JP6335080B2 - Bonding material composition, aluminum nitride bonded body, and manufacturing method thereof - Google Patents
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本発明は、接合材組成物、窒化アルミニウム接合体及びその製法に関する。 The present invention relates to a bonding material composition, an aluminum nitride bonded body, and a manufacturing method thereof.
窒化アルミニウム焼結体同士を接合する方法は、従来より種々知られている。例えば、特許文献１には、窒化アルミニウム焼結体同士の間に、イットリウム化合物などの窒化アルミニウムの焼結助剤を溶液として塗布し、１８５０℃以上の接合温度で加熱し、接合界面の窒化アルミニウム粒子を粒成長させることで接合する方法が開示されている。特許文献２には、窒化アルミニウム焼結体同士の間に、窒化アルミニウムと希土類酸化物とを混合した接合材組成物を塗布し、１７００〜２０００℃の接合温度で加熱して、接合材組成物を焼結させることで接合する方法が開示されている。特許文献３には、窒化アルミニウム焼結体同士の間に、酸化カルシウムアルミニウムと希土類元素の酸化物からなる融材と窒化アルミニウムとを塗布し、１４５０℃の接合温度で加熱することで、融材を溶融させて接合する方法が開示されている。特許文献４には、窒化アルミニウム焼結体同士の間に、塩化アルミニウムと尿素の融合体を塗布し、７００〜１５００℃の接合温度で加熱し、窒化アルミニウムを生成させ接合する方法が開示されている。 Various methods for joining aluminum nitride sintered bodies are conventionally known. For example, in Patent Document 1, an aluminum nitride sintering aid such as an yttrium compound is applied as a solution between aluminum nitride sintered bodies, heated at a bonding temperature of 1850 ° C. or higher, and aluminum nitride at the bonding interface. A method of joining by growing grains is disclosed. In Patent Document 2, a bonding material composition in which aluminum nitride and a rare earth oxide are mixed is applied between aluminum nitride sintered bodies and heated at a bonding temperature of 1700 to 2000 ° C. to form a bonding material composition. A method of joining by sintering is disclosed. Patent Document 3 discloses that a flux composed of calcium aluminum oxide and a rare earth element oxide and aluminum nitride are applied between aluminum nitride sintered bodies and heated at a bonding temperature of 1450 ° C. A method of melting and joining the materials is disclosed. Patent Document 4 discloses a method in which a fusion body of aluminum chloride and urea is applied between aluminum nitride sintered bodies, heated at a joining temperature of 700 to 1500 ° C., and aluminum nitride is generated and joined. Yes.
しかしながら、特許文献１，２の方法では、１８５０℃以上や１７００℃以上という窒化アルミニウムの焼結温度領域（高温領域）まで加熱するため、窒化アルミニウム焼結体が変形してしまうことがあった。また、半導体製造装置用等のヒーターや静電チャックのような製品では、窒化アルミニウム内部にヒーター電極や静電チャック電極となる導電性材料を埋設しているため、これらの材料が高い接合温度に晒されることで、変質したり、周囲の成分と過度に反応したりして導電性等の電極材特性が変化することがあった。その結果、ヒーターの発熱性や静電チャックの吸着力といった特性に影響を与え、特にそれらが不均一になることが問題となっている。特許文献３の方法では１４５０℃という比較的低温で接合体が得られるものの、接合材組成物に含まれる酸化カルシウム成分は耐水性が乏しいため、長期間特性変化なく安定的に使用することが難しいという課題があった。特許文献４の方法では、７００℃〜１５００℃という比較的低温で接合体が得られるものの、尿素と塩化アルミニウムの反応途中に、ガス化した塩化アンモニウムが発生するため、産業への適用は難しいことが懸念された。 However, in the methods of Patent Documents 1 and 2, since the aluminum nitride is heated to a sintering temperature region (high temperature region) of 1850 ° C. or higher or 1700 ° C. or higher, the aluminum nitride sintered body may be deformed. In addition, in products such as heaters and electrostatic chucks for semiconductor manufacturing equipment, etc., conductive materials that serve as heater electrodes and electrostatic chuck electrodes are embedded in aluminum nitride, so these materials have a high bonding temperature. When exposed, the electrode material characteristics such as conductivity may change due to alteration or excessive reaction with surrounding components. As a result, it affects the characteristics such as the heat generation property of the heater and the attractive force of the electrostatic chuck. In the method of Patent Document 3, a joined body can be obtained at a relatively low temperature of 1450 ° C., but the calcium oxide component contained in the joining material composition has poor water resistance, so it is difficult to use it stably without changing characteristics for a long time. There was a problem. In the method of Patent Document 4, although a joined body can be obtained at a relatively low temperature of 700 ° C. to 1500 ° C., gasified ammonium chloride is generated in the course of the reaction between urea and aluminum chloride, so that it is difficult to apply to the industry. There was concern.
本発明はこのような課題を解決するためになされたものであり、窒化アルミニウム焼結体同士の接合を比較的低温で厄介なガスを発生することなく良好に安定して行うことを主目的とする。 The present invention has been made in order to solve such problems, and its main purpose is to satisfactorily and stably join aluminum nitride sintered bodies at a relatively low temperature without generating troublesome gas. To do.
本発明の接合材組成物は、希土類金属酸化物を含む窒化アルミニウム焼結体同士を接合する際に用いられる接合材組成物であって、Ｏ元素を含む窒化アルミニウム原料のほかに
、（ａ）フッ素化合物としてアルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方を含むか、（ｂ）フッ素化合物としてアルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方を含み、さらに希土類金属酸化物を含むもの（以下「第１の接合材組成物」という）である。
The bonding material composition of the present invention is a bonding material composition used when bonding aluminum nitride sintered bodies containing rare earth metal oxides, and in addition to an aluminum nitride raw material containing O element, (a) A fluorine compound containing at least one of an alkaline earth metal fluorine compound and a rare earth metal fluorine compound, or (b) a fluorine compound containing at least one of an alkaline earth metal fluorine compound and a rare earth metal fluorine compound, and further comprising a rare earth metal oxide (Hereinafter referred to as “first bonding material composition”).
また、本発明の接合材組成物は、希土類金属酸化物を含まない窒化アルミニウム焼結体と希土類金属酸化物を含んでいてもよい窒化アルミニウム焼結体とを接合する際に用いられる接合材組成物であって、Ｏ元素を含む窒化アルミニウム原料のほかに、（ａ）アルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方と希土類金属酸化物を含むか、（ｂ）希土類金属フッ素化合物を含むか、（ｃ）アルカリ土類金属フッ素化合物及び希土類金属フッ素化合物を含むもの（以下「第２の接合材組成物」という）である。 In addition, the bonding material composition of the present invention is a bonding material composition used when bonding an aluminum nitride sintered body that does not contain a rare earth metal oxide and an aluminum nitride sintered body that may contain a rare earth metal oxide. In addition to the aluminum nitride raw material containing element O, (a) at least one of an alkaline earth metal fluorine compound and a rare earth metal fluorine compound and a rare earth metal oxide, or (b) a rare earth metal fluorine compound Or (c) one containing an alkaline earth metal fluorine compound and a rare earth metal fluorine compound (hereinafter referred to as “second bonding material composition”).
本発明の窒化アルミニウム接合体は、窒化アルミニウム焼結体同士を接合層を介して接合した窒化アルミニウム接合体であって、前記接合層は、結晶相としてＡｌＮのほかに、アルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方を含むものである。本発明の窒化アルミニウム接合体は、別の視点で捉えると、窒化アルミニウム焼結体同士を接合層を介して接合した窒化アルミニウム接合体であって、前記窒化アルミニウム焼結体は、前記接合層との界面に、窒化アルミニウム焼結体に含まれる酸化物と前記接合層になる前の接合材組成物に含まれるフッ素化合物との反応層を有するものである。 The aluminum nitride bonded body of the present invention is an aluminum nitride bonded body in which aluminum nitride sintered bodies are bonded to each other via a bonding layer, and the bonding layer includes an alkaline earth metal fluorine compound in addition to AlN as a crystal phase. And at least one of rare earth metal fluorine compounds. From another viewpoint, the aluminum nitride bonded body of the present invention is an aluminum nitride bonded body in which aluminum nitride sintered bodies are bonded to each other via a bonding layer, and the aluminum nitride sintered body includes the bonding layer and the aluminum nitride bonded body. The reaction layer of the oxide contained in the aluminum nitride sintered body and the fluorine compound contained in the bonding material composition before becoming the bonding layer is provided at the interface.
本発明の窒化アルミニウム接合体の製法は、窒化アルミニウム焼結体同士の間に、上述した接合材組成物を挟み込んで接合荷重を加えた状態で、１４５０℃以下の温度で加熱することにより、前記窒化アルミニウム焼結体同士を接合した窒化アルミニウム接合体を製造するものである。 The manufacturing method of the aluminum nitride joined body of the present invention is performed by heating at a temperature of 1450 ° C. or lower while sandwiching the above-mentioned joining material composition between aluminum nitride sintered bodies and applying a joining load. An aluminum nitride joined body is produced by joining aluminum nitride sintered bodies together.
本発明によれば、窒化アルミニウム焼結体同士の接合を比較的低温で厄介なガスを発生することなく良好に安定して行うことができる。例えば、希土類金属酸化物を含む窒化アルミニウム焼結体同士の間に本発明の第１の接合材組成物を挟み込んで接合荷重を加えた状態で、比較的低温（例えば１３５０℃とか１４００℃とか１４５０℃）で焼成することにより、良好な接合状態の窒化アルミニウム接合体を得ることができる。また、希土類金属酸化物を含まない窒化アルミニウム焼結体と希土類金属酸化物を含んでいてもよい窒化アルミニウム焼結体との間に本発明の第２の接合材組成物を挟み込んで接合荷重を加えた状態で、比較的低温で焼成することにより、良好な接合状態の窒化アルミニウム接合体を得ることができる。 According to the present invention, aluminum nitride sintered bodies can be bonded to each other satisfactorily and stably without generating troublesome gas at a relatively low temperature. For example, a relatively low temperature (for example, 1350 ° C., 1400 ° C., or 1450 ° C.) in a state where the first bonding material composition of the present invention is sandwiched between aluminum nitride sintered bodies containing rare earth metal oxides and a bonding load is applied. The aluminum nitride bonded body in a good bonded state can be obtained by firing at a temperature of [° C.]. Further, the second bonding material composition of the present invention is sandwiched between an aluminum nitride sintered body that does not contain a rare earth metal oxide and an aluminum nitride sintered body that may contain a rare earth metal oxide. By firing at a relatively low temperature in the added state, it is possible to obtain an aluminum nitride bonded body having a good bonded state.
本発明の接合材組成物が比較的低温で焼成して窒化アルミニウム接合体同士を良好に接合するメカニズムは、以下のように推定している。すなわち、希土類金属酸化物を含む窒化アルミニウム焼結体同士を接合する場合、本発明の第１の接合材組成物を挟み込んで接合荷重を加えた状態で比較的低温の焼成温度で加熱すると、第１の接合材組成物中においてフッ素化合物を主とした液相が生成し、その液相が窒化アルミニウム焼結体へ拡散して窒化アルミニウム焼結体中の酸化物と反応して新たな液相が生成すると考えられる。その新たな液相は、希土類金属元素、Ａｌ元素、Ｏ元素、Ｆ元素を含んでいると考えられる。このうち、希土類金属元素は、窒化アルミニウム焼結体に含まれていたものである。その液相の一部が接合材組成物に拡散すると考えられる。接合材組成物中のＡｌＮは、その液相の存在下、比較的低温で焼結して、十分な接合強度でもって窒化アルミニウム焼結体同士を接合すると考えられる。また、希土類金属酸化物を含まない窒化アルミニウム焼結体同士を接合する場合、本発明の第２の接合材組成物を挟み込んで接合荷重を加えた状態で比較的低温の焼成温度で加熱すると、第２の接合材組成物中の成分が反応して液相を生成
すると考えられる。その液相は、希土類金属元素、Ａｌ元素、Ｏ元素、Ｆ元素を含んでいると考えられる。接合材組成物中のＡｌＮは、その液相の存在下、比較的低温で焼結して、十分な接合強度でもって窒化アルミニウム焼結体同士を接合すると考えられる。一方が希土類金属酸化物を含む窒化アルミニウム焼結体で、他方が希土類金属酸化物を含まない窒化アルミニウム焼結体の場合においても、同様にして、希土類金属元素、Ａｌ元素、Ｏ元素、Ｆ元素を含む液相が生成し、焼結体同士が接合される。いずれの場合も、接合温度が低温なため、接合前の窒化アルミニウム焼結体が熱によって変形することがない。また、塩化アンモニウムなどの厄介なガスが発生することもない。
The mechanism by which the bonding material composition of the present invention is baked at a relatively low temperature to bond the aluminum nitride bonded bodies well together is estimated as follows. That is, when joining aluminum nitride sintered bodies containing rare earth metal oxides, when the first bonding material composition of the present invention is sandwiched and heated at a relatively low firing temperature with a joining load applied, A liquid phase mainly composed of a fluorine compound is produced in the bonding material composition 1 and the liquid phase diffuses into the aluminum nitride sintered body and reacts with the oxide in the aluminum nitride sintered body to form a new liquid phase. Is considered to generate. The new liquid phase is considered to contain rare earth metal elements, Al elements, O elements, and F elements. Among these, the rare earth metal element is contained in the aluminum nitride sintered body. It is considered that a part of the liquid phase diffuses into the bonding material composition. It is considered that AlN in the bonding material composition sinters at a relatively low temperature in the presence of the liquid phase and bonds the aluminum nitride sintered bodies with sufficient bonding strength. In addition, when joining aluminum nitride sintered bodies that do not contain rare earth metal oxides, when heated at a relatively low firing temperature with a joining load applied by sandwiching the second joining material composition of the present invention, It is considered that the components in the second bonding material composition react to generate a liquid phase. The liquid phase is considered to contain rare earth metal elements, Al elements, O elements, and F elements. It is considered that AlN in the bonding material composition sinters at a relatively low temperature in the presence of the liquid phase and bonds the aluminum nitride sintered bodies with sufficient bonding strength. Similarly, in the case where one is an aluminum nitride sintered body containing a rare earth metal oxide and the other is an aluminum nitride sintered body not containing a rare earth metal oxide, the rare earth metal element, Al element, O element, and F element are similarly used. A liquid phase containing is produced, and the sintered bodies are joined together. In either case, since the joining temperature is low, the aluminum nitride sintered body before joining is not deformed by heat. Moreover, troublesome gas such as ammonium chloride is not generated.
本発明の接合材組成物は、第１の接合材組成物、すなわち、希土類金属酸化物を含む窒化アルミニウム焼結体同士を接合する際に用いられる接合材組成物であって、Ｏ元素を含む窒化アルミニウム原料のほかに、（ａ）フッ素化合物としてアルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方を含むか、（ｂ）フッ素化合物としてアルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方を含み、さらに希土類金属酸化物を含むもの、あるいは、第２の接合材組成物、すなわち、希土類金属酸化物を含まない窒化アルミニウム焼結体と希土類金属酸化物を含んでいてもよい窒化アルミニウム焼結体とを接合する際に用いられる接合材組成物であって、Ｏ元素を含む窒化アルミニウム原料のほかに、（ａ）アルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方と希土類金属酸化物を含むか、（ｂ）希土類金属フッ素化合物を含むか、（ｃ）アルカリ土類金属フッ素化合物及び希土類金属フッ素化合物を含むものである。 A bonding material composition of the present invention is a first bonding material composition, that is, a bonding material composition used when bonding aluminum nitride sintered bodies containing rare earth metal oxides, and includes an O element. In addition to the aluminum nitride raw material, (a) contains at least one of an alkaline earth metal fluorine compound and a rare earth metal fluorine compound as the fluorine compound, or (b) at least one of an alkaline earth metal fluorine compound and a rare earth metal fluorine compound as the fluorine compound. One containing one or more rare earth metal oxides, or the second bonding material composition, that is, the aluminum nitride sintered body not containing the rare earth metal oxide and the aluminum nitride optionally containing the rare earth metal oxide A joining material composition used when joining a sintered body, in addition to an aluminum nitride raw material containing an O element, a) at least one of an alkaline earth metal fluorine compound and a rare earth metal fluorine compound and a rare earth metal oxide, or (b) a rare earth metal fluorine compound, or (c) an alkaline earth metal fluorine compound and a rare earth metal fluorine compound Is included.
ここで、希土類金属酸化物を含む窒化アルミニウム焼結体は、例えば、窒化アルミニウム粉末に焼結助剤として希土類金属酸化物を加えて混合し、その混合粉末にバインダーを添加したあと造粒し、その造粒粉を所望の形状に成形後、ホットプレス法で焼成することにより、得られる。希土類金属酸化物としては、Ｙ2Ｏ3，Ｌａ2Ｏ3，Ｃｅ2Ｏ3，Ｎｄ2Ｏ3，Ｓｍ2Ｏ3，Ｅｕ2Ｏ3，Ｇｄ2Ｏ3，Ｄｙ2Ｏ3，Ｈｏ2Ｏ3，Ｔｍ2Ｏ3，Ｙｂ2Ｏ3，Ｌｕ2Ｏ3などが挙げられるが、このうちＹ2Ｏ3，Ｙｂ2Ｏ3が好ましい。混合粉末中の希土類金属酸化物の含有量は、ＲＥ2Ｏ3換算で０．１〜１０質量％であることが好ましい（ＲＥ：希土類金属元素を表す）。バインダーとしては、例えばポリビニルブチラール、ポリビニルアセタールなどの有機バインダーが挙げられる。ホットプレス法では、真空雰囲気、窒素ガス雰囲気、アルゴンガス雰囲気などの不活性雰囲気下、加圧して焼成する。加圧条件は、１００〜４００ｋｇｆ／ｃｍ2が好ましく、１５０〜３００ｋｇｆ／ｃｍ2がより好ましい。焼成温度は、１７００〜２０００℃が好ましく、１７５０〜１９００℃がより好ましい。ただし、焼成はホットプレス法だけでなく常圧焼成でも構わない。 Here, the aluminum nitride sintered body containing the rare earth metal oxide is, for example, mixed with the aluminum nitride powder by adding the rare earth metal oxide as a sintering aid, granulated after adding a binder to the mixed powder, After the granulated powder is formed into a desired shape, it is obtained by firing with a hot press method. Examples of rare earth metal oxides include Y 2 O 3 , La 2 O 3 , Ce 2 O 3 , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Dy 2 O 3 and Ho 2 O. 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 and the like. Among these, Y 2 O 3 and Yb 2 O 3 are preferable. The content of the rare earth metal oxide in the mixed powder is preferably 0.1 to 10% by mass in terms of RE 2 O 3 (RE represents a rare earth metal element). Examples of the binder include organic binders such as polyvinyl butyral and polyvinyl acetal. In the hot press method, baking is performed under pressure in an inert atmosphere such as a vacuum atmosphere, a nitrogen gas atmosphere, or an argon gas atmosphere. Pressurization condition is preferably 100~400kgf / cm 2, 150~300kgf / cm 2 is more preferable. The firing temperature is preferably 1700 to 2000 ° C, more preferably 1750 to 1900 ° C. However, firing may be performed not only by a hot press method but also by normal pressure firing.
また、希土類金属酸化物を含まない窒化アルミニウム焼結体は、例えば、窒化アルミニウム粉末にバインダーを添加したあと造粒し、その造粒粉を所望の形状に成形後、ホットプレス法で焼成することにより、得られる。バインダーとしては、例えばポリビニルブチラール、ポリビニルアセタールなどの有機バインダーが挙げられる。ホットプレス法では、真空雰囲気、窒素ガス雰囲気、アルゴンガス雰囲気などの不活性雰囲気下、加圧して焼成する。加圧条件は、１００〜４００ｋｇｆ／ｃｍ2が好ましく、１５０〜３００ｋｇｆ／ｃｍ2がより好ましい。焼成温度は、１７００〜２０００℃が好ましく１８００〜１９００℃がより好ましい。なお、造粒粉を調製するにあたり、窒化アルミニウム粉末にバインダーに代えて又は加えて焼結助剤（例えば酸化マグネシウムや酸化カルシウムなど）を添加したあと造粒してもよい。 In addition, an aluminum nitride sintered body containing no rare earth metal oxide is granulated after adding a binder to aluminum nitride powder, and the granulated powder is formed into a desired shape and then fired by a hot press method. Is obtained. Examples of the binder include organic binders such as polyvinyl butyral and polyvinyl acetal. In the hot press method, baking is performed under pressure in an inert atmosphere such as a vacuum atmosphere, a nitrogen gas atmosphere, or an argon gas atmosphere. Pressurization condition is preferably 100~400kgf / cm 2, 150~300kgf / cm 2 is more preferable. The firing temperature is preferably 1700 to 2000 ° C, more preferably 1800 to 1900 ° C. In preparing the granulated powder, it may be granulated after adding a sintering aid (for example, magnesium oxide or calcium oxide) instead of or in addition to the binder to the aluminum nitride powder.
接合材組成物中の窒化アルミニウム原料は、粉末状であることが好ましい。窒化アルミニウム原料は、高純度のものであっても表面が酸化されていて必ず不回避的にＯ元素を含んでいる。窒化アルミニウム原料に含まれるＯ元素の含有量は、特に限定するものではないが、例えば０．４〜３０質量％としてもよい。この範囲であれば、本発明の効果を十分得られるからである。Ｏ元素の含有量は、窒化アルミニウム原料粉末を大気炉で加熱するときの加熱条件（加熱温度や加熱時間）によって原料粉末の酸化の度合いを制御したり、窒化アルミニウム原料粉末を粉砕し粉末の表面積を制御したりすることによって、調整することができる。また、粉砕と加熱による酸化の両方を行ってもよい。加熱温度は、例えば６００〜９００℃の範囲で適宜設定すればよく、加熱時間は、例えば０．５〜１０時間の範囲で適宜設定すればよい。粉砕時間は、例えば２〜５０時間程度の間で適宜設定すればよい。また、接合材組成物中の窒化アルミニウムやフッ素化合物の含有率は、窒化アルミニウムを２０〜８５質量％（酸素含有量の酸化アルミニウム換算量を除く）、フッ素化合物を１０〜５０質量％含有するのが好ましい。この範囲であれば、本発明の効果を十分得られるからである。 The aluminum nitride raw material in the bonding material composition is preferably in the form of powder. Even if the aluminum nitride raw material is of high purity, the surface is oxidized and the O element is inevitably included. Although content of O element contained in an aluminum nitride raw material is not specifically limited, For example, it is good also as 0.4-30 mass%. This is because the effect of the present invention can be sufficiently obtained within this range. The content of the O element is controlled by controlling the degree of oxidation of the raw material powder according to the heating conditions (heating temperature and heating time) when the aluminum nitride raw material powder is heated in an atmospheric furnace, or by pulverizing the aluminum nitride raw material powder. It can be adjusted by controlling. Further, both pulverization and oxidation by heating may be performed. The heating temperature may be set as appropriate within a range of 600 to 900 ° C., for example, and the heating time may be set as appropriate within a range of 0.5 to 10 hours, for example. What is necessary is just to set grinding | pulverization time suitably between about 2 to 50 hours, for example. Moreover, the content rate of the aluminum nitride and fluorine compound in the bonding material composition is 20 to 85% by mass of aluminum nitride (excluding aluminum oxide equivalent of oxygen content) and 10 to 50% by mass of fluorine compound. Is preferred. This is because the effect of the present invention can be sufficiently obtained within this range.
アルカリ土類金属フッ素化合物としては、アルカリ土類金属元素とフッ素元素を含む化合物であればよいが、アルカリ土類金属フッ化物が好ましい。アルカリ土類金属フッ化物としては、ＭｇＦ2，ＣａＦ2，ＳｒＦ2，ＢａＦ2などが好ましく、特にＭｇＦ2が好まし
い。希土類金属フッ素化合物としては、希土類金属元素とフッ素元素を含む化合物であればよいが、希土類金属フッ化物が好ましい。希土類金属フッ化物としては、ＹＦ3，Ｌａ
Ｆ3，ＣｅＦ3，ＮｄＦ3，ＴｂＦ3，ＹｂＦ3，ＬｕＦ3などが好ましく、特にＹＦ3，Ｙｂ
Ｆ3が好ましい。
The alkaline earth metal fluorine compound may be a compound containing an alkaline earth metal element and a fluorine element, but an alkaline earth metal fluoride is preferable. As the alkaline earth metal fluoride, MgF 2 , CaF 2 , SrF 2 , BaF 2 and the like are preferable, and MgF 2 is particularly preferable. The rare earth metal fluorine compound may be any compound containing a rare earth metal element and a fluorine element, but rare earth metal fluorides are preferred. As rare earth metal fluorides, YF 3 , La
F 3 , CeF 3 , NdF 3 , TbF 3 , YbF 3 , LuF 3 and the like are preferable, and YF 3 , Yb are particularly preferable.
F 3 is preferred.
本発明の接合材組成物は、酸化アルミニウムを、窒化アルミニウム原料に含まれるＯ元素の含有量をＡｌ2Ｏ3に換算した値を含めて、接合材組成物全体に対して、０．４〜６０質量％含有していてもよい。この数値範囲であれば、十分な量の液相が生成し、接合材組成物中の窒化アルミニウムの焼結が進み、十分な接合強度を有する接合体が得られるという点で好ましい。このように酸化アルミニウムを含有する接合材組成物は、更に希土類金属酸化物を、酸化アルミニウムの含有量（窒化アルミニウム原料に含まれるＯ元素を酸化アルミニウムに換算した値を含む）に対して４０〜１５０質量％含んでいてもよい。この数値範囲であれば、十分な量の液相が生成し、接合材組成物中の窒化アルミニウムの焼結が進み、十分な接合強度を有する接合体が得られるという点で好ましい。なお、希土類金属酸化物、酸化アルミニウムは、接合過程で酸化物を形成するような前駆体物質として含有されてもよい。 The bonding material composition of the present invention includes aluminum oxide, the value obtained by converting the content of the O element contained in the aluminum nitride raw material into Al 2 O 3 , and is 0.4 to You may contain 60 mass%. This numerical range is preferable in that a sufficient amount of liquid phase is generated, sintering of aluminum nitride in the bonding material composition proceeds, and a bonded body having sufficient bonding strength can be obtained. As described above, the bonding material composition containing aluminum oxide further contains rare earth metal oxides in an amount of 40 to 40 with respect to the content of aluminum oxide (including a value obtained by converting O element contained in the aluminum nitride raw material into aluminum oxide). It may contain 150% by mass. This numerical range is preferable in that a sufficient amount of liquid phase is generated, sintering of aluminum nitride in the bonding material composition proceeds, and a bonded body having sufficient bonding strength can be obtained. The rare earth metal oxide and aluminum oxide may be contained as a precursor material that forms an oxide in the bonding process.
本発明の窒化アルミニウム接合体は、窒化アルミニウム焼結体同士を接合層を介して接合した窒化アルミニウム接合体であって、その接合層は、結晶相としてＡｌＮのほかに、アルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方を含むものである。本発明の窒化アルミニウム接合体は、別の視点で捉えると、窒化アルミニウム焼結体同士を接合層を介して接合した窒化アルミニウム接合体であって、前記窒化アルミニウム焼結体は、前記接合層との界面に、窒化アルミニウム焼結体に含まれる酸化物と前記接合層になる前の接合材組成物に含まれるフッ素化合物との反応層を有するものである。こうした接合体は、希土類金属酸化物を含む窒化アルミニウム焼結体同士の間に本発明の第１の接合材組成物を挟み込んで接合荷重を加えた状態で、比較的低温（例えば１３５０℃とか１４００℃とか１４５０℃）で焼成することにより、得られる。あるいは、希土類金属酸化物を含まない窒化アルミニウム焼結体と希土類金属酸化物を含んでいてもよい窒化アルミニウム焼結体との間に本発明の第２の接合材組成物を挟み込んで接合荷重を加え
た状態で、比較的低温（例えば１３５０℃とか１４００℃とか１４５０℃）で焼成することにより、得られる。
The aluminum nitride bonded body of the present invention is an aluminum nitride bonded body in which aluminum nitride sintered bodies are bonded to each other through a bonding layer, and the bonding layer includes an alkaline earth metal fluorine compound in addition to AlN as a crystal phase. And at least one of rare earth metal fluorine compounds. From another viewpoint, the aluminum nitride bonded body of the present invention is an aluminum nitride bonded body in which aluminum nitride sintered bodies are bonded to each other via a bonding layer, and the aluminum nitride sintered body includes the bonding layer and the aluminum nitride bonded body. The reaction layer of the oxide contained in the aluminum nitride sintered body and the fluorine compound contained in the bonding material composition before becoming the bonding layer is provided at the interface. Such a bonded body has a relatively low temperature (for example, 1350 ° C. or 1400 ° C.) in a state where a bonding load is applied by sandwiching the first bonding material composition of the present invention between aluminum nitride sintered bodies containing rare earth metal oxides. Or 1450 ° C.). Alternatively, the second bonding material composition of the present invention is sandwiched between an aluminum nitride sintered body that does not contain a rare earth metal oxide and an aluminum nitride sintered body that may contain a rare earth metal oxide. It is obtained by baking at a relatively low temperature (for example, 1350 ° C., 1400 ° C., or 1450 ° C.) in the added state.
本発明の窒化アルミニウム接合体において、アルカリ土類金属フッ素化合物はアルカリ土類金属酸フッ化物であってもよい。また、希土類金属フッ素化合物は希土類金属酸フッ化物であってもよい。希土類金属酸フッ化物としては、ＹＯＦ，ＬａＯＦ，ＣｅＯＦ，ＮｄＯＦ，ＴｂＯＦ，ＹｂＯＦ，ＬｕＯＦなどが好ましく、特にＹＯＦ，ＹｂＯＦが好ましい。 In the aluminum nitride joined body of the present invention, the alkaline earth metal fluorine compound may be an alkaline earth metal oxyfluoride. The rare earth metal fluorine compound may be a rare earth metal oxyfluoride. As the rare earth metal oxyfluoride, YOF, LaOF, CeOF, NdOF, TbOF, YbOF, LuOF and the like are preferable, and YOF and YbOF are particularly preferable.
本発明の窒化アルミニウム接合体において、接合層は、結晶相としてアルカリ土類金属−アルミニウム酸化物及び希土類金属−アルミニウム酸化物の少なくとも一方を含んでいてもよい。アルカリ土類金属−アルミニウム酸化物は、ＭｇＡｌ2Ｏ4が好ましい。 In the aluminum nitride bonded body of the present invention, the bonding layer may contain at least one of alkaline earth metal-aluminum oxide and rare earth metal-aluminum oxide as a crystal phase. The alkaline earth metal-aluminum oxide is preferably MgAl 2 O 4 .
本発明の窒化アルミニウム接合体は、接合強度が２００ＭＰａ以上であることが好ましい。こうすれば、種々の半導体製造装置用部材に適用することができる。半導体製造装置用部材としては、例えば、半導体製造装置に用いられる静電チャックやサセプター、ヒーター、プレート、内壁材、監視窓、マイクロ波導入窓、マイクロ波結合用アンテナなどが挙げられる。 The aluminum nitride bonded body of the present invention preferably has a bonding strength of 200 MPa or more. If it carries out like this, it can apply to various members for semiconductor manufacturing apparatuses. Examples of the semiconductor manufacturing apparatus member include an electrostatic chuck and a susceptor, a heater, a plate, an inner wall material, a monitoring window, a microwave introduction window, and a microwave coupling antenna used in the semiconductor manufacturing apparatus.
本発明の窒化アルミニウム接合体の製法は、希土類金属酸化物を含む窒化アルミニウム焼結体同士の間に、上述した本発明の接合材組成物を挟み込んで接合荷重を加えた状態で、１４５０℃以下の温度で加熱することにより、窒化アルミニウム焼結体同士を接合した窒化アルミニウム接合体を製造するものである。例えば、（１）希土類金属酸化物を含む窒化アルミニウム焼結体同士の間に本発明の第１の接合材組成物を挟み込んで接合荷重を加えた状態で、１４５０℃以下の比較的低温（例えば１３５０℃とか１４００℃とか１４５０℃）で焼成するか、あるいは、（２）希土類金属酸化物を含まない窒化アルミニウム焼結体と希土類金属酸化物を含んでいてもよい窒化アルミニウム焼結体との間に本発明の第２の接合材組成物を挟み込んで接合荷重を加えた状態で、１４５０℃の比較的低温（例えば１３５０℃とか１４００℃とか１４５０℃）で焼成することにより、窒化アルミニウム焼結体同士を接合した窒化アルミニウム接合体を製造することができる。 The method for producing an aluminum nitride joined body of the present invention is performed at 1450 ° C. or less in a state where a joining load is applied by sandwiching the above-described joining material composition of the present invention between aluminum nitride sintered bodies containing rare earth metal oxides. By heating at this temperature, an aluminum nitride bonded body in which the aluminum nitride sintered bodies are bonded to each other is manufactured. For example, (1) the first bonding material composition of the present invention is sandwiched between sintered aluminum nitrides containing rare earth metal oxides and a bonding load is applied, and a relatively low temperature of 1450 ° C. or lower (for example, Firing at 1350 ° C., 1400 ° C., or 1450 ° C.), or (2) between an aluminum nitride sintered body that does not contain a rare earth metal oxide and an aluminum nitride sintered body that may contain a rare earth metal oxide. By sintering at a relatively low temperature of 1450 ° C. (for example, 1350 ° C., 1400 ° C., or 1450 ° C.) in a state in which the second bonding material composition of the present invention is sandwiched and a bonding load is applied, an aluminum nitride sintered body An aluminum nitride joined body obtained by joining together can be manufactured.
ここで、接合荷重は、１００ｋｇｆ／ｃｍ2以下であることが好ましく、１０〜７０ｋ
ｇｆ／ｃｍ2であることがより好ましい。温度は、１４５０℃以下が好ましく、１３５０
〜１４５０℃がより好ましい。このような条件で接合することにより、得られる窒化アルミニウム接合体は十分な接合強度を有し、しかも接合前後で窒化アルミニウム焼結体が熱変形することがなく元の形状が維持される。また、塩化アンモニウムなどの厄介なガスも発生しない。
Here, the bonding load is preferably 100 kgf / cm 2 or less, and 10 to 70 k.
More preferably, it is gf / cm 2 . The temperature is preferably 1450 ° C. or lower, and 1350
˜1450 ° C. is more preferable. By joining under such conditions, the obtained aluminum nitride joined body has sufficient joining strength, and the original shape is maintained without the aluminum nitride sintered body being thermally deformed before and after joining. Moreover, troublesome gas such as ammonium chloride is not generated.
［実験例１〜１１］
（窒化アルミニウム焼結体）
市販の純度９９％以上（酸素含有量を除く）の窒化アルミニウム粉末１００質量部に、焼結助剤として酸化イットリウム５質量部を加え、ボールミルを用いて混合した。得られた混合粉末に、バインダーを添加し、噴霧造粒法により造粒した。得られた造粒粉を金型成形により板状に成形した。得られた板状の成形体を窒素ガス中でホットプレス法により、圧力を加えた状態で、１８５０℃で４時間焼成し、窒化アルミニウム焼結体を得た。得られた窒化アルミニウム焼結体から、直径５０ｍｍ×厚み１０ｍｍのサイズで窒化アルミニウム焼結体テストピースを切り出した。なお、接合面の表面粗さ（Ｒａ）は１μｍ以下に仕上げた。また、純度の単位は質量％であるが、便宜上、単に％と表記した。
[Experimental Examples 1 to 11]
(Sintered aluminum nitride)
5 parts by mass of yttrium oxide as a sintering aid was added to 100 parts by mass of commercially available aluminum nitride powder having a purity of 99% or more (excluding the oxygen content), and mixed using a ball mill. A binder was added to the obtained mixed powder and granulated by a spray granulation method. The obtained granulated powder was molded into a plate shape by mold molding. The obtained plate-like molded body was fired at 1850 ° C. for 4 hours in a nitrogen gas by a hot press method under a pressure, thereby obtaining an aluminum nitride sintered body. From the obtained aluminum nitride sintered body, an aluminum nitride sintered body test piece was cut out in a size of diameter 50 mm × thickness 10 mm. The surface roughness (Ra) of the joint surface was finished to 1 μm or less. Moreover, the unit of purity is mass%, but is simply expressed as% for convenience.
（接合材組成物）
窒化アルミニウム原料として、表１に示すＮｏ．１〜４のものを用意した。Ｎｏ．１は市販の窒化アルミニウム粉末（粒径０．８μｍ、酸素含有量４．８質量％）、Ｎｏ．２は市販の窒化アルミニウム粉末（粒径１．２μｍ、酸素含有量０．８質量％）、Ｎｏ．３はＮｏ．２の窒化アルミニウム粉末をボールミルで粉砕したもの（粒径０．７μｍ、酸素含有量３．９質量％）、Ｎｏ．４はＮｏ．３の窒化アルミニウム粉末を大気炉で８５０℃で２時間加熱したものを用いた。窒化アルミニウム原料の酸素量は、不活性ガス融解−赤外線吸収法により測定した。そして、窒化アルミニウム原料と、市販のフッ化マグネシウム（純度９９．９％以上）もしくは市販のフッ化イットリウム（純度９９．９％以上）とを、表２及び表３の実験例１〜１１の接合材組成物仕込量の欄に示す質量％となるように秤量し、アルミナ乳鉢を用いて混合し、接合材組成物（混合粉末）を得た。なお、表２及び表３の接合材組成物換算量（質量％）は、窒化アルミニウム原料に含まれるＯ元素がすべてＡｌ2Ｏ3として存在しているものとして換算した値である。
(Bonding material composition)
As the aluminum nitride raw material, No. 1 shown in Table 1 was used. 1-4 were prepared. No. No. 1 is a commercially available aluminum nitride powder (particle size 0.8 μm, oxygen content 4.8 mass%), No. 1 No. 2 is a commercially available aluminum nitride powder (particle size 1.2 μm, oxygen content 0.8% by mass). 3 is No.3. No. 2 aluminum nitride powder pulverized with a ball mill (particle size 0.7 μm, oxygen content 3.9 mass%), No. 2 4 is No.4. No. 3 aluminum nitride powder heated in an atmospheric furnace at 850 ° C. for 2 hours was used. The amount of oxygen in the aluminum nitride raw material was measured by an inert gas melting-infrared absorption method. And joining of the aluminum nitride raw material and commercially available magnesium fluoride (purity 99.9% or more) or commercially available yttrium fluoride (purity 99.9% or more) in Experimental Examples 1 to 11 in Tables 2 and 3 It weighed so that it might become the mass% shown in the column of material composition preparation amount, and mixed using the alumina mortar, and the joining material composition (mixed powder) was obtained. The bonding material composition equivalent amount in Table 2 and Table 3 (wt%) is a value converted as O elements contained in the aluminum nitride raw material is present as all Al 2 O 3.
（接合材ペースト）
エスレックＡＳ（積水化学製）をテルピネオールに溶解させ４５質量％溶液としたものをバインダーとして、接合材組成物に対して３０％の質量比で加え、アルミナ乳鉢で混合することにより、接合材ペーストを得た。
(Joint paste)
A bonding material paste was prepared by adding a 45% by mass solution of ESREC AS (manufactured by Sekisui Chemical Co., Ltd.) to terpineol, using a binder at a mass ratio of 30% to the bonding material composition and mixing in an alumina mortar. Obtained.
（接合）
接合材ペーストを、窒化アルミニウム焼結体テストピースの接合面の片側にスクリーン印刷で塗布し、乾燥し、接合材ペーストの溶媒を揮発させることにより、接合材組成物をテストピースに固着させた。接合材ペーストの窒化アルミニウム焼結体への塗布量は、乾燥後で５〜１５ｍｇ／ｃｍ2となるようにした。窒化アルミニウム焼結体の接合面同士を
貼り合わせ、窒素ガス中で、接合温度（最高温度）１４００℃で２時間保持した。昇温速度は１０℃／分とし、窒素ガスは９００℃から導入した。又、接合面と垂直な方向から窒化アルミニウム焼結体同士を押しつけるように加圧した。加圧は、圧力４０ｋｇｆ／ｃｍ2又は２０ｋｇｆ／ｃｍ2で常温から開始し、接合温度１４００℃で保持している間続け、常温に冷却した時点で終了した。このようにして窒化アルミニウム接合体を得た。
(Joining)
The bonding material paste was applied to one side of the bonding surface of the aluminum nitride sintered body test piece by screen printing, dried, and the bonding material paste was volatilized to fix the bonding material composition to the test piece. The amount of the bonding material paste applied to the aluminum nitride sintered body was set to 5 to 15 mg / cm 2 after drying. The joining surfaces of the aluminum nitride sintered body were bonded together and held in a nitrogen gas at a joining temperature (maximum temperature) of 1400 ° C. for 2 hours. The heating rate was 10 ° C./min, and nitrogen gas was introduced from 900 ° C. Moreover, it pressed so that aluminum nitride sintered compact might be pressed from the direction perpendicular | vertical to a joining surface. The pressurization was started from room temperature at a pressure of 40 kgf / cm 2 or 20 kgf / cm 2 , continued while maintaining the bonding temperature at 1400 ° C., and ended when the temperature was cooled to room temperature. In this way, an aluminum nitride joined body was obtained.
（評価項目）
得られた窒化アルミニウム接合体について、接合強度、微構造、接合層の結晶相を評価
した。
・接合強度
接合強度は、ＪＩＳ１６０１に従い、室温で４点曲げ強度を測定した。抗折棒は、得られた窒化アルミニウム接合体から、接合界面が中心となるように約２０ｍｍ長さ（ハーフサイズ）に切り出し作製した。実験例１〜１１の接合強度を表２及び表３に示す。なお、接合強度の測定数は４〜８本とし、その平均値を記した。
・微構造
微構造は、得られた窒化アルミ接合体の微構造写真より評価した。具体的には、接合層を含む面を研磨し、走査型電子顕微鏡（ＳＥＭ）により観察した。ＳＥＭ観察は、フィリップス社製ＸＬ３０を用い、加速電圧２０ｋＶ、スポットサイズ４．０にて行った。代表例として、実験例１の微構造写真を図１に、その模式図を図２に、実験例１０の微構造写真を図３に示す。
・接合層の結晶相
接合層の結晶相は、微小部Ｘ線回折より測定した。測定装置はBrukerAXS社製D8DISCOVERμHR Hybridを用いた。実験例１〜１１の接合層の結晶相を表２及び表３に示す。
・反応層の結晶相
反応層の結晶相は、接合層の結晶相と同じ方法により測定した。実験例１〜１１の反応層の結晶相を表２及び表３に示す。
(Evaluation item)
The obtained aluminum nitride bonded body was evaluated for bonding strength, microstructure, and crystal phase of the bonding layer.
-Joint strength The joint strength measured 4 point bending strength at room temperature according to JIS1601. The anti-folding rod was cut out from the obtained aluminum nitride bonded body to a length (half size) of about 20 mm so that the bonding interface was at the center. Tables 2 and 3 show the bonding strengths of Experimental Examples 1 to 11. In addition, the number of measurements of bonding strength was 4-8, and the average value was described.
-Microstructure The micro structure was evaluated from the micro structure photograph of the obtained aluminum nitride bonded body. Specifically, the surface including the bonding layer was polished and observed with a scanning electron microscope (SEM). SEM observation was performed using Philips XL30 at an acceleration voltage of 20 kV and a spot size of 4.0. As representative examples, a microstructure photograph of Experimental Example 1 is shown in FIG. 1, a schematic diagram thereof is shown in FIG. 2, and a microstructure photograph of Experimental Example 10 is shown in FIG.
-Crystal phase of the bonding layer The crystal phase of the bonding layer was measured by microscopic X-ray diffraction. The measuring device used was BrukerAXS D8DISCOVERμHR Hybrid. The crystal phases of the bonding layers of Experimental Examples 1 to 11 are shown in Tables 2 and 3.
-Crystal phase of the reaction layer The crystal phase of the reaction layer was measured by the same method as the crystal phase of the bonding layer. The crystal phases of the reaction layers of Experimental Examples 1 to 11 are shown in Tables 2 and 3.
（評価結果）
実験例１〜５では、Ｎｏ．１（酸素量４．８質量％）の窒化アルミニウム原料と、ＭｇＦ2原料とを含み、ＭｇＦ2原料の含有率が１０〜５０質量％の接合材組成物を調製し、その接合材組成物により窒化アルミニウム焼結体同士を接合した。そうしたところ、いずれも、接合強度が２００ＭＰａ以上である高強度の窒化アルミニウム接合体が得られた。厄介なガスの発生は見られなかった。また、窒化アルミニウム焼結体は接合前後で変形せず元の形状を維持していた。接合層の結晶相は、いずれもＡｌＮ，ＭｇＡｌ2Ｏ4及びＹＯＦであった。ＭｇＡｌ2Ｏ4やＹＯＦに含まれるＯ元素は、窒化アルミニウム原料中のＯ元素に由来するものであり、ＹＯＦに含まれるＹ元素は、主に窒化アルミニウム焼結体中の酸化イットリウムに由来するものであると推察された。
(Evaluation results)
In Experimental Examples 1-5, no. 1 and the aluminum nitride raw material (oxygen content 4.8 mass%), and a MgF 2 material, MgF 2 raw material content to prepare a bonding material composition of 10 to 50 wt%, by the bonding material composition The aluminum nitride sintered bodies were joined together. In these cases, a high-strength aluminum nitride bonded body having a bonding strength of 200 MPa or more was obtained. No troublesome gas generation was observed. In addition, the aluminum nitride sintered body was not deformed before and after joining and maintained the original shape. The crystal phase of the bonding layer was all AlN, MgAl 2 O 4 and YOF. The O element contained in MgAl 2 O 4 or YOF is derived from the O element in the aluminum nitride raw material, and the Y element contained in YOF is derived mainly from yttrium oxide in the aluminum nitride sintered body. It was guessed that.
ここで、実験例１の微構造写真（図１）について考察する。接合前の窒化アルミニウム焼結体の微構造写真は、図示しないが、全体が濃いグレーでそこに白い斑点が多数散らばっていた。濃いグレーはＡｌＮ、白い斑点はＹＡＭ（Ｙ4Ａｌ2Ｏ9）であった。ＹＡＭは
、窒化アルミニウム焼結体を製造する際に窒化アルミニウム粉末に不純物として含まれるＡｌ2Ｏ3と焼結助剤のＹ2Ｏ3とが反応して生成したものである。一方、窒化アルミニウム接合体中の窒化アルミニウム焼結体は、３層に分かれていた（図２参照）。接合層に最も近い第１層は、全体が濃いグレー（ＡｌＮ）で、そこに黒い斑点が散らばっていた。黒い斑点は、気孔であった。気孔内やその近傍には、ＭｇＡｌ2Ｏ4が存在していることを確認した。第１層に隣接する第２層は、全体が濃いグレー（ＡｌＮ）で、そこに白い斑点（ＹＡＭ）が散らばり、更に白い筋（液相が広がった部分と思われる）が見られた。第１層及び第２層を反応層と称する。第２層に隣接する第３層は、図１には写っていないが、接合前と同じ状態であり、全体が濃いグレー（ＡｌＮ）でそこに白い斑点（ＹＡＭ）が多数散らばっていた。なお、図２は、実験例１の微構造を示す模式図である。また、他の実験例の微構造も、実験例１と同様であった。
Here, the microstructure photograph (FIG. 1) of Experimental Example 1 will be considered. Although the microstructure photograph of the aluminum nitride sintered body before joining is not shown in the drawing, the whole was dark gray and many white spots were scattered there. The dark gray was AlN, and the white spots were YAM (Y 4 Al 2 O 9 ). YAM is produced by reacting Al 2 O 3 contained as an impurity in the aluminum nitride powder and Y 2 O 3 as a sintering aid when an aluminum nitride sintered body is produced. On the other hand, the aluminum nitride sintered body in the aluminum nitride joined body was divided into three layers (see FIG. 2). The first layer closest to the bonding layer was dark gray (AlN) as a whole, and black spots were scattered there. The black spots were stomatal. It was confirmed that MgAl 2 O 4 was present in the pores and in the vicinity thereof. The second layer adjacent to the first layer was dark gray (AlN) as a whole, and white spots (YAM) were scattered there, and white streaks (which seemed to have spread the liquid phase) were observed. The first layer and the second layer are called reaction layers. Although the third layer adjacent to the second layer is not shown in FIG. 1, it is in the same state as before joining, and the whole is dark gray (AlN), and many white spots (YAM) are scattered there. FIG. 2 is a schematic diagram showing the microstructure of Experimental Example 1. The microstructures of the other experimental examples were the same as those of Experimental example 1.
このような微構造が形成されたメカニズムは、以下のように推測される。まず、接合材組成物において、ＭｇＦ2を主とした液相が加熱によって生成する。その液相が窒化アル
ミニウム焼結体へ移動して粒界相のＹＡＭと反応して、新たな液相（Ｙ−Ｍｇ−Ａｌ−Ｏ−Ｆ）が生成する。この新たな液相がＡｌＮの粒界に沿って移動し、一部が接合材組成物に流入し、その流入した液相が焼結助剤として機能した結果、ＡｌＮが低温で焼結し緻密
化が促進されたと考えられる。また、ＭｇＦ2を主とした液相がＹＡＭと反応した際に、
上記液相の他にＭｇＡｌ2Ｏ4も生成し、かつ、上記反応や液相の拡散が活発であった場合、ＹＡＭが存在した場所が気孔（黒い斑点）となることで、第１層を形成したと考えられる。液相は接合層の反対側にも拡散し、第２層を形成したと考えられる。つまり、新たな液相（Ｙ−Ｍｇ−Ａｌ−Ｏ−Ｆ）が接合の重要成分である。なお、接合材組成物が同じである実験例１，３を比較すると、実験例１の接合体の方が強度が高かった。実験例１では、実験例３よりも接合荷重を高くしたため、接合材の緻密化や接合材組成物とＡｌＮ基材との反応が促進され、結果として接合強度が高まったものと推察された。
The mechanism by which such a microstructure is formed is presumed as follows. First, in the bonding material composition, a liquid phase mainly composed of MgF 2 is generated by heating. The liquid phase moves to the aluminum nitride sintered body and reacts with YAM in the grain boundary phase to generate a new liquid phase (Y—Mg—Al—O—F). This new liquid phase moves along the grain boundary of AlN, and part of it flows into the bonding material composition. As a result of the flowing liquid phase functioning as a sintering aid, AlN is sintered at a low temperature and becomes dense. It is thought that the conversion was promoted. When a liquid phase mainly composed of MgF 2 reacts with YAM,
When MgAl 2 O 4 is also generated in addition to the liquid phase, and the reaction and the diffusion of the liquid phase are active, the location where YAM is present becomes pores (black spots), and the first layer is formed. It is thought that it formed. It is considered that the liquid phase diffused to the opposite side of the bonding layer to form the second layer. That is, a new liquid phase (Y—Mg—Al—O—F) is an important component for bonding. In addition, when Experimental Examples 1 and 3 having the same bonding material composition were compared, the bonded body of Experimental Example 1 was higher in strength. In Experimental Example 1, since the bonding load was higher than in Experimental Example 3, it was speculated that the bonding material was densified and the reaction between the bonding material composition and the AlN substrate was promoted, resulting in an increase in bonding strength.
実験例６〜９では、酸素量の異なるＮｏ．２〜４（酸素量は０．８〜５．０質量％）の窒化アルミニウム原料とＭｇＦ2原料とを質量比７０：３０で含有する接合材組成物（実
験例８ではＡｌＮ原料にＡｌ2Ｏ3原料を加えたものとＭｇＦ2原料とを質量比７０：３０
で含有する接合材組成物）を調製し、その接合材組成物により窒化アルミニウム焼結体同士を接合した。そうしたところ、いずれも、接合強度が２００ＭＰａ以上である高強度の窒化アルミニウム接合体が得られた。厄介なガスの発生は見られなかった。また、窒化アルミニウム焼結体は接合前後で変形せず元の形状を維持していた。接合層の結晶相は、いずれもＡｌＮ，ＭｇＡｌ2Ｏ4及びＹＯＦであった。これらの微構造も、実験例１と同様であった。また、反応層の結晶相はいずれもＡｌＮ，ＭｇＡｌ2Ｏ4及びＹＯＦであった。これら実験例６〜９の接合体の特性評価より、接合材組成物換算量において、Ａｌ2Ｏ3の質量％が多い実験例８，９の接合強度が高い傾向が認められた。
In Experimental Examples 6 to 9, Nos. With different oxygen amounts. A bonding material composition containing 2 to 4 (oxygen amount 0.8 to 5.0 mass%) aluminum nitride raw material and MgF 2 raw material in a mass ratio of 70:30 (in Experimental Example 8, the AlN raw material contains Al 2 O The mass ratio of the three raw materials added to the MgF 2 raw material is 70:30.
The aluminum nitride sintered bodies were bonded to each other by the bonding material composition. In these cases, a high-strength aluminum nitride bonded body having a bonding strength of 200 MPa or more was obtained. No troublesome gas generation was observed. In addition, the aluminum nitride sintered body was not deformed before and after joining and maintained the original shape. The crystal phase of the bonding layer was all AlN, MgAl 2 O 4 and YOF. These microstructures were also the same as in Experimental Example 1. The crystal phase of the reaction layer was all AlN, MgAl 2 O 4 and YOF. From the characteristic evaluation of the joined bodies of Experimental Examples 6 to 9, there was a tendency that the bonding strengths of Experimental Examples 8 and 9 having a large mass percentage of Al 2 O 3 were high in terms of the bonding material composition.
実験例１０では、ＭｇＦ2原料の代わりにＹＦ3原料を用いた以外は、実験例１と同様にして窒化アルミニウム焼結体同士を接合した。そうしたところ、接合強度が３４０ＭＰａである高強度の窒化アルミニウム接合体が得られた。厄介なガスの発生は見られなかった。また、窒化アルミニウム焼結体は接合前後で変形せず元の形状を維持していた。接合層の結晶相は、ＡｌＮ及びＹＯＦであった。実験例１０では、接合荷重が４０ｋｇｆ／ｃｍ2と高かったことと、接合材組成物換算量においてＡｌ2Ｏ3量が実験例８，９と同様に多
かったことが、良好に作用したと推察された。
In Experimental Example 10, aluminum nitride sintered bodies were joined in the same manner as in Experimental Example 1 except that a YF 3 raw material was used instead of the MgF 2 raw material. As a result, a high-strength aluminum nitride bonded body having a bonding strength of 340 MPa was obtained. No troublesome gas generation was observed. In addition, the aluminum nitride sintered body was not deformed before and after joining and maintained the original shape. The crystal phase of the bonding layer was AlN and YOF. In Experimental Example 10, it was speculated that the bonding load was as high as 40 kgf / cm 2, and that the amount of Al 2 O 3 in the equivalent amount of the bonding material composition was the same as in Experimental Examples 8 and 9, which worked well. It was done.
実験例１０の微構造写真を図３に示す。実験例１０の窒化アルミニウム接合体中の窒化アルミニウム焼結体は、２層に分かれていた。接合層に近い第１層は、反応層であり、全体が濃いグレー（ＡｌＮ）で、そこに白い斑点（ＹＡＭ）が散らばり、更に白い筋（液相が固化した部分と思われる）が見られた。第１層に隣接する第２層は、接合前と同様、全体が濃いグレー（ＡｌＮ）でそこに白い斑点（ＹＡＭ）が多数散らばっていた。実験例１０では、実験例１（図１及び図２）で観察された黒い斑点状の気孔を含む相が生成しなかったため、更に高い接合強度が得られたと推察された。 A microstructure photograph of Experimental Example 10 is shown in FIG. The aluminum nitride sintered body in the aluminum nitride joined body of Experimental Example 10 was divided into two layers. The first layer close to the bonding layer is a reaction layer, which is dark gray (AlN) as a whole, with white spots (YAM) scattered there, and white streaks (which seems to have solidified the liquid phase). It was. The second layer adjacent to the first layer was dark gray (AlN) as a whole, and many white spots (YAM) were scattered there as before the bonding. In Experimental Example 10, since the phase including the black spotted pores observed in Experimental Example 1 (FIGS. 1 and 2) was not generated, it was assumed that higher bonding strength was obtained.
このような微構造が形成されたメカニズムは、以下のように推察される。まず、接合材組成物中のＹＦ3が、同じく接合材組成物中のＡｌＮ原料に不純物として存在するＡｌ2Ｏ3と反応して、液相（Ｙ−Ａｌ−Ｏ−Ｆ）が生成した。生成した液相は一部が窒化アルミ
ニウム焼結体に拡散し、第１層を形成し、残った液相は接合材に留まり、ＡｌＮの焼結助剤として機能した結果、ＡｌＮが低温で焼結し緻密化が促進されたと考えられる。実験例１０では、実験例１の場合と異なり、接合材組成物中にＭｇＦ2が存在しないため、接合
材組成物中の成分とＡｌＮ基材中のＹＡＭとが著しく反応することがなく、その結果、気孔の存在する相が生成せず、高い接合強度が得られたと推察された。
The mechanism by which such a microstructure is formed is inferred as follows. First, YF 3 in the bonding material composition reacted with Al 2 O 3 present as an impurity in the AlN raw material in the bonding material composition, and a liquid phase (Y—Al—O—F) was generated. Part of the generated liquid phase diffuses into the aluminum nitride sintered body to form the first layer, and the remaining liquid phase remains in the bonding material and functions as a sintering aid for AlN. It is thought that densification was promoted. In Experimental Example 10, unlike in Experimental Example 1, since MgF 2 is not present in the bonding material composition, the components in the bonding material composition and the YAM in the AlN base material do not react significantly. As a result, it was presumed that a phase having pores was not generated and a high bonding strength was obtained.
実験例１１では、接合温度を１２００℃に下げた以外は実験例３と同じ条件で接合を試みたが、接合できなかった。これは、接合温度が低くて十分な液相が生成せず、その結果、接合材組成物中の窒化アルミニウムの焼結が不十分であったためである。 In Experimental Example 11, bonding was attempted under the same conditions as in Experimental Example 3 except that the bonding temperature was lowered to 1200 ° C., but could not be bonded. This is because the bonding temperature is low and a sufficient liquid phase is not generated, and as a result, sintering of aluminum nitride in the bonding material composition is insufficient.
［実験例１２〜１４］
（窒化アルミニウム焼結体）
実験例１〜１１と同じ窒化アルミニウム焼結体テストピースを用意した。
[Experimental Examples 12 to 14]
(Sintered aluminum nitride)
The same aluminum nitride sintered compact test piece as Experimental Examples 1-11 was prepared.
（接合材組成物）
表１に示すＮｏ．１（酸素量４．８質量％）の窒化アルミニウム原料と、市販のフッ化マグネシウム原料（純度９９．９％以上）と、市販のイットリア原料（純度９９．９％以上）と、市販のアルミナ原料（純度９９．９％以上）とを、表４の実験例１２〜１４の接合材組成物仕込量の欄に示す質量％となるように秤量し、アルミナ乳鉢を用いて混合し、接合材組成物（混合粉末）を得た。なお、表４の接合材組成物換算量（質量％）は、窒化アルミニウム原料に含まれるＯ元素がすべてＡｌ2Ｏ3として存在しているものとして換算した値である。
(Bonding material composition)
No. shown in Table 1. 1 (oxygen 4.8 mass%) aluminum nitride raw material, commercially available magnesium fluoride raw material (purity 99.9% or higher), commercially available yttria raw material (purity 99.9% or higher), and commercially available alumina raw material (Purity 99.9% or more) is weighed so as to be the mass% shown in the column of the amount of the bonding material composition charged in Experimental Examples 12 to 14 in Table 4, mixed using an alumina mortar, and the bonding material composition A product (mixed powder) was obtained. In addition, the bonding material composition conversion amount (mass%) in Table 4 is a value converted assuming that all of the O elements contained in the aluminum nitride raw material are present as Al 2 O 3 .
上述した実験例３，６，７，９では、窒化アルミニウム原料に含まれる酸素量を変化させることにより接合材組成物中の酸素量を変化させたが、実験例１２〜１４では、窒化アルミニウム原料に含まれる酸素量を一定とし、イットリア原料やアルミナ原料の添加量を変化させることにより接合材組成物中の酸素量を変化させた。 In Experimental Examples 3, 6, 7, and 9 described above, the amount of oxygen in the bonding material composition was changed by changing the amount of oxygen contained in the aluminum nitride raw material. In Experimental Examples 12 to 14, the aluminum nitride raw material was changed. The amount of oxygen in the bonding material composition was changed by changing the amount of yttria raw material or alumina raw material added while keeping the amount of oxygen contained in the material constant.
（接合材ペースト）
実験例１〜１１と同様にして、接合材ペーストを得た。
(Joint paste)
In the same manner as in Experimental Examples 1 to 11, a bonding material paste was obtained.
（接合）
実験例１〜１１と同様にして、窒化アルミニウム接合体を得た。接合荷重は２０ｋｇｆ／ｃｍ2とした。
(Joining)
Aluminum nitride joined bodies were obtained in the same manner as in Experimental Examples 1 to 11. The bonding load was 20 kgf / cm 2 .
（評価項目及び評価結果）
得られた窒化アルミニウム接合体について、実験例１〜１１と同様にして、接合強度、微構造、接合層の結晶相を評価した。そうしたところ、いずれも、接合強度が２５０ＭＰａ以上である高強度の窒化アルミニウム接合体が得られた。厄介なガスの発生は見られなかった。また、窒化アルミニウム焼結体は接合前後で変形せず元の形状を維持していた。接合体の微構造を観察すると、反応層の気孔量が減少しており、そのため高強度の窒化アルミニウム接合体が得られたと考えられた。接合層の結晶相は、いずれもＡｌＮ，ＭｇＡｌ2Ｏ4及びＹＯＦであった。また、反応層の結晶相はいずれもＡｌＮ，ＭｇＡｌ2Ｏ4及びＹＯＦであった。これら実験例１２〜１４の接合材組成物と接合強度との関係を考察すると、接合材組成物換算量における「Ａｌ2Ｏ3量に対するＹ2Ｏ3量」に関し、接合強度が最も高くなるのは、実験例１２の９８．５質量％の近傍であった（図４参照）。
(Evaluation items and evaluation results)
About the obtained aluminum nitride joined body, it carried out similarly to Experimental Examples 1-11, and evaluated joint strength, the microstructure, and the crystal phase of the joining layer. As a result, a high-strength aluminum nitride bonded body having a bonding strength of 250 MPa or more was obtained. No troublesome gas generation was observed. In addition, the aluminum nitride sintered body was not deformed before and after joining and maintained the original shape. When the microstructure of the joined body was observed, the amount of pores in the reaction layer was reduced, and it was considered that a high-strength aluminum nitride joined body was obtained. The crystal phase of the bonding layer was all AlN, MgAl 2 O 4 and YOF. The crystal phase of the reaction layer was all AlN, MgAl 2 O 4 and YOF. Considering the relationship between the bonding material compositions and the bonding strengths of these experimental examples 12 to 14, the bonding strength becomes the highest with respect to the “Y 2 O 3 amount relative to the Al 2 O 3 amount” in the bonding material composition equivalent amount. Was in the vicinity of 98.5% by mass of Experimental Example 12 (see FIG. 4).
以上のことから、接合材組成物中の酸素量の調整は、実験例３，６，７，９のように窒化アルミニウム原料に含まれる酸素量を調整することで行ってもよいし、実験例１２〜１４のように窒化アルミニウム原料とは別に添加する酸化物の量を調整することで行ってもよいことがわかった。 From the above, the adjustment of the amount of oxygen in the bonding material composition may be performed by adjusting the amount of oxygen contained in the aluminum nitride raw material as in Experimental Examples 3, 6, 7, and 9. It turned out that you may carry out by adjusting the quantity of the oxide added separately from an aluminum nitride raw material like 12-14.
［実験例１５〜２２］
実験例１５〜２２では、実験例１と同じ窒化アルミニウム焼結体テストピースを用意し、表５に示した接合材組成物の仕込量及び換算量、接合条件で窒化アルミニウム接合体を作製し、特性を評価した。表５には、各実験例の接合強度も示した。なお、実験例１５，１６，１８〜２１で使用したＡｌＮ原料Ｎｏ．５は、ＡｌＮ原料Ｎｏ．２をボールミルで粉砕したものであり、酸素量は２．９４質量％、粒径は０．８μｍであった（ＡｌＮ原料Ｎｏ．３よりも粒径が大きいため、酸素量が少ない）。また、実験例１５〜２２のいずれも１２６０℃で３０分間保持した後、接合温度である１４３０℃に昇温し、所定時間の保持によって強固に接合した接合体を得た。表５には記載していないが、接合体の接合層、反応層の結晶相は、すべて実験例１２と同様の構成であった。
[Experimental Examples 15 to 22]
In Experimental Examples 15 to 22, the same aluminum nitride sintered body test piece as in Experimental Example 1 was prepared, and an aluminum nitride bonded body was prepared with the charging amount and conversion amount of the bonding material composition shown in Table 5 and bonding conditions. The characteristics were evaluated. Table 5 also shows the bonding strength of each experimental example. In addition, the AlN raw material No. used in Experimental Examples 15, 16, 18 to 21 was used. 5 is an AlN raw material No. No. 2 was pulverized with a ball mill, and the amount of oxygen was 2.94% by mass and the particle size was 0.8 μm (the particle size is larger than that of AlN raw material No. 3, so the amount of oxygen is small). Moreover, after hold | maintaining all of Experimental Examples 15-22 for 30 minutes at 1260 degreeC, it heated up to 1430 degreeC which is joining temperature, and obtained the joined body firmly joined by holding | maintenance for predetermined time. Although not described in Table 5, all of the crystal phases of the bonding layer and the reaction layer of the bonded body had the same configuration as in Experimental Example 12.
実験例１５〜２０は、接合荷重を実験例１２〜１４と同じく２０ｋｇｆ／ｃｍ2とした
が、接合温度を１４３０℃と実験例１２〜１４より高くし、保持時間を１０時間と実験例１２〜１４より長くした。これらの接合体の強度は２７０〜３２６ＭＰａであり、全般的に実験例１２〜１４（２５０〜３１０ＭＰａ）より高かった。実験例１５〜２０は、接合温度を高くし、保持時間も長くしたため、接合材内での反応や接合材とＡｌＮ焼結体との反応が十分進み、高強度の接合体が得られたと推察された。
In Experimental Examples 15 to 20, the bonding load was set to 20 kgf / cm 2 as in Experimental Examples 12 to 14, but the bonding temperature was 1430 ° C., higher than Experimental Examples 12 to 14, and the holding time was 10 hours. It was longer than 14. The strengths of these joined bodies were 270 to 326 MPa, and were generally higher than those of Experimental Examples 12 to 14 (250 to 310 MPa). In Experimental Examples 15 to 20, since the bonding temperature was increased and the holding time was increased, the reaction in the bonding material and the reaction between the bonding material and the AlN sintered body proceeded sufficiently, and it was assumed that a high-strength bonded body was obtained. It was done.
実験例２１，２２では、接合荷重を６０ｋｇｆ／ｃｍ2に高めた一方、保持時間を２時
間に短くした。これらの接合強度は、それぞれ３２８，３２６ＭＰａであり、最も高い強度が安定的に得られた。実験例２１，２２では、実験例１５〜２０と比べて接合条件を高荷重とし短時間保持とすることで、接合材組成物内での反応や接合材組成物とＡｌＮ焼結体との反応が進み、高強度の接合体が得られたと推察された。
In Experimental Examples 21 and 22, the bonding load was increased to 60 kgf / cm 2 while the holding time was shortened to 2 hours. These bonding strengths were 328 and 326 MPa, respectively, and the highest strength was stably obtained. In Experimental Examples 21 and 22, the reaction in the bonding material composition and the reaction between the bonding material composition and the AlN sintered body are performed by setting the bonding condition to be a high load and holding for a short time as compared with Experimental Examples 15 to 20. It was speculated that a high-strength bonded body was obtained.
図４は、実験例１２〜２０の接合材組成物換算量における「Ａｌ2Ｏ3量に対するＹ2Ｏ3量」（以下、Ｙ2Ｏ3／Ａｌ2Ｏ3と表す）に対する、接合強度の関係をプロットしたものである。図４では、実験例１２〜１４のグループと実験例１５〜２０のグループに分けてプロットした。実験例１２〜１４は、接合温度１４００℃、保持時間２時間、接合荷重２０ｋｇ／ｃｍ2という共通の接合条件を採用したため同じグループとした。また、実験例１
５〜２０は、接合温度１４３０℃、保持時間１０時間、接合荷重２０ｋｇ／ｃｍ2という
共通の接合条件を採用したため同じグループとした。図４より、実験例１２〜１４では、Ｙ2Ｏ3／Ａｌ2Ｏ3＝４０〜１５０（質量％）の場合に２５０ＭＰａ以上の高強度な接合体が得られた。また、実験例１５〜２０でも、Ｙ2Ｏ3／Ａｌ2Ｏ3＝４０〜１５０（質量％）の場合に３００ＭＰａ以上の一層高強度な接合体が得られた。このことから、接合条件によらず、Ｙ2Ｏ3／Ａｌ2Ｏ3＝４０〜１５０（質量％）の場合に高強度な接合体が得られることが分かった。
FIG. 4 shows the bonding strength with respect to “the amount of Y 2 O 3 relative to the amount of Al 2 O 3 ” (hereinafter referred to as Y 2 O 3 / Al 2 O 3 ) in the equivalent amount of the bonding material composition of Experimental Examples 12 to 20. The relationship is plotted. In FIG. 4, the plots were divided into groups of Experimental Examples 12-14 and Experimental Examples 15-20. Since Experimental Examples 12-14 employ | adopted common joining conditions with joining temperature 1400 degreeC, holding time 2 hours, and joining load 20kg / cm < 2 >, it was set as the same group. Experimental Example 1
Nos. 5 to 20 were in the same group because the common bonding conditions of a bonding temperature of 1430 ° C., a holding time of 10 hours, and a bonding load of 20 kg / cm 2 were adopted. 4, in Experimental Examples 12 to 14, high strength bonded bodies of 250 MPa or more were obtained when Y 2 O 3 / Al 2 O 3 = 40 to 150 (mass%). Also in Experimental Examples 15 to 20, a bonded body having a higher strength of 300 MPa or more was obtained when Y 2 O 3 / Al 2 O 3 = 40 to 150 (mass%). From this, it was found that a high-strength bonded body was obtained when Y 2 O 3 / Al 2 O 3 = 40 to 150 (mass%) regardless of bonding conditions.
なお、接合のメカニズムについては、次のように推察される。実験例１２〜２２において、接合材として、窒化アルミニウム焼結体に挟み込まれた成分は、ＡｌＮ，ＭｇＦ2，
Ｙ2Ｏ3及びＡｌ2Ｏ3であるが、この中でＡｌＮは主に接合層に留まり、接合層の骨材として機能している成分である。一方、ＭｇＦ2，Ｙ2Ｏ3及びＡｌ2Ｏ3（ＡｌＮ粉末が有する
酸素成分由来のＡｌ2Ｏ3を含む）は、先に示した実験例１〜１１と同様に、加熱によって液相を形成し、骨材として導入したＡｌＮ成分を焼結し、接合層を緻密化していくと共に、基材のＡｌＮとも一部が反応し、基材内に拡散することによって界面で接合していく。接合材組成物による接合は、このような反応と拡散とによって実現されると考えられる。このとき、ＭｇＦ2やＹＦ3などのフッ化物は、それ自身の融点が１２４８℃，１１５２℃程度と比較的低く、接合の最高温度に達する前に十分に液相化していると考えられる。また、更にその液相成分と他の接合材組成物の成分との反応が十分に生じると考えられ、他の接合材組成物の成分の少なくとも一部が液相に溶け込むために重要となっているのが、希土類金属酸化物とＡｌ2Ｏ3成分との割合であると考えられる。
The bonding mechanism is presumed as follows. In Experimental Examples 12 to 22, as the bonding material, the components sandwiched between the aluminum nitride sintered bodies are AlN, MgF 2 ,
Among them, Y 2 O 3 and Al 2 O 3 , but AlN is a component that mainly stays in the bonding layer and functions as an aggregate of the bonding layer. On the other hand, MgF 2 , Y 2 O 3 and Al 2 O 3 (including Al 2 O 3 derived from the oxygen component of the AlN powder) change the liquid phase by heating, as in Experimental Examples 1 to 11 shown above. The AlN component formed and sintered as an aggregate is sintered to densify the bonding layer, and a part of the substrate reacts with AlN and diffuses into the substrate to bond at the interface. It is considered that the bonding with the bonding material composition is realized by such reaction and diffusion. At this time, fluorides such as MgF 2 and YF 3 have relatively low melting points of about 1248 ° C. and 1152 ° C., and are considered to be sufficiently liquid phase before reaching the maximum junction temperature. Further, it is considered that the reaction between the liquid phase component and the other bonding material composition is sufficiently generated, and it is important for at least a part of the other bonding material composition components to be dissolved in the liquid phase. It is considered that the ratio between the rare earth metal oxide and the Al 2 O 3 component is present.
［実験例２３〜２５］
実験例２３〜２５は、ＡｌＮ焼結体の条件を変えて実施した例である。これらＡｌＮ焼結体の作製は、以下で断りの無い条件は、実験例１と同様にした。実験例２３，２４では、焼結助剤として加える酸化イットリウムの量をそれぞれ０．１質量部、０．５質量部とし、焼成温度をいずれも１９００℃としてＡｌＮ焼結体を作製した。次に、実験例１と同様なテストピースに加工し、実験例２１と同様な接合材組成物仕込量及び接合条件でＡｌＮ接合体を作製し、接合強度を評価した。その結果、実験例２３が３０５ＭＰａ、実験例２４が３１７ＭＰａとなり、いずれも十分高い接合強度を得た。実験例２５では、焼結助剤として酸化イッテルビウムを用い、添加量を５重量部として、ＡｌＮ焼結体を作製し、テストピースを用意した。次に、実験例２１と同様な条件で接合体を作製し、３３０ＭＰａの高い接合強度を得た。
[Experimental Examples 23 to 25]
Experimental Examples 23 to 25 are examples performed by changing the conditions of the AlN sintered body. The production of these AlN sintered bodies was carried out in the same manner as in Experimental Example 1 unless otherwise specified. In Experimental Examples 23 and 24, the amounts of yttrium oxide added as a sintering aid were 0.1 parts by mass and 0.5 parts by mass, respectively, and the firing temperature was 1900 ° C. to produce an AlN sintered body. Next, it processed into the test piece similar to Experimental example 1, the AlN bonded body was produced with the same joining material composition preparation amount and bonding conditions as Experimental example 21, and the joint strength was evaluated. As a result, Experimental Example 23 was 305 MPa and Experimental Example 24 was 317 MPa, and both obtained sufficiently high bonding strength. In Experimental Example 25, ytterbium oxide was used as a sintering aid, and the addition amount was 5 parts by weight. An AlN sintered body was prepared, and a test piece was prepared. Next, a joined body was produced under the same conditions as in Experimental Example 21, and a high joining strength of 330 MPa was obtained.
これらの結果より、実験例２３，２４のようにＡｌＮ焼結体中の希土類金属酸化物量が異なる場合であっても、あるいは、実験例２５のようにＡｌＮの焼結助剤として用いた希土類金属酸化物と接合材に用いた希土類金属酸化物とが異なる場合であっても、本発明の接合材組成物及びその製法は有効に作用することが分かった。 From these results, even when the amount of rare earth metal oxide in the AlN sintered body is different as in Experimental Examples 23 and 24, or the rare earth metal used as a sintering aid for AlN as in Experimental Example 25. Even when the oxide and the rare earth metal oxide used for the bonding material are different from each other, it has been found that the bonding material composition of the present invention and the manufacturing method thereof work effectively.
［実験例２６］
実験例２６は、ＡｌＮ焼結体の条件を変えて実施した例である。このＡｌＮ焼結体は、焼結助剤としての希土類金属酸化物を含まないものであり、次のようにして作製した。
[Experiment 26]
Experimental Example 26 is an example implemented by changing the conditions of the AlN sintered body. This AlN sintered body does not contain a rare earth metal oxide as a sintering aid, and was produced as follows.
市販の純度９９％以上（酸素含有量を除く）の窒化アルミニウム粉末１００質量部に、市販の酸化マグネシウム粉末（純度９９．９５％以上、平均粒径１μｍ）を１質量部を加え、イソプロピルアルコールを溶媒とし、ボールミルを用いて４時間湿式混合を行った。次に、得られたスラリーを取り出し、窒素フロー下で乾燥し、窒化アルミニウムと酸化マグネシウムからなる混合粉末を得た。この混合粉末を金型成形により直径５０ｍｍで厚さが２５ｍｍ程度の板状に成形した後、黒鉛型に収め、窒素ガス中で２０ＭＰａの圧力を加えながら１８００℃で４時間、ホットプレス焼成を行い、緻密な窒化アルミニウム焼結体を得た。この窒化アルミニウム焼結体から、直径５０ｍｍ×厚み１０ｍｍのサイズでテストピースを切り出し、接合用の窒化アルミニウム焼結体に用いた。なお、接合面の表面粗さ（Ｒａ）は１μｍ以下に仕上げた。 To 100 parts by mass of a commercially available aluminum nitride powder with a purity of 99% or more (excluding oxygen content), 1 part by mass of a commercially available magnesium oxide powder (purity 99.95% or more, average particle size 1 μm) is added, and isopropyl alcohol is added. Wet mixing was performed for 4 hours using a ball mill as a solvent. Next, the obtained slurry was taken out and dried under a nitrogen flow to obtain a mixed powder composed of aluminum nitride and magnesium oxide. This mixed powder was molded into a plate shape having a diameter of 50 mm and a thickness of about 25 mm by molding, and then stored in a graphite mold and subjected to hot press firing at 1800 ° C. for 4 hours while applying a pressure of 20 MPa in nitrogen gas. A dense aluminum nitride sintered body was obtained. From this aluminum nitride sintered body, a test piece having a diameter of 50 mm × thickness of 10 mm was cut out and used as an aluminum nitride sintered body for bonding. The surface roughness (Ra) of the joint surface was finished to 1 μm or less.
このように作製した希土類金属酸化物を含まない窒化アルミニウム焼結体同士を、実験例２１と同様の接合材組成物仕込み量及び接合条件にて、ＡｌＮ接合体を作製し、実験例２１と同様の方法で接合強度を評価した。その結果、２６０ＭＰａの高い接合強度を得た。これらの結果より、本発明の接合材組成物及び接合方法は、希土類金属酸化物を含まない窒化アルミニウム焼結体の接合にも十分適用できることが示された。 An aluminum nitride sintered body that does not contain rare earth metal oxides thus produced was prepared with the same amount of bonding material composition and bonding conditions as in Experimental Example 21, and an AlN bonded body was prepared. The bonding strength was evaluated by this method. As a result, a high bonding strength of 260 MPa was obtained. From these results, it was shown that the bonding material composition and the bonding method of the present invention can be sufficiently applied to bonding of an aluminum nitride sintered body not containing a rare earth metal oxide.
なお、実験例１〜２６の接合材組成物が本発明の接合材組成物に相当し、実験例１〜１０，１２〜２６の窒化アルミニウム接合体及びその製法が本発明の窒化アルミニウム接合体及びその製法に相当する。本発明は上述した実施例に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 The bonding material compositions of Experimental Examples 1 to 26 correspond to the bonding material composition of the present invention, and the aluminum nitride bonded bodies of Experimental Examples 1 to 10 and 12 to 26 and the manufacturing method thereof are the aluminum nitride bonded bodies of the present invention and It corresponds to the manufacturing method. It goes without saying that the present invention is not limited to the above-described embodiments, and can be implemented in various modes as long as they belong to the technical scope of the present invention.
Claims (11)
Ｏ元素を含む窒化アルミニウム原料のほかに、フッ素化合物としてアルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方を含み、さらに希土類金属酸化物を含むものであり、
酸化アルミニウムを、前記窒化アルミニウム原料に含まれるＯ元素の含有量をＡｌ 2 Ｏ 3 に換算した値を含めて０．４〜６０質量％含有し、
希土類金属酸化物を、Ａｌ 2 Ｏ 3 の含有量（前記窒化アルミニウム原料に含まれるＯ元素をＡｌ 2 Ｏ 3 に換算した値を含む）に対して４０〜１５０質量％含む、
接合材組成物。 A bonding material composition used when bonding aluminum nitride sintered bodies containing rare earth metal oxides,
In addition to the aluminum nitride raw material containing O element comprises at least one of alkaline earth metal fluoride compound and a rare earth metal fluoride compound as off Tsu-containing compounds are those further containing a rare earth metal oxide,
Containing 0.4 to 60% by mass of aluminum oxide , including the value of the content of O element contained in the aluminum nitride raw material converted to Al 2 O 3 ;
40 to 150% by mass of the rare earth metal oxide with respect to the content of Al 2 O 3 ( including the value obtained by converting the O element contained in the aluminum nitride raw material into Al 2 O 3 ),
Bonding material composition.
Ｏ元素を含む窒化アルミニウム原料のほかに、アルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方と希土類金属酸化物を含むものであり、
酸化アルミニウムを、前記窒化アルミニウム原料に含まれるＯ元素の含有量をＡｌ 2 Ｏ 3 に換算した値を含めて０．４〜６０質量％含有し、
希土類金属酸化物を、Ａｌ 2 Ｏ 3 の含有量（前記窒化アルミニウム原料に含まれるＯ元素をＡｌ 2 Ｏ 3 に換算した値を含む）に対して４０〜１５０質量％含む、
接合材組成物。 A bonding material composition used for bonding an aluminum nitride sintered body that does not contain a rare earth metal oxide and an aluminum nitride sintered body that may contain a rare earth metal oxide,
In addition to the aluminum nitride raw material containing element O is Dressings containing at least one rare earth metal oxide A alkaline earth metal fluoride compound and a rare earth metal fluoride compound,
Containing 0.4 to 60% by mass of aluminum oxide , including the value of the content of O element contained in the aluminum nitride raw material converted to Al 2 O 3 ;
40 to 150% by mass of the rare earth metal oxide with respect to the content of Al 2 O 3 ( including the value obtained by converting the O element contained in the aluminum nitride raw material into Al 2 O 3 ),
Bonding material composition.
請求項１又は２に記載の接合材組成物。 The content of O element contained in the aluminum nitride raw material is 0.4 to 30% by mass,
The bonding material composition according to claim 1 or 2.
請求項１〜３のいずれか１項に記載の接合材組成物。 20 to 85% by mass of aluminum nitride (excluding the Al 2 O 3 equivalent amount of oxygen content), 10 to 50% by mass of fluorine compound,
The bonding material composition according to claim 1.
前記接合層は、結晶相としてＡｌＮのほかに、アルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方を含む、
窒化アルミニウム接合体。 An aluminum nitride joined body in which aluminum nitride sintered bodies are joined together through a joining layer,
The bonding layer includes at least one of an alkaline earth metal fluorine compound and a rare earth metal fluorine compound in addition to AlN as a crystal phase.
Aluminum nitride bonded body.
請求項５に記載の窒化アルミニウム接合体。 The alkaline earth metal fluorine compound is an alkaline earth metal oxyfluoride, and the rare earth metal fluorine compound is a rare earth metal oxyfluoride,
The aluminum nitride joined body according to claim 5 .
請求項５又は６に記載の窒化アルミニウム接合体。 The bonding layer includes at least one of alkaline earth metal-aluminum oxide and rare earth metal-aluminum oxide as a crystalline phase.
The aluminum nitride joined body according to claim 5 or 6 .
前記窒化アルミニウム焼結体は、前記接合層との界面に、窒化アルミニウム焼結体に含まれる酸化物と前記接合層になる前の接合材組成物に含まれるフッ素化合物との反応層を有し、
前記反応層は結晶相としてＡｌＮのほかに、アルカリ土類金属フッ素化合物及び希土類金属フッ素化合物の少なくとも一方を含む
窒化アルミニウム接合体。 An aluminum nitride joined body in which aluminum nitride sintered bodies are joined together through a joining layer,
The aluminum nitride sintered body has a reaction layer of an oxide contained in the aluminum nitride sintered body and a fluorine compound contained in the joining material composition before becoming the joining layer at the interface with the joining layer. ,
The reaction layer includes, in addition to AlN as a crystalline phase, at least one of an alkaline earth metal fluorine compound and a rare earth metal fluorine compound.
請求項８に記載の窒化アルミニウム接合体。 The aluminum nitride joined body according to claim 8 , wherein the reaction layer includes at least one of an alkaline earth metal oxyfluoride and a rare earth metal oxyfluoride.
請求項５〜９のいずれか１項に記載の窒化アルミニウム接合体。 The bonding strength is 200 MPa or more,
The aluminum nitride joined body according to any one of claims 5 to 9 .
窒化アルミニウム接合体の製法。 By heating at a temperature of 1450 ° C. or lower while sandwiching the bonding material composition according to any one of claims 1 to 4 and applying a bonding load between the aluminum nitride sintered bodies, Producing an aluminum nitride joined body in which aluminum nitride sintered bodies are joined together;
Manufacturing method of aluminum nitride bonded body.
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| TW103143433A TWI655990B (en) | 2013-12-27 | 2014-12-12 | Bonding material composition, aluminum nitride bonded body, and method for producing the same |
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