JPH0881263A - Aluminum nitride sintered compact - Google Patents
Aluminum nitride sintered compactInfo
- Publication number
- JPH0881263A JPH0881263A JP6220718A JP22071894A JPH0881263A JP H0881263 A JPH0881263 A JP H0881263A JP 6220718 A JP6220718 A JP 6220718A JP 22071894 A JP22071894 A JP 22071894A JP H0881263 A JPH0881263 A JP H0881263A
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- aln
- oxide
- oxyfluoride
- acid solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、窒化アルミニウム焼結
体（ＡｌＮ焼結体）に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum nitride sintered body (AlN sintered body).
【０００２】[0002]
【従来の技術】電子機器においては、ＩＣ、ＬＳＩ等の
電子デバイスの実装、回路形成、および絶縁を目的とし
てアルミナ基材とする回路基板が使用されている。しか
しながら、前記アルミナ基材は熱伝導率が約２０Ｗ／ｍ
・Ｋと低いため、近年のＬＳＩの高密度化、高集積化に
対応して高熱伝導性のＡｌＮ焼結体からなる基材を有す
る回路基板が注目されている。2. Description of the Related Art In electronic equipment, a circuit board having an alumina base material is used for the purpose of mounting, circuit formation and insulation of electronic devices such as IC and LSI. However, the alumina base material has a thermal conductivity of about 20 W / m.
Since it is as low as K, a circuit board having a base material made of a highly heat-conductive AlN sintered body has attracted attention in response to the recent trend toward higher density and higher integration of LSI.
【０００３】ところで、ＡｌＮは共有結合を持つため、
高硬度で、熱伝導率が高いものの、難焼結性である。こ
のため、Ｙ2 Ｏ3 、ＹＦ3 などの種々の焼結助剤が開発
され、現在ではＡｌＮ粉末にＹ2 Ｏ3 を添加し、成形し
た成形体を常圧、窒素雰囲気中、１９００℃、９６時間
の焼結を行うことにより内部の不純物酸素量が５００ｐ
ｐｍ以下、熱伝導率が２６０Ｗ／ｍ・Ｋである良好なＡ
ｌＮ焼結体が得られている。また、ＹＦ3 の添加では１
６００℃の低温焼結が可能になっている。By the way, since AlN has a covalent bond,
It has high hardness and high thermal conductivity, but it is difficult to sinter. For this reason, various sintering aids such as Y 2 O 3 and YF 3 have been developed, and at present, a compact formed by adding Y 2 O 3 to AlN powder and molding at normal pressure in a nitrogen atmosphere at 1900 ° C. By sintering for 96 hours, the amount of impurity oxygen inside is 500p
Good A with pm or less and thermal conductivity of 260 W / mK
An IN sintered body is obtained. With addition of YF 3 , it is 1
Low temperature sintering at 600 ° C is possible.
【０００４】前記焼結助剤添加成形体が１８００℃の温
度で常圧焼結することができるのは、焼結時に酸化物、
フッ化物、酸フッ化物の液相成分がＡｌＮ粒界に存在
し、ＡｌＮの拡散を助長しているからであると考えられ
ている。このようなメカニズムにより焼結がなされるも
のの、焼結完了後の焼結体表面に前記液相成分が固化し
たものが存在し、ＡｌＮ焼結体の外観や表面粗さを悪化
させる。The sintering aid-added compacts can be sintered at a temperature of 1800 ° C. under atmospheric pressure because of oxides during sintering.
It is considered that this is because the liquid phase components of fluoride and oxyfluoride exist in the AlN grain boundaries and promote the diffusion of AlN. Although the sintering is performed by such a mechanism, the liquid phase component is solidified on the surface of the sintered body after the completion of sintering, which deteriorates the appearance and surface roughness of the AlN sintered body.
【０００５】ＡｌＮ焼結体をＰＫＧなどのパッケージや
回路基板の基材に応用する場合には、従来、前記液相成
分の固化物を研磨により除去してから用いているために
問題がなかった。しかしながら、キャビティ付きのＡｌ
Ｎ焼結体ＰＫＧの場合には形状が変化してしまう研磨工
程を採用することが不可能であるために問題を生じる。When the AlN sintered body is applied to a package such as PKG or a base material of a circuit board, there has been no problem because the solidified substance of the liquid phase component has been conventionally removed by polishing. . However, Al with cavity
In the case of the N-sintered body PKG, it is impossible to adopt a polishing process in which the shape changes, which causes a problem.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、研磨
などにより形状が変化されることなく、外観性および表
面平滑性が良好なＡｌＮ焼結体を提供しようとするもの
である。SUMMARY OF THE INVENTION An object of the present invention is to provide an AlN sintered body having good appearance and surface smoothness without changing its shape by polishing or the like.
【０００７】[0007]
【課題を解決するための手段】本発明に係わるＡｌＮ焼
結体は、内部の酸化物または酸フッ化物の濃度（Ｃ1）
に対する表面の酸化物または酸フッ化物の濃度（Ｃ2 ）
の比（Ｃ2 ／Ｃ1 ）が０．１以下であることを特徴とす
るものである。The AlN sintered body according to the present invention has a concentration (C 1 ) of oxide or oxyfluoride inside.
Surface oxide or acid fluoride concentration (C 2 )
The ratio (C 2 / C 1 ) of 0.1 is 0.1 or less.
【０００８】前記濃度比Ｃ2 ／Ｃ1 を規定したのは理由
は、その比が０．１を越えると外観性および表面平滑が
良好なＡｌＮ焼結体を得ることができなるからである。
本発明に係わるＡｌＮ焼結体は、次のような方法により
製造される。The reason for defining the concentration ratio C 2 / C 1 is that if the ratio exceeds 0.1, it is possible to obtain an AlN sintered body having good appearance and surface smoothness.
The AlN sintered body according to the present invention is manufactured by the following method.
【０００９】まず、ＡｌＮ粉末に希土類元素の酸化物、
フッ化物または酸フッ化物を焼結助剤として添加し、ボ
ールミル中で混合粉砕する。前記ＡｌＮ粉末は、実質的
にあらゆる入手可能な粉末を用いることができるが、焼
結性の観点から不純物酸素量が０．２〜１．８重量％、
平均一次粒子径が３．５μｍ以下、より好ましくは０．
１〜２．５μｍであることが望ましい。First, AlN powder is mixed with oxides of rare earth elements,
Fluoride or oxyfluoride is added as a sintering aid and mixed and ground in a ball mill. As the AlN powder, virtually any available powder can be used, but the amount of impurity oxygen is 0.2 to 1.8% by weight from the viewpoint of sinterability.
The average primary particle diameter is 3.5 μm or less, more preferably 0.
It is preferably 1 to 2.5 μm.
【００１０】前記混合粉末中には、必要に応じて着色
化、高強度化のためにＴｉ、Ｗ、Ｍｏ、Ｔａ、Ｎｂ等の
遷移金属の酸化物、炭化物、フッ化物、炭酸塩、シュウ
酸塩、硝酸塩を前記ＡｌＮ粉末に対して遷移金属換算で
０．０５〜１重量％で配合することを許容する。また、
焼結温度の低減化のために酸化アルミニウム、フッ化ア
ルミニウム等のアルミニウム化合物や酸化珪素、窒化珪
素等の珪素化合物をＡｌＮ粉末に対して１重量％以下の
範囲で配合することを許容する。In the mixed powder, oxides, carbides, fluorides, carbonates and oxalic acids of transition metals such as Ti, W, Mo, Ta and Nb are added to the mixed powder for coloring and strengthening, if necessary. It is allowed to mix the salt and the nitrate with the AlN powder in an amount of 0.05 to 1% by weight in terms of a transition metal. Also,
In order to reduce the sintering temperature, an aluminum compound such as aluminum oxide or aluminum fluoride or a silicon compound such as silicon oxide or silicon nitride may be mixed in the range of 1% by weight or less with respect to the AlN powder.
【００１１】次いで、前記混合粉末をアクリル系バイン
ダ、ポリビニルブチラール系バインダのような有機バイ
ンダにｎ−ブタノールなどのアルコール系溶媒またはメ
チルイソブチルケトン、トルエンのような有機溶剤と共
に混練した後、金型プレス、静水圧プレスまたはシート
成形等により成形して成形体を作製する。ひきつづき、
前記成形体を窒素等の非酸化性雰囲気中、１５００〜１
９００℃、１〜１００時間焼結することによりＡｌＮ焼
結体を製造する。この後、この焼結体表面に存在する酸
化物、フッ化物または酸フッ化物を塩酸、硝酸、硫酸お
よびこれらの混酸からなる酸溶液で選択的に溶解、除去
することにより、前記酸化物または酸フッ化物の濃度比
Ｃ2 ／Ｃ1 が０．１以下のＡｌＮ焼結体とする。Next, the mixed powder is kneaded with an organic binder such as an acrylic binder or a polyvinyl butyral binder together with an alcohol solvent such as n-butanol or an organic solvent such as methyl isobutyl ketone or toluene, and then a die press. Then, a molded body is prepared by molding by isostatic pressing or sheet molding. Continued,
The molded body is heated to 1500 to 1 in a non-oxidizing atmosphere such as nitrogen.
An AlN sintered body is manufactured by sintering at 900 ° C. for 1 to 100 hours. Thereafter, the oxide, fluoride or oxyfluoride existing on the surface of the sintered body is selectively dissolved and removed with an acid solution consisting of hydrochloric acid, nitric acid, sulfuric acid and a mixed acid thereof to remove the oxide or the acid. The AlN sintered body has a fluoride concentration ratio C 2 / C 1 of 0.1 or less.
【００１２】前記酸溶液は、０．０５〜１０規定の濃
度、１２０℃以下の温度であることが好ましい。この理
由は、前記酸溶液の濃度を０．０５規定未満にするとに
酸化物、フッ化物または酸フッ化物を溶解するのに多大
な時間を要する。一方、前記酸溶液の濃度が１０規定を
越えるとＡｌＮそのものが溶解される恐れがある。より
好ましい前記酸溶液の濃度は、１〜５規定、さらに好ま
しくは１〜３規定である。また、酸溶液のより好ましい
温度は常温から１００℃である。The acid solution preferably has a concentration of 0.05 to 10 N and a temperature of 120 ° C. or lower. The reason for this is that when the concentration of the acid solution is less than 0.05 N, it takes a lot of time to dissolve the oxide, fluoride or oxyfluoride. On the other hand, if the concentration of the acid solution exceeds 10 N, AlN itself may be dissolved. The more preferable concentration of the acid solution is 1 to 5N, and more preferably 1 to 3N. Further, the more preferable temperature of the acid solution is from room temperature to 100 ° C.
【００１３】[0013]
【作用】本発明によれば、内部の酸化物または酸フッ化
物の濃度（Ｃ1 ）に対する表面の酸化物または酸フッ化
物の濃度（Ｃ2 ）の比（Ｃ2 ／Ｃ1 ）が０．１以下にす
ることにより研磨などにより形状が変化されることな
く、外観性および表面平滑性が良好なＡｌＮ焼結体を得
ることができる。このようなＡｌＮ焼結体は、その表面
の酸化物、フッ化物または酸フッ化物を塩酸、硝酸、硫
酸およびこれらの混酸からなる酸溶液で選択的に溶解、
除去することにより簡単に得ることができる。また、本
発明に係わるＡｌＮ焼結体は平均粒径が小さく、かつ高
い熱伝導率、高い強度を有する。According to the present invention, the ratio of the concentration of an oxide or oxyfluoride surface to the concentration of internal oxide or oxyfluoride (C 1) (C 2) (C 2 / C 1) is 0. By setting the ratio to 1 or less, it is possible to obtain an AlN sintered body having good appearance and surface smoothness without changing the shape due to polishing or the like. Such an AlN sintered body selectively dissolves oxides, fluorides or oxyfluorides on its surface with an acid solution consisting of hydrochloric acid, nitric acid, sulfuric acid and a mixed acid thereof,
It can be easily obtained by removing. Further, the AlN sintered body according to the present invention has a small average particle size, and has high thermal conductivity and high strength.
【００１４】[0014]
【実施例】以下、本発明の実施例を詳細に説明する。 （実施例１）まず、不純物酸素量０．９８重量％、平均
一次粒子径０．６μｍのＡｌＮ粉末９６．２重量％、平
均粒径０．１μｍ、純度９９．９％のＹ2 Ｏ3 ３．０重
量％、平均粒径０．５μｍ、純度９９．９％のＡｌ2 Ｏ
3 ０．５重量％および平均粒径０．１μｍ、純度９９．
９％のＷＯ3 がＷ換算で０．３重量％からなる混合粉体
にｎ−ブタノールを添加し、湿式ボールミルにより解
砕、混合した後、ｎ−ブタノールを除去して原料粉末を
調製した。つづいて、この原料粉末にアクリル系バイン
ダ５重量％を添加して造粒した後、この造粒粉を５０Ｍ
Ｐａの一軸加圧下で成形して圧粉体とした。この圧粉体
を窒素ガス雰囲気中、７００℃まで加熱して脱脂処理を
行った。ひきつづき、前記脱バインダ圧粉体をＡｌＮ焼
結体からなる容器中にセットし、この容器をカーボンヒ
ータを有する焼結炉内に入れ、１気圧の純窒素ガスの雰
囲気下にて、１６００℃、６時間焼結することによりＡ
ｌＮ焼結体を製造した。EXAMPLES Examples of the present invention will be described in detail below. Example 1 First, Y 2 O 3 3 having an impurity oxygen content of 0.98% by weight, an AlN powder having an average primary particle diameter of 0.6 μm of 96.2% by weight, an average particle diameter of 0.1 μm, and a purity of 99.9%. Al 2 O with 0.0% by weight, average particle size of 0.5 μm, and purity of 99.9%
3 0.5% by weight, average particle size 0.1 μm, purity 99.
N-Butanol was added to a mixed powder containing 9% of WO 3 in an amount of 0.3% by weight in terms of W, crushed and mixed by a wet ball mill, and then n-butanol was removed to prepare a raw material powder. Subsequently, 5% by weight of an acrylic binder was added to the raw material powder to granulate the granulated powder.
It was molded under a uniaxial pressure of Pa to obtain a green compact. This green compact was heated to 700 ° C. in a nitrogen gas atmosphere for degreasing treatment. Subsequently, the binder-removed powder compact was set in a container made of an AlN sintered body, and the container was placed in a sintering furnace having a carbon heater, at 1600 ° C. in an atmosphere of pure nitrogen gas at 1 atm, By sintering for 6 hours A
An IN sintered body was manufactured.
【００１５】得られたＡｌＮ焼結体の密度をアルキメデ
ス法により測定した。その結果、３．３０ｇ／ｃｍ3 と
十分に緻密化されていた。また、前記ＡｌＮ焼結体から
直径１０ｍｍ、厚さ３ｍｍの円板を切り出し、２１±２
℃の室温下でＪＩＳ−Ｒ１６１１に従ってレーザフラッ
シュ法により熱伝導率を測定した。その結果、１４０Ｗ
／ｍ・Ｋであった。The density of the obtained AlN sintered body was measured by the Archimedes method. As a result, it was sufficiently densified at 3.30 g / cm 3 . Further, a disk with a diameter of 10 mm and a thickness of 3 mm was cut out from the AlN sintered body, and 21 ± 2
The thermal conductivity was measured by the laser flash method according to JIS-R1611 at room temperature of ° C. As a result, 140W
/ M · K.
【００１６】さらに、前記ＡｌＮ焼結体について表面Ｘ
線回折装置で調べた。その結果、ＡｌＮ焼結体表面に存
在する物質はフッ化物、酸フッ化物であることがわかっ
た。同時に、表面をＳＥＭ電子顕微鏡で観察した。その
結果、焼結体表面は多量のフッ化物、酸フッ化物で覆わ
れていた。ＡｌＮ焼結体の表面粗さは、Ｒａで３μｍで
あった。Further, the surface X of the AlN sintered body is
It was examined with a line diffractometer. As a result, it was found that the substances existing on the surface of the AlN sintered body were fluoride and oxyfluoride. At the same time, the surface was observed with a SEM electron microscope. As a result, the surface of the sintered body was covered with a large amount of fluoride and oxyfluoride. The surface roughness Ra of the AlN sintered body was 3 μm in Ra.
【００１７】次いで、前記ＡｌＮ焼結体を１００℃、１
規定の塩酸溶液に２時間浸漬した後、乾燥した。前記塩
酸溶液処理後のＡｌＮ焼結体について表面Ｘ線回折装置
で調べたところ、ＡｌＮ焼結体表面にはＡｌＮ粒子のみ
が存在し、フッ化物、酸フッ化物は存在しないことがわ
かった。同時に焼結体内部をＸ線回折で調べたところ、
酸化物およびフッ化物が観察された。これらの結果から
内部の酸化物または酸フッ化物の濃度（Ｃ1 ）に対する
表面の酸化物または酸フッ化物の濃度（Ｃ2 ）の比（Ｃ
2／Ｃ1 ）は零であることが確認された。Next, the AlN sintered body is treated at 100 ° C. for 1
It was immersed in a specified hydrochloric acid solution for 2 hours and then dried. When the AlN sintered body after the treatment with the hydrochloric acid solution was examined by a surface X-ray diffractometer, it was found that only AlN particles were present on the surface of the AlN sintered body, and no fluoride or oxyfluoride was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction,
Oxides and fluorides were observed. From these results, the ratio (C 2 ) of the surface oxide or oxyfluoride concentration (C 2 ) to the internal oxide or oxyfluoride concentration (C 1 ).
It was confirmed that 2 / C 1 ) was zero.
【００１８】また、前記塩酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子のみが観察された。ＡｌＮ
焼結体の表面粗さは、Ｒａで０．１μｍと極めて平滑で
あった。The surface of the AlN sintered body after the treatment with the hydrochloric acid solution was observed with a SEM electron microscope. As a result, only AlN particles were observed on the surface of the sintered body. AlN
The surface roughness of the sintered body was 0.1 μm in terms of Ra, which was extremely smooth.
【００１９】（比較例１）実施例１と同様な焼結後のＡ
ｌＮ焼結体を１００℃、１規定のリン酸溶液に２時間浸
漬し、その後乾燥した。(Comparative Example 1) A after sintering similar to Example 1
The 1N sintered body was dipped in a 1N phosphoric acid solution at 100 ° C. for 2 hours and then dried.
【００２０】前記リン酸溶液理後のＡｌＮ焼結体につい
て表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が存在することがわかった。同時に
焼結体内部をＸ線回折で調べたところ、内部にもＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が存在することがわかった。これら
の結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1 ）は、１０であり、表面の方
が酸フッ化物等の濃度が高いことがわかった。The AlN sintered body after the phosphoric acid solution treatment was examined by a surface X-ray diffractometer.
It was found that F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, YO
It was found that F, Y 4 Al 2 O 9 was present. The ratio of the concentration of an oxide or oxyfluoride surface to the concentration of these oxides internal results or acid fluoride (C 1) (C 2) (C 2 / C 1) is 10, the surface of the It was found that the concentration of oxyfluoride was higher.
【００２１】また、前記リン酸溶液処理後のＡｌＮ焼結
体について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が多く観
察された。ＡｌＮ焼結体の表面粗さは、Ｒａで２．６μ
ｍであり、表面が粗悪な状態であった。The surface of the AlN sintered body after the phosphoric acid solution treatment was observed with a SEM electron microscope. As a result, many island-shaped foreign matters were observed on the surface of the sintered body in addition to the AlN particles. The surface roughness of the AlN sintered body is Ra of 2.6μ.
m, and the surface was in a poor state.
【００２２】（比較例２）実施例１と同様な焼結後のＡ
ｌＮ焼結体を１００℃、１規定のリン酸溶液に１２時間
浸漬し、その後乾燥した。(Comparative Example 2) A after sintering as in Example 1
The 1N sintered body was immersed in a 1N phosphoric acid solution at 100 ° C for 12 hours, and then dried.
【００２３】前記リン酸溶液理後のＡｌＮ焼結体につい
て表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が存在することがわかった。同時に
焼結体内部をＸ線回折で調べたところ、内部にもＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が存在することがわかった。これら
の結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1 ）は、８であり、表面の方が
酸フッ化物等の濃度が高いことがわかった。The AlN sintered body after the phosphoric acid solution treatment was examined by a surface X-ray diffractometer.
It was found that F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, YO
It was found that F, Y 4 Al 2 O 9 was present. The ratio of the concentration of an oxide or oxyfluoride surface to the concentration of these oxides internal results or acid fluoride (C 1) (C 2) (C 2 / C 1) is 8, the surface of the It was found that the concentration of oxyfluoride was higher.
【００２４】また、前記リン酸溶液処理後のＡｌＮ焼結
体について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が多く観
察された。ＡｌＮ焼結体の表面粗さは、Ｒａで２．２μ
ｍであり、表面が粗悪な状態であった。The surface of the AlN sintered body after the phosphoric acid solution treatment was observed with a SEM electron microscope. As a result, many island-shaped foreign matters were observed on the surface of the sintered body in addition to the AlN particles. The surface roughness of the AlN sintered body is Ra of 2.2μ.
m, and the surface was in a poor state.
【００２５】（比較例３）実施例１と同様な焼結後のＡ
ｌＮ焼結体を１００℃、０．０３規定の塩酸溶液に２４
時間浸漬し、その後乾燥した。(Comparative Example 3) A after sintering as in Example 1
The 1N sintered body is placed in a 0.03N hydrochloric acid solution at 100 ° C for 24 hours.
It was dipped for a time and then dried.
【００２６】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が存在することがわかった。同時に
焼結体内部をＸ線回折で調べたところ、内部にもＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が存在することがわかった。これら
の結果から内部の酸化物または酸フッ化物の濃度（Ｃ
1 ）に対する表面の酸化物または酸フッ化物の濃度（Ｃ
2 ）の比（Ｃ2 ／Ｃ1 ）は１２であり、表面の方が酸フ
ッ化物等の濃度が高いことがわかった。When the surface of the AlN sintered body after the hydrochloric acid solution treatment was examined by a surface X-ray diffractometer, YO
It was found that F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, YO
It was found that F, Y 4 Al 2 O 9 was present. From these results, the concentration of the internal oxide or oxyfluoride (C
1 ) Concentration of surface oxide or oxyfluoride (C
2 ratio) (C 2 / C 1) is 12, towards the surface it was found that a high concentration of such acid fluorides.
【００２７】また、前記塩酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が多く観
察された。ＡｌＮ焼結体の表面粗さは、Ｒａで２．６μ
ｍであり、表面が粗悪な状態であった。The surface of the AlN sintered body after the treatment with the hydrochloric acid solution was observed with a SEM electron microscope. As a result, many island-shaped foreign matters were observed on the surface of the sintered body in addition to the AlN particles. The surface roughness of the AlN sintered body is Ra of 2.6μ.
m, and the surface was in a poor state.
【００２８】（実施例２）まず、不純物酸素量０．９８
重量％、平均一次粒子径０．６μｍのＡｌＮ粉末９４．
７重量％、平均粒径０．１μｍ、純度９９．９％のＹ2
Ｏ3 ５．０重量％、および平均粒径０．１μｍ、純度９
９．９％のＷＯ3 がＷ換算で０．３重量％からなる混合
粉体にｎ−ブタノールを添加し、湿式ボールミルにより
解砕、混合した後、ｎ−ブタノールを除去して原料粉末
を調製した。つづいて、この原料粉末にアクリル系バイ
ンダ５重量％を添加して造粒した後、この造粒粉を５０
ＭＰａの一軸加圧下で成形して圧粉体とした。この圧粉
体を窒素ガス雰囲気中、７００℃まで加熱して脱脂処理
を行った。ひきつづき、前記脱バインダ圧粉体をＡｌＮ
焼結体からなる容器中にセットし、この容器をカーボン
ヒータを有する焼結炉内に入れ、１気圧の純窒素ガスの
雰囲気下にて、１８００℃、６時間焼結することにより
ＡｌＮ焼結体を製造した。Example 2 First, the impurity oxygen amount is 0.98.
% AlN powder having an average primary particle diameter of 0.6 μm 94.
Y 2 with 7% by weight, average particle size of 0.1 μm, and purity of 99.9%
O 3 5.0% by weight, average particle size 0.1 μm, purity 9
N-Butanol was added to a mixed powder containing 9.9% WO 3 in an amount of 0.3% by weight in terms of W, crushed and mixed by a wet ball mill, and then n-butanol was removed to prepare a raw material powder. did. Subsequently, 5% by weight of an acrylic binder was added to this raw material powder to granulate, and then this granulated powder was mixed with 50
It was molded under uniaxial pressure of MPa to obtain a green compact. This green compact was heated to 700 ° C. in a nitrogen gas atmosphere for degreasing treatment. Next, the binder-removed green compact is treated with AlN.
It is set in a container made of a sintered body, placed in a sintering furnace having a carbon heater, and sintered at 1800 ° C. for 6 hours in an atmosphere of pure nitrogen gas at 1 atm to perform AlN sintering. Manufactured body.
【００２９】得られたＡｌＮ焼結体の密度をアルキメデ
ス法により測定した。その結果、３．３０ｇ／ｃｍ3 と
十分に緻密化されていた。また、前記ＡｌＮ焼結体から
直径１０ｍｍ、厚さ３ｍｍの円板を切り出し、２１±２
℃の室温下でＪＩＳ−Ｒ１６１１に従ってレーザフラッ
シュ法により熱伝導率を測定した。その結果、１４０Ｗ
／ｍ・Ｋであった。The density of the obtained AlN sintered body was measured by the Archimedes method. As a result, it was sufficiently densified at 3.30 g / cm 3 . Further, a disk with a diameter of 10 mm and a thickness of 3 mm was cut out from the AlN sintered body, and 21 ± 2
The thermal conductivity was measured by the laser flash method according to JIS-R1611 at room temperature of ° C. As a result, 140W
/ M · K.
【００３０】さらに、前記ＡｌＮ焼結体について表面Ｘ
線回折装置で調べた。その結果、ＡｌＮ焼結体表面に存
在する物質はフッ化物、酸フッ化物であることがわかっ
た。同時に、表面をＳＥＭ電子顕微鏡で観察した。その
結果、焼結体表面は多量のフッ化物、酸フッ化物で覆わ
れていた。ＡｌＮ焼結体の表面粗さは、Ｒａで２．６μ
ｍであった。Further, the surface X of the AlN sintered body was
It was examined with a line diffractometer. As a result, it was found that the substances existing on the surface of the AlN sintered body were fluoride and oxyfluoride. At the same time, the surface was observed with a SEM electron microscope. As a result, the surface of the sintered body was covered with a large amount of fluoride and oxyfluoride. The surface roughness of the AlN sintered body is Ra of 2.6μ.
It was m.
【００３１】次いで、前記ＡｌＮ焼結体を１００℃、１
規定の塩酸溶液に２時間浸漬した後、乾燥した。前記塩
酸溶液処理後のＡｌＮ焼結体について表面Ｘ線回折装置
で調べたところ、ＡｌＮ焼結体表面にはＡｌＮ粒子のみ
が存在し、フッ化物、酸フッ化物は存在しないことがわ
かった。同時に焼結体内部をＸ線回折で調べたところ、
酸化物およびフッ化物が観察された。これらの結果から
内部の酸化物または酸フッ化物の濃度（Ｃ1 ）に対する
表面の酸化物または酸フッ化物の濃度（Ｃ2 ）の比（Ｃ
2／Ｃ1 ）は零であることが確認された。Next, the AlN sintered body was heated at 100 ° C. for 1 hour.
It was immersed in a specified hydrochloric acid solution for 2 hours and then dried. When the AlN sintered body after the treatment with the hydrochloric acid solution was examined by a surface X-ray diffractometer, it was found that only AlN particles were present on the surface of the AlN sintered body, and no fluoride or oxyfluoride was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction,
Oxides and fluorides were observed. From these results, the ratio (C 2 ) of the surface oxide or oxyfluoride concentration (C 2 ) to the internal oxide or oxyfluoride concentration (C 1 ).
It was confirmed that 2 / C 1 ) was zero.
【００３２】また、前記塩酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子のみが観察された。ＡｌＮ
焼結体の表面粗さは、Ｒａで０．１μｍと極めて平滑で
あった。The surface of the AlN sintered body after the treatment with the hydrochloric acid solution was observed with a SEM electron microscope. As a result, only AlN particles were observed on the surface of the sintered body. AlN
The surface roughness of the sintered body was 0.1 μm in terms of Ra, which was extremely smooth.
【００３３】（実施例３）実施例２と同様な焼結後のＡ
ｌＮ焼結体を１００℃、０．１規定の塩酸溶液に２４時
間浸漬し、その後乾燥した。(Example 3) A after sintering similar to Example 2
The 1N sintered body was immersed in a 0.1 N hydrochloric acid solution at 100 ° C. for 24 hours and then dried.
【００３４】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が少量存在することがわかった。同
時に焼結体内部をＸ線回折で調べたところ、内部にも酸
化物（Ｙ4 Ａｌ2 Ｏ9 ）が存在することがわかった。こ
れらの結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1）は０．０２であることが確
認された。When the surface of the AlN sintered body after the above hydrochloric acid solution treatment was examined by a surface X-ray diffractometer, YO
It was found that a small amount of F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, it was found that an oxide (Y 4 Al 2 O 9 ) was also present inside. From these results, the ratio (C 2 / C 1 ) of the concentration (C 2 ) of the oxide or oxyfluoride on the surface to the concentration (C 1 ) of the oxide or oxyfluoride inside was 0.02. confirmed.
【００３５】また、前記塩酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が僅かに
観察された。ＡｌＮ焼結体の表面粗さはＲａで０．６μ
ｍと極めて平滑であった。The surface of the AlN sintered body after the treatment with the hydrochloric acid solution was observed with a SEM electron microscope. As a result, island-shaped foreign matters were slightly observed in addition to the AlN particles on the surface of the sintered body. The surface roughness of the AlN sintered body is Ra 0.6 μm.
m was extremely smooth.
【００３６】（実施例４）実施例２と同様な焼結後のＡ
ｌＮ焼結体を１００℃、１規定の硝酸溶液に２時間浸漬
し、その後乾燥した。(Example 4) A after sintering similar to Example 2
The 1N sintered body was immersed in a 1N nitric acid solution at 100 ° C. for 2 hours and then dried.
【００３７】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が少量存在することがわかった。同
時に焼結体内部をＸ線回折で調べたところ、内部にも酸
化物（Ｙ4 Ａｌ2 Ｏ9 ）が存在することがわかった。こ
れらの結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1）は０．０６であることが確
認された。When the AlN sintered body after the above hydrochloric acid solution treatment was examined by a surface X-ray diffractometer, YO
It was found that a small amount of F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, it was found that an oxide (Y 4 Al 2 O 9 ) was also present inside. From these results, the ratio (C 2 / C 1 ) of the concentration (C 2 ) of the oxide or oxyfluoride on the surface to the concentration (C 1 ) of the oxide or oxyfluoride inside was 0.06. confirmed.
【００３８】また、前記硝酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が僅かに
観察された。ＡｌＮ焼結体の表面粗さはＲａで０．９μ
ｍと極めて平滑であった。The surface of the AlN sintered body after the treatment with the nitric acid solution was observed with a SEM electron microscope. As a result, island-shaped foreign matters were slightly observed in addition to the AlN particles on the surface of the sintered body. The surface roughness Ra of the AlN sintered body is 0.9μ.
m was extremely smooth.
【００３９】（実施例５）実施例２と同様な焼結後のＡ
ｌＮ焼結体を１００℃、０．１規定の硝酸溶液に２時間
浸漬し、その後乾燥した。(Example 5) A after sintering similar to Example 2
The 1N sintered body was immersed in a 0.1N nitric acid solution at 100 ° C. for 2 hours and then dried.
【００４０】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が少量存在することがわかった。同
時に焼結体内部をＸ線回折で調べたところ、内部にも酸
化物（Ｙ4 Ａｌ2 Ｏ9 ）が存在することがわかった。こ
れらの結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1）は０．０８であることが確
認された。When the surface of the AlN sintered body after the above hydrochloric acid solution treatment was examined by a surface X-ray diffractometer, YO
It was found that a small amount of F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, it was found that an oxide (Y 4 Al 2 O 9 ) was also present inside. From these results, the ratio (C 2 / C 1 ) of the concentration (C 2 ) of the oxide or oxyfluoride on the surface to the concentration (C 1 ) of the oxide or oxyfluoride inside was 0.08. confirmed.
【００４１】また、前記硝酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が僅かに
観察された。ＡｌＮ焼結体の表面粗さはＲａで１．６μ
ｍであった。The surface of the AlN sintered body after the treatment with the nitric acid solution was observed with a SEM electron microscope. As a result, island-shaped foreign matters were slightly observed in addition to the AlN particles on the surface of the sintered body. The surface roughness of the AlN sintered body is Ra 1.6 μm.
It was m.
【００４２】（実施例６）実施例２と同様な焼結後のＡ
ｌＮ焼結体を５０℃、１規定の塩酸溶液に２時間浸漬
し、その後乾燥した。(Example 6) A after sintering similar to Example 2
The 1N sintered body was immersed in a 1N hydrochloric acid solution at 50 ° C. for 2 hours and then dried.
【００４３】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が少量存在することがわかった。同
時に焼結体内部をＸ線回折で調べたところ、内部にも酸
化物（Ｙ4 Ａｌ2 Ｏ9 ）が存在することがわかった。こ
れらの結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1）は０．０５であることが確
認された。When the AlN sintered body after the above hydrochloric acid solution treatment was examined by a surface X-ray diffractometer, YO
It was found that a small amount of F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, it was found that an oxide (Y 4 Al 2 O 9 ) was also present inside. From these results, the ratio (C 2 / C 1 ) of the concentration (C 2 ) of the oxide or oxyfluoride on the surface to the concentration (C 1 ) of the oxide or oxyfluoride inside was 0.05. confirmed.
【００４４】また、前記塩酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が僅かに
観察された。ＡｌＮ焼結体の表面粗さはＲａで１．２μ
ｍであった。The surface of the AlN sintered body after the treatment with the hydrochloric acid solution was observed with a SEM electron microscope. As a result, island-shaped foreign matters were slightly observed in addition to the AlN particles on the surface of the sintered body. The surface roughness of the AlN sintered body is Ra of 1.2μ.
It was m.
【００４５】（実施例７）実施例２と同様な焼結後のＡ
ｌＮ焼結体を２５℃、１規定の塩酸溶液に２時間浸漬
し、その後乾燥した。(Example 7) A after sintering similar to Example 2
The 1N sintered body was immersed in a 1N hydrochloric acid solution at 25 ° C. for 2 hours and then dried.
【００４６】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が少量存在することがわかった。同
時に焼結体内部をＸ線回折で調べたところ、内部にも酸
化物（Ｙ4 Ａｌ2 Ｏ9 ）が存在することがわかった。こ
れらの結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1）は０．０８であることが確
認された。The surface of the AlN sintered body after the hydrochloric acid solution treatment was examined by a surface X-ray diffractometer.
It was found that a small amount of F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, it was found that an oxide (Y 4 Al 2 O 9 ) was also present inside. From these results, the ratio (C 2 / C 1 ) of the concentration (C 2 ) of the oxide or oxyfluoride on the surface to the concentration (C 1 ) of the oxide or oxyfluoride inside was 0.08. confirmed.
【００４７】また、前記塩酸硝酸溶液処理後のＡｌＮ焼
結体について表面をＳＥＭ電子顕微鏡で観察した。その
結果、焼結体表面はＡｌＮ粒子以外に島状の異物が僅か
に観察された。ＡｌＮ焼結体の表面粗さはＲａで１．８
μｍてあった。The surface of the AlN sintered body after the treatment with the hydrochloric acid / nitric acid solution was observed with a SEM electron microscope. As a result, island-shaped foreign matters were slightly observed in addition to the AlN particles on the surface of the sintered body. The surface roughness Ra of the AlN sintered body is 1.8.
It was μm.
【００４８】（実施例８）実施例２と同様な焼結後のＡ
ｌＮ焼結体を１００℃、１０規定の塩酸溶液に３０分間
浸漬し、その後乾燥した。(Example 8) A after sintering similar to Example 2
The 1N sintered body was immersed in a 10N hydrochloric acid solution at 100 ° C. for 30 minutes, and then dried.
【００４９】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が少量存在することがわかった。同
時に焼結体内部をＸ線回折で調べたところ、内部にも酸
化物（Ｙ4 Ａｌ2 Ｏ9 ）が存在することがわかった。こ
れらの結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1）は０．００１であることが
確認された。When the AlN sintered body after the above hydrochloric acid solution treatment was examined by a surface X-ray diffractometer, YO
It was found that a small amount of F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, it was found that an oxide (Y 4 Al 2 O 9 ) was also present inside. From these results, the ratio (C 2 / C 1 ) of the concentration (C 2 ) of the oxide or oxyfluoride on the surface to the concentration (C 1 ) of the oxide or oxyfluoride inside was 0.001. confirmed.
【００５０】また、前記塩酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が僅かに
観察された。ＡｌＮ焼結体の表面粗さはＲａで０．１６
μｍと極めて平滑であった。The surface of the AlN sintered body after the treatment with the hydrochloric acid solution was observed with a SEM electron microscope. As a result, island-shaped foreign matters were slightly observed in addition to the AlN particles on the surface of the sintered body. The surface roughness Ra of the AlN sintered body is 0.16.
It was extremely smooth as μm.
【００５１】（実施例９）実施例２と同様な焼結後のＡ
ｌＮ焼結体を１００℃、５規定の塩酸溶液に１時間浸漬
し、その後乾燥した。(Example 9) A after sintering similar to Example 2
The 1N sintered body was immersed in a 5N hydrochloric acid solution at 100 ° C. for 1 hour and then dried.
【００５２】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が少量存在することがわかった。同
時に焼結体内部をＸ線回折で調べたところ、内部にも酸
化物（Ｙ4 Ａｌ2 Ｏ9 ）が存在することがわかった。こ
れらの結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1）は０．０１であることが確
認された。When the AlN sintered body after the above hydrochloric acid solution treatment was examined by a surface X-ray diffractometer, YO
It was found that a small amount of F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, it was found that an oxide (Y 4 Al 2 O 9 ) was also present inside. From these results, the ratio (C 2 / C 1 ) of the concentration (C 2 ) of oxide or oxyfluoride on the surface to the concentration (C 1 ) of oxide or oxyfluoride inside was 0.01. confirmed.
【００５３】また、前記塩酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が僅かに
観察された。ＡｌＮ焼結体の表面粗さはＲａで０．１８
μｍと極めて平滑であった。The surface of the AlN sintered body after the treatment with the hydrochloric acid solution was observed with a SEM electron microscope. As a result, island-shaped foreign matters were slightly observed in addition to the AlN particles on the surface of the sintered body. The surface roughness Ra of the AlN sintered body is 0.18.
It was extremely smooth as μm.
【００５４】（実施例１０）実施例２と同様な焼結後の
ＡｌＮ焼結体を１００℃、０．５規定の塩酸溶液に６時
間浸漬し、その後乾燥した。Example 10 The same sintered AlN sintered body as in Example 2 was immersed in a 0.5N hydrochloric acid solution at 100 ° C. for 6 hours and then dried.
【００５５】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が少量存在することがわかった。同
時に焼結体内部をＸ線回折で調べたところ、内部にも酸
化物（Ｙ4 Ａｌ2 Ｏ9 ）が存在することがわかった。こ
れらの結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1）は０．００２であることが
確認された。When the AlN sintered body after the above hydrochloric acid solution treatment was examined by a surface X-ray diffractometer, YO
It was found that a small amount of F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, it was found that an oxide (Y 4 Al 2 O 9 ) was also present inside. From these results, the ratio (C 2 / C 1 ) of the concentration (C 2 ) of the oxide or oxyfluoride on the surface to the concentration (C 1 ) of the oxide or oxyfluoride inside was 0.002. confirmed.
【００５６】また、前記塩酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が僅かに
観察された。ＡｌＮ焼結体の表面粗さはＲａで０．１５
μｍと極めて平滑であった。The surface of the AlN sintered body after the treatment with the hydrochloric acid solution was observed with a SEM electron microscope. As a result, island-shaped foreign matters were slightly observed in addition to the AlN particles on the surface of the sintered body. The surface roughness Ra of the AlN sintered body is 0.15.
It was extremely smooth as μm.
【００５７】（実施例１１）実施例２と同様な焼結後の
ＡｌＮ焼結体を１００℃、０．０５規定の塩酸溶液に３
６時間浸漬し、その後乾燥した。Example 11 The same sintered AlN sintered body as in Example 2 was immersed in a 0.05N hydrochloric acid solution at 100 ° C.
It was dipped for 6 hours and then dried.
【００５８】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が少量存在することがわかった。同
時に焼結体内部をＸ線回折で調べたところ、内部にも酸
化物（Ｙ4 Ａｌ2 Ｏ9 ）が存在することがわかった。こ
れらの結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1）は０．００１であることが
確認された。When the AlN sintered body after the hydrochloric acid solution treatment was examined by a surface X-ray diffractometer, YO
It was found that a small amount of F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, it was found that an oxide (Y 4 Al 2 O 9 ) was also present inside. From these results, the ratio (C 2 / C 1 ) of the concentration (C 2 ) of the oxide or oxyfluoride on the surface to the concentration (C 1 ) of the oxide or oxyfluoride inside was 0.001. confirmed.
【００５９】また、前記塩酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が僅かに
観察された。ＡｌＮ焼結体の表面粗さはＲａで０．１３
μｍと極めて平滑であった。The surface of the AlN sintered body after the treatment with the hydrochloric acid solution was observed with a SEM electron microscope. As a result, island-shaped foreign matters were slightly observed in addition to the AlN particles on the surface of the sintered body. The surface roughness Ra of the AlN sintered body is 0.13.
It was extremely smooth as μm.
【００６０】（実施例１２）実施例２と同様な焼結後の
ＡｌＮ焼結体を１００℃、１規定の硝酸溶液に１時間浸
漬し、その後乾燥した。Example 12 The same sintered AlN sintered body as in Example 2 was immersed in a 1N nitric acid solution at 100 ° C. for 1 hour and then dried.
【００６１】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が少量存在することがわかった。同
時に焼結体内部をＸ線回折で調べたところ、内部にも酸
化物（Ｙ4 Ａｌ2 Ｏ9 ）が存在することがわかった。こ
れらの結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1）は０．１００であることが
確認された。When the surface of the AlN sintered body after the hydrochloric acid solution treatment was examined by a surface X-ray diffractometer, YO
It was found that a small amount of F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, it was found that an oxide (Y 4 Al 2 O 9 ) was also present inside. From these results, the ratio (C 2 / C 1 ) of the concentration (C 2 ) of the oxide or oxyfluoride on the surface to the concentration (C 1 ) of the oxide or oxyfluoride inside was 0.100. confirmed.
【００６２】また、前記塩酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が僅かに
観察された。ＡｌＮ焼結体の表面粗さはＲａで１．９μ
ｍであった。The surface of the AlN sintered body after the treatment with the hydrochloric acid solution was observed with a SEM electron microscope. As a result, island-shaped foreign matters were slightly observed in addition to the AlN particles on the surface of the sintered body. The surface roughness Ra of the AlN sintered body is 1.9μ.
It was m.
【００６３】（実施例１３）実施例２と同様な焼結後の
ＡｌＮ焼結体を１００℃、１規定の塩酸−硝酸混合溶液
に１時間浸漬し、その後乾燥した。Example 13 The same sintered AlN sintered body as in Example 2 was immersed in a 1N hydrochloric acid-nitric acid mixed solution at 100 ° C. for 1 hour and then dried.
【００６４】前記塩酸溶液理後のＡｌＮ焼結体について
表面Ｘ線回折装置で調べたところ、ＡｌＮ以外にＹＯ
Ｆ、Ｙ4 Ａｌ2 Ｏ9 が少量存在することがわかった。同
時に焼結体内部をＸ線回折で調べたところ、内部にも酸
化物（Ｙ4 Ａｌ2 Ｏ9 ）が存在することがわかった。こ
れらの結果から内部の酸化物または酸フッ化物の濃度
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1）は０．００１であることが
確認された。When the AlN sintered body after the above hydrochloric acid solution treatment was examined by a surface X-ray diffractometer, YO
It was found that a small amount of F, Y 4 Al 2 O 9 was present. At the same time, when the inside of the sintered body was examined by X-ray diffraction, it was found that an oxide (Y 4 Al 2 O 9 ) was also present inside. From these results, the ratio (C 2 / C 1 ) of the concentration (C 2 ) of the oxide or oxyfluoride on the surface to the concentration (C 1 ) of the oxide or oxyfluoride inside was 0.001. confirmed.
【００６５】また、前記塩酸溶液処理後のＡｌＮ焼結体
について表面をＳＥＭ電子顕微鏡で観察した。その結
果、焼結体表面はＡｌＮ粒子以外に島状の異物が僅かに
観察された。ＡｌＮ焼結体の表面粗さはＲａで０．１２
μｍと極めて平滑性であった。The surface of the AlN sintered body after the treatment with the hydrochloric acid solution was observed with a SEM electron microscope. As a result, island-shaped foreign matters were slightly observed in addition to the AlN particles on the surface of the sintered body. The surface roughness Ra of the AlN sintered body is 0.12.
It was extremely smooth with μm.
【００６６】（実施例１４）まず、不純物酸素量０．９
８重量％、平均一次粒子径０．６μｍのＡｌＮ粉末９
６．２重量％、平均粒径０．１μｍ、純度９９．９％の
ＹＦ3 ３．０重量％、平均粒径０．５μｍ、純度９９．
９％のＡｌ2 Ｏ3 ０．５重量％および平均粒径０．１μ
ｍ、純度９９．９％のＷＯ3 がＷ換算で０．３重量％か
らなる混合粉体にｎ−ブタノールを添加し、湿式ボール
ミルにより解砕、混合した後、ｎ−ブタノールを除去し
て原料粉末を調製した。つづいて、この原料粉末にアク
リル系バインダ５重量％を添加して造粒した後、この造
粒粉を５０ＭＰａの一軸加圧下で成形して圧粉体とし
た。この圧粉体を窒素ガス雰囲気中、７００℃まで加熱
して脱脂処理を行った。ひきつづき、前記脱バインダ圧
粉体をＡｌＮ焼結体からなる容器中にセットし、この容
器をカーボンヒータを有する焼結炉内に入れ、１気圧の
純窒素ガスの雰囲気下にて、１６００℃、６時間焼結し
た。その後、得られた焼結体をＡｌＮ焼結体からなる容
器中にセットし、０．９気圧の純窒素雰囲気中、１６５
０℃、９６時間焼結することによりＡｌＮ焼結体を製造
した。(Example 14) First, the amount of impurity oxygen was 0.9.
8% by weight, AlN powder 9 having an average primary particle size of 0.6 μm 9
6.2% by weight, average particle size 0.1 μm, purity 99.9% YF 3 3.0% by weight, average particle size 0.5 μm, purity 99.
0.5% by weight of 9% Al 2 O 3 and 0.1 μ average particle size
n-butanol was added to a mixed powder containing 0.3% by weight of WO 3 having a purity of m and a purity of 99.9% in terms of W, crushed and mixed by a wet ball mill, and then n-butanol was removed to obtain a raw material A powder was prepared. Subsequently, 5% by weight of an acrylic binder was added to the raw material powder for granulation, and the granulated powder was molded under a uniaxial pressure of 50 MPa to obtain a green compact. This green compact was heated to 700 ° C. in a nitrogen gas atmosphere for degreasing treatment. Subsequently, the binder-removed powder compact was set in a container made of an AlN sintered body, and the container was placed in a sintering furnace having a carbon heater, at 1600 ° C. in an atmosphere of pure nitrogen gas at 1 atm, Sintered for 6 hours. After that, the obtained sintered body was set in a container made of an AlN sintered body, and was placed in a pure nitrogen atmosphere of 0.9 atm for 165
An AlN sintered body was manufactured by sintering at 0 ° C. for 96 hours.
【００６７】得られたＡｌＮ焼結体の密度をアルキメデ
ス法により測定した。その結果、３．３０ｇ／ｃｍ3 と
十分に緻密化されていた。また、前記ＡｌＮ焼結体から
直径１０ｍｍ、厚さ３ｍｍの円板を切り出し、２１±２
℃の室温下でＪＩＳ−Ｒ１６１１に従ってレーザフラッ
シュ法により熱伝導率を測定した。その結果、１４０Ｗ
／ｍ・Ｋであった。The density of the obtained AlN sintered body was measured by the Archimedes method. As a result, it was sufficiently densified at 3.30 g / cm 3 . Further, a disk with a diameter of 10 mm and a thickness of 3 mm was cut out from the AlN sintered body, and 21 ± 2
The thermal conductivity was measured by the laser flash method according to JIS-R1611 at room temperature of ° C. As a result, 140W
/ M · K.
【００６８】さらに、前記ＡｌＮ焼結体について表面Ｘ
線回折装置で調べた。その結果、ＡｌＮ焼結体表面に存
在する物質はフッ化物、酸フッ化物であることがわかっ
た。同時に、表面をＳＥＭ電子顕微鏡で観察した。その
結果、焼結体表面は多量のフッ化物、酸フッ化物で覆わ
れていた。ＡｌＮ焼結体の表面粗さは、Ｒａで５．０μ
ｍであった。Further, the surface X of the AlN sintered body was
It was examined with a line diffractometer. As a result, it was found that the substances existing on the surface of the AlN sintered body were fluoride and oxyfluoride. At the same time, the surface was observed with a SEM electron microscope. As a result, the surface of the sintered body was covered with a large amount of fluoride and oxyfluoride. The surface roughness of the AlN sintered body is 5.0μ in Ra.
It was m.
【００６９】次いで、前記ＡｌＮ焼結体を１００℃、１
規定の塩酸溶液に２時間浸漬した後、乾燥した。前記塩
酸溶液処理後のＡｌＮ焼結体について表面Ｘ線回折装置
で調べたところ、ＡｌＮ焼結体表面にはＡｌＮ粒子のみ
が存在し、フッ化物、酸フッ化物は存在しないことがわ
かった。同時に焼結体断面をＸ線回折で調べたところ、
見掛け上、粒界に異物が見られなかった。ＡｌＮ粒子の
平均粒径は、４μｍであった。ＡｌＮ焼結体の表面粗さ
は、Ｒａで０．１μｍと極めて平滑であった。Next, the AlN sintered body was heated at 100 ° C. for 1 hour.
It was immersed in a specified hydrochloric acid solution for 2 hours and then dried. When the AlN sintered body after the treatment with the hydrochloric acid solution was examined with a surface X-ray diffractometer, it was found that only AlN particles were present on the surface of the AlN sintered body, and no fluoride or oxyfluoride was present. At the same time, when the cross section of the sintered body was examined by X-ray diffraction,
Apparently, no foreign matter was found at the grain boundaries. The average particle size of the AlN particles was 4 μm. The surface roughness of the AlN sintered body was Ra of 0.1 μm, which was extremely smooth.
【００７０】また、ＪＩＳ−Ｒ１６０１に従って、Ａｌ
Ｎ焼結体の４点曲げ強度を測定した。その結果、３６０
ＭＰａの強度を有していた。密度をアルキメデス法によ
り測定したところ、３．２６ｇ／ｃｍ3 であった。Further, according to JIS-R1601, Al
The 4-point bending strength of the N sintered body was measured. As a result, 360
It had a strength of MPa. When the density was measured by the Archimedes method, it was 3.26 g / cm 3 .
【００７１】さらに、前記ＡｌＮ焼結体から直径１０ｍ
ｍ、厚さ３ｍｍの円板を切り出し、２１±２℃の室温下
でＪＩＳ−Ｒ１６１１に従ってレーザフラッシュ法によ
り熱伝導率を測定した。その結果、２６０Ｗ／ｍ・Ｋで
あった。Further, the diameter of the AlN sintered body is 10 m.
A disk having a thickness of 3 mm and a thickness of 3 mm was cut out, and the thermal conductivity was measured by a laser flash method according to JIS-R1611 at room temperature of 21 ± 2 ° C. As a result, it was 260 W / m · K.
【００７２】（比較例４）まず、不純物酸素量０．９８
重量％、平均一次粒子径０．６μｍのＡｌＮ粉末９６．
２重量％、平均粒径０．１μｍ、純度９９．９％のＹＦ
3 ３．０重量％、平均粒径０．５μｍ、純度９９．９％
のＡｌ2 Ｏ3 ０．５重量％および平均粒径０．１μｍ、
純度９９．９％のＷＯ3 がＷ換算で０．３重量％からな
る混合粉体にｎ−ブタノールを添加し、湿式ボールミル
により解砕、混合した後、ｎ−ブタノールを除去して原
料粉末を調製した。つづいて、この原料粉末にアクリル
系バインダ５重量％を添加して造粒した後、この造粒粉
を５０ＭＰａの一軸加圧下で成形して圧粉体とした。こ
の圧粉体を窒素ガス雰囲気中、７００℃まで加熱して脱
脂処理を行った。ひきつづき、前記脱バインダ圧粉体を
ＡｌＮ焼結体からなる容器中にセットし、この容器をカ
ーボンヒータを有する焼結炉内に入れ、１気圧の純窒素
ガスの雰囲気下にて、１６００℃、６時間焼結した。そ
の後、得られた焼結体をカーボンヒータからなる容器中
にセットし、１気圧の還元窒化雰囲気中、１９００℃、
９６時間焼結することによりＡｌＮ焼結体を製造した。(Comparative Example 4) First, the impurity oxygen amount is 0.98.
% AlN powder having an average primary particle diameter of 0.6 μm 96.
2% by weight, average particle size 0.1 μm, purity 99.9% YF
3 3.0% by weight, average particle size 0.5 μm, purity 99.9%
0.5% by weight of Al 2 O 3 and an average particle size of 0.1 μm,
N-Butanol was added to a mixed powder containing 0.3 wt% of WO 3 having a purity of 99.9% in terms of W, crushed and mixed by a wet ball mill, and then n-butanol was removed to obtain a raw material powder. Prepared. Subsequently, 5% by weight of an acrylic binder was added to the raw material powder for granulation, and the granulated powder was molded under a uniaxial pressure of 50 MPa to obtain a green compact. This green compact was heated to 700 ° C. in a nitrogen gas atmosphere for degreasing treatment. Subsequently, the binder-removed powder compact was set in a container made of an AlN sintered body, and the container was placed in a sintering furnace having a carbon heater, at 1600 ° C. in an atmosphere of pure nitrogen gas at 1 atm, Sintered for 6 hours. Then, the obtained sintered body was set in a container composed of a carbon heater, and the atmosphere was reduced at 1900 ° C. in a reducing nitriding atmosphere at 1900 ° C.
An AlN sintered body was manufactured by sintering for 96 hours.
【００７３】得られたＡｌＮ焼結体を１００℃の湯中で
洗浄し、その後乾燥した。前記ＡｌＮ焼結体について表
面Ｘ線回折装置で調べたところ、ＡｌＮ焼結体表面には
ＡｌＮ粒子のみが存在し、フッ化物、酸フッ化物は存在
しないことがわかった。同時に表面をＳＥＭ電子顕微鏡
で観察したところ、焼結体表面はＡｌＮ粒子のみが観察
された。さらに、焼結体断面をＳＥＭで観察したとこ
ろ、見掛け上、粒界に異物が見られなかった。ＡｌＮ粒
子の平均粒径は、１２μｍであった。ＡｌＮ焼結体の表
面粗さは、Ｒａで０．１μｍと極めて平滑であった。The AlN sintered body thus obtained was washed in hot water at 100 ° C. and then dried. When the surface of the AlN sintered body was examined by a surface X-ray diffractometer, it was found that only AlN particles existed on the surface of the AlN sintered body, and neither fluoride nor oxyfluoride existed. At the same time, when observing the surface with an SEM electron microscope, only AlN particles were observed on the surface of the sintered body. Further, when the cross section of the sintered body was observed by SEM, apparently no foreign matter was found at the grain boundaries. The average particle size of the AlN particles was 12 μm. The surface roughness of the AlN sintered body was Ra of 0.1 μm, which was extremely smooth.
【００７４】また、密度をアルキメデス法により測定し
たところ、３．２６ｇ／ｃｍ3 であった。前記ＡｌＮ焼
結体から直径１０ｍｍ、厚さ３ｍｍの円板を切り出し、
２１±２℃の室温下でＪＩＳ−Ｒ１６１１に従ってレー
ザフラッシュ法により熱伝導率を測定した。その結果、
２６０Ｗ／ｍ・Ｋであった。さらに、ＪＩＳ−Ｒ１６０
１に従って、ＡｌＮ焼結体の４点曲げ強度を測定した。
その結果、２５０ＭＰａで前記実施例１４に比べて強度
が劣っていた。When the density was measured by the Archimedes method, it was 3.26 g / cm 3 . A disk with a diameter of 10 mm and a thickness of 3 mm was cut out from the AlN sintered body,
The thermal conductivity was measured by a laser flash method according to JIS-R1611 at room temperature of 21 ± 2 ° C. as a result,
It was 260 W / mK. Furthermore, JIS-R160
According to 1, the 4-point bending strength of the AlN sintered body was measured.
As a result, the strength was inferior to that of Example 14 at 250 MPa.
【００７５】[0075]
【発明の効果】以上詳述したように、本発明によれば研
磨などにより形状が変化されることなく、外観性および
表面平滑性が良好で、さらに高強度、高熱伝導性を有す
るＡｌＮ焼結体を提供できる。As described above in detail, according to the present invention, the AlN sintered body having a good appearance and a smooth surface without being changed in shape by polishing or the like, and having high strength and high thermal conductivity. Can provide the body.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 角野 裕康 神奈川県川崎市幸区小向東芝町１番地 株 式会社東芝研究開発センター内 (72)発明者 上野 文雄 神奈川県川崎市幸区小向東芝町１番地 株 式会社東芝研究開発センター内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroyasu Tsunono 1 Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa, Ltd. Toshiba Research & Development Center (72) Inventor Fumio Ueno Komukai-Toshiba, Kawasaki-shi, Kanagawa Town No. 1 Toshiba Corporation Research & Development Center
Claims (1)
（Ｃ1 ）に対する表面の酸化物または酸フッ化物の濃度
（Ｃ2 ）の比（Ｃ2 ／Ｃ1 ）が０．１以下であることを
特徴とする窒化アルミニウム焼結体。1. The ratio (C 2 / C 1 ) of the concentration (C 2 ) of oxide or oxyfluoride on the surface to the concentration (C 1 ) of oxide or oxyfluoride inside is 0.1 or less. An aluminum nitride sintered body characterized by the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6220718A JPH0881263A (en) | 1994-09-16 | 1994-09-16 | Aluminum nitride sintered compact |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6220718A JPH0881263A (en) | 1994-09-16 | 1994-09-16 | Aluminum nitride sintered compact |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0881263A true JPH0881263A (en) | 1996-03-26 |
Family
ID=16755433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6220718A Pending JPH0881263A (en) | 1994-09-16 | 1994-09-16 | Aluminum nitride sintered compact |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0881263A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012092015A (en) * | 2003-11-21 | 2012-05-17 | Toshiba Corp | Substrate for semiconductor device |
-
1994
- 1994-09-16 JP JP6220718A patent/JPH0881263A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012092015A (en) * | 2003-11-21 | 2012-05-17 | Toshiba Corp | Substrate for semiconductor device |
| JP2012092014A (en) * | 2003-11-21 | 2012-05-17 | Toshiba Corp | High thermally conductive aluminum nitride sintered compact |
| JP2012116750A (en) * | 2003-11-21 | 2012-06-21 | Toshiba Corp | Heat dissipation plate for semiconductor device |
| JP5060048B2 (en) * | 2003-11-21 | 2012-10-31 | 株式会社東芝 | High thermal conductivity aluminum nitride sintered body |
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