JPH0455369A - Production of aluminum nitride powder - Google Patents
Production of aluminum nitride powderInfo
- Publication number
- JPH0455369A JPH0455369A JP2167730A JP16773090A JPH0455369A JP H0455369 A JPH0455369 A JP H0455369A JP 2167730 A JP2167730 A JP 2167730A JP 16773090 A JP16773090 A JP 16773090A JP H0455369 A JPH0455369 A JP H0455369A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum nitride
- nitride powder
- sintering aid
- powder
- film
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 84
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000005245 sintering Methods 0.000 claims abstract description 45
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 230000002829 reductive effect Effects 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical group O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 8
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 8
- 239000002344 surface layer Substances 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 28
- 239000000758 substrate Substances 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、窒化アルミニウム粉末の製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing aluminum nitride powder.
ＩＣ等に代表される半導体素子の高集積化や大電力化が
進み、これに従って、放熱性の非常に良い電気絶縁基板
が必要になってきた。この要望に応えて、各種の高熱伝
導性絶縁基板が提案されている。中でも窒化アルミニウ
ム（セラミック）基板は熱伝導性、電気絶縁性、熱膨張
性等の点で優れているために、実用化が進められている
。BACKGROUND ART As semiconductor devices such as ICs and the like have become more highly integrated and have more power, electrically insulating substrates with very good heat dissipation properties have become necessary. In response to this demand, various high thermal conductivity insulating substrates have been proposed. Among these, aluminum nitride (ceramic) substrates are being put into practical use because they are excellent in terms of thermal conductivity, electrical insulation, thermal expansion, etc.
しかしながら、従来、十分な熱伝導率（例えば、２６０
Ｗ／ｍ −Ｋ程度）をもつ窒化アルミニウム基板は製造
が容易でなかった。製造工程で高温かつ長時間の焼成が
必要だからである。上記程度の熱伝導率の窒化アルミニ
ウム基板を得る場合、窒化アルミニウム粉末に酸化イツ
トリウム、酸化カルシウム等の粉末状の焼結助剤等を少
量添加し成形してから、１８００℃以上、２０時間以上
、常圧還元雰囲気下で焼成し焼結させるようにする長い
焼成時期が必要なのは、窒化アルミニウム粉末が表面を
中心に１ｗｔ％程度の不純物酸素（通常、Ａｌ５ｏ、の
形で存在する）を含んでいるからである。不純物酸素は
熱伝導率を劣化させるため、除去しなければならない、
焼成工程では、酸化イツトリウム、酸化カルシウム等の
焼結助剤とアルミニウムおよび酸素との間で複合酸化物
液相を粒界に現出し、不純物酸素をトラップしつつ窒化
アルミニウム結晶粒間の三重点および四重点のところに
液相を集中させることにより、酸化物からなる粒界層に
よるフォノン伝導の阻害・散乱を出来るだけ低減させて
いるのである。加えて、還元雰囲気中の長時間焼成の間
、液相中の酸化物が徐々に揮発して除かれる結果、十分
な熱伝導率を有する焼結体になる。焼成時間が短いと、
不純物酸素のトラップや酸化物の揮発除去が不十分にし
かできずに、十分な熱伝導率をもたせられない。However, conventionally, sufficient thermal conductivity (e.g. 260
It has not been easy to manufacture aluminum nitride substrates having a high performance (on the order of W/m -K). This is because the manufacturing process requires high-temperature and long-time firing. In order to obtain an aluminum nitride substrate with a thermal conductivity of the above level, a small amount of powdered sintering aid such as yttrium oxide or calcium oxide is added to aluminum nitride powder, and after molding, the substrate is heated at 1800°C or higher for 20 hours or more. The long firing period required for firing and sintering in a reducing atmosphere at normal pressure is because the aluminum nitride powder contains about 1 wt% of impurity oxygen (usually present in the form of Al5O) mainly on the surface. It is from. Impurity oxygen deteriorates thermal conductivity and must be removed.
In the firing process, a complex oxide liquid phase appears at grain boundaries between sintering aids such as yttrium oxide and calcium oxide, aluminum and oxygen, and traps impurity oxygen while forming triple points between aluminum nitride crystal grains and By concentrating the liquid phase at the quadruple point, the inhibition and scattering of phonon conduction by the grain boundary layer made of oxides is reduced as much as possible. In addition, during long-term firing in a reducing atmosphere, oxides in the liquid phase are gradually volatilized and removed, resulting in a sintered body with sufficient thermal conductivity. If the firing time is short,
The trapping of impurity oxygen and the volatilization removal of oxides are insufficient, and sufficient thermal conductivity cannot be achieved.
高温焼成が必要なのは、焼結助剤を添加するからである
。窒化アルミニウム粉末、バインダー、分散剤、可塑剤
、溶剤等と共に混合され、焼成開始時には、窒化アルミ
ニウム粉末の間に散らばっている粉末状の焼結助剤の場
合は、１８００℃以上の高い温度で焼成しないと複合酸
化物液相がうまく粒界全体にわたって生じてくれない。The reason why high temperature firing is necessary is because a sintering aid is added. In the case of a powdered sintering aid that is mixed with aluminum nitride powder, binder, dispersant, plasticizer, solvent, etc. and scattered between the aluminum nitride powder at the start of firing, it is fired at a high temperature of 1800°C or higher. Otherwise, the complex oxide liquid phase will not form properly throughout the grain boundaries.
このように、従来、窒化アルミニウム粉末表面の不純物
酸素を除去するために長時間の焼成が必要であり、粉末
で添加した焼結助剤があるために高温焼成が必要であっ
た。製造工程での高温長時間焼成は基板コストの上昇を
招くので窒化アルミニウム基板の利用がなかなか進まな
い。コスト高を招来してしまう。還元性雰囲気で酸素除
去をしながら焼成すると得られる基板表面が荒れるとい
う別の問題を生じる。As described above, conventionally, a long firing time was required to remove the impurity oxygen on the surface of the aluminum nitride powder, and high temperature firing was required due to the presence of the sintering aid added in the form of a powder. The use of aluminum nitride substrates has been slow because long-term firing at high temperatures during the manufacturing process increases substrate costs. This results in high costs. Another problem arises in that the surface of the resulting substrate becomes rough if it is fired in a reducing atmosphere while removing oxygen.
この発明は、上記事情に鑑み、従来よりも緩やかな焼成
温度条件あるいは焼成時間条件で十分な熱伝導率の窒化
アルミニウム基板を作れる窒化アルミニウム粉末が得ら
れる方法を提供することを課題とする。In view of the above circumstances, it is an object of the present invention to provide a method for obtaining aluminum nitride powder that can produce an aluminum nitride substrate with sufficient thermal conductivity under firing temperature conditions or firing time conditions that are gentler than conventional ones.
前記課題を解決するため、請求項１〜４記載の窒化アル
ミニウム粉末の製造方法では、原料粉末たる窒化アルミ
ニウム粉末を、炭化水素および窒素を含む雰囲気で還元
処理した後、この窒化アルミニウム粉末の表面に焼結助
剤膜を形成するようにしている。In order to solve the above problems, in the method for producing aluminum nitride powder according to claims 1 to 4, aluminum nitride powder as a raw material powder is reduced in an atmosphere containing hydrocarbons and nitrogen, and then the surface of the aluminum nitride powder is reduced. A sintering aid film is formed.
焼結助剤膜の形成にあたっては、請求項２のように、焼
結助剤膜形成用物質を蒸着で粉末表面に蒸着するように
する。In forming the sintering aid film, the material for forming the sintering aid film is deposited on the powder surface by vapor deposition.
この発明における焼結助剤としては、請求項３のように
、希土類酸化物、アルカリ土類酸化物等が挙げられる。Examples of the sintering aid in this invention include rare earth oxides and alkaline earth oxides.
複数種の希土類酸化物を併用したり、複数種のアルカリ
土類酸化物を併用したり、あるいは、１ないし複数種の
希土類酸化物と１ないし複数種のアルカリ土類酸化物を
併用したりしてもよい、希土類酸化物としては、請求項
４のように、酸化イツトリウム（Ｙ＊ Ｏｓ ）等があ
り、アルカリ土類酸化物としては、請求項４のように、
酸化カルシウム（Ｃａ Ｏ）等がある。Multiple types of rare earth oxides are used together, multiple types of alkaline earth oxides are used together, or one or more types of rare earth oxides and one or more types of alkaline earth oxides are used together. Examples of rare earth oxides that may be used include yttrium oxide (Y*Os), etc., and examples of alkaline earth oxides include, as shown in claim 4,
Examples include calcium oxide (CaO).
続いて、この発明をより具体的に説明する。Next, this invention will be explained in more detail.
まず、第１図にみるように、酸化アルミニウムの多い表
面層１ａのある窒化アルミニウム粉末（原料粉末）１を
、炭化水素および窒素を含む雰囲気で熱処理して還元す
る。First, as shown in FIG. 1, aluminum nitride powder (raw material powder) 1 having a surface layer 1a containing a large amount of aluminum oxide is heat-treated and reduced in an atmosphere containing hydrocarbons and nitrogen.
原料粉末の粒径は、通常、０．１〜１μｍ程度、より好
ましくは０．１〜０．３μｍ程度である。粒径が小さい
ほど焼成温度が低くできる傾向がある。The particle size of the raw material powder is usually about 0.1 to 1 μm, more preferably about 0.1 to 0.3 μm. The smaller the particle size, the lower the firing temperature tends to be.
炭化水素および窒素を含む雰囲気としては、炭化水素用
としてのメタン、エチレン、アセチレン等の各ガスの少
なくともひとつと、窒素用としての窒素ガス、アンモニ
アガス等の少なくともひとつからなる混合ガス雰囲気が
例示される。還元処理で使う加熱炉としては、各窒化ア
ルミニウム粉末を等しく十分に混合ガスと接触させるこ
とが望ましいので、例えば、混合ガスをオーバーフロー
させて処理粉末を舞わせ（流動化させ）ながら熱処理で
きる流動層型の炉か、あるいは、処理粉末を機械的に攪
拌しながら熱処理できる横型回転炉を用いることが好ま
しい。An example of an atmosphere containing hydrocarbons and nitrogen is a mixed gas atmosphere consisting of at least one of methane, ethylene, acetylene, etc. for hydrocarbons and at least one of nitrogen gas, ammonia gas, etc. for nitrogen. Ru. As for the heating furnace used in the reduction treatment, it is desirable to bring each aluminum nitride powder into equal and sufficient contact with the mixed gas. It is preferable to use a type furnace or a horizontal rotary furnace that can perform heat treatment while mechanically stirring the treated powder.
熱処理中、使用ガスの種類に応じて主として下記のよう
な／ｌｏｏｍ還元窒化反応が起こる。During the heat treatment, the following /room reduction and nitridation reactions mainly occur depending on the type of gas used.
（１） Ａ ＊Ｌ ＋３ＣＨａ ＋Ｎｔ−２ＡＩＮ
＋３ＣＯ＋ ６８２（２） １０ｉ＋３ｃＨ４＋２
ＮＨｓ→２ＡＩＮ＋３ＣＯ＋９Ｈ。(1) A *L +3CHa +Nt-2AIN
+3CO+ 682(2) 10i+3cH4+2
NHs→2AIN+3CO+9H.
（３） 八 ｔＯｍ＋３／２ＣｔＨｔ ＋Ｎｔ→
２＾ＩＮ＋３ＣＯ＋３／２＋１゜（４１Ａ ！０１＋３
／２ＣｔＨｆｆｉ ＋２Ｎ）Ｉ！→２＾ＩＮ＋３ＣＯ
＋９／２Ｈ。(3) Eight tOm+3/2CtHt +Nt→
2^IN+3CO+3/2+1゜(41A !01+3
/2CtHffi +2N)I! →2^IN+3CO
+9/2H.
（５１Ａ ＊Ｏ＊＋３／２ＣＪ４＋Ｎ！→２ＡＩＮ＋３
ＣＯ＋３ｔｌ。(51A *O*+3/2CJ4+N!→2AIN+3
CO+3tl.
（６） Ａ ｉｏｓ＋３／２ｃよＨａ ”２ＮＨ
ｓ→２ＡＩＮ＋３ＣＯ＋９１１１熱処理温度は、使用ガ
スの種類に応じて若干具なるが、通常、６００〜１２０
０℃程度の温度範囲で反応が良好に進行する。(6) A ios+3/2c yo Ha “2NH
s→2AIN+3CO+9111 The heat treatment temperature varies slightly depending on the type of gas used, but is usually 600 to 120.
The reaction proceeds well in a temperature range of about 0°C.
第２図にみるように、還元窒化された窒化アルミニウム
粉末１′は、酸化アルミニウムの多い表面層がなくなっ
ているが、表面が非常に活性であるため、冷却の際でも
炉内に酸素が侵入しないように注意する必要がある。酸
素が侵入すると表面が酸化される恐れがあるからである
。As shown in Figure 2, the aluminum nitride powder 1' that has been reduced and nitrided has no surface layer containing a large amount of aluminum oxide, but since the surface is very active, oxygen can enter the furnace even during cooling. You need to be careful not to do this. This is because the surface may be oxidized if oxygen enters.
還元処理工程の次ぎに、焼結助剤膜の形成工程に移り、
第３図にみるように、焼結助剤膜１”ａを表面に形成し
た窒化アルミニウム粉末１″を作る。Next to the reduction treatment process, proceed to the formation process of the sintering aid film,
As shown in FIG. 3, aluminum nitride powder 1'' having a sintering aid film 1''a formed on its surface is prepared.
焼結助剤膜の形成にあたっては、通常、窒化アルミニウ
ム粉末表面に焼結助剤膜形成用物質を蒸着するようにす
る。同焼結助剤膜形成用物質は、既に焼結助剤（例えば
、酸化イツトリウム）である（蒸着した膜がそのまま焼
結助剤膜になる）場合に限らず、まだ焼結助剤前段階物
質（例えば、イツトリウム）である場合もあり、この場
合には蒸着後さらに後処理（例えば、酸化処理）し焼結
助剤（例えば、酸化イツトリウム）化し焼結助剤膜とす
るようにする。In forming the sintering aid film, a substance for forming the sintering aid film is usually vapor-deposited on the surface of the aluminum nitride powder. The substance for forming the sintering aid film is not limited to the case where it is already a sintering aid (e.g., yttrium oxide) (the deposited film becomes the sintering aid film as it is), but it is still in the pre-sintering aid stage. In some cases, it is a substance (for example, yttrium), and in this case, after vapor deposition, it is further post-treated (for example, oxidation treatment) to form a sintering aid (for example, yttrium oxide) to form a sintering aid film.
焼結助剤膜形成用物質を蒸着する具体的方法としては、
真空蒸着法、スパッタリング蒸着法、ＣＶ Ｄ （Ｃｈ
ｅｍｉｃａｌνａｐｏｕｒ Ｄｅｐｏｓｉｔｉｏｎ）法
等が例示されるが、まわり込みがよく均一な膜形成が行
えるＣＶＤ法が適当である。他の蒸着法を用いる場合、
例えば、ファンで攪拌して処理粉末を舞わせたり、容器
を回転させて処理粉末を舞わせたりする機械的攪拌を併
用するようにすることが好ましい。The specific method for depositing the sintering aid film forming substance is as follows:
Vacuum deposition method, sputtering deposition method, CV D (Ch
For example, the CVD method is suitable because it can form a uniform film with good wrapping. When using other deposition methods,
For example, it is preferable to use mechanical stirring such as stirring with a fan to scatter the treated powder or rotating a container to cause the treated powder to scatter.
焼結助剤膜は、完全単一層の状態である場合だけでなく
、多数の微粒子が集合した状態である場合もある。The sintering aid film may not only be in the form of a complete single layer, but may also be in the form of a collection of many fine particles.
窒化アルミニウム粉末に付着した焼結助剤量は、通常、
粉末に対して１〜５ｗｔ％程度である。The amount of sintering aid attached to aluminum nitride powder is usually
It is about 1 to 5 wt% based on the powder.
還元処理工程と焼結助剤膜形成工程は、それぞれ別々に
バッチ式に行ってもよいが、ひとつの装置で連続して行
う方が、還元窒化後の窒化アルミニウム粉末の酸化防止
の上からも好ましい。The reduction treatment process and the sintering aid film formation process may be performed separately in a batch manner, but it is better to perform them continuously in one device in order to prevent oxidation of the aluminum nitride powder after reductive nitridation. preferable.
この発明は、勿論、上記例示の材料や処理条件を使うこ
とに限らないことはいうまでもない。It goes without saying that the present invention is not limited to the use of the materials and processing conditions exemplified above.
この発明の製造方法では、原料粉末の窒化アルミニウム
粉末を、炭化水素および窒素を含む雰囲気で還元処理す
るので、例えば、雰囲気がメタンとアンモニアを含む場
合、八Ｉｔ’ｓ ＋ ３Ｃ）＋４ ＋ ２ＮＨ１→２Ａ
ＩＮ＋３ＣＯ＋９）Ｉｔ という反応が起こり粉末表面
の酸化アルミニウムが還元窒化され不純物酸素量が激減
する。そのため、焼成時間を短くすることができる。焼
成時間条件を緩和できるようになるのである。In the manufacturing method of the present invention, aluminum nitride powder as a raw material powder is reduced in an atmosphere containing hydrocarbons and nitrogen. For example, when the atmosphere contains methane and ammonia, 8It's + 3C) + 4 + 2NH1→ 2A
The reaction IN+3CO+9)It occurs, and the aluminum oxide on the powder surface is reduced and nitrided, and the amount of impurity oxygen is drastically reduced. Therefore, the firing time can be shortened. This allows the firing time conditions to be relaxed.
焼結助剤は各窒化アルミニウム粉末表面に付着している
ため、焼成する成形体では焼結助剤が全体に広く薄くま
んべんなく分散して混じり合った状態にある。このため
、従来より低目でも、焼結助剤、アルミニウム、酸素が
、複合酸化物液相を全粒界に素早く現出させられるよう
になる。焼成温度条件を緩和できるようになるのである
。Since the sintering aid is attached to the surface of each aluminum nitride powder, the sintering aid is thinly and evenly dispersed and mixed throughout the molded body to be fired. Therefore, the sintering aid, aluminum, and oxygen can quickly cause the composite oxide liquid phase to appear at all grain boundaries, even if the content is lower than before. This makes it possible to relax the firing temperature conditions.
窒化アルミニウム粉末は粒径が小さいほど焼成温度は低
くてすむ。しかし、従来、粒径の小さな粉末は酸化し易
く使い難かった。一方、還元処理した窒化アルミニウム
粉末表面も非常に活性で再酸化し易い。還元処理したま
まの粉末だと、保存過程、バインダー・溶剤混合過程、
造粒過程、成形過程で再酸化される恐れが強い、しかし
、この発明で得た窒化アルミニウム粉末は表面に焼結助
剤膜があるため、粒径が小さくても酸化され難い。した
がって、原料粉末に粒径の小さいものを用い焼成温度を
下げることもできるようになる。The smaller the particle size of aluminum nitride powder, the lower the firing temperature. However, in the past, powders with small particle sizes were easily oxidized and difficult to use. On the other hand, the surface of the reduced aluminum nitride powder is also very active and easily reoxidized. If the powder remains after reduction treatment, it will be difficult to preserve the powder during the storage process, binder/solvent mixing process,
There is a strong possibility that it will be re-oxidized during the granulation and molding processes, but since the aluminum nitride powder obtained by this invention has a sintering aid film on its surface, it is difficult to be oxidized even if the particle size is small. Therefore, it becomes possible to use a raw material powder with a small particle size and lower the firing temperature.
以下、この発明の詳細な説明する。 The present invention will be explained in detail below.
一実施例１−
窒化アルミ゛ニウム粉末（徳山曹達製 Ｆグレード 酸
素含有率０．８９ｗｔ％ −次粒子径０．６ｎ）を透明
石英製管状炉にて還元処理した。雰囲気は、メタン、ア
ンモニア、窒素の混合ガス雰囲気である。混合ガスをオ
ーバフローさせるようにして、１０００℃、１時間熱処
理した。Example 1 - Aluminum nitride powder (F grade, manufactured by Tokuyama Soda, oxygen content 0.89 wt% - primary particle size 0.6 n) was reduced in a transparent quartz tubular furnace. The atmosphere is a mixed gas atmosphere of methane, ammonia, and nitrogen. Heat treatment was performed at 1000° C. for 1 hour while allowing the mixed gas to overflow.
続いて、炉内温度を８００℃に落として、トリスジピバ
ロイルメタナトイツトリウム（￥（ＤＰＭ）、：日本化
学産業製〕を１６０℃で蒸発させＮ鵞をキャリアガスに
して炉内に送り込み、窒化アルミニウム粉末表面に（Ｃ
ＶＤ法による）イツトリウム膜を形成し、その後、続い
て酸素５ ｐｐｍ含有のＮ、ガスを導入しイツトリウム
膜を酸化し焼結助剤膜を形成した。酸化イツトリウム付
着量は窒化アルミニウム粉末に対して３ｗｔ％の量であ
った。Next, the temperature inside the furnace was lowered to 800°C, tris-dipivaloylmethanatritrium (DPM, manufactured by Nippon Kagaku Sangyo) was evaporated at 160°C, and nitrogen was used as a carrier gas and sent into the furnace. , on the surface of aluminum nitride powder (C
A yttrium film (by VD method) was formed, and then N gas containing 5 ppm of oxygen was introduced to oxidize the yttrium film to form a sintering aid film. The amount of yttrium oxide deposited was 3 wt% based on the aluminum nitride powder.
このようにして得た窒化アルミニウム粉末を常法により
成形し、１７００℃、Ｎ、雰囲気中、１時間焼成し、直
径１０龍、厚み３龍の窒化アルミニウム基板を得た。The aluminum nitride powder thus obtained was molded by a conventional method and fired at 1700° C. in a N atmosphere for 1 hour to obtain an aluminum nitride substrate having a diameter of 10 mm and a thickness of 3 mm.
一実施例２−
焼成温度を１８００℃とした他は、実施例１と同様にし
て直径１（ｉｎ、厚み３１１の窒化アルミニウム基鈑を
得た。Example 2 An aluminum nitride base plate having a diameter of 1 inch and a thickness of 311 mm was obtained in the same manner as in Example 1, except that the firing temperature was 1800°C.
一実施例３−
原料粉末である窒化アルミニウム粉末として、（三井東
圧製 ＬＴグレード 酸素含有率０．８ｗｔ％ −次粒
子径０．２ｐｍ）を用いるとともに、焼成温度を１６５
０℃とした他は、実施例１と同様にして直径１０關、厚
み３ｎの窒化アルミニウム基板を得た。Example 3 - (Mitsui Toatsu LT grade, oxygen content 0.8 wt% - primary particle size 0.2 pm) was used as the raw material powder, aluminum nitride powder, and the firing temperature was 165 pm.
An aluminum nitride substrate having a diameter of 10 mm and a thickness of 3 nm was obtained in the same manner as in Example 1, except that the temperature was 0°C.
一実施例４−
焼成温度を１６５０℃、焼成時間を３時間とした他は、
実施例１と同様にして直径１０ｎ、厚み３鰭の窒化アル
ミニウム基板を得た。Example 4 - The firing temperature was 1650°C and the firing time was 3 hours.
An aluminum nitride substrate having a diameter of 10 nm and a thickness of 3 fins was obtained in the same manner as in Example 1.
一実施例５−
窒化アルミニウム粉末（徳山曹達製 Ｆグレード 酸素
含有率０．８９ｗｔ％ −次粒子径０．６ｎ）を９９．
５％のＡｊ’ｔＯｍ管を用いた縦型管状炉で還元処理し
た。雰囲気は、エチレン、アンモニア、窒素の混合ガス
雰囲気である。混合ガスをオーバフローさせるようにし
て処理粉末を流動化させておいて、８００℃、１時間熱
処理した。Example 5 - Aluminum nitride powder (manufactured by Tokuyama Soda, F grade, oxygen content 0.89 wt% - particle size 0.6 n) was 99.
Reduction treatment was carried out in a vertical tube furnace using a 5% Aj'tOm tube. The atmosphere is a mixed gas atmosphere of ethylene, ammonia, and nitrogen. The treated powder was fluidized by overflowing the mixed gas, and heat treated at 800° C. for 1 hour.
その後、窒素ガスを流しながら室温まで冷却し、素早く
スパッタリングチャンバー内に移し、機械的に攪拌しな
がら（ファンで処理粉末を舞わせながら）、酸化イツト
リウムをスパッタリング法にて蒸着形成し焼結助剤膜を
形成した。酸化イツトリウム付着量は窒化アルミニウム
粉末に対して３ｗｔ％の量であった。After that, it is cooled to room temperature while flowing nitrogen gas, quickly transferred to a sputtering chamber, and while being mechanically stirred (while scattering the treated powder with a fan), yttrium oxide is deposited by sputtering to form a sintering aid. A film was formed. The amount of yttrium oxide deposited was 3 wt% based on the aluminum nitride powder.
このようにして得た窒化アルミニウム粉末を常法により
成形し、１７００℃、Ｎ、雰囲気中、１時間焼成し、直
径１０霞、厚み３鶴の窒化アルミニウム基板を得た。The aluminum nitride powder thus obtained was molded by a conventional method and fired at 1700° C. in a N atmosphere for 1 hour to obtain an aluminum nitride substrate having a diameter of 10 mm and a thickness of 3 mm.
一比較例１−
窒化アルミニウム粉末（徳山曹達製 Ｆグレード 酸素
含有率０．８９ｗｔ％ −次粒子径０．６Ｊ１ｍ）に酸
化イツトリウム粉末を３ｗｔ％添加混合し常法により成
形して、１８００℃、Ｎ、雰囲気中、１時間焼成し、直
径１０１１、厚み３１１の窒化アルミニウム基板を得た
。Comparative Example 1 - 3 wt % yttrium oxide powder was added to and mixed with aluminum nitride powder (F grade manufactured by Tokuyama Soda, oxygen content 0.89 wt % - secondary particle size 0.6 J1 m), molded by a conventional method, and heated to 1800°C with N , in an atmosphere for 1 hour to obtain an aluminum nitride substrate having a diameter of 1011 mm and a thickness of 311 mm.
実施例１〜５および比較例１の各窒化アルミニウム基板
の熱伝導率をレーザフラッシュ法により測定した。測定
結果を、第１表に記す。The thermal conductivity of each aluminum nitride substrate of Examples 1 to 5 and Comparative Example 1 was measured by a laser flash method. The measurement results are shown in Table 1.
第
表
第１表にみるように、実施例１〜５で得た窒化アルミニ
ウム粉末を用いた場合、従来はどの高温・長時間焼成で
なくとも十分な熱伝導率の窒化アルミニウム基板を得る
ことが出来ることが分かる。実施例１と比較例１を比べ
れば、この発明による窒化アルミニウム粉末を用いた場
合、焼成温度が１００℃低く、焼成時間が１／３で十分
な熱伝導率の窒化アルミニウム基板が得られることが分
かる。As shown in Table 1, when using the aluminum nitride powders obtained in Examples 1 to 5, it was conventionally possible to obtain aluminum nitride substrates with sufficient thermal conductivity without any high-temperature, long-time firing. I know it can be done. Comparing Example 1 and Comparative Example 1, it can be seen that when the aluminum nitride powder according to the present invention is used, an aluminum nitride substrate with sufficient thermal conductivity can be obtained at a 100°C lower firing temperature and 1/3 the firing time. I understand.
以上に述べたように、この発明の製造方法によれば、焼
成温度条件あるいは焼成時間条件を従来よりも緩めて安
価に良熱伝導率の窒化アルミニウム基板を作れる窒化ア
ルミニウム粉末を得ることができる。As described above, according to the manufacturing method of the present invention, it is possible to obtain aluminum nitride powder that enables the production of aluminum nitride substrates with good thermal conductivity at low cost by relaxing firing temperature conditions or firing time conditions compared to conventional ones.
第１図は、原料粉末である窒化アルミニウム粉末の模式
的断面図、第２図は、還元処理後の窒化アルミニウム粉
末の模式的断面図、第３図は、焼結助剤膜形成後の窒化
アルミニウム粉末の模式的断面図である。
１・・・原料粉末の窒化アルミニウム粉末 １′・・・
還元処理後の窒化アルミニウム粉末 １″・・・焼結助
剤膜形成後の窒化アルミニウム粉末
代理人 弁理士 松 本 武 彦
第
図
第２ 図
第
図
手続補正書（自如
平成２年）月、５−日
１．１１牛の耘
情評２−１６７７３０号
２、発明の名称
窒化アルミニウム粉末の製造方法
３、補正をする者
躬牛との■系 特許出願人
住 所 大阪府門真市大字門真１０４８番地名
称（５８３）松下電工株式会社
代表者 （（ＪＭＪ役三 好 俊夫
４、代理人
な
し
６、補正の対象
明細書
７、補正の内容
■ 明細書の特許請求の範囲欄の全文を下記のとおりに
訂正する。
一記一
「１ 原料粉末たる窒化アルミニウム粉末を、炭化水素
および窒素を含む雰囲気で熱処理した後、この窒化アル
ミニウム粉末の表面に焼結助剤膜を形成するようにする
窒化アルミニウム粉末の製造方法。
２ 焼結助剤膜形成用物質を窒化アルミニウム粉末の表
面に蒸着するようにする請求項１記載の窒化アルミニウ
ム粉末の製造方法。
３ 焼結助剤が、希土類酸化物、アルカリ土類酸化物の
うちの少なくともひとつである請求項１または２記載の
窒化アルミニウム粉末の製造方法４ 希土類酸化物が酸
化イツトリウムであり、アルカリ土類酸化物が酸化カル
シウムである請求項３記載の窒化アルミニウム粉末の製
造方法。」■ 明細書第３頁第２０行〜第４頁第１行に
「焼結助剤を添加するからである。」とあるを、「焼結
助剤を粉末で添加することに起因している。
」と訂正する。
■ 明細書第４頁第９行に「粉末で添加した焼結助剤が
あるために」とあるを、「焼結助剤を粉末で添加するた
めに」と訂正する。
■ 明細書第５頁第５行、第７頁第１８行、第９頁第６
行および第９頁第１５行の計４個所に「還元処理」とあ
るを、「熱処理」と訂正する。
■ 明細書第１４頁第１〜２行に「１時間」とあるを、
「３時間」と訂正する。Fig. 1 is a schematic cross-sectional view of aluminum nitride powder, which is a raw material powder, Fig. 2 is a schematic cross-sectional view of aluminum nitride powder after reduction treatment, and Fig. 3 is a schematic cross-sectional view of aluminum nitride powder after forming a sintering aid film. FIG. 2 is a schematic cross-sectional view of aluminum powder. 1... Aluminum nitride powder as raw material powder 1'...
Aluminum nitride powder after reduction treatment 1″...Aluminum nitride powder after sintering aid film formation Agent Patent attorney Takehiko Matsumoto Figure 2 Figure Procedure Amendment (Jijo 1990) May, 5 -Japanese 1.11 Ushi no Genjohyo 2-167730 No. 2, Title of the invention: Process for producing aluminum nitride powder 3, Person making the amendment ■ System with Ugyu Patent applicant address: 1048 Kadoma, Kadoma City, Osaka Prefecture Name (583) Representative of Matsushita Electric Works Co., Ltd. 1. Aluminum nitride powder that forms a sintering aid film on the surface of the aluminum nitride powder after heat treating the aluminum nitride powder, which is the raw material powder, in an atmosphere containing hydrocarbons and nitrogen. 2. The method for producing aluminum nitride powder according to claim 1, wherein the sintering aid film-forming substance is vapor-deposited on the surface of the aluminum nitride powder. 3. The sintering aid is a rare earth oxide, an alkaline earth 4. The method for producing aluminum nitride powder according to claim 1 or 2, wherein the rare earth oxide is yttrium oxide, and the alkaline earth oxide is calcium oxide. ``Method for producing powder.''■ On page 3, line 20 to page 4, line 1 of the specification, ``This is because a sintering aid is added.'' is replaced with ``The sintering aid is added in the form of a powder.'' ”. ■ On page 4, line 9 of the specification, the statement “due to the presence of a sintering aid added in the form of powder” has been corrected to “due to the addition of the sintering aid in the form of powder.” "For the purpose". ■ Page 5, line 5 of the specification, page 7, line 18, page 9, line 6
The words ``reduction treatment'' in four places in the following lines and page 9, line 15 have been corrected to read ``heat treatment.'' ■ The statement “1 hour” on page 14, lines 1-2 of the specification,
Correct it to "3 hours."
Claims (1)
よび窒素を含む雰囲気で還元処理した後、この窒化アル
ミニウム粉末の表面に焼結助剤膜を形成するようにする
窒化アルミニウム粉末の製造方法。 ２ 焼結助剤膜形成用物質を窒化アルミニウム粉末の表
面に蒸着するようにする請求項１記載の窒化アルミニウ
ム粉末の製造方法。 ３ 焼結助剤が、希土類酸化物、アルカリ土類酸化物の
うちの少なくともひとつである請求項１または２記載の
窒化アルミニウム粉末の製造方法４ 希土類酸化物が酸
化イットリウムであり、アルカリ土類酸化物が酸化カル
シウムである請求項３記載の窒化アルミニウム粉末の製
造方法。[Claims] 1. Aluminum nitride powder, which is a raw material powder, is reduced in an atmosphere containing hydrocarbons and nitrogen, and then a sintering aid film is formed on the surface of the aluminum nitride powder. Production method. 2. The method for producing aluminum nitride powder according to claim 1, wherein the sintering aid film-forming substance is vapor-deposited on the surface of the aluminum nitride powder. 3. The method for producing aluminum nitride powder according to claim 1 or 2, wherein the sintering aid is at least one of a rare earth oxide and an alkaline earth oxide. 4. The rare earth oxide is yttrium oxide, and the alkaline earth oxide 4. The method for producing aluminum nitride powder according to claim 3, wherein the substance is calcium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2167730A JPH0455369A (en) | 1990-06-25 | 1990-06-25 | Production of aluminum nitride powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2167730A JPH0455369A (en) | 1990-06-25 | 1990-06-25 | Production of aluminum nitride powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0455369A true JPH0455369A (en) | 1992-02-24 |
Family
ID=15855090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2167730A Pending JPH0455369A (en) | 1990-06-25 | 1990-06-25 | Production of aluminum nitride powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0455369A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0732445A (en) * | 1993-07-23 | 1995-02-03 | Shinagawa Refract Co Ltd | Mgo part stabilized zro2 sintered body die or nipple |
-
1990
- 1990-06-25 JP JP2167730A patent/JPH0455369A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0732445A (en) * | 1993-07-23 | 1995-02-03 | Shinagawa Refract Co Ltd | Mgo part stabilized zro2 sintered body die or nipple |
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