeled off during the spraying, making it impossible to prepare test pieces. These results are also shown in Table 1.
[0036]
[Examples 6 to 15]
In the same manner as in Examples 1 to 5, an oxidation treatment layer 2 having a thickness of 3 μm was formed on the surface of a polished molded substrate 1 made of an aluminum nitride sintered body. Except for using the nitrides, carbides, borides and silicides shown in Table 2 as the thermal spray material for the undercoat, each thermal spray material powder ( (Particle size: 10 to 45 μm) was plasma-sprayed in the air to form three test pieces for each material on which the sprayed coating 3 was formed. The thickness of the thermal spray coating 3 was 30 to 70 μm as shown in Table 2.
[0037]
Next, the thermal spray coating 3 of each of the test pieces was used as an undercoat, and Cu powder (particle size: 45 to 74 μm) was plasma-sprayed in the air in the same manner as in Examples 1 to 5 to form a film. A test piece was prepared in which a 110 μm Cu thermal spray coating 4 was formed as a top coat, a tensile test was performed in the same manner as in Examples 1 to 5, the adhesion strength was measured, and the results are shown in Table 2.
[0038]
[Comparative Examples 7 to 16]
The same thermal spraying materials (TiN, ZrN, TiC, WC, Mo ₂ C, TiB) as in Examples 6 to 15 were used in the same manner as in Examples 6 to 15 except that the oxidation treatment layer 2 was not formed on the aluminum nitride polished molded substrate 1. ₂ , ZrB ₂ , MoB, CrB, MoSi ₂ ) were plasma-sprayed, and all of the coatings were peeled off during the spraying, and test pieces could not be prepared. These results are also shown in Table 2.
[0039]
[Examples 16 to 20]
Sand blasting with a compressed air pressure of 0.49MP on one side surface of the same polished molded substrate of aluminum nitride sintered body used in Examples 1 to 5 using a grain size # 60 alumina abrasive. And subjected to a surface roughening treatment, whereby the surface roughness was Ra 1.5 μm (Rz 8 μm). The substrate subjected to the one-side surface roughening treatment as described above was subjected to a heat oxidation treatment in air at 1000 ° C. for 10 hours in the same manner as in Examples 1 to 5, and as shown in FIG. An oxidation treatment layer 10 having a thickness of 3 μm was formed thereon. Further, five types of thermal spraying material powders shown in Table 3 were plasma-sprayed on the oxidized layer on one surface of the substrate 9 subjected to the surface roughening treatment in the same manner as in Examples 1 to 5, and the thermal spray coating 11 was formed. Three test pieces were formed for each sprayed material. As shown in Table 3, the thickness of the thermal spray coating 11 was 40 to 70 μm.
[0040]
Next, the thermal spray coating 11 of the test piece was used as an undercoat, and Cu powder (particle size: 45 to 74 μm) was plasma-sprayed in the air in the same manner as in Examples 1 to 5 to form a film having a thickness of 110 μm. A test piece having the Cu sprayed coating 12 as a top coat was prepared. A tensile test was performed in the same manner as in Examples 1 to 5, and the results of measuring the adhesion strength are shown in Table 3.
[0041]
Comparison between Example 1 and Example 16 in which the undercoat is Mo, comparison between Example 6 and Example 17 in which the undercoat is TiN, comparison between Example 8 and Example 19 in which the undercoat is TiC, From the comparison between Examples 12 and 18 of ZrB ₂ and the comparison of Examples 15 and 20 with MoSi ₂ undercoat, the surface of the aluminum nitride sintered body substrate was roughened before the formation of the oxidized layer. It can be seen that the treatment improves the adhesion strength of the thermal spray coating by about 3 to 5 MPa.
[0042]
[Comparative Examples 17 to 21]
The same thermal spray material as in Examples 16 to 20 was plasma-sprayed on the roughened aluminum nitride polished molded substrate 9 in the same manner as in Examples 16 to 20, except that the oxidation treatment layer 10 was not formed. When a coat was formed and a Cu powder was sprayed thereon to form a Cu top coat, a sprayed coating was formed. However, the coating floated off from the substrate surface when left to cool after spraying, and peeled off. These results are also shown in Table 3.
[0043]
[Examples 21 and 22]
In the same manner as in Examples 1 to 5, an oxidation treatment layer having a thickness of 3 μm was formed on the surface of the polished molded substrate of the aluminum nitride sintered body. Except that Al ₂ O ₃ or Y ₂ O ₃ was used instead of the thermal spray material for the undercoat in Examples 1 to 5, each of these was placed on the oxidation treatment layer 2 in the same manner as in Examples 1 to 5. A test piece having a thermal spray coating formed by plasma spraying the thermal spray material powder (particle size: 10 to 45 μm) in the atmosphere. The thickness of each of the thermal spray coatings was 150 μm.
[0044]
With respect to these test pieces, a tensile test was performed in the same manner as in Examples 1 to 5, except that an epoxy resin was used instead of the 100% Sn solder 5 in the tensile test shown in FIG. Table 4 shows the results of measuring the adhesion strength. After heating these test pieces at 200 ° C. for 1 hour, the test pieces were immediately put into ordinary-temperature tap water. A thermal shock test was carried out for 5 cycles. As a result, the sprayed coating of each test piece was peeled, cracked, chipped, etc. No change was observed in the thermal spray coating.
[0045]
[Comparative Examples 22, 23]
A thermal spray coating of Al ₂ O ₃ or Y ₂ O ₃ was formed on the surface of a polished molded substrate of an aluminum nitride sintered body in the same manner as in Examples 21 and 22 except that the oxidation treatment layer was not formed. The coating floated off the substrate surface during standing cooling after the completion of thermal spraying and peeled off. These results are shown in Table 4.
[0046]
[Examples 23 and 24]
In the same manner as in Examples 16 to 20, an oxidation-treated layer having a thickness of 3 μm was formed on the surface of the aluminum nitride sintered body-formed substrate having one surface roughened. Further, a thermal spray coating of Al ₂ O ₃ or Y ₂ O ₃ was formed on the oxidized layer on the roughened one side surface of the substrate instead of the undercoat thermal spray material powder of Examples 16 to 20. Test pieces were prepared. The thickness of each of the thermal spray coatings was 150 μm. In the same manner as in Examples 21 and 22, a tensile test was performed on the test piece, and the results of measuring the adhesion strength are shown in Table 5.
[0047]
[Comparative Examples 24 and 25]
In the same manner as in Examples 23 and 24, except that the oxidized layer 2 was not formed, Al ₂ O ₃ or Y ₂ O _When the thermal spray coating of No. ₃ was formed, the thermal spray coating lifted off and peeled off from the substrate surface during standing cooling after the completion of thermal spraying. The results are shown in Table 5.
[0048]
Comparison between Examples 21 and 22 in Table 4 and Examples 23 and 24 in Table 5 reveals that when the surface of the aluminum nitride sintered body substrate is roughened before the formation of the oxidized layer, the adhesion strength is reduced. It can be seen that it is improved by about 3 MPa.
[0049]
[Table 1]

[0050]
[Table 2]

[0051]
[Table 3]

[0052]
[Table 4]

[0053]
[Table 5]

[0054]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the aluminum nitride sintered compact which consists of a metal, a metal nitride, a metal carbide, a metal boride, a metal silicide, or a metal oxide, and which forms the thermal spray coating with excellent adhesion strength is easily obtained. Therefore, it is useful as a semiconductor element substrate, an electronic circuit substrate, a heat sink, or a member used in a semiconductor manufacturing apparatus.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram of an aluminum nitride sintered body substrate having an oxidized layer formed thereon. FIG. 2 is an explanatory diagram of an aluminum nitride sintered substrate having an undercoat sprayed film formed on the oxidized layer. Explanatory drawing of an aluminum nitride sintered body substrate having an undercoat sprayed coating and a topcoat Cu sprayed coating formed on a layer. [FIG. 4] Schematic drawing of a tensile test. [FIG. 5] Oxidized layer on a roughened surface Diagram of an aluminum nitride sintered body substrate on which an undercoat sprayed coating and a topcoat Cu sprayed coating are formed
DESCRIPTION OF SYMBOLS 1 ... Polishing molded substrate of aluminum nitride sintered body 2 ... Oxidized treatment layer 3 ... Undercoat sprayed coating 4 ... Top coat Cu sprayed coating 5 ... Sn solder layer 6 ... For tensile test Terminal 7: Terminal clamp member for tensile test 8: Terminal chuck jig 9 for tensile test 9: Polished and molded aluminum nitride sintered body 10 with one surface roughened 10: Oxidized layer 11 ... Undercoat sprayed coating 12 ... Topcoat Cu sprayed coating

Claims (9)

Metals, metal nitrides, metal carbides, metal borides having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less on the oxidized layer formed on the surface of the aluminum nitride sintered body An aluminum nitride sintered body having a thermal spray coating formed by forming at least one thermal spray coating selected from metal silicides and metal oxides. 2. The aluminum nitride sintered body having a thermal spray coating according to claim 1, wherein the oxidation treatment layer is formed on the surface of the aluminum nitride sintered body that has been subjected to the surface roughening treatment. The thermal sprayed coating according to claim 1, wherein the metal having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less is one selected from Mo, W, Nb, Ta, and Ti. Aluminum nitride sintered body. The thermal spray coating according to claim 1, wherein the metal nitride having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less is a kind selected from TiN, ZrN, TaN, and NbN. Aluminum nitride sintered body. The metal carbide having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less is a kind selected from TiC, WC, NbC, TaC, Mo ₂ C, NbC and VC. 3. An aluminum nitride sintered body having the sprayed coating according to 2. The metal boride having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less is a kind selected from TiBr ₂ , ZrB ₂ , TaB ₂ , NbB ₂ , CrB, MoB and WB. Item 3. An aluminum nitride sintered body having the thermal spray coating according to item 1 or 2. The metal silicide having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less is a kind selected from TaSi ₂ , NbSi ₂ , MoSi ₂ and WSi. An aluminum nitride sintered body having a thermal spray coating. The thermal spray according to claim 1, wherein the metal oxide having a melting point of 1800 ° C. or more and a thermal expansion coefficient of 10 × 10 ⁻⁶ [1 / ° C.] or less is a kind selected from Al ₂ O ₃ and Y ₂ O _3. An aluminum nitride sintered body having a coating. 8. A nitride having a thermal spray coating, wherein a metal thermal spray coating having solderability and electrical conductivity is formed on the thermal spray coating of the aluminum nitride sintered body according to any one of claims 3 to 7. Aluminum sintered body.

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