JPWO2011155319A1 - 回路基板用窒化アルミニウム基板及びその製造方法 - Google Patents
回路基板用窒化アルミニウム基板及びその製造方法 Download PDFInfo
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- JPWO2011155319A1 JPWO2011155319A1 JP2012519327A JP2012519327A JPWO2011155319A1 JP WO2011155319 A1 JPWO2011155319 A1 JP WO2011155319A1 JP 2012519327 A JP2012519327 A JP 2012519327A JP 2012519327 A JP2012519327 A JP 2012519327A JP WO2011155319 A1 JPWO2011155319 A1 JP WO2011155319A1
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- aluminum nitride
- grain boundary
- boundary phase
- nitride substrate
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 126
- 239000000758 substrate Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
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- 238000000034 method Methods 0.000 claims abstract description 17
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 5
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- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 4
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- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 239000002244 precipitate Substances 0.000 description 3
- 150000002909 rare earth metal compounds Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- -1 acrylate ester Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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Abstract
Description
上記において、一態様では、粒界相は、不連続に分散した非樹枝状の粒界相である。また別の態様では、窒化アルミニウム基板の鏡面研磨面から測定される粒界相の個数基準粒子径分布における累積10%粒子径d10が0.6μm以上であり、累積50%粒子径d50が1.6μm以下である。
ここで、窒化アルミニウム粉末は、特に限定されないが、一実施態様では、不純物として、酸素含有量が1.2質量%以下、カーボン含有量が0.04質量%以下、Fe含有量が30ppm以下、Si含有量が60ppm以下である粉末が挙げられる。また、原料には、通常は焼結助剤が含められるが、かかる焼結助剤としては、一実施態様では、希土類金属化合物、アルカリ土類金属化合物、遷移金属化合物が使用される。
(i)窒化アルミニウム粉末を含む原料を準備する原料準備工程と、
(ii)前記原料を圧力150Pa以下で1500℃まで加熱し、その後、非酸化性ガスで圧力0.4MPa以上の加圧雰囲気として1700〜1900℃まで昇温、保持した後、1600℃まで10℃/分以下の冷却速度で冷却する焼結工程と
を具備する。
窒化アルミニウム粉末の他に、焼結助剤、バインダー、可塑剤、分散媒、離型剤等の添加剤が適宜使用される。窒化アルミニウム粉末は、特に限定されるものではなく、金属アルミニウムを窒素雰囲気下で窒化する直接窒化法、アルミナをカーボンで還元する還元窒化法等の公知の方法で製造された窒化アルミニウム粉末が使用できるが、中でも、高純度かつ微粉であるものが好ましい。具体的には、不純物として、酸素含有量が1.2質量%以下、カーボン含有量が0.04質量%以下、Fe含有量が30ppm以下、Si含有量が60ppm以下であるものが好適に使用され、また、最大粒子径が20μm以下であることがより好ましい。ここで、酸素は基本的には不純物であるが、焼結過多を防止する作用を有しており、よって、焼結過多による焼結体の強度低下を防止するためには、酸素含有量が0.7質量%以上のものを使用するのが好ましい。
原料準備工程(i)で得られた原料(脱脂体)を焼結して窒化アルミニウム焼結体を得る。当該工程では、先ず、焼結炉内の圧力を150Pa以下とし、1500℃まで加熱する。これにより、脱脂体中の残留カーボンが除去され、好ましい焼結体組織と熱伝導性を有する窒化アルミニウム焼結体が得られる。ここで、炉内圧力が150Paを越えると、カーボンの除去が不十分となり、また1500℃を越えて加熱すると、窒化アルミニウム結晶粒子の緻密化が一部で進行し、カーボンの拡散経路が閉ざされてしまうため、カーボンの除去が不十分となってしまう。
ここで、非酸化性雰囲気とは、酸素等の酸化性ガスを含まない不活性ガス雰囲気や還元性雰囲気等を意味する。
また、炉内の圧力は、0.4MPa以上とするのが好ましく、0.4MPa未満では液相化した焼結助剤が粒界相として析出する前に揮発し、窒化アルミニウム結晶粒子間に空隙が発生するため、窒化アルミニウム基板の絶縁特性が低下してしまう。また、冷却方法は、焼結炉のヒーター温度を制御することにより、実施できる。
窒化アルミニウム粉末97質量部に、酸化イットリウム粉末3質量部を添加し、ボールミルにおいて1時間混合して混合粉末を得た。この混合粉末100質量部にセルロースエーテル系バインダー6質量部、グリセリン5質量部、イオン交換水10質量部を添加し、ヘンシェルミキサーにおいて1分間混合し、混合物を得た。次に、この混合物を単軸押出機において厚み0.8mmのシート状に成形し、金型付きプレス機により90mm×90mmの寸法に打ち抜いた。成形シートに離型剤として窒化ホウ素粉を塗布した後、15枚を積層し、空気中において570℃で5時間加熱し脱脂した。次に、脱脂体を真空・加圧炉に移し、炉内圧力100Paで1500℃まで加熱した。その後、窒素を導入して炉内圧力0.6MPaの加圧雰囲気として1750℃まで昇温し、2時間保持した後、1600℃までを1℃/分の冷却速度で冷却し、窒化アルミニウム基板を得た。得られた窒化アルミニウム基板について、窒化アルミニウム結晶粒子の平均粒子径、樹枝状粒界相の有無、粒界相の個数基準粒子径分布、熱伝導率、25℃及び400℃における絶縁破壊電圧を評価した。結果を表1に示す。
窒化アルミニウム粉末:平均粒径1.2μm、酸素含有量0.8質量%。
酸化イットリウム粉末:信越化学工業社製、商品名「Yttrium Oxide」
バインダー:信越化学工業社製、商品名「メトローズ」
グリセリン:花王社製、商品名「エキセパール」
窒化ホウ素粉:電気化学工業社製、商品名「デンカボロンナイトライドMGP」
窒化アルミニウム結晶粒子の平均粒子径:窒化アルミニウム基板の破断面を走査型電子顕微鏡で2000倍に拡大し、50個の窒化アルミニウム結晶粒子の粒子径を測定し、平均値を算出した。
樹枝状粒界相の有無:1gの窒化アルミニウム基板を50mlの20%水酸化ナトリウム水溶液に入れ、130℃で12時間保持し、窒化アルミニウム結晶粒子が溶解するまで静置し、その後、濾過、洗浄により残留した粒界相を取り出し、走査型電子顕微鏡によって観察することで確認した。
粒界相の個数基準粒子径分布:窒化アルミニウム基板の破断面をビューラー社製「自動研磨装置エコメット3」により研磨し、その研磨面を走査型電子顕微鏡で500倍に拡大し、粒界相の分布状態を観察した(観察領域155μm×231μm)。図3に窒化アルミニウム基板の鏡面研磨面を走査型電子顕微鏡で観察した一例を示す。得られた画像をMedia Cybernetics社製「Image−Pro Plus 6.2J」により画像解析処理し、累積10%粒子径d10及び累積50%粒子径d50を算出した。
熱伝導率:アルバック理工社製「レーザーフラッシュ法熱定数測定装置TC−7000」により測定した。
25℃及び400℃における絶縁破壊電圧:400℃に加熱できる加熱炉内に電極を設け、交流耐電圧測定装置を併設することにより測定できる。測定時の雰囲気の影響を排除するために、炉内の雰囲気を窒素雰囲気0.3MPaとして測定を行った。所定の温度に保たれた加熱炉において、窒化アルミニウム基板の上下面に球状電極を配置し、JIS C2110に準じて試料に電圧を加え、絶縁破壊が生じたときの電圧を測定した。絶縁破壊が生じたときの電圧を試料の厚みで除することで絶縁破壊電圧を算出した。
1500℃までの焼結雰囲気を表1に示すように変えたこと以外は、実施例1と同様にして窒化アルミニウム基板を得た。結果を表1に示す。
1500℃から焼結温度までの焼結雰囲気を表1に示すように変えたこと以外は、実施例1と同様にして窒化アルミニウム基板を得た。結果を表1に示す。
焼結温度を表1に示すように変えたこと以外は、実施例1と同様にして窒化アルミニウム基板を得た。結果を表1に示す。
冷却速度を表1に示すように変えたこと以外は、実施例1と同様にして窒化アルミニウム基板を得た。結果を表1に示す。
焼結雰囲気と冷却速度を表1に示すように変えたこと以外は、実施例1と同様にして窒化アルミニウム基板を得た。結果を表1に示す。
1500℃までの焼結雰囲気を表1に示すように変えたこと以外は、実施例1と同様にして窒化アルミニウム基板を得た。結果を表1に示す。
1500℃から焼結温度までの焼結雰囲気を表1に示すように変えたこと以外は、実施例1と同様にして窒化アルミニウム基板を得た。結果を表1に示す。
焼結温度を表1に示すように変えたこと以外は、実施例1と同様にして窒化アルミニウム基板を得た。結果を表1に示す。
冷却速度を表1に示すように変えたこと以外は、実施例1と同様にして窒化アルミニウム基板を得た。結果を表1に示す。
Claims (5)
- 平均粒子径が2〜5μmである窒化アルミニウム結晶粒子を有し、熱伝導率が170W/m・K以上である回路基板用窒化アルミニウム基板において、樹枝状の粒界相を含有せず、400℃における絶縁破壊電圧が30kV/mm以上である、回路基板用窒化アルミニウム基板。
- 粒界相が不連続に分散した非樹枝状の粒界相である、請求項1に記載の回路基板用窒化アルミニウム基板。
- 窒化アルミニウム基板の鏡面研磨面から測定される粒界相の個数基準粒子径分布における累積10%粒子径d10が0.6μm以上であり、累積50%粒子径d50が1.6μm以下である、請求項1又は2に記載の回路基板用窒化アルミニウム基板。
- 窒化アルミニウム粉末を含む原料を圧力150Pa以下で1500℃まで加熱し、その後、非酸化性ガスで圧力0.4MPa以上の加圧雰囲気として1700〜1900℃まで昇温、保持した後、1600℃まで10℃/分以下の冷却速度で冷却することにより製造される、請求項1から3の何れか一項に記載の回路基板用窒化アルミニウム基板。
- 窒化アルミニウム粉末を含む原料を圧力150Pa以下で1500℃まで加熱し、その後、非酸化性ガスで圧力0.4MPa以上の加圧雰囲気として1700〜1900℃まで昇温、保持した後、1600℃まで10℃/分以下の冷却速度で冷却する工程を具備する、請求項1から3の何れか一項に記載の回路基板用窒化アルミニウム基板の製造方法。
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