JPH04188892A - Metallizing paste - Google Patents
Metallizing pasteInfo
- Publication number
- JPH04188892A JPH04188892A JP31969690A JP31969690A JPH04188892A JP H04188892 A JPH04188892 A JP H04188892A JP 31969690 A JP31969690 A JP 31969690A JP 31969690 A JP31969690 A JP 31969690A JP H04188892 A JPH04188892 A JP H04188892A
- Authority
- JP
- Japan
- Prior art keywords
- molybdenum
- powder
- paste
- metallizing
- metallizing paste
- 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 48
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 42
- 239000011733 molybdenum Substances 0.000 claims abstract description 42
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005078 molybdenum compound Substances 0.000 claims abstract description 16
- 150000002752 molybdenum compounds Chemical group 0.000 claims abstract description 16
- 229910021344 molybdenum silicide Inorganic materials 0.000 claims abstract description 14
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 28
- 238000001465 metallisation Methods 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011863 silicon-based powder Substances 0.000 claims description 11
- 229910021343 molybdenum disilicide Inorganic materials 0.000 claims description 8
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 22
- 230000000694 effects Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000017525 heat dissipation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000002739 metals Chemical group 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- 101100291844 Caenorhabditis elegans moc-5 gene Proteins 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910020968 MoSi2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- LGLOITKZTDVGOE-UHFFFAOYSA-N boranylidynemolybdenum Chemical compound [Mo]#B LGLOITKZTDVGOE-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Surface Treatment Of Glass (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は半導体から発生する熱を放出するために用いら
れる放熱板及びセラミック上に回路を形成する回路基板
等の製造において、アルミナ及び窒化アルミ等のセラミ
ックの表面に塗布し還元性雰囲気中で焼成してメタライ
ズ層を形成するために用いられるメタライズペーストに
関する。Detailed Description of the Invention [Field of Industrial Application] The present invention is applicable to the production of heat sinks used to dissipate heat generated from semiconductors and circuit boards on which circuits are formed on ceramics, using alumina and aluminum nitride. This invention relates to a metallization paste used to form a metallization layer by coating the surface of ceramics such as ceramics and firing in a reducing atmosphere.
従来のメタライズペーストはモリブデン粉末とマンガン
粉末とガラス成分粉末を主成分とするもので、該ペース
トをアルミナ及び窒化アルミ等のセラミック上に塗布し
、水素と水蒸気を含む還元性雰囲気中で最高温度が１３
００°Ｃから１４００°Ｃの範囲で焼成してセラミック
の表面にメタライズ層を形成するものである。Conventional metallizing paste is mainly composed of molybdenum powder, manganese powder, and glass component powder.The paste is applied onto ceramics such as alumina and aluminum nitride, and the paste is heated to a maximum temperature in a reducing atmosphere containing hydrogen and water vapor. 13
A metallized layer is formed on the surface of the ceramic by firing at a temperature ranging from 00°C to 1400°C.
このように形成されたメタライズ層にその後二・ツケル
メッキ或いは金メツキ等を施して放熱のための金属部品
や半導体をロウ付けする放熱基板として用いたり、又、
多種の部品やリードを取着して回路基板等の電子工業用
部品として使用している。The metallized layer thus formed can then be plated with silver or gold, and used as a heat dissipation board to which metal parts or semiconductors for heat dissipation are brazed, or
It is used as electronic industry parts such as circuit boards by attaching various parts and leads.
特に、メタライズ層とセラミックとの接着が強固である
為、信頼性を要求される分野に広く利用されている。In particular, since the adhesion between the metallized layer and the ceramic is strong, it is widely used in fields where reliability is required.
しかしながら、従来のメタライズペーストはメタライズ
層の金属成分であるモリブデン粉末を充分に焼結させる
ために焼成温度を低くすることがテキス、ペースト中の
マンガンを含めたガラス成分等が焼成中にセラミック内
に拡散してセラミックの反りを誘発したり、或いはメタ
ライズ層のガラスが欠乏して強度が不安定となったりす
る欠点がある。また、窒化アルミ等の非酸化物の焼成に
おいては表面の酸化物層の膜厚が不安定となり接着強度
が不安定になると言われている。However, with conventional metallization pastes, the firing temperature must be kept low in order to sufficiently sinter the molybdenum powder, which is the metal component of the metallization layer. It has the disadvantage that it diffuses and causes warping of the ceramic, or that the glass in the metallized layer becomes insufficient and its strength becomes unstable. Furthermore, it is said that when non-oxide materials such as aluminum nitride are fired, the thickness of the oxide layer on the surface becomes unstable and the adhesive strength becomes unstable.
それ故、品質の安定化と信頼性向上のためには焼成温度
を低下させる必要がある。ところが焼成温度が低いと金
属成分であるモリブデンの焼結が不充分となって強度不
足となるので、この対策としてモリブデンの一部又は全
部をニジケルやクロム等のより焼結し易い金属に置き換
えることも考えられるが、モリブデン又はタングステン
以外の金属を含むと金属のガラスとの濡れが悪くなり強
度が不安定となるとか、焼成中に酸化して金属として存
在しなくなるとか、着色するとかの種々の問題を生ずる
。Therefore, in order to stabilize quality and improve reliability, it is necessary to lower the firing temperature. However, if the firing temperature is low, the metal component molybdenum will not be sufficiently sintered, resulting in a lack of strength, so as a countermeasure, some or all of the molybdenum can be replaced with metals that are easier to sinter, such as Niskel or chromium. However, if metals other than molybdenum or tungsten are included, there are various problems such as poor wettability of the metal with the glass and unstable strength, oxidation during firing and no longer existing as a metal, and coloring. cause problems.
そこで、焼成温度低下のネックであらた焼結不足対策の
ため微粉化したモリブデン粉末を使用することとなるが
、余りに微粉であると自然発火したり、ペーストにした
ときにスクリーン印刷ができない状態となり実用に供し
難いものとなる等の問題を生じ、現状では約０．８μｍ
程度のモリブデン粉末を使用し、焼成温度は１３００°
Ｃから１４００°Ｃ前後が一般的である。Therefore, in order to prevent insufficient sintering due to the problem of lowering the firing temperature, finely divided molybdenum powder was used.However, if the powder is too fine, it may spontaneously ignite, or when it is made into a paste, it will not be able to be screen printed. This causes problems such as making it difficult to use for
The firing temperature is 1300°.
Celsius to around 1400°C is common.
その他、製造コストにおいても焼成温度は炉のヒーター
の寿命にも大きく影響し、ヒーターに高価なモリブデン
を使用することから、可能な限り低い温度で焼成する事
が望まれていた。In addition, in terms of manufacturing costs, the firing temperature greatly affects the life of the furnace heater, and since expensive molybdenum is used in the heater, it has been desired to fire at the lowest possible temperature.
本発明は、上記の問題点を解決するためになされたもの
で、品質の安定化、信鯨性の向上及びコストダウンのた
め、従来よりも低い焼成温度でも強固且つ信顧性の高い
メタライズ層が得られるメタライズペーストを提供する
ことを目的とするものである。The present invention was made to solve the above problems, and in order to stabilize quality, improve reliability, and reduce costs, the present invention has been made to create a metallized layer that is strong and highly reliable even at lower firing temperatures than conventional ones. The purpose of the present invention is to provide a metallized paste that provides the following.
上記の目的を達成するために、本発明はセラミックやガ
ラス上に塗布し、水蒸気と水素を含む還元性雰囲気中で
焼成してモリブデンを主成分とするメタライズ層を形成
するメタライズペーストにおいて、該メタライズペース
トの主成分であるモリブデン成分の一部又は全部をモリ
ブデンの炭化物又は酸化物又は珪化物等のモリブデン化
合物粉末の形で加えたものである。In order to achieve the above object, the present invention provides a metallization paste that is coated on ceramic or glass and fired in a reducing atmosphere containing water vapor and hydrogen to form a metallization layer containing molybdenum as a main component. Part or all of the molybdenum component, which is the main component of the paste, is added in the form of molybdenum compound powder such as molybdenum carbide, oxide, or silicide.
そして、メタライズペーストの主成分であるモリブデン
をモリブデン化合物粉末の形で加える場合は、全モリブ
デンに対するモリブデン化合物粉末に含まれるモリブデ
ンの割合が１０重量％以上であると効果的である。また
、モリブデン化合物粉末として三酸化モリブデン粉末を
使用する場合は、三酸化モリブデン粉末に含まれるモリ
ブデンの割合を５０重量％以下として使用することが望
ましい。When molybdenum, which is the main component of the metallizing paste, is added in the form of a molybdenum compound powder, it is effective if the proportion of molybdenum contained in the molybdenum compound powder to the total molybdenum is 10% by weight or more. Further, when using molybdenum trioxide powder as the molybdenum compound powder, it is desirable to use the molybdenum trioxide powder with a proportion of molybdenum contained in the molybdenum trioxide powder of 50% by weight or less.
さらに、セラミックやガラス上に塗布し、水蒸気と水素
を含む還元性雰囲気中で焼成してモリブデンとガラスを
主成分とするメタライズ層を形成するメタライズペース
トにおいて、該メタライズペーストの主成分であるガラ
スのその成分中の二酸化珪素の一部又は全部を珪素粉末
又はモリブデン珪化物粉末の形で加えても最低焼成温度
を低下させることができる。二珪化モリブデン粉末を使
用する場合は、全モリブデンに対する二珪化モリブデン
粉末に含まれるモリブデンの割合を５重量％〜２０重景
％とし、珪素粉末を使用する場合は全モリブデンに対す
る珪素粉末の割合を３重量％〜１０重量％とじて使用す
ることが好ましい。Furthermore, in a metallization paste that is coated on ceramic or glass and fired in a reducing atmosphere containing water vapor and hydrogen to form a metallization layer containing molybdenum and glass as the main components, glass, which is the main component of the metallization paste, is Addition of some or all of the silicon dioxide in the component in the form of silicon powder or molybdenum silicide powder can also lower the minimum firing temperature. When using molybdenum disilicide powder, the proportion of molybdenum contained in molybdenum disilicide powder to the total molybdenum should be 5% to 20% by weight, and when using silicon powder, the proportion of silicon powder to the total molybdenum should be 3% by weight. It is preferable to use it in a range of 10% by weight.
上記のようにメタライズペーストの主成分であるモリブ
デンの一部又は全部をモリブデンの炭化物、酸化物、珪
化物等のモリブデン化合物で置き換えると、モリブデン
のみを使用する時よりも少なくとも同程度の粒径であれ
ば、モリブデン化合物が焼成中に雰囲気中の水素或いは
水蒸気と反応して、−酸化炭素、水蒸気、二酸化珪素を
形成しつつ分解して金属化する際活性化し焼結が進みメ
タライズ強度が増加する。As mentioned above, if part or all of the molybdenum, which is the main component of the metallizing paste, is replaced with a molybdenum compound such as molybdenum carbide, oxide, or silicide, the particle size will be at least the same as when using only molybdenum. If present, the molybdenum compound reacts with hydrogen or water vapor in the atmosphere during firing, decomposing and metallizing while forming -carbon oxide, water vapor, and silicon dioxide, and becomes activated, sintering progresses, and metallization strength increases. .
そして、強固且つ安定した接着力を得る為には、少なく
とも炭化モリブデン粉末及び三酸化モリブンデ粉末にあ
ってはこれに含まれるモリブデンの合計が全モリブデン
の１０重量％以上であることが必要である。In order to obtain strong and stable adhesive strength, it is necessary that the total amount of molybdenum contained in at least molybdenum carbide powder and molybdenum trioxide powder be 10% by weight or more of the total molybdenum.
しかし、三酸化モリブデン粉末の場合は５０重量％を越
えるとペーストとした時にスクリーン印刷に不向きな状
態となり実用に供し難くなり不都合である。However, in the case of molybdenum trioxide powder, if it exceeds 50% by weight, it becomes unsuitable for screen printing when made into a paste, making it difficult to put it to practical use, which is disadvantageous.
次に、メタライズペーストのガラス成分中の二酸化珪素
をモリブデン珪化物粉末や珪素粉末の形で加えると、酸
化物の形で添加するより体積が少なくなるためペースト
印刷乾燥後の粉末成分の密度が上がることとなり、その
結果焼成後のモリブデン密度も上がるためメタライズ強
度が向上する。Next, if silicon dioxide in the glass component of the metallizing paste is added in the form of molybdenum silicide powder or silicon powder, the density of the powder component after paste printing will increase because the volume will be smaller than when it is added in the form of oxide. As a result, the molybdenum density after firing also increases, and the metallization strength improves.
モリブデン珪化物の場合は、この効果と共に先の分解し
て金属化する際活性化し焼結が進む効果も生じ、メタラ
イズ強度向上の効果は更に大きく、全モリブデンに対す
る二珪化モリブデンに含まれるモリブデンの割合は、５
重量％以上であれば効果があられれる。ただし、多過ぎ
るとガラス過多或いはガラス融点が上がり溶融不足とな
り、メタライズ強度が弱くなったりメツキに不具合が生
ずるので注意を要する。In the case of molybdenum silicide, in addition to this effect, there is also an effect of activation and progress of sintering during the previous decomposition and metallization, and the effect of improving metallization strength is even greater, and the proportion of molybdenum contained in molybdenum disilicide to the total molybdenum. 5
If the amount is at least % by weight, the effect can be improved. However, if it is too large, there will be too much glass or insufficient melting due to a rise in the glass melting point, which will weaken the metallization strength and cause problems with plating, so care must be taken.
二酸化三ホウ素をガラス成分に含む場合は、モリブデン
ホウ化物もモリブデン珪化物と同様の作用があるものと
推定される。When triboron dioxide is included in the glass component, molybdenum boride is also presumed to have the same effect as molybdenum silicide.
実施例について、表及び図面を参照して説明する。 Examples will be described with reference to tables and drawings.
先ず、後記する表の粉末（モリブデン粉末ＭＯ３炭化モ
リブデン粉末ＭｏＣ５三酸化モリブデン粉末ＭｏＯ３、
二珪化モリブデン粉末Ｍｏ５ｔ２ 、珪素粉末Ｓｔ）を
アセトンと共に通量のアルミナ玉石の入ったポットに入
れ所定時間ボンドミル粉砕する。この場合のモリブデン
粉末の粒径は約０．３μｍのものを使用する。これにア
セトンを乾燥したのちバインダーとしてエチルセルロー
ス、可塑剤としてジブチルフタレート、溶剤としてαテ
ルピネオールを各々適量前え混練してメタライズペース
トを作成する。First, the powders in the table below (molybdenum powder MO3 molybdenum carbide powder MoC5 molybdenum trioxide powder MoO3,
Molybdenum disilicide powder (Mo5t2) and silicon powder (St) were placed in a pot containing a sufficient amount of alumina cobbles together with acetone and ground in a bond mill for a predetermined period of time. In this case, the molybdenum powder used has a particle size of about 0.3 μm. After drying acetone, appropriate amounts of ethyl cellulose as a binder, dibutyl phthalate as a plasticizer, and α-terpineol as a solvent are kneaded in advance to prepare a metallized paste.
次に、純度９６％厚さ０．６４ｍのアルミナ基板を用意
し、その上にスクリーン印刷により所定のパターンを塗
布厚２０μｍ前後で印刷する。Next, an alumina substrate with a purity of 96% and a thickness of 0.64 m is prepared, and a predetermined pattern is printed on it by screen printing at a coating thickness of about 20 μm.
そして、水素２０％と窒素８０％の混合ガスを所定の温
度の水中を通過させたウェットガス中で毎時２００″Ｃ
で昇温し、１２００’Ｃ，１２２０°Ｃ，１２４０°Ｃ
１１２６０°Ｃ１１２８０’Ｃ１１３００°Ｃで各々２
時間保持して焼成し、セラミック上にモリブデンを主成
分とするメタライズ層を形成する。Then, a mixed gas of 20% hydrogen and 80% nitrogen was passed through water at a predetermined temperature in a wet gas at 20"C per hour.
Raise the temperature at 1200'C, 1220°C, 1240°C
2 each at 11260°C11280'C11300°C
It is fired for a certain period of time to form a metallized layer containing molybdenum as a main component on the ceramic.
次に、メタライズ表面をカッターの刃先でこすり硬度を ａ、セラミック上から簡単に削とれる。Next, rub the metallized surface with the cutting edge of the cutter to check the hardness. a. It can be easily scraped off from the ceramic surface.
ｂ、粘りがあるが削りとれる。b. It is sticky but can be scraped off.
Ｃ１表面のみ削りとれる。Only the C1 surface can be scraped off.
ｄ、刃がたたない。d. The blade does not strike.
の４ランクに分類し２．３ランク以上の硬度となる最低
温度を最低焼成温度としたところ下記の表に示す結果を
得た。The results are shown in the table below.
そして、所定の条件で１μｍ厚のニッケル系の無電解メ
ツキを行い、その後８００ ’Ｃでシンターしたものを
２０倍で観察してメタライズ層上のニッケルメンキに浮
き上がりがあるが否が確認した。Then, nickel-based electroless plating was performed to a thickness of 1 μm under predetermined conditions, and then sintered at 800'C. The resultant was observed at a magnification of 20 times to confirm whether there was any lifting of the nickel coating on the metallized layer.
表
注−Ｉ ＭｏＳｉ２に含まれるＳｉ分のみ３ｔ０２の
添加量を削除注−２５ｉ０２の添加ゼロ。Table Note - I Delete the amount of 3t02 added only for the Si contained in MoSi2 Note - 25 Zero addition of i02.
注−３ｓｔ分のみ５ｔ０２の添加量を削除注−４ＭｏＳ
ｉ２のみ予備粉砕実施。Note-Delete the addition amount of 5t02 only for 3st Note-4MoS
Preliminary crushing is performed only for i2.
注−５Ｓｉのみ予備粉砕実施・
上記表において、測定ナンノ゛ζ−岡１番まモマＪフ゛
デン粉末のみを使用した場合の最低焼成温度の測定値で
あり、阻２〜阻１１＆まモリブデン粉末の一部又は全部
を炭化モリブデン粉末の形で加えた場合、階１２ばモリ
ブデン粉末の一部を炭化モリブデン粉末と三酸化モリブ
デン粉末の形で加えた場合、恥１３〜Ｎｏ、１７はモリ
ブデン粉末の一部又は全部を三酸化モリブデン粉末の形
で加えた場合、Ｎα１８〜魔２０及び患２２、驚２３は
モリブデン粉末の一部を二珪化モリブデン粉末で、ＮＯ
，２１はモリブデン粉末の全部を炭化モリブデン粉末と
二珪化モリブデン粉末の形で加えた場合、隔、２４〜患
２６はガラス成分中の二酸化珪素を珪素粉末の形で加え
た場合のそれぞれ最低焼成温度の測定値を表したもので
ある。Note-5 Pre-pulverization is performed only for Si. In the above table, the lowest firing temperature is measured when only the measured nano-ζ-Oka 1st Mamoma J powder is used. If part or all of the molybdenum powder is added in the form of molybdenum carbide powder, if part or all of the molybdenum powder is added in the form of molybdenum carbide powder and molybdenum trioxide powder, 13~No. 17 is a part of the molybdenum powder. Or, if all of the molybdenum powder is added in the form of molybdenum trioxide powder, Nα 18 to 20, 22, and 23 are added by adding a part of the molybdenum powder to molybdenum disilicide powder.
, 21 is the minimum firing temperature when all of the molybdenum powder is added in the form of molybdenum carbide powder and molybdenum disilicide powder, and 24 to 26 are the minimum firing temperatures when silicon dioxide in the glass component is added in the form of silicon powder. This represents the measured value of .
これらの測定値より以下の特性が判明した。The following characteristics were found from these measured values.
イ、モリブデン粉末を炭化物、酸化物、珪化物等のモリ
ブデン化合物粉末の形で加えると焼成温度を下げること
ができる。そして、第１図及び第２図より明らかなよう
に炭化モリブデン粉末及び三酸化モリブデン粉末の形で
加える場合はその割合が大きい程最低焼成温度を下げる
効果が大きい。B. If molybdenum powder is added in the form of molybdenum compound powder such as carbide, oxide, or silicide, the firing temperature can be lowered. As is clear from FIGS. 1 and 2, when molybdenum carbide powder and molybdenum trioxide powder are added in the form of powder, the larger the proportion, the greater the effect of lowering the minimum firing temperature.
ただし二酸化モリブデン粉末の場合は量的に制限がある
。However, in the case of molybdenum dioxide powder, there is a limit in quantity.
ロ、ガラス成分の二酸化珪素の一部又は全部をモリブデ
ン珪化物粉末や珪素粉末の形で加えても焼成温度を下げ
るこ七ができる。(b) It is also possible to lower the firing temperature by adding part or all of the glass component silicon dioxide in the form of molybdenum silicide powder or silicon powder.
ハ、モリブデン珪化物粉末は上記イ、口両方において焼
成温度を下げる効果が最も顕著であるが、量的に制限が
ある。(c) Molybdenum silicide powder has the most remarkable effect of lowering the firing temperature in both (a) and (b) above, but there are limits to its quantity.
上述の如く、本発明によればメタライズペーストの主成
分であるモリブデンの一部又は全部をモリブデンの炭化
物、酸化物、珪化物等のモリブデン化合物粉末の形で加
えることにより、また、メタライズペーストのガラス成
分中の二酸化珪素をモリブデン珪化物や珪素粉末の形で
加えることにより、モリブデンの焼結度を高め且つ密度
を上げる事ができるため、従来よりも低い温度で焼成し
ても実用に足るメタライズ層度を得ることができる。As described above, according to the present invention, by adding part or all of molybdenum, which is the main component of metallizing paste, in the form of molybdenum compound powder such as molybdenum carbide, oxide, and silicide, glass of metallizing paste can be added. By adding silicon dioxide as a component in the form of molybdenum silicide or silicon powder, it is possible to increase the degree of sintering of molybdenum and increase the density, making it possible to create a metallized layer that is practical even when fired at a lower temperature than before. degree can be obtained.
それ故、放熱板の製造に本発明に係るメタライズペース
トを使用すれば反りの少ない強度の安定した安価なメタ
ライズされたセラミック基板を得ることができ、銅等の
放熱板とメタライズ層との接合部に気泡が生ずることが
少なく放熱性が安定し、熱膨張歪に対しても剥離が生じ
難く、かつ安価な放熱板を提供することができる。また
、回路基板に使用すれば反りが少なく品質の安定した信
鯨性の高い安価な製品を提供することができる。Therefore, if the metallized paste according to the present invention is used in the production of a heat sink, it is possible to obtain an inexpensive metallized ceramic substrate with less warpage, stable strength, and a joint between a heat sink made of copper or the like and a metallized layer. It is possible to provide a heat dissipation plate that is less likely to generate bubbles, has stable heat dissipation properties, is less likely to peel off due to thermal expansion strain, and is inexpensive. Furthermore, when used in circuit boards, it is possible to provide inexpensive products with little warpage, stable quality, and high reliability.
第１図シよ全モリブデンＭｏ中の炭化モリブデンＭ。
Ｃに含まれるモリブデンＭｏＩと最低焼成温度との関係
を示す図、第２図は全モリブデンＭｏ中の三酸化モリブ
デンＭｏＯ３に含まれるモリブデンＭｏ１ｉと最低焼成
温度との関係を示す図である。
特許出願人 水 野 福 三
代 理 人 弁理士 宮武陽男Figure 1 shows molybdenum carbide M in total molybdenum Mo. FIG. 2 is a diagram showing the relationship between molybdenum MoI contained in C and the minimum firing temperature, and FIG. 2 is a diagram showing the relationship between molybdenum MoI contained in molybdenum trioxide MoO3 in all molybdenum Mo and the minimum firing temperature. Patent applicant: Fuku Mizuno, Michihito Mizuno, patent attorney: Haruo Miyatake
Claims (1)
む還元性雰囲気中で焼成してモリブデンを主成分とする
メタライズ層を形成するメタライズペーストにおいて、
該メタライズペーストの主成分であるモリブデンの一部
又は全部をモリブデンの炭化物又は酸化物又は珪化物等
のモリブデン化合物粉末の形で加えたことを特徴とする
メタライズペースト。 ２ メタライズペーストの主成分であるモリブデンをモ
リブデン化合物粉末の形で加える場合、全モリブデンに
対するモリブデン化合物粉末に含まれるモリブデンの割
合を１０重量％以上とした第１項記載のメタライズペー
スト。 ３ モリブデン化合物粉末として三酸化モリブデン粉末
を使用する場合、全モリブデンに対する三酸化モリブデ
ン粉末に含まれるモリブデンの割合を５０重量％以下と
した第１項記載のメタライズペースト。 ４ セラミックやガラス上に塗布し、水蒸気と水素を含
む還元性雰囲気中で焼成してモリブデンとガラスを主成
分とするメタライズ層を形成するメタライズペーストに
おいて、該メタライズペーストのガラス成分中の二酸化
珪素の一部又は全部を珪素粉末又はモリブデン珪化物粉
末の形で加えたことを特徴とするメタライズペースト。 ５ 二珪化モリブデン粉末を使用する場合、全モリブデ
ンに対する二珪化モリブデン粉末に含まれるモリブデン
の割合を５重量％〜２０重量％とし、珪素粉末を使用す
る場合は全モリブデンに対する珪素粉末の割合を３重量
％〜１０重量％とした第４項記載のメタライズペースト
。[Claims] 1. A metallization paste that is coated on ceramic or glass and fired in a reducing atmosphere containing water vapor and hydrogen to form a metallization layer containing molybdenum as a main component,
A metallizing paste characterized in that part or all of molybdenum, which is a main component of the metallizing paste, is added in the form of molybdenum compound powder such as molybdenum carbide, oxide, or silicide. 2. The metallized paste according to item 1, in which when molybdenum, which is a main component of the metallized paste, is added in the form of a molybdenum compound powder, the proportion of molybdenum contained in the molybdenum compound powder to the total molybdenum is 10% by weight or more. 3. The metallized paste according to item 1, in which when molybdenum trioxide powder is used as the molybdenum compound powder, the ratio of molybdenum contained in the molybdenum trioxide powder to the total molybdenum is 50% by weight or less. 4 In a metallization paste that is coated on ceramic or glass and fired in a reducing atmosphere containing water vapor and hydrogen to form a metallization layer mainly composed of molybdenum and glass, silicon dioxide in the glass component of the metallization paste is A metallizing paste characterized in that a part or all of it is added in the form of silicon powder or molybdenum silicide powder. 5 When using molybdenum disilicide powder, the ratio of molybdenum contained in molybdenum disilicide powder to the total molybdenum is 5% to 20% by weight, and when using silicon powder, the ratio of silicon powder to the total molybdenum is 3% by weight. % to 10% by weight of the metallizing paste according to item 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31969690A JPH04188892A (en) | 1990-11-22 | 1990-11-22 | Metallizing paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31969690A JPH04188892A (en) | 1990-11-22 | 1990-11-22 | Metallizing paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04188892A true JPH04188892A (en) | 1992-07-07 |
Family
ID=18113165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31969690A Pending JPH04188892A (en) | 1990-11-22 | 1990-11-22 | Metallizing paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04188892A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06232520A (en) * | 1993-01-29 | 1994-08-19 | Sumitomo Metal Ind Ltd | Alumina wiring board |
| WO2008142804A1 (en) * | 2007-04-25 | 2008-11-27 | Kabushiki Kaisha Toshiba | Ceramic part for magnetron, magnetron employing the same, and process for producing ceramic part for magnetron |
-
1990
- 1990-11-22 JP JP31969690A patent/JPH04188892A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06232520A (en) * | 1993-01-29 | 1994-08-19 | Sumitomo Metal Ind Ltd | Alumina wiring board |
| WO2008142804A1 (en) * | 2007-04-25 | 2008-11-27 | Kabushiki Kaisha Toshiba | Ceramic part for magnetron, magnetron employing the same, and process for producing ceramic part for magnetron |
| JP5450059B2 (en) * | 2007-04-25 | 2014-03-26 | 株式会社東芝 | Magnetron stem, magnetron using the same, and method for manufacturing magnetron stem |
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