JP2000087248A - Method for depositing noble metal - Google Patents
Method for depositing noble metalInfo
- Publication number
- JP2000087248A JP2000087248A JP10250774A JP25077498A JP2000087248A JP 2000087248 A JP2000087248 A JP 2000087248A JP 10250774 A JP10250774 A JP 10250774A JP 25077498 A JP25077498 A JP 25077498A JP 2000087248 A JP2000087248 A JP 2000087248A
- Authority
- JP
- Japan
- Prior art keywords
- noble metal
- thin film
- colloid
- oxide thin
- metal oxide
- 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
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 31
- 238000000151 deposition Methods 0.000 title 1
- 239000010409 thin film Substances 0.000 claims abstract description 32
- 239000000084 colloidal system Substances 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 24
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001771 vacuum deposition Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract description 2
- 239000002736 nonionic surfactant Substances 0.000 abstract description 2
- 238000004544 sputter deposition Methods 0.000 abstract description 2
- 229910017083 AlN Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 38
- 229910052763 palladium Inorganic materials 0.000 description 19
- 239000007789 gas Substances 0.000 description 16
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 13
- 229910001887 tin oxide Inorganic materials 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 239000010931 gold Substances 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 4
- 229940076131 gold trichloride Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000000935 solvent evaporation Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- BSYLOTSXNQZYFW-UHFFFAOYSA-K trichlorogold;hydrate Chemical compound O.Cl[Au](Cl)Cl BSYLOTSXNQZYFW-UHFFFAOYSA-K 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、貴金属の担持方法
に関する。更に詳しくは、担持量を増加し得る貴金属の
担持方法に関する。[0001] The present invention relates to a method for supporting a noble metal. More specifically, the present invention relates to a method of supporting a noble metal, which can increase the amount of supported noble metal.
【０００２】[0002]
【従来の技術】従来から、触媒やガスセンサ等の分野に
おいて触媒活性やガス感度を向上させるために、金属酸
化物等の担体に貴金属を担持させることが多く行われて
いる。2. Description of the Related Art Conventionally, in the fields of catalysts and gas sensors, noble metals are often carried on carriers such as metal oxides in order to improve catalytic activity and gas sensitivity.
【０００３】貴金属の担持法には、溶媒蒸発法、沈殿担
持法、平衡吸着法などがある。溶媒蒸発法は、担体を貴
金属塩水溶液中に浸漬し、加熱して溶媒を蒸発除去する
方法であるが、基板上に形成させた薄膜を担体に用いた
場合には、薄膜上に析出する貴金属塩はわずかであっ
て、貴金属塩の大部分は担持に利用されないという欠点
がある。[0003] As a method of supporting a noble metal, there are a solvent evaporation method, a precipitation supporting method, an equilibrium adsorption method and the like. The solvent evaporation method is a method in which a carrier is immersed in an aqueous solution of a noble metal salt and heated to evaporate and remove the solvent.When a thin film formed on a substrate is used as a carrier, the noble metal deposited on the thin film is used. The disadvantage is that the salts are small and most of the noble metal salts are not available for loading.
【０００４】沈殿担持法では、溶媒蒸発法の加熱による
溶媒除去の代りに、貴金属塩水溶液中に沈殿剤を加えて
担体上に沈殿を析出させているが、この場合にも溶媒蒸
発法と同じ欠点がみられる。In the precipitation supporting method, a precipitation agent is added to an aqueous solution of a noble metal salt to precipitate a precipitate on a carrier, instead of removing the solvent by heating in the solvent evaporation method. There are drawbacks.
【０００５】また、平衡吸着法は、担体を貴金属塩水溶
液中に浸漬し、担体上に貴金属塩を吸着させる方法であ
り、基板上に形成させた薄膜を担体として用いる場合に
も利用できるが、やはり担持量を多くすることはできな
い。The equilibrium adsorption method is a method in which a carrier is immersed in an aqueous solution of a noble metal salt and the noble metal salt is adsorbed on the carrier. The method can also be used when a thin film formed on a substrate is used as the carrier. After all, it is not possible to increase the carrying amount.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、絶縁
性基板上に堆積させた金属酸化物薄膜上に貴金属を担持
させるに際し、その担持量を増加せしめる方法を提供す
ることにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for increasing the amount of a noble metal carried on a metal oxide thin film deposited on an insulating substrate.
【０００７】[0007]
【課題を解決するための手段】かかる本発明の目的は、
絶縁性基板上に堆積させた金属酸化物薄膜を、貴金属塩
化物水溶液中にポリエチレングリコールモノオレイルエ
ーテル水溶液を添加することによって得られた貴金属コ
ロイド中に浸漬し、金属酸化物薄膜上に貴金属を担持さ
せる貴金属の担持方法によって達成される。SUMMARY OF THE INVENTION The object of the present invention is as follows.
A metal oxide thin film deposited on an insulating substrate is immersed in a noble metal colloid obtained by adding a polyethylene glycol monooleyl ether aqueous solution to a noble metal chloride aqueous solution, and the noble metal is supported on the metal oxide thin film This is achieved by a method of supporting a noble metal.
【０００８】[0008]
【発明の実施の形態】絶縁性基板としては、アルミナ、
窒化アルミニウム、石英等が用いられ、これらの絶縁性
基板上に堆積される金属酸化物薄膜、好ましくは酸化錫
薄膜は、真空蒸着法、イオンプレーティング法、スパッ
タリング法などにより直接SnO2薄膜を形成させる方法、
金属Sn薄膜を形成させた後熱処理して酸化する方法、Sn
を含む有機金属モノマーのプラズマ重合膜を熱処理する
方法などによって形成される。DESCRIPTION OF THE PREFERRED EMBODIMENTS As an insulating substrate, alumina,
Aluminum oxide, quartz, etc. are used, and a metal oxide thin film, preferably a tin oxide thin film, which is deposited on these insulating substrates, forms a SnO 2 thin film directly by a vacuum deposition method, an ion plating method, a sputtering method, or the like. How to make
A method of forming a metal Sn thin film and then oxidizing by heat treatment, Sn
It is formed by a method of heat-treating a plasma polymerized film of an organometallic monomer containing, for example.
【０００９】金属酸化物薄膜、好ましくは酸化錫薄膜上
への貴金属、好ましくはパラジウムまたは金の担持は、
貴金属コロイド、好ましくはパラジウムコロイドまたは
金コロイド中へ酸化錫薄膜部分を浸漬することによって
行われる。浸漬は、室温乃至約50℃の温度条件下で約0.
5〜5時間程度行われ、その後純水による洗浄が行われ
る。The loading of a noble metal, preferably palladium or gold, on a metal oxide thin film, preferably a tin oxide thin film, comprises:
This is performed by immersing the tin oxide thin film portion in a noble metal colloid, preferably a palladium colloid or a gold colloid. The immersion is performed at about 0.
The cleaning is performed for about 5 to 5 hours, and then cleaning with pure water is performed.
【００１０】貴金属コロイドは、貴金属塩化物水溶液中
にポリエチレングリコールモノオレイルエーテルを添加
することによって調製される。貴金属塩化物としては、
三塩化金またはその水和物などの他に、塩化パラジウム
アンモニウムの如く三塩化パラジウムの塩化アンモニウ
ム付加塩なども用いることができる。The noble metal colloid is prepared by adding polyethylene glycol monooleyl ether to a noble metal chloride aqueous solution. As precious metal chlorides,
In addition to gold trichloride or its hydrate, an ammonium chloride addition salt of palladium trichloride such as ammonium palladium chloride can also be used.
【００１１】パラジウムコロイドは、塩化パラジウムア
ンモニウム(NH4)2PdCl4水溶液中に非イオン系界面活性
剤であるポリエチレングリコールモノオレイルエーテル
C18H 35(OCH2CH2)nOH(n:2〜50）水溶液を添加することに
よって調製される。塩化パラジウムアンモニウムは約0.
01〜10重量％、好ましくは約0.1〜3重量％の水溶液とし
て、またポリエチレングリコールモノオレイルエーテル
は約0.01〜20重量％、好ましくは約0.1〜20重量％の水
溶液として用いられ、またこれら両者は塩化パラジウム
アンモニウムに対してポリエチレングリコールモノオレ
イルエーテルが約0.1〜20、好ましくは約1〜10のモル比
となる添加割合で用いられる。これ以下の添加割合では
コロイドが凝集して沈殿が生じ易くなり、一方これ以上
の添加割合ではポリエチレングリコールモノオレイルエ
ーテルが溶解し難くなる。The palladium colloid is palladium chloride
Nmonium (NHFour)TwoPdClFourNonionic surfactant in aqueous solution
Polyethylene glycol monooleyl ether
C18H 35(OCHTwoCHTwo) Adding an aqueous solution of nOH (n: 2-50)
It is thus prepared. Palladium ammonium chloride is approx.
01 to 10% by weight, preferably about 0.1 to 3% by weight aqueous solution
And also polyethylene glycol monooleyl ether
Is about 0.01-20% by weight, preferably about 0.1-20% by weight of water
Used as solutions, both of which are palladium chloride
Polyethylene glycol monoole for ammonium
Ilether is in a molar ratio of about 0.1-20, preferably about 1-10
It is used at an addition ratio as follows. With the addition ratio below this,
Colloids aggregate and precipitate easily, while
Polyethylene glycol monooleyl ester
-It becomes difficult to dissolve
【００１２】従来から知られている貴金属コロイドの調
製法としては、大きく分けると水溶液中で貴金属塩を還
元してコロイド粒子を析出させる凝縮法と金属蒸気から
得られる金属微粒子を液体中に捕集する分散法とがあ
る。Conventionally known methods for preparing noble metal colloids are roughly classified into a condensation method in which a noble metal salt is reduced in an aqueous solution to precipitate colloidal particles, and a method in which metal fine particles obtained from metal vapor are collected in a liquid. There is a dispersion method.
【００１３】前者の方法には、(1)貴金属塩および保護
コロイドを溶解させた水溶液に、水素、水素化ホウ素ナ
トリウム、アルコール（還元される物質との酸化還元電
位のバランスにより還元剤として作用する）等の還元剤
を添加し、コロイド粒子を析出させる方法や(2)貴金属
塩および保護コロイドを溶解させた水溶液に光照射して
貴金属イオンを還元し、コロイド粒子を析出させる方法
などが知られている。ここで、保護コロイドはコロイド
粒子間の凝集を防ぐ役割を果しており、ゼラチン、ポリ
ビニルアルコール、ポリビニルピロリドン等の水溶性高
分子あるいは界面活性剤が用いられている。In the former method, (1) hydrogen, sodium borohydride, alcohol (which acts as a reducing agent in an aqueous solution in which a noble metal salt and a protective colloid are dissolved by balancing the redox potential with the substance to be reduced) ), Etc. to precipitate colloid particles, and (2) a method in which an aqueous solution in which a noble metal salt and a protective colloid are dissolved is irradiated with light to reduce noble metal ions to precipitate colloid particles. ing. Here, the protective colloid has a role of preventing aggregation between colloid particles, and a water-soluble polymer such as gelatin, polyvinyl alcohol, or polyvinylpyrrolidone or a surfactant is used.
【００１４】しかしながら、(1)の方法において水素化
ホウ素ナトリウム等の還元剤を用いた場合には、生成し
たコロイド粒子中への還元剤の混入が懸念され、またア
ルコールを還元剤として用いた場合には加熱還流しなけ
れば反応せず、更に(2)の方法では光照射源が必要とな
るなどの問題点を有するが、本発明で用いられるパラジ
ウムコロイドの調製方法にはそのような問題がみられな
い。However, when a reducing agent such as sodium borohydride is used in the method (1), there is a concern that the reducing agent may be mixed into the formed colloid particles, and when alcohol is used as the reducing agent. Does not react unless heated and refluxed, and the method (2) has a problem that a light irradiation source is required.However, such a method is not suitable for the method of preparing the palladium colloid used in the present invention. I can't see it.
【００１５】また、金コロイドも、パラジウムコロイド
調製に用いられた塩化パラジウムアンモニウムの代りに
三塩化金（その水和物を含む）を用いることにより、同
様の条件下で調製することができ、それを用いての酸化
錫薄膜上への浸漬法による担持も、パラジウムコロイド
の場合と同様に行われる。なお、三塩化金水溶液にメタ
ノールを添加するだけでも金コロイドは形成されるが、
それには数日を要するのに対し、本発明方法ではわずか
１時間程度の短時間で金コロイドを形成させることがで
きる。The gold colloid can also be prepared under similar conditions by using gold trichloride (including its hydrate) instead of palladium ammonium chloride used in the preparation of the palladium colloid. Is carried on the tin oxide thin film by dipping in the same manner as in the case of palladium colloid. In addition, colloidal gold is formed only by adding methanol to the aqueous solution of gold trichloride,
While it takes several days, the method of the present invention can form a gold colloid in a short time of only about one hour.
【００１６】酸化錫薄膜上に担持されたパラジウムまた
は金は、それらを純水で洗浄した後乾燥し、次いで約40
0〜800℃の空気中に約0.5〜10時間程度保持する加熱処
理が適用される。このようにして絶縁性基板上に堆積さ
せた金属酸化物薄膜上に貴金属を担持させたものを、例
えばガスセンサとして用いる場合には、ガス感応性膜と
しての金属酸化物薄膜は、絶縁性基板上に形成させた作
用極および対極よりなる一対の電極間にまたがる状態で
形成され、更に絶縁性基板には、白金、Al2O3含有白
金、金等よりなるヒーターも設けられている。The palladium or gold supported on the tin oxide thin film is washed with pure water, dried, and then dried for about 40 minutes.
A heat treatment of maintaining the air in the air at 0 to 800 ° C. for about 0.5 to 10 hours is applied. In the case where the metal oxide thin film deposited on the insulating substrate and the noble metal is supported on the insulating substrate, for example, used as a gas sensor, the metal oxide thin film as the gas-sensitive film is placed on the insulating substrate. And a heater made of platinum, Al 2 O 3 -containing platinum, gold or the like is provided on the insulating substrate.
【００１７】[0017]
【発明の効果】金属酸化物薄膜を貴金属コロイド中に浸
漬させて担持せしめることにより、貴金属塩の水溶液中
に浸漬して担持させる場合と比較して、貴金属の担持量
の増加が図られる。By immersing the metal oxide thin film in the noble metal colloid and supporting it, the amount of noble metal supported can be increased as compared with the case where the metal oxide thin film is immersed and supported in an aqueous solution of a noble metal salt.
【００１８】[0018]
【実施例】次に、実施例について本発明を説明する。Next, the present invention will be described with reference to examples.
【００１９】実施例１ (1)塩化パラジウムアンモニウム140mgを水2.5gに溶解さ
せた水溶液中に、ポリエチレングリコールモノオレイル
エーテル(n=10)1gを溶解させた水溶液11gを滴下した。
滴下、混合と共に、塩化パラジウムアンモニウム水溶液
の色は褐色から黒色に変化し、そこにパラジウムコロイ
ドを形成させた。このような操作を暗室下においても行
ったが、同様にパラジウムコロイドが得られた。Example 1 (1) 11 g of an aqueous solution of 1 g of polyethylene glycol monooleyl ether (n = 10) was added dropwise to an aqueous solution of 140 mg of palladium ammonium chloride dissolved in 2.5 g of water.
With dropping and mixing, the color of the aqueous solution of palladium ammonium chloride changed from brown to black, and a palladium colloid was formed there. Although such an operation was performed in a dark room, a palladium colloid was similarly obtained.
【００２０】(2)石英基板上に、真空蒸着法を用いて、
それぞれAl2O3含有Ptよりなる一対の電極およびヒータ
ーを形成させた。更に、原料としてテトラメチル錫およ
び酸素を用いたプラズマＣＶＤ法により、これら電極間
にまたがる酸化錫薄膜を300nmの膜厚で製膜し、空気
中、973K、24時間の条件下で加熱処理した。次いで、こ
れを上記パラジウムコロイド中に室温下で３時間浸漬
し、500mlの純水で洗浄、乾燥した後、空気中、973K、
５時間の加熱処理を行ない、パラジウムを担持させた酸
化錫薄膜をガス感応性膜とするガスセンサ素子を得た。(2) On a quartz substrate, using a vacuum evaporation method,
A pair of electrodes and a heater each made of Pt containing Al 2 O 3 were formed. Further, a thin film of tin oxide over the electrodes was formed to a thickness of 300 nm by a plasma CVD method using tetramethyltin and oxygen as raw materials, and was heat-treated in air at 973K for 24 hours. Then, this was immersed in the above-mentioned palladium colloid at room temperature for 3 hours, washed with 500 ml of pure water and dried, and then in air at 973K.
Heat treatment was performed for 5 hours to obtain a gas sensor element using a tin oxide thin film carrying palladium as a gas-sensitive film.
【００２１】酸化錫薄膜上に担持されたパラジウム量は
3.0原子％（Ｘ線光電子分光法により測定）であり、こ
のガスセンサ素子を用いて、623KでのCO 550ppmに対す
るガス感度を、空気中とガス中での素子抵抗の比として
測定すると2.0であった。The amount of palladium supported on the tin oxide thin film is
3.0 atomic% (measured by X-ray photoelectron spectroscopy). Using this gas sensor element, the gas sensitivity to 550 ppm of CO at 623K was 2.0 as the ratio of the element resistance in air to that in gas. .
【００２２】比較例１ 実施例１における酸化錫薄膜上へのパラジウムの担持
を、塩化パラジウムアンモニウムの１重量％水溶液中へ
の室温下での３時間浸漬によって行ない、以下同様に処
理すると、その担持量は1.0原子％であり、また623Kで
のCO 550ppmに対するガス感度は1.6であった。Comparative Example 1 Palladium was carried on the tin oxide thin film in Example 1 by immersion in a 1% by weight aqueous solution of ammonium palladium chloride at room temperature for 3 hours. The amount was 1.0 at.% And the gas sensitivity at 623K to 550 ppm CO was 1.6.
【００２３】実施例２ (1)三塩化金・水和物AuCl3・nH2O 30mgを水20gに溶解さ
せた水溶液中に、ポリエチレングリコールモノオレイル
エーテル(n=10)70mgを溶解させた水溶液５ｇを滴下、混
合すると、三塩化金水溶液の色は黄色から赤紫色に徐々
に変化し、いずれも１時間程度で金コロイドが形成され
た。このような操作を暗色下においても行ったが、いず
れも同様に金コロイドが得られた。Example 2 (1) An aqueous solution in which 70 mg of polyethylene glycol monooleyl ether (n = 10) was dissolved in an aqueous solution in which 30 mg of AuCl 3 .nH 2 O was dissolved in 20 g of water. When 5 g was dropped and mixed, the color of the aqueous solution of gold trichloride gradually changed from yellow to reddish purple, and a gold colloid was formed in about 1 hour in each case. Although such an operation was performed under a dark color, gold colloid was obtained in each case.
【００２４】(2)実施例１(2)において、パラジウムコロ
イドの代りに上記金コロイドを用い、金を担持させた酸
化錫薄膜をガス感応性膜とするガスセンサ素子を得た。(2) In Example 1 (2), the above gold colloid was used in place of the palladium colloid to obtain a gas sensor element using a tin oxide thin film carrying gold as a gas-sensitive film.
【００２５】酸化錫薄膜上に担持された金量は3.0原子
％(Ｘ線光電子分光法)であり、このガスセンサ素子を用
いて、623KでのC0 550ppmに対するガス感度を、空気中
とガス中での素子抵抗の比として測定すると4.8であっ
た。The amount of gold supported on the tin oxide thin film was 3.0 atomic% (X-ray photoelectron spectroscopy). Using this gas sensor element, the gas sensitivity to 550 ppm of C0 at 623 K was measured in air and gas. It was 4.8 when measured as the ratio of the element resistances.
【００２６】比較例２ 実施例２における酸化錫薄膜上への金の担持を、三塩化
金・水和物の0.1重量％水溶液中への室温下での３時間
浸漬によって行ない、以下同様に処理すると、その担持
量は1.0原子％であり、また623KでのCO 550ppmに対する
ガス感度は3.0であった。Comparative Example 2 Gold was supported on the tin oxide thin film in Example 2 by immersion in a 0.1% by weight aqueous solution of gold trichloride hydrate at room temperature for 3 hours, and the same treatment was carried out. As a result, the carried amount was 1.0 atomic%, and the gas sensitivity to 550 ppm of CO at 623 K was 3.0.
フロントページの続き Ｆターム(参考） 4G069 AA03 AA08 BA01B BA02B BC22B BC33B BC69A BC72B BC75B BD12A BD12B BE07A BE07B BE33A BE33B CA01 EA08 EB15X FA02 FA04 FA06 FB03 FB14 FB30 4K022 AA04 AA46 BA03 BA18 BA36 CA28 DA06 DA08 DB01 DB03 DB04 Continued on the front page F-term (reference) 4G069 AA03 AA08 BA01B BA02B BC22B BC33B BC69A BC72B BC75B BD12A BD12B BE07A BE07B BE33A BE33B CA01 EA08 EB15X FA02 FA04 FA06 FB03 FB14 FB30 4K022 AA04 DB03 DA06
Claims (1)
膜を、貴金属塩化物水溶液中にポリエチレングリコール
モノオレイルエーテル水溶液を添加することによって得
られた貴金属コロイド中に浸漬し、金属酸化物薄膜上に
貴金属を担持させることを特徴とする貴金属の担持方
法。1. A metal oxide thin film deposited on an insulating substrate is immersed in a noble metal colloid obtained by adding a polyethylene glycol monooleyl ether aqueous solution to a noble metal chloride aqueous solution, and A method for supporting a noble metal, comprising supporting a noble metal thereon.
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|---|---|---|---|
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|---|---|---|---|
| JP10250774A JP2000087248A (en) | 1998-09-04 | 1998-09-04 | Method for depositing noble metal |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013118860A1 (en) | 2012-02-09 | 2013-08-15 | 田中貴金属工業株式会社 | Metal colloidal solution and method for producing same |
| WO2014051061A1 (en) | 2012-09-28 | 2014-04-03 | 田中貴金属工業株式会社 | Substrate processing method for supporting a catalyst particle for plating process |
-
1998
- 1998-09-04 JP JP10250774A patent/JP2000087248A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013118860A1 (en) | 2012-02-09 | 2013-08-15 | 田中貴金属工業株式会社 | Metal colloidal solution and method for producing same |
| US10220377B2 (en) | 2012-02-09 | 2019-03-05 | Tanaka Kikinzoku Kogoy K.K. | Metal colloidal solution and method for producing the same |
| WO2014051061A1 (en) | 2012-09-28 | 2014-04-03 | 田中貴金属工業株式会社 | Substrate processing method for supporting a catalyst particle for plating process |
| JP2014070245A (en) * | 2012-09-28 | 2014-04-21 | Tanaka Kikinzoku Kogyo Kk | Method for treating substrate carrying catalyst particles for plating treatment |
| CN104685098A (en) * | 2012-09-28 | 2015-06-03 | 田中贵金属工业株式会社 | Substrate processing method for supporting a catalyst particle for plating process |
| KR20150060888A (en) | 2012-09-28 | 2015-06-03 | 다나카 기킨조쿠 고교 가부시키가이샤 | Substrate processing method for supporting a catalyst particle for plating process |
| KR101641031B1 (en) | 2012-09-28 | 2016-07-19 | 다나카 기킨조쿠 고교 가부시키가이샤 | Method for treating substrate that supports catalyst particles for plating processing |
| US9565776B2 (en) | 2012-09-28 | 2017-02-07 | Tanaka Kikinzoku Kogyo K.K. | Method for treating substrate that support catalyst particles for plating processing |
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