JPH0369873B2 - - Google Patents
Info
- Publication number
- JPH0369873B2 JPH0369873B2 JP3382486A JP3382486A JPH0369873B2 JP H0369873 B2 JPH0369873 B2 JP H0369873B2 JP 3382486 A JP3382486 A JP 3382486A JP 3382486 A JP3382486 A JP 3382486A JP H0369873 B2 JPH0369873 B2 JP H0369873B2
- Authority
- JP
- Japan
- Prior art keywords
- metallized layer
- aln
- group
- sintering
- elements
- 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.)
- Expired
Links
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 49
- 238000005245 sintering Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000005219 brazing Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000833 kovar Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 235000000396 iron Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
［発明の技術分野］
本発明は、その表面に高い接合強度で導電性メ
タライズ層が形成されている窒化アルミニウム
（AlN）焼結体の製造方法に関し、更に詳しく
は、AlNの焼結前駆体を焼結すると同時にその
表面に高い接合強度で導電性メタライズ層を形成
する方法に関する。
［従来技術とその問題点］
AlN焼結体は熱伝導性が良好で放熱性に優れ、
かつ電気絶縁性を有するので、半導体用の基板材
料として注目を集めている。
このAlN焼結体は概ね次のようにして製造さ
れる。すなわち、AlN粉末にY2O3，Sm2O3，
CaOのような焼結助剤を所定量配合し、更に必要
に応じてアクリル系樹脂バインダーなどを添加し
て全体を充分に混合し、得られた混合体を例えば
加圧成形して所定形状のAlN焼結前駆体（生成
形体）としたのち、これを例えば窒素雰囲気中に
て所定温度で焼結するのである。
ところで、半導体用の基板としてAlN焼結体
を用いる場合には、このAlN焼結体の表面に導
電性の薄層を形成することが必要となる。従来、
この薄層はAlN焼結体の表面にDBC法（Direct
Bond Cupper法）や厚膜法を適用して形成され
た銅（Cu），金（Au），銀−パラジウム（Ag−
Pd）のメタライズ層であつた。
しかしながら、従来のこの基板においては次の
ような問題がある。
その第１は、形成された上記メタライズ層と
AlN焼結体表面との接合強度が低く往々にして
両者間に剥離現象が発生して基板の信頼性が低い
ということである。
第２の問題は、形成したメタライズ層に所定の
半導体素子若しくはワイヤをろう付けしたり高温
半田付けしたりする際に生起する問題である。す
なわち、例えばろう付けの場合は水素−窒素混合
ガス中において約800℃近辺の温度で行なわれる
が、しかしながら上記メタライズ層焼付け処理時
の温度は通常600〜1000℃程度の低温であるため、
このろう付け時にメタライズ層とAlN焼結体表
面との間の接合強度が著しく低下してしまい事実
上ろう付けが不可能になるということである。ま
た、高温半田付けの場合も同様の問題が発生す
る。
第３の問題は、AlN焼結体とメタライズ層と
の熱膨張率の差異に基づく問題である。すなわ
ち、ろう付け、高温半田付けの場合もそうである
が、シリコンウエハーのような半導体素子をマウ
ントせしめた基板はその使用時に過酷な加熱−冷
却の熱サイクルを経験する。その結果、AlN焼
結体−メタライズ層−ろう付け層（又は半田層）
−半導体素子のそれぞれの接合面では、各層の熱
膨張率の差異に基づく熱応力が発生してそれぞれ
を剥離せしめる作用が生ずる。
上記したメタライズ層の場合、AlN焼結体
（熱膨張率は約4.6×10-6／℃）の熱膨張率よりも
その値が約２〜４倍大きく、またろう付層（又は
半田層）と同等の値から1/2位の値であつてAlN
との差が大きいので、熱サイクル時にメタライズ
層又はろう付け層（若しくは半田層）とAlNの
界面に微小クラツクが発生し易い。熱サイクルが
加重されるにつれてこの微小クラツクは徐々に発
達し、最終的にはマウントした半導体素子の剥離
を招くことがある。
このような問題は半導体素子をマウントせしめ
た基板を実装した装置の信頼性を低下せしめて極
めて不都合である。
第４の問題は、上記メタライズ層とAlN焼結
体との高温下における接合強度が小さく、第２の
場合と同様に高温使用時の信頼性は低いというこ
とである。
第５は、完成された基板からその製作工程を逆
視した場合、熱エネルギー使用の面で不経済であ
るということである。すなわち、完成基板を得る
ためには、AlN焼結前駆体を焼結し、その上で
この焼結したものをメタライズ層形成のために再
び焼成するという問題である。
［発明の目的］
本発明は上記したような問題を解決し、AlN
焼結前駆体を焼結すると同時にその表面に、
AlN焼結体と熱膨張率が近似しており、耐熱性
も高く、しかも接合強度も高い導電性メタライズ
層を形成する方法の提供を目的とする。
［発明の概要］
本発明者らは上記目的を達成すべく鋭意研究を
重ねた結果、焼結前のAlN成形体に後述するペ
ーストを塗布し、両者を同時に焼結すると優れた
メタライズ層をAlN焼結体の表面に形成するこ
とができるとの事実を確認して本発明方法を開発
するに到つた。
すなわち、本発明の導電性メタライズ層を有す
るAlN焼結体の製造方法は、AlNの焼結前駆体
にモリブデン（Mo）、タングステン（Ｗ）およ
びタンタル（Ta）からなる群から選ばれる単体
またはそれらの１種若しくは２種以上を含有する
化合物の少なくとも１種と、Al、周期律表の
ａ族元素および希土類元素（希土類元素はSc，
Ｙを含むランタン系である）からなる群から選ば
れる単体またはそれらの１種若しくは２種以上を
含有する化合物の少なくとも１種とを含むペース
トを塗布し、ついで全体を同時に焼結することを
特徴とする。
まず、本発明方法が適用されるAlN焼結前駆
体は、例えば所定粒度のAlN粉末と、Y2O3，
YF3，Sm2O3，CaCO3のよえな焼結助剤の粉末と
ワツクス系または、プラスチツク系のようなバイ
ンダー成分とを所定量比で混合し、この混合体を
室温下において加圧成形又はドクターブレードに
よりシート状に成形した成形体である。AlN粉
末，焼結助剤粉末の粒度，混合比，または成形圧
等は目的とするAlN焼結体の特性との関係で適
宜選定される。
本発明方法においては、このAlN焼結前駆体
は焼結後にその熱伝導率が50W／ｍ・Ｋ以上とな
るようなものであることが好ましい。
このAlN焼結前駆体に、後述する組成のペー
ストが塗布される。塗布方法としては、例えばス
クリーン印刷，刷毛塗り，スピンローラー塗りな
ど周知の方法を適用すればよい。
本発明方法にかかるペーストは、焼結後メタラ
イズ層に転化する２つのグループ成分，とそ
れらを分散せしめる媒体とで構成される。
Mo，ＷおよびTaの群から選ばれた単体または
これら元素をそれぞれ１種若しくは２種以上化む
化合物の少なくとも１種である。
具体的には次のような成分である。すなわち、
Mo，ＷまたはTaの単体金属；これらの各種酸化
物；これらの各種炭化物；これらの各種ホウ化
物；これらの各種ケイ化物；これらの各種酸窒化
物；これらの各種炭窒化物；これらの各種ハロゲ
ン化物；これらの各種水素化物；これらの各種水
酸化物；これらの元素の亜硝酸塩，硝酸塩，亜硫
酸塩，硫酸塩，ホウ酸塩，炭酸塩，ケイ酸塩，リ
ン酸塩，亜リン酸塩，塩酸塩，塩素酸塩，シユウ
酸塩，アルミニウム塩のような各種の塩；アトロ
ンNTa／700（商品名：日本曹達(株)製）等のアル
コキシド，ゾルーゲルのような各種の有機金属化
合物；並びに上記した成分の２種以上を適宜に混
合した混合物をあげることができる。これらの成
分はそれぞれ単独で用いてもよいし、また適宜に
選定した２種以上を組合わせて用いてもよい。
形成すべきメタライズ層の導電性を高めるとい
う点では、とくにMo，Ｗ，Taの各単体金属であ
ることが好ましい。また、融点が高く、メタライ
ズ層の高温における安定性が優れている点で、Ｗ
がとくに好ましい。
グループの成分としては、Al、周期律表の
ａ族元素および希土類元素（希土類元素はSc，
Ｙを含むランタン系である）からなる群から選ば
れる単体またはこれら元素をそれぞれ１種若しく
は２種以上含む化合物の少なくとも１種である。
これらのうち、ａ族元素としては、Ti，Zr，
Hfをあげることができる。とくにTiはグループ
の成分がいかなるものであつた場合でも、焼結
後は良好なメタライズ層を形成することができて
好適である。希土類元素としては、Sc，Ｙ，La，
Ce，Pr，Nd，Sm，Gd，Dy等をあげることがで
きる。このうち、Ｙ，Ce，Pr，Nd，Sm，Dyが
効果的であり、とくにＹ，Smは好適である。
グループの成分としては具体的に次のような
ものをあげることができる。すなわち、Alａ
族元素および希土類元素のそれぞれの単体；これ
ら各元素の酸化物；これらの各元素の窒化物；こ
れらの各元素の炭化物；これら各元素のホウ化
物；これらの各元素のケイ化物；これら各元素の
酸窒化物；これら各元素の炭窒化物；これら各元
素のハロゲン化物；これら各元素の水素化物；こ
れらの各元素の水酸化物；これら各元素の亜硝酸
塩，硝酸塩，亜硫酸塩，硫酸塩，ホウ酸塩，炭酸
塩，ケイ酸塩，リン酸塩，亜リン酸、塩酸塩，塩
素酸塩，シユウ酸塩，アルミニウム塩のような各
種の塩；アトロンNTi（商品名：日本曹達(株)製）
等のアルコキシド，ゾルーゲルのような各種の有
機金属化合物；並びに上記した成分の２種以上を
適宜に混合した混合物をあげることができる。こ
れらの成分はそれぞれ単独で用いてもよいし、ま
た適宜に選定した２種以上を組合わせて用いても
よい。
これらグループの成分とグループの成分と
を媒体に均一分散せしめて本発明にかかるペース
トが調製される。用いる媒体としては、例えばエ
チルセルロース，ニトロセルロースとそれら溶剤
としてテレピネオール，テトラリン，ブチルカル
ビトールをあげることができる。
なお、グループの成分は、形成されたメタラ
イズ層において主にその導電性及び耐熱性を高位
の水準に維持するための有効成分であり、また、
グループの成分は、上記グループの成分を結
着せしめてメタライズ層の強度を保持するに有効
な成分であると推考される。
このときグループ成分とグループ成分との
量比関係は、それぞれに選定された成分の種類に
よつて変動するが、通常、重量比で、グループ
成分／グループ成分＝１〜100〜100／１であれ
ばよい。
また、グループ成分のうち、第族系のもの
が重量比で１／２〜２／１，第族系のものが
１／５〜１／１であるものは好適である。
グループの成分がグループの成分よりもあ
まり多すぎる場合は形成されたメタライズ層の強
度が低下し、また逆の場合はその導電性が満足す
べき水準に達しないからである。
グループの成分とグループの成分の媒体へ
の分散量は、得られたペーストの粘稠性との関係
で適宜決められる。前者が過多量である場合は、
得られたペーストが高粘稠となりAlN焼結前駆
体の表面への均一塗布が困難となる。また、その
逆の場合は、ペースト粘度が低くなり塗布したペ
ーストはAlN焼結前駆体の表面から流下してし
まう。通常、ペースト粘度が1.0×105〜2.5×105
ポイズとなるように前者を後者に分散せしめれば
よい。
本発明方法は、上記したペーストをAlN焼結
前駆体の表面に塗布したのち全体を同時に焼結す
る。この同時焼結に先立ち、AlN焼結前駆体の
バインダ成分およびペーストの媒体を除去するた
めに、例えば50〜700℃というような温度で脱脂
処理を施してもよい。
焼結は窒素雰囲気中で行なわれる。焼結温度，
焼結時間は、焼結後のAlN焼結体が所望の特性，
例えば熱伝導率50W／ｍ・Ｋ以上となるような条
件として設定される。具体的には、焼結温度1600
〜2000℃，好ましくは1700〜1800℃であり、焼結
時間は0.2〜５時間，好ましくは0.5〜1.5時間であ
る。
かくして、AlN焼結体の表面には塗布された
ペーストのメタライズ層が導電性の薄層として形
成される。
［発明の実施例］
実施例 １
(1) ペーストの調製
グループの成分として粒径0.5〜1.0μmのMo
粉末を用意し、グループの成分として粒径1.0
〜2.0μmのTiN粉末を用意した。前者50重量部と
後者50重量部とを混合した。得られた混合粉100
重量部をエチルセルロース７重量部に分散せしめ
て粘度2.0×105ポイズのペーストとした。
(2) メタライズ層の形成
焼結助剤としてY2O3を３重量％含有するAlN
のグリーンシートの片面に、(1)で調製したペース
トを厚み15μmでローラー塗布した。
ついで、700℃の窒素雰囲気中で180分間焼成し
て脱脂処理を施したのち、全体を窒素気流中、温
度1800℃で約１時間焼結した。
得られたAlN焼結体イートの表面には、メタ
ライズ層が形成されていた。このメタライズ層の
構成相はMoとTiNであることがＸ線回折によつ
て確認された。
(3) メタライズ層とAlN焼結体シートとの接合
強度
(2)で得られたメタライズ層の上に無電解めつき
法によつて厚み約３〜5μmのNiめつき層を形成
した。ついで、800℃のホーミングガス中でめつ
き層をアニールしたのち、ここに、線径0.5mm，
引張り強度55Kg／mm2のコバール線を銀ろうを用い
てろう付けした。ろう付け温度は800℃，雰囲気
は水素50vol％，窒素50vol％の混合ガス雰囲気で
あつた。
その後、AlN焼結体シートを固定し室温（20
℃）下でコバール線を引張り、メタライズ層の剥
離状態を観察した。
引張り強さ５Kg／mm2のときにメタライズ層とコ
バール線のろう付部分が引きちぎられた。すなわ
ち、AlN焼結体シートとメタライズ層との接合
強度は５Kg／mm2以上であることが判明した。
実施例 ２〜19
グループの成分，グループの成分をそれぞ
れ表示のように選定して各種のペーストを調製し
た。これらのペーストを実施例１と同様のAlN
グリーンシートの表面に塗布し、脱脂処理を施し
たのち、表示の条件で焼結した。
得られた各種の焼結体シートにおけるメタライ
ズ層とAlN焼結体シートとの接合強度を実施例
１と同様の方法で測定した。その結果を一括して
表に示した。
比較例 １
熱伝導率が70〜130W／ｍ・Ｋである３枚の
AlN焼結板の表面に厚膜法を適用してそれぞれ
Au，Cu，Ag−Pd層を焼付けた。
得られたメタライズ層のそれぞれにニツケルメ
ツキを施した銅ピンを半田付けしたのち、このピ
ンを引張つてメタライズ層とAlN焼結板表面と
の接合強度を測定した。いずれの場合も、約１
Kg／mm2であつた。
比較例 ２
熱伝導率が70〜130W／ｍ・ＫであるAlN焼結
板の表面に実施例３で用いたペーストを塗布し
1700℃で焼付けた。得られたメタライズ層に700
〜800℃でコバールピンをろう付けし、このピン
を引張ることによつて接合強度を測定した。2.0
Kg／mm2であつた。
比較例 ３
用いたペーストが実施例２で用いたペーストで
あつたことを除いては、比較例２と同様にしてメ
タライズ層を形成した。接合強度は比較例２と略
同じ値であつた。
[Technical Field of the Invention] The present invention relates to a method for producing an aluminum nitride (AlN) sintered body having a conductive metallized layer formed on its surface with high bonding strength. This invention relates to a method for forming a conductive metallized layer on the surface of the sintered metal layer with high bonding strength at the same time as sintering. [Conventional technology and its problems] AlN sintered bodies have good thermal conductivity and excellent heat dissipation.
Since it also has electrical insulating properties, it is attracting attention as a substrate material for semiconductors. This AlN sintered body is generally manufactured as follows. That is, Y 2 O 3 , Sm 2 O 3 ,
A predetermined amount of a sintering aid such as CaO is blended, an acrylic resin binder is added as needed, the whole is thoroughly mixed, and the resulting mixture is, for example, pressure molded into a predetermined shape. After forming an AlN sintered precursor (formed body), this is sintered at a predetermined temperature in, for example, a nitrogen atmosphere. By the way, when using an AlN sintered body as a substrate for a semiconductor, it is necessary to form a conductive thin layer on the surface of this AlN sintered body. Conventionally,
This thin layer is applied to the surface of the AlN sintered body using the DBC method (Direct
Copper (Cu), gold (Au), silver-palladium (Ag-
It was a metallized layer of Pd). However, this conventional substrate has the following problems. The first is the formed metallized layer and
This means that the bonding strength with the surface of the AlN sintered body is low, and peeling phenomenon often occurs between the two, resulting in low reliability of the substrate. The second problem is a problem that occurs when a predetermined semiconductor element or wire is brazed or high-temperature soldered to the formed metallized layer. That is, for example, in the case of brazing, it is carried out in a hydrogen-nitrogen mixed gas at a temperature of around 800°C, however, the temperature during the metallized layer baking process is usually a low temperature of about 600 to 1000°C.
During this brazing, the bonding strength between the metallized layer and the surface of the AlN sintered body decreases significantly, making brazing virtually impossible. A similar problem also occurs in the case of high-temperature soldering. The third problem is a problem based on the difference in coefficient of thermal expansion between the AlN sintered body and the metallized layer. That is, as is the case with brazing and high-temperature soldering, a substrate on which a semiconductor element is mounted, such as a silicon wafer, undergoes severe thermal cycles of heating and cooling during use. As a result, AlN sintered body - metallized layer - brazing layer (or solder layer)
- At each bonding surface of the semiconductor element, thermal stress is generated due to the difference in coefficient of thermal expansion of each layer, causing an effect that causes each layer to separate. In the case of the above-mentioned metallized layer, the value is about 2 to 4 times larger than the thermal expansion coefficient of the AlN sintered body (the thermal expansion coefficient is about 4.6 × 10 -6 /℃), and the brazing layer (or solder layer) 1/2 of the value equivalent to AlN
Since the difference between the two is large, microcracks are likely to occur at the interface between the metallized layer or brazing layer (or solder layer) and AlN during thermal cycling. As thermal cycles are applied, these microcracks gradually develop and may eventually lead to delamination of the mounted semiconductor device. Such a problem is extremely inconvenient because it reduces the reliability of a device mounted with a substrate on which a semiconductor element is mounted. The fourth problem is that the bonding strength between the metallized layer and the AlN sintered body at high temperatures is low, and as in the second case, reliability during high temperature use is low. Fifth, when looking at the manufacturing process from the perspective of a completed board, it is uneconomical in terms of thermal energy usage. That is, in order to obtain a completed substrate, the problem is that an AlN sintered precursor is sintered, and then the sintered material is fired again to form a metallized layer. [Object of the invention] The present invention solves the above-mentioned problems and
At the same time as the sintering precursor is sintered, on its surface,
The purpose of the present invention is to provide a method for forming a conductive metallized layer that has a coefficient of thermal expansion similar to that of an AlN sintered body, has high heat resistance, and has high bonding strength. [Summary of the Invention] As a result of extensive research in order to achieve the above object, the inventors of the present invention have found that by applying the paste described below to an AlN molded body before sintering and sintering both at the same time, an excellent metallized layer can be formed in AlN. After confirming the fact that it can be formed on the surface of a sintered body, we developed the method of the present invention. That is, in the method for producing an AlN sintered body having a conductive metallized layer of the present invention, a single substance selected from the group consisting of molybdenum (Mo), tungsten (W), and tantalum (Ta) or any of them is used as a sintering precursor of AlN. At least one compound containing one or more of the following: Al, a group a element of the periodic table, and a rare earth element (the rare earth element is Sc,
A paste containing a single substance selected from the group consisting of lanthanum-based compounds containing Y or at least one compound containing one or more thereof is applied, and then the whole is sintered at the same time. shall be. First, the AlN sintering precursor to which the method of the present invention is applied includes, for example, AlN powder of a predetermined particle size, Y 2 O 3 ,
Powders of various sintering aids such as YF 3 , Sm 2 O 3 , and CaCO 3 are mixed with a wax-based or plastic-based binder component in a predetermined ratio, and this mixture is pressure-molded at room temperature. Alternatively, it is a molded product formed into a sheet shape using a doctor blade. The particle size, mixing ratio, compacting pressure, etc. of the AlN powder and sintering aid powder are appropriately selected in relation to the characteristics of the intended AlN sintered body. In the method of the present invention, the AlN sintering precursor preferably has a thermal conductivity of 50 W/m·K or more after sintering. A paste having a composition described below is applied to this AlN sintered precursor. As a coating method, well-known methods such as screen printing, brush coating, spin roller coating, etc. may be used. The paste according to the method of the invention consists of two groups of components, which are converted into a metallized layer after sintering, and a medium for dispersing them. At least one element selected from the group of Mo, W, and Ta, or a compound containing one or more of these elements. Specifically, the ingredients are as follows. That is,
Elemental metals of Mo, W or Ta; various oxides of these; various carbides of these; various borides of these; various silicides of these; various oxynitrides of these; various carbonitrides of these; various halogens of these various hydrides; various hydroxides; nitrites, nitrates, sulfites, sulfates, borates, carbonates, silicates, phosphates, phosphites of these elements; Various salts such as hydrochlorides, chlorates, oxalates, and aluminum salts; various organometallic compounds such as alkoxides and sol-gels such as Atron NTa/700 (product name: Nippon Soda Co., Ltd.); and A mixture of two or more of the above-mentioned components may be used. These components may be used alone or in combination of two or more appropriately selected. In terms of increasing the conductivity of the metallized layer to be formed, single metals such as Mo, W, and Ta are particularly preferred. In addition, W has a high melting point and excellent stability of the metallized layer at high temperatures.
is particularly preferred. Group components include Al, group a elements of the periodic table, and rare earth elements (rare earth elements include Sc,
It is a simple substance selected from the group consisting of lanthanum-based elements containing Y, or at least one compound containing one or more of these elements. Among these, group a elements include Ti, Zr,
You can give Hf. In particular, Ti is suitable because it can form a good metallized layer after sintering, regardless of the group components. Rare earth elements include Sc, Y, La,
Examples include Ce, Pr, Nd, Sm, Gd, Dy, etc. Among these, Y, Ce, Pr, Nd, Sm, and Dy are effective, and Y and Sm are particularly suitable. Specifically, the components of the group can include the following: That is, Ala
Each element of group elements and rare earth elements; oxides of these elements; nitrides of these elements; carbides of these elements; borides of these elements; silicides of these elements; oxynitrides of these elements; carbonitrides of these elements; halides of these elements; hydrides of these elements; hydroxides of these elements; nitrites, nitrates, sulfites, and sulfates of these elements Various salts such as , borate, carbonate, silicate, phosphate, phosphorous acid, hydrochloride, chlorate, oxalate, aluminum salt; Atron NTi (trade name: Nippon Soda Co., Ltd.) ) made)
and various organometallic compounds such as alkoxides and sol-gels; and mixtures of two or more of the above-mentioned components as appropriate. These components may be used alone or in combination of two or more appropriately selected. The paste according to the present invention is prepared by uniformly dispersing the components of these groups in a medium. Examples of the medium used include ethyl cellulose and nitrocellulose, and their solvents include terpineol, tetralin, and butyl carbitol. In addition, the components of the group are effective components mainly for maintaining the conductivity and heat resistance of the formed metallized layer at a high level, and
The components of this group are considered to be effective components for binding the components of the above group and maintaining the strength of the metallized layer. At this time, the quantitative relationship between the group components varies depending on the type of each component selected, but usually the weight ratio is group component/group component = 1 to 100 to 100/1. Bye. Furthermore, among the group components, it is preferable that the weight ratio of the group components is 1/2 to 2/1, and the weight ratio of the group components is 1/5 to 1/1. This is because if the number of group components is too large compared to the group components, the strength of the formed metallized layer will decrease, and if the opposite is the case, the electrical conductivity will not reach a satisfactory level. The group components and the amount of the group components dispersed in the medium are appropriately determined in relation to the viscosity of the resulting paste. If the former is excessive,
The resulting paste becomes highly viscous, making it difficult to uniformly apply it to the surface of the AlN sintered precursor. In the opposite case, the paste viscosity decreases and the applied paste flows down from the surface of the AlN sintered precursor. Usually the paste viscosity is 1.0×10 5 to 2.5×10 5
The former should be dispersed into the latter so that it becomes a poison. In the method of the present invention, the paste described above is applied to the surface of the AlN sintering precursor, and then the whole is sintered at the same time. Prior to this simultaneous sintering, a degreasing treatment may be performed at a temperature of, for example, 50 to 700° C. in order to remove the binder component of the AlN sintering precursor and the paste medium. Sintering takes place in a nitrogen atmosphere. Sintering temperature,
The sintering time is determined so that the AlN sintered body has the desired characteristics after sintering.
For example, the condition is set such that the thermal conductivity is 50 W/m·K or more. Specifically, the sintering temperature is 1600
-2000°C, preferably 1700-1800°C, and the sintering time is 0.2-5 hours, preferably 0.5-1.5 hours. In this way, a metallized layer of the applied paste is formed as a conductive thin layer on the surface of the AlN sintered body. [Embodiments of the invention] Example 1 (1) Preparation of paste Mo with a particle size of 0.5 to 1.0 μm as a group component
Prepare a powder, particle size 1.0 as a group component
~2.0 μm TiN powder was prepared. 50 parts by weight of the former and 50 parts by weight of the latter were mixed. Obtained mixed powder 100
Parts by weight were dispersed in 7 parts by weight of ethyl cellulose to form a paste with a viscosity of 2.0×10 5 poise. (2) Formation of metallized layer AlN containing 3% by weight of Y 2 O 3 as a sintering aid
The paste prepared in (1) was applied with a roller to a thickness of 15 μm on one side of the green sheet. Then, after degreasing by firing in a nitrogen atmosphere at 700°C for 180 minutes, the whole was sintered in a nitrogen stream at a temperature of 1800°C for about 1 hour. A metallized layer was formed on the surface of the obtained AlN sintered body. It was confirmed by X-ray diffraction that the constituent phases of this metallized layer were Mo and TiN. (3) Bonding strength between metallized layer and AlN sintered sheet A Ni plating layer with a thickness of approximately 3 to 5 μm was formed on the metallized layer obtained in (2) by electroless plating. Next, after annealing the plating layer in a homing gas at 800℃, a wire with a diameter of 0.5 mm and
Kovar wire with a tensile strength of 55 Kg/mm 2 was brazed using silver solder. The brazing temperature was 800°C, and the atmosphere was a mixed gas atmosphere of 50 vol% hydrogen and 50 vol% nitrogen. After that, the AlN sintered sheet was fixed at room temperature (20
The Kovar wire was pulled under the temperature (°C) and the peeling state of the metallized layer was observed. When the tensile strength was 5 Kg/mm 2 , the brazed portion between the metallized layer and the Kovar wire was torn off. That is, it was found that the bonding strength between the AlN sintered sheet and the metallized layer was 5 Kg/mm 2 or more. Examples 2 to 19 Various pastes were prepared by selecting the group components and group components as shown. These pastes were mixed with AlN similar to Example 1.
It was applied to the surface of a green sheet, degreased, and then sintered under the indicated conditions. The bonding strength between the metallized layer and the AlN sintered sheet in each of the obtained sintered sheets was measured in the same manner as in Example 1. The results are summarized in the table. Comparative example 1 Three sheets with thermal conductivity of 70 to 130 W/m・K
By applying the thick film method to the surface of the AlN sintered plate,
The Au, Cu, and Ag-Pd layers were baked. After soldering a nickel-plated copper pin to each of the obtained metallized layers, the pins were pulled to measure the bonding strength between the metallized layer and the surface of the AlN sintered plate. In either case, approximately 1
It was Kg/ mm2 . Comparative Example 2 The paste used in Example 3 was applied to the surface of an AlN sintered plate with a thermal conductivity of 70 to 130 W/m・K.
Baked at 1700℃. 700 on the resulting metallized layer
Kovar pins were brazed at ~800°C and bond strength was measured by pulling the pins. 2.0
It was Kg/ mm2 . Comparative Example 3 A metallized layer was formed in the same manner as Comparative Example 2, except that the paste used was the paste used in Example 2. The bonding strength was approximately the same value as Comparative Example 2.
【表】
［発明の効果］
以上の説明で明らかなように、本発明方法は、
AlN焼結体表面にそれとの接合強度が高い導
電性メタライズ層を形成することができる。そ
のメタライズ層はMo，Ｗ，Taなどの高融点金属
を含有していて耐熱性に優れ、かつ熱膨張率も
AlN焼結体と近似した値であるため熱衝撃層と
しての機能をも有する。そしてAlN焼結前駆
体を焼結すると同時に塗布したペーストをメタラ
イズ層に転化せしめるので熱経済的に有利であ
る、などの効果を奏しその工業的価値は大であ
る。
本発明方法で製造されたAlN焼結体は上記し
た効果を奏するので、イグナイター，高周波トラ
ンス，コンデンサーのような基板部材；レーザ管
用絶縁管，電力管用絶縁外囲器，高周波電磁波進
行波管の窓，高エネルギービーム照射用窓，マグ
ネトロンのような部材；チユーブヒーター，面ヒ
ーター，シースヒーター，ハンダゴテ，アイロン
のプレス板，灸用器具，コーヒーメーカー用のヒ
ーター，ズボンプレツサー，ホツトプレート，便
座，調理用なべ、熱転写プリンターのヘツド，プ
ラグ，熱電対の保護管，るつぼばさみの先端部，
金属溶融用るつぼ，単結晶引上げ用るつぼなどの
部材に適用することができて有用である。[Table] [Effects of the invention] As is clear from the above explanation, the method of the present invention has the following effects:
A conductive metallized layer with high bonding strength can be formed on the surface of the AlN sintered body. The metallized layer contains high melting point metals such as Mo, W, and Ta, and has excellent heat resistance and a low coefficient of thermal expansion.
Since the value is similar to that of the AlN sintered body, it also functions as a thermal shock layer. Since the applied paste is converted into a metallized layer at the same time as the AlN sintering precursor is sintered, it is thermoeconomically advantageous and has great industrial value. Since the AlN sintered body produced by the method of the present invention exhibits the above-mentioned effects, it can be used for substrate parts such as igniters, high-frequency transformers, and condensers; insulating tubes for laser tubes, insulating envelopes for power tubes, and windows for high-frequency electromagnetic wave traveling wave tubes. , windows for high-energy beam irradiation, components such as magnetrons; tube heaters, surface heaters, sheath heaters, soldering irons, press plates for irons, moxibustion equipment, heaters for coffee makers, trouser presses, hot plates, toilet seats, cooking pots. , thermal transfer printer heads, plugs, thermocouple protection tubes, crucible scissor tips,
It is useful because it can be applied to members such as metal melting crucibles and single crystal pulling crucibles.
Claims (1)
ン，タングステンおよびタンタルからなる群から
選ばれる単体またはそれらの１種若しくは２種以
上を含有する化合物の少なくとも１種と、Al、
周期律表のａ族元素および希土類元素（希土類
元素はSc，Ｙを含むランタン系である）からな
る群から選ばれる単体またはそれらの１種若しく
は２種以上を含有する化合物の少なくとも１種と
を含むペーストを塗布し、ついで全体を同時に焼
結することを特徴とする導電性メタライズ層を有
する窒化アルミニウム焼結体の製造方法。1 A sintered precursor of aluminum nitride, at least one element selected from the group consisting of molybdenum, tungsten, and tantalum, or a compound containing one or more thereof, and Al,
At least one element selected from the group consisting of group A elements of the periodic table and rare earth elements (rare earth elements are lanthanum-based elements including Sc and Y) or a compound containing one or more of them. 1. A method for producing an aluminum nitride sintered body having a conductive metallized layer, the method comprising applying a paste containing the aluminum nitride and then sintering the entire body at the same time.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3382486A JPS62197372A (en) | 1986-02-20 | 1986-02-20 | Manufacture of aluminum nitride sintered body with electroconductive metallized layer |
| DE3789628T DE3789628T3 (en) | 1986-02-20 | 1987-02-19 | Sintered body made of aluminum nitride with conductive metallized layer. |
| US07/016,557 US4770953A (en) | 1986-02-20 | 1987-02-19 | Aluminum nitride sintered body having conductive metallized layer |
| EP87102344A EP0235682B2 (en) | 1986-02-20 | 1987-02-19 | Aluminium nitride sintered body having conductive metallized layer |
| KR1019870001437A KR900006122B1 (en) | 1986-02-20 | 1987-02-20 | Aluminum nitride sintered body and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3382486A JPS62197372A (en) | 1986-02-20 | 1986-02-20 | Manufacture of aluminum nitride sintered body with electroconductive metallized layer |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6037555A Division JP2898877B2 (en) | 1994-02-14 | 1994-02-14 | Aluminum nitride sintered body having conductive metallized layer and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62197372A JPS62197372A (en) | 1987-09-01 |
| JPH0369873B2 true JPH0369873B2 (en) | 1991-11-05 |
Family
ID=12397234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3382486A Granted JPS62197372A (en) | 1986-02-20 | 1986-02-20 | Manufacture of aluminum nitride sintered body with electroconductive metallized layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62197372A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0738491B2 (en) * | 1986-07-23 | 1995-04-26 | 株式会社東芝 | Method of manufacturing circuit board and circuit board |
| JPS63195183A (en) * | 1987-02-06 | 1988-08-12 | 住友電気工業株式会社 | Aln sintered body with metallized surface and manufacture |
| JPH01122984A (en) * | 1987-11-06 | 1989-05-16 | Sumitomo Electric Ind Ltd | Aluminum nitride sintered form provided with metallization treatment |
| JP2685216B2 (en) * | 1988-04-08 | 1997-12-03 | 株式会社東芝 | Metallization paste composition for nitride ceramics substrate |
| JPH02159797A (en) * | 1988-12-14 | 1990-06-19 | Toshiba Corp | Ceramic multilayer board |
-
1986
- 1986-02-20 JP JP3382486A patent/JPS62197372A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62197372A (en) | 1987-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR900006122B1 (en) | Aluminum nitride sintered body and manufacture thereof | |
| EP0574956B1 (en) | Metallized circuit substrate comprising nitride type ceramics | |
| US4961987A (en) | Aluminum nitride sintered body with high thermal conductivity and process for producing same | |
| US4761345A (en) | Aluminum nitride substrate | |
| JPS58223678A (en) | Sic sintered body with metallized layer and manufacture | |
| JPH0369873B2 (en) | ||
| JP3193305B2 (en) | Composite circuit board | |
| JPH10144459A (en) | Conductive heating element | |
| JP2704159B2 (en) | Aluminum nitride sintered body having conductive metallized layer and method of manufacturing the same | |
| JPH08109084A (en) | Aluminum nitride sintered material having electrically conductive metallized layer and its manufacture | |
| JP2772274B2 (en) | Composite ceramic substrate | |
| EP0200950B1 (en) | Paste containing a eutectic composition, method of forming such a paste and its application | |
| JPH0788266B2 (en) | Aluminum nitride substrate and manufacturing method thereof | |
| JPH0369874B2 (en) | ||
| JPS62197376A (en) | Aluminum nitride substrate | |
| JP2704158B2 (en) | Aluminum nitride sintered body having conductive metallized layer and method of manufacturing the same | |
| JPH05221759A (en) | Aluminum nitride substrate with metallizing layer and metallizing method | |
| JP2898851B2 (en) | Aluminum nitride sintered body having conductive metallized layer and method of manufacturing the same | |
| JPH0450186A (en) | Method for forming metallized layer on aluminum nitride substrate | |
| JP2616060B2 (en) | Substrate material for semiconductor devices with excellent heat dissipation | |
| JP2590558B2 (en) | Substrate for semiconductor device with excellent heat dissipation | |
| JPH0631186B2 (en) | Substrate for igniter | |
| JPH0964235A (en) | Silicon nitride circuit board | |
| JPS6381787A (en) | Ceramic heater | |
| JPH05319944A (en) | Ceramic circuit board and joining agent for circuit board |