JPH0441676A - Formation of thin metal film on heat resistant substrate - Google Patents
Formation of thin metal film on heat resistant substrateInfo
- Publication number
- JPH0441676A JPH0441676A JP14933190A JP14933190A JPH0441676A JP H0441676 A JPH0441676 A JP H0441676A JP 14933190 A JP14933190 A JP 14933190A JP 14933190 A JP14933190 A JP 14933190A JP H0441676 A JPH0441676 A JP H0441676A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- resinate
- thin film
- substrate
- oxidation resistance
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 239000000758 substrate Substances 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000010409 thin film Substances 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 17
- 229910052737 gold Inorganic materials 0.000 abstract description 9
- 229910052763 palladium Inorganic materials 0.000 abstract description 7
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 229940116411 terpineol Drugs 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 229910052741 iridium Inorganic materials 0.000 abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 20
- 239000010931 gold Substances 0.000 description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 9
- 229910052721 tungsten Inorganic materials 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910001316 Ag alloy Inorganic materials 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910001020 Au alloy Inorganic materials 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003779 heat-resistant material Substances 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- HMMSZUQCCUWXRA-UHFFFAOYSA-N 4,4-dimethyl valeric acid Chemical compound CC(C)(C)CCC(O)=O HMMSZUQCCUWXRA-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- AAOISIQFPPAFQO-UHFFFAOYSA-N 7:0(6Me,6Me) Chemical group CC(C)(C)CCCCC(O)=O AAOISIQFPPAFQO-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、工業材料として特に耐熱材料として有用なタ
ングステンやモリブデン等の金属基村上に金属の薄膜を
形成する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for forming a thin metal film on a metal substrate such as tungsten or molybdenum, which is useful as an industrial material, particularly as a heat-resistant material.
（従来技術とその問題点）
タングステンやモリブデン等の高温強度に優れる耐熱材
料は抵抗体や発熱体等に利用されているが、高温の酸化
雰囲気中で用いると、酸化して上記の抵抗体や発熱体と
しての性能が低下するだけでなく、該耐熱材料が薄い板
状や細い線状の場合では亀裂や断線等の原因となるため
、酸化雰囲気中で高温で使用する材料では貴金属が用い
られているが、該貴金属は高価であるためその改良とし
て、各種の複合材料が用いられている。(Prior art and its problems) Heat-resistant materials such as tungsten and molybdenum, which have excellent high-temperature strength, are used for resistors, heating elements, etc., but when used in a high-temperature oxidizing atmosphere, they oxidize, causing the above-mentioned resistors and Not only does the performance as a heating element deteriorate, but if the heat-resistant material is in the form of a thin plate or thin wire, it may cause cracks or disconnections, so noble metals are not used in materials that will be used at high temperatures in an oxidizing atmosphere. However, since the precious metals are expensive, various composite materials have been used to improve them.
その複合材料の製法としては耐酸化性に優れた貴金属の
板状のものを張り合わせるものや、薄膜層を形成する方
法として、スパッタリング法、蒸着法、電気メツキ法、
ペースト法等があるが、薄膜（１，μ以下）を形成する
方法となるとスパッタリング法、蒸着法、電気メツキ法
、が行えるものであるが、スパッタリング法、蒸着法は
装置が高価であることと工業的な量産性に欠ける点かあ
り、電気メツキ法では細部へのメツキが困難であるのと
密着性に欠けることや電着させる金属を任意に選択する
にはメツキ液の種類が十分ではなく、開発をする必要と
する等の問題がある。Methods for manufacturing such composite materials include laminating plates of precious metals with excellent oxidation resistance, and methods for forming thin film layers such as sputtering, vapor deposition, electroplating, etc.
There are paste methods, etc., but sputtering, vapor deposition, and electroplating methods can be used to form thin films (less than 1 μm), but sputtering and vapor deposition require expensive equipment. It is not suitable for industrial mass production, and the electroplating method has difficulty in plating fine details, lacks adhesion, and there are not enough types of plating liquid to arbitrarily select the metal to be electrodeposited. , there are problems such as the need for development.
（発明の目的）
本発明は上記従来法の欠点を解決するために成されたも
ので、高温強度に優れる耐熱材料で抵抗体や発熱体等に
利用されているタングステンやモリブデン等の基材上に
耐酸化性を向上させるための金属薄膜を形成する方法を
提供するものである。(Purpose of the Invention) The present invention has been made to solve the drawbacks of the above-mentioned conventional methods. The present invention provides a method for forming a thin metal film to improve oxidation resistance.
（問題点を解決するための手段）
本発明は、金属基材に耐酸化性の金属または金属合金の
薄膜を形成する方法において、金属レジネートと有機溶
媒の混合物を該金属基材に塗布、乾燥したのち、３００
〜４００℃大気中で焼成し、次いで還元性ガスまたは還
元性ガスを含む不活性ガス雰囲気中で５００〜９００℃
焼成することを特徴とする耐熱基材への金属薄膜形成方
法である。(Means for Solving the Problems) The present invention provides a method for forming a thin film of an oxidation-resistant metal or metal alloy on a metal substrate, in which a mixture of a metal resinate and an organic solvent is applied to the metal substrate, and then dried. After that, 300
Calcinate in the air at ~400°C, then at 500-900°C in a reducing gas or an inert gas atmosphere containing a reducing gas.
This is a method for forming a metal thin film on a heat-resistant base material, which is characterized by firing.
本発明の詳細について説明する。The details of the present invention will be explained.
耐酸化性の金属または金属合金の薄膜を形成する方法は
、金属として耐酸化性に優れた性能を持つ貴金属を基と
するもので、白金、金、銀、パラジウム、ロジウム、イ
リジウム、ルテニウム、銅およびニッケルより選ばれた
金属のレジネートを用いるものである。The method for forming thin films of oxidation-resistant metals or metal alloys is based on noble metals that have excellent oxidation resistance as metals, such as platinum, gold, silver, palladium, rhodium, iridium, ruthenium, and copper. and nickel.
該金属レジネートは３５０℃以下で熱分解して金属とな
るものでなくてはならない。The metal resinate must be thermally decomposed to metal at 350° C. or lower.
上記の３５０℃以下で熱分解する金属レジネートであれ
ば市販品を用いても良いが、有機酸をアンモニアまたは
トリエチルアミンで中和した溶液に、数％程度の金属の
塩化物または硝酸塩の水溶液を攪拌下でゆっくり加えて
油状のレジネートを生成させ、ついで、クロロホルムに
該油状のレジネートを抽出し水洗浄したのち、エバポレ
ーションすると金属のレジネートが得られる。Commercially available metal resinates that thermally decompose at temperatures below 350°C may be used, but a few percent of a metal chloride or nitrate aqueous solution is stirred into a solution prepared by neutralizing an organic acid with ammonia or triethylamine. The resin is added slowly at the bottom to form an oily resinate, and then the oily resinate is extracted into chloroform, washed with water, and then evaporated to obtain a metal resinate.
前記の有機酸には、ネオペンタン酸、ネオヘプタン酸、
ネオノナン酸、ネオデカン酸、ｎ−へブタン酸、２−エ
チルヘキサン酸のうちから選んで用いられる。The organic acids mentioned above include neopentanoic acid, neoheptanoic acid,
It is selected from neononanoic acid, neodecanoic acid, n-hebutanoic acid, and 2-ethylhexanoic acid.
上記で得られた金属レジネートであれば３５０℃以下の
熱分解で金属となるものが得られるばかりでなく、形成
した薄膜に有害となるような不純物が残らないのでより
好ましいものである。The metal resinate obtained above is more preferable because not only can it be turned into a metal by thermal decomposition at 350° C. or lower, but it also does not leave any harmful impurities in the formed thin film.
有機溶媒としてはターピネオール等で良く、その加える
量は薄膜形成の厚みと塗布操作等を考慮して変えること
ができるが、−回の塗布、乾燥、焼成してＯ，１〜０．
５μｍ程度の厚みが得られ均一な薄膜を得やすいのは金
属レジネートに対して５〜３０％である。The organic solvent may be terpineol or the like, and the amount added can be changed depending on the thickness of the thin film to be formed and the coating operation.
It is easy to obtain a uniform thin film with a thickness of about 5 μm at a ratio of 5 to 30% of the metal resinate.
以上で調製した金属レジネートと有機溶媒の混合したも
のを耐熱基材上に塗布する方法は、筆塗り法、スクリー
ン印刷法、スタンプ法、スプレー法、ディッピング法、
スピンコーティング法から基材の形状や薄膜形成のさせ
かた（部分的か全体的か等）により選択できる。Methods for applying the mixture of metal resinate and organic solvent prepared above onto a heat-resistant substrate include brush coating method, screen printing method, stamping method, spraying method, dipping method,
The spin coating method can be selected depending on the shape of the base material and the method of thin film formation (partial or total, etc.).
該塗布したのち室温で約１０分間乾燥したのち、３５０
℃で約１０分間焼成する。After applying the coating and drying it at room temperature for about 10 minutes,
Bake at ℃ for about 10 minutes.
ついで、水素等の還元性ガス雰囲気中で５００〜９００
℃で約１０分間加熱して完全に金属化させると目的とす
る耐酸化性金属薄膜層が基材上に密着力の優れたもので
得られる。Then, in an atmosphere of reducing gas such as hydrogen, 500 to 900
By heating for about 10 minutes at .degree. C. for complete metallization, the desired oxidation-resistant metal thin film layer with excellent adhesion can be obtained on the substrate.
以下、本発明に係わる実施例を記載するが、該実施例は
本発明を限定するものではない。Examples related to the present invention will be described below, but the examples are not intended to limit the present invention.
（実施例１）
タングステン基板（２５，４ｍｍＸ ２５． ４＋ｎｍ
Ｘ厚さ１．２ｍｍ）上に２−エチルヘキサン酸とトリエ
チルアミンの中和した溶液に塩化白金酸カリウム溶液を
４０℃でゆっくり反応させクロロポルムに抽出したのち
、水洗浄し、エバポレーションして得た白金レジネート
に対し７％のターピネオールを加えて混合したものを、
スクリーン印刷法で塗布シ、室温（２０’Ｃ）で１０分
間乾燥したのち、３５０℃大気中で１０分間焼成し、つ
いで水素カス雰囲気中の電気炉で７０００（：ＩＱ分間
焼成したところ、タンクステン基板上に白金の０． ５
μｍの厚さの均一な薄膜を形成できた。(Example 1) Tungsten substrate (25.4mm x 25.4+nm
A potassium chloroplatinate solution was slowly reacted with a neutralized solution of 2-ethylhexanoic acid and triethylamine at 40°C, extracted with chloroporm, washed with water, and evaporated onto a 1.2 mm thick A mixture of platinum resinate and 7% terpineol,
It was coated using a screen printing method, dried at room temperature (20'C) for 10 minutes, then fired at 350°C for 10 minutes in the air, and then fired for 7000 (IQ) minutes in an electric furnace in a hydrogen scum atmosphere. 0.5 of platinum on the substrate
A uniform thin film with a thickness of μm could be formed.
ここで得た、タンクステン基板上に形成した白金薄膜を
テーピング法により密着強度を確認したところ全く剥が
れることがなかった。When the adhesion strength of the platinum thin film formed on the tanksten substrate obtained here was checked by the taping method, no peeling was found.
また、大気中で１０００’ｃ３０分間加熱したところ、
白金の薄膜を形成させた面は酸化することがなかったが
、白金の薄膜を形成させながった面はタングステンが酸
化してしまった。Also, when heated in the air at 1000'C for 30 minutes,
The surface on which the platinum thin film was formed was not oxidized, but the tungsten on the surface on which the platinum thin film was not formed was oxidized.
（実施例２）
タングステン基板に変えてモリブデン基板（２５，４−
ｍｍＸ ２５． ４ｍｍＸ厚さ１．２ｍｍ）を用いたほ
かは実施例１と同様に操作して白金の薄膜を形成させた
ところ、実施例Ｉと同様の結果が得られた。(Example 2) Molybdenum substrate (25,4-
mmX 25. When a platinum thin film was formed in the same manner as in Example 1 except that a platinum material (4 mm x 1.2 mm thick) was used, the same results as in Example I were obtained.
（実施例３）
ネオデカン酸をトリエチルアミンまたはアンモニアで中
和した溶液にそれぞれの金属の塩化物または硝酸塩溶液
として塩化金酸カリウム溶液、塩化金（Ｉ［）溶液、硝
酸銀溶液、塩化パラジウム酸カリウム溶液、塩化パラジ
ウム溶液、塩化ロジウム酸カリウム溶液、硝酸ロジウム
溶液、塩化ロジウム溶液、塩化イリジウム酸カリウム溶
液、塩化イリジウム溶液、塩化ルテニウム酸カリウム溶
液、塩化ルテニウム溶液、硝酸銅溶液、塩化銅溶液、硝
酸ニッケル溶液、塩化ニッケル溶液をそれぞれ４０℃で
ゆっ（り反応させクロロホルムに抽出したのち、水洗浄
し、エバポレーションして、金レジネート、銀レジネー
ト、パラジウムレジネート、ロジウムレジネート、イリ
ジウムレジネート、ルテニウムレジネート、銅レジネー
ト、ニッケルレジネートを得た。(Example 3) Potassium chloroaurate solution, gold(I[) chloride solution, silver nitrate solution, potassium chloropalladate solution, Palladium chloride solution, potassium chloride rhodate solution, rhodium nitrate solution, rhodium chloride solution, potassium chloriridate solution, iridium chloride solution, potassium chlororuthenate solution, ruthenium chloride solution, copper nitrate solution, copper chloride solution, nickel nitrate solution, The nickel chloride solutions were slowly reacted at 40°C and extracted into chloroform, washed with water, and evaporated to produce gold resinate, silver resinate, palladium resinate, rhodium resinate, iridium resinate, ruthenium resinate, copper resinate, and nickel. Got resinate.
上記で得たそれぞれの金属レジネートを熱分析して分解
温度を測定したところ下記表−１のような結果であった
。When each of the metal resinates obtained above was thermally analyzed to measure the decomposition temperature, the results were as shown in Table 1 below.
また、上記の金属レジネートを有機溶媒としてターピネ
オール、メンタノール、ジブチルカルピトールを用いて
それぞれ溶解したところ均一な溶液状となった。Further, when the above metal resinate was dissolved using terpineol, menthanol, and dibutylcarpitol as organic solvents, a uniform solution was obtained.
（実施例４）
タングステン基板（２５，４ｍｍＸ ２５． ４ｍｍＸ
厚さ１．２ｍｍ）上に実施例３で得た金レジネート、銀
レジネートおよび銅レジネートを重量比で９２：５：３
のものに対し１０％のターピネオールを加えて混合した
ものを、スクリーン印刷法で塗布し、室温（２０８Ｃ）
で１０分間乾燥したのち、３５０℃大気中で１０分間焼
成し、ついで水素ガス（窒素ガス５０％含む）雰囲気中
の電気炉で６００℃ＩＯ分間焼成したところ、タングス
テン基板上に金、銀、銅の合金の０．５μｍの厚さの均
一な薄膜を形成できた。(Example 4) Tungsten substrate (25.4mmX 25.4mmX
The gold resinate, silver resinate, and copper resinate obtained in Example 3 were placed on top of the resin (thickness 1.2 mm) in a weight ratio of 92:5:3.
A mixture of 10% terpineol was applied by screen printing, and the temperature was kept at room temperature (208C).
After drying for 10 minutes at 350°C, it was fired for 10 minutes in the air at 350°C, and then fired at 600°C for IO minutes in an electric furnace in a hydrogen gas (containing 50% nitrogen gas) atmosphere. A uniform thin film of 0.5 μm thick could be formed of the alloy.
ここで得た、タングステン基板上に形成した金、銀、銅
の合金薄膜をテーピング法により密着強度を確認したと
ころ全く剥がれることがなかった。When the adhesion strength of the gold, silver, and copper alloy thin film formed on the tungsten substrate thus obtained was checked by a taping method, no peeling was found.
また、大気中で６００℃３０分間加熱したところ、金、
銀、銅の合金の薄膜を形成させた面は酸化することがな
かったが、金、銀、銅の合金の薄膜を形成させなかった
面はタングステンが酸化してしまった。In addition, when heated in the atmosphere at 600°C for 30 minutes, gold,
The surface on which the thin film of silver and copper alloy was formed did not oxidize, but the tungsten oxidized on the surface on which the thin film of gold, silver, and copper alloy was not formed.
（実施例５）
タングステン基板に変えてモリブデン基板（２５，４ｍ
ｍＸ ２５． ４ｎ＋ｍＸ厚さ１．２ｎ＋ｍ）を用いた
ほかは実施例４と同様に操作して金、銀、銅の合金の薄
膜を形成させたところ、実施例４と同様の結果が得られ
た。(Example 5) Molybdenum substrate (25.4 m
mX 25. When a thin film of an alloy of gold, silver, and copper was formed in the same manner as in Example 4, except that 4n+m×1.2n+m in thickness was used, the same results as in Example 4 were obtained.
（実施例６）
実施例１と同様に金属レジネートを下記のような割合と
したものを用いて塗布、乾燥、焼成したところ実施例１
と同様の結果であった。(Example 6) In the same manner as in Example 1, metal resinate was applied in the following proportions, dried, and fired. Example 1
The results were similar.
なお、密着強度、耐酸化温度試験も下記表−２のような
結果であった。In addition, the results of the adhesion strength and oxidation resistance temperature tests were as shown in Table 2 below.
■白金レジネート９０ｗｔ％−ロジウムレジネー）１０
ｗｔ％
■白金レジネート８５ｗｔ％−金レジネート１５ｗｔ％
■白金レジネート９０ｗｔ％−パラジウムレジネート１
０ｗｔ％
■白金レジネート９０ｗｔ％−イリジウムレジネート１
０ｗｔ％
■白金レジネート８５ｗｔ％−パラジウムレジネ−ト１
０ｗｔ％−ルテニウムレジネート５ｗｔ％■金レジネー
）９０ｗｔ％−ニッケルレジネートｉ ０ｗｔ％
■金しジネート９０ｗｔ％−パラジウムレジネー）１．
０ｗｔ％
■白金レジネート８５ｗｔ％−パラジウムレジネート１
０ｗｔ％−銅しジネート５ｗｔ％■白金レジネート９０
ｗｔ％−ニツケルレジネー）１０ｗｔ％
（実施例７）
アルミナ基板上にタングステン１．０μｍの膜が形成さ
れている基板（２５，４ｍｍＸ ２５． ４ｍｍ×厚さ
１．２ｍｍ）に変えたほかは実施例１と同様に白金レジ
ネートを塗布、乾燥、焼成して口金の薄膜を形成して密
着試験と耐酸化性試験として酸素雰囲気中９００℃で３
０分間加熱したところ、密着性も良く耐酸化性試験でも
まった（異常は見られなかった。■Platinum resinate 90wt%-Rhodium resinate) 10
wt% ■Platinum resinate 85wt% - Gold resinate 15wt% ■Platinum resinate 90wt% - Palladium resinate 1
0wt% ■Platinum resinate 90wt% - Iridium resinate 1
0wt% ■Platinum resinate 85wt% - Palladium resinate 1
0wt% - Ruthenium resinate 5wt% ■ Gold resinate) 90wt% - Nickel resinate i 0wt% ■ Gold resinate 90wt% - Palladium resinate) 1.
0wt% ■Platinum resinate 85wt% - Palladium resinate 1
0wt%-Copper resinate 5wt% ■Platinum resinate 90
(wt% - Nickel Resinane) 10wt% (Example 7) The same procedure was carried out except that the substrate was changed to a substrate (25.4 mm x 25.4 mm x thickness 1.2 mm) in which a 1.0 μm tungsten film was formed on an alumina substrate. In the same manner as in Example 1, platinum resinate was applied, dried, and fired to form a thin film for the cap, and then tested at 900°C in an oxygen atmosphere for adhesion tests and oxidation resistance tests.
When heated for 0 minutes, the adhesion was good and it passed the oxidation resistance test (no abnormality was observed).
（発明の効果）
本発明は、上記結果からも明確のように耐酸化性の金属
または金属合金である貴金属を基とする金属レジネート
を用いて、少量の有機溶媒で酸化しやすい金属上に塗布
、乾燥、焼成するという極めて簡便な方法で耐酸化性に
優れた薄膜を形成することができ、従来高温の還元性雰
囲気においてのみ使用されてきた比較的酸化しやすいタ
ングステンやモリブデンを酸化から保護するという目的
から、技術の発展と信頼性の向上に大いに貢献するもの
である。(Effects of the Invention) As is clear from the above results, the present invention uses a metal resinate based on a noble metal that is an oxidation-resistant metal or metal alloy, and coats it onto a metal that is easily oxidized with a small amount of an organic solvent. It is possible to form a thin film with excellent oxidation resistance using an extremely simple method of drying and firing, and protects tungsten and molybdenum, which are relatively easily oxidized, from oxidation, and which have traditionally been used only in high-temperature reducing atmospheres. For this purpose, it will greatly contribute to the development of technology and the improvement of reliability.
Claims (1)
を形成する方法において、金属レジネートと有機溶媒の
混合物を該金属基材に塗布、乾燥したのち、３００〜４
００℃大気中で焼成し、次いで還元性ガスまたは還元性
ガスを含む不活性ガス雰囲気中で５００〜９００℃焼成
することを特徴とする耐熱基材への金属薄膜形成方法。(1) In a method of forming a thin film of an oxidation-resistant metal or metal alloy on a metal substrate, a mixture of a metal resinate and an organic solvent is applied to the metal substrate, dried, and then coated with a
1. A method for forming a metal thin film on a heat-resistant substrate, which comprises firing in the atmosphere at 00°C, and then firing at 500 to 900°C in a reducing gas or an inert gas atmosphere containing a reducing gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14933190A JP2885886B2 (en) | 1990-06-07 | 1990-06-07 | Method for forming metal thin film on heat-resistant substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14933190A JP2885886B2 (en) | 1990-06-07 | 1990-06-07 | Method for forming metal thin film on heat-resistant substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0441676A true JPH0441676A (en) | 1992-02-12 |
| JP2885886B2 JP2885886B2 (en) | 1999-04-26 |
Family
ID=15472775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14933190A Expired - Lifetime JP2885886B2 (en) | 1990-06-07 | 1990-06-07 | Method for forming metal thin film on heat-resistant substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2885886B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002129341A (en) * | 2000-10-24 | 2002-05-09 | Huei-Tarng Liou | Method for coating gold on quartz tube or high alumina- content tube with durability under high temperature and high voltage, and gold coated quartz tube and high alumina-content tube for ozonizer |
| WO2002077306A1 (en) * | 2001-03-21 | 2002-10-03 | Vishay Intertechnology, Inc. | Method of suppressing the oxidation characteristics of nickel |
| US6723280B2 (en) | 2001-04-02 | 2004-04-20 | Vishay Vitramon Incorporated | Method of suppressing the oxidation characteristics of nickel |
-
1990
- 1990-06-07 JP JP14933190A patent/JP2885886B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002129341A (en) * | 2000-10-24 | 2002-05-09 | Huei-Tarng Liou | Method for coating gold on quartz tube or high alumina- content tube with durability under high temperature and high voltage, and gold coated quartz tube and high alumina-content tube for ozonizer |
| WO2002077306A1 (en) * | 2001-03-21 | 2002-10-03 | Vishay Intertechnology, Inc. | Method of suppressing the oxidation characteristics of nickel |
| US7208218B2 (en) | 2001-03-21 | 2007-04-24 | Vishay Vitramon Incorporated | Method of suppressing the oxidation characteristics of nickel |
| US6723280B2 (en) | 2001-04-02 | 2004-04-20 | Vishay Vitramon Incorporated | Method of suppressing the oxidation characteristics of nickel |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2885886B2 (en) | 1999-04-26 |
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