JP2014145110A - Electroless plating bath, method of producing molybdenum trioxide film and chemical sensor - Google Patents
Electroless plating bath, method of producing molybdenum trioxide film and chemical sensor Download PDFInfo
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title claims abstract description 294
- 238000007772 electroless plating Methods 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000126 substance Substances 0.000 title claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 120
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 11
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 11
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 239000010408 film Substances 0.000 description 166
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 239000010409 thin film Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000767 polyaniline Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- -1 lanthanum aluminate Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
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Abstract
Description
本発明は、基板に三酸化モリブデン膜を形成するための無電解めっき浴、この無電解めっき浴を用いて製造される三酸化モリブデン膜の製造方法、及びこの製造方法で製造された三酸化モリブデン膜を用いて形成された化学センサに関する。 The present invention relates to an electroless plating bath for forming a molybdenum trioxide film on a substrate, a method for manufacturing a molybdenum trioxide film manufactured using the electroless plating bath, and a molybdenum trioxide manufactured by the manufacturing method. The present invention relates to a chemical sensor formed using a film.
従来より、膜を基板上に被覆させる際に、スパッタリング法やゾルゲル法等の種々の方法が用いられており、これらの方法は生産性や効率性等を考慮して最適なものが選択されているが、膜と基板の特性や種類によっては基板上に形成された膜が使用される状態として適していないことがある。 Conventionally, when coating a film on a substrate, various methods such as a sputtering method and a sol-gel method have been used, and these methods are selected in consideration of productivity and efficiency. However, depending on the characteristics and types of the film and the substrate, the film formed on the substrate may not be suitable for use.
例えば、ガスセンサの作成に用いられる膜として、内部に導電性高分子がインターカレートされた層状の三酸化モリブデン膜（ＭｏＯ３）が用いられるものがあるが、この三酸化モリブデン膜は基板との密着性が良くないので、三酸化モリブデン膜が使用時に基板から剥がれる虞があった。そこで、三酸化モリブデン膜と基板との密着性を改善する従来技術の１つとして、例えば特許文献１に示す有機無機ハイブリッド薄膜の作成方法が提案されている。 For example, as a film used for making a gas sensor, a layered molybdenum trioxide film (MoO 3 ) in which a conductive polymer is intercalated is used, and this molybdenum trioxide film is connected to a substrate. Since the adhesion is not good, the molybdenum trioxide film may be peeled off from the substrate during use. Thus, as one of the prior arts for improving the adhesion between the molybdenum trioxide film and the substrate, for example, a method for producing an organic-inorganic hybrid thin film disclosed in Patent Document 1 has been proposed.
この従来技術の有機無機ハイブリッド薄膜の作成方法では、三酸化モリブデンの高配向薄膜の作成、この三酸化モリブデン膜への水和アルカリイオンのインターカレート、及びこの水和アルカリイオンと導電性ポリマーあるいは有機イオンとの置換反応の３段階の工程が行われる。 In this prior art method for producing an organic-inorganic hybrid thin film, a highly oriented thin film of molybdenum trioxide, intercalation of hydrated alkali ions into the molybdenum trioxide film, and the hydrated alkali ions and conductive polymer or A three-stage process of substitution reaction with organic ions is performed.
これらの３段階の工程のうち１段階目の工程において、基板上に形成される三酸化モリブデン膜の結晶構造をｂ軸方向に高配向化させる、すなわち三酸化モリブデン膜の層方向を基板の表面に対して平行に配置し、インターカレート時において三酸化モリブデン膜が基板の表面に対して垂直方向に膨張することを抑えることにより、三酸化モリブデン膜と基板との密着性の改善が図られており、この際に効率的に三酸化モリブデン膜を生産できるようにＣＶＤ法が用いられている。しかしながら、このＣＶＤ法は真空を利用した方法であり、装置が大きくなって高価になり易いので、三酸化モリブデン膜を基板上により簡便に形成できる方法が要望されていた。 In the first step among these three steps, the crystal structure of the molybdenum trioxide film formed on the substrate is highly oriented in the b-axis direction, that is, the layer direction of the molybdenum trioxide film is set to the surface of the substrate. By arranging them parallel to each other and suppressing the expansion of the molybdenum trioxide film in the direction perpendicular to the surface of the substrate during intercalation, the adhesion between the molybdenum trioxide film and the substrate can be improved. At this time, the CVD method is used so that the molybdenum trioxide film can be efficiently produced. However, this CVD method is a method using a vacuum, and since the apparatus tends to be large and expensive, there has been a demand for a method by which a molybdenum trioxide film can be more easily formed on a substrate.
そこで、ＣＶＤ法を用いてなくても三酸化モリブデン膜を基板上に形成できる従来技術の１つとして、例えば特許文献２に示す酸化モリブデン薄膜の製造方法が提案されている。この従来技術の酸化モリブデン薄膜の製造方法は、モリブデン酸化物から成る析出物をアルコールに分散させた後、この析出物を含有するアルコールを基板に供給し、乾燥・焼成することにより、三酸化モリブデン膜の層方向が基板の表面に対して平行に配向した高配向（ｂ軸方向への高配向をいう。以下の説明において、高配向とはｂ軸方向の配向を指す）の薄膜を基板上に形成している。 Thus, as one of the prior arts that can form a molybdenum trioxide film on a substrate without using the CVD method, for example, a method for manufacturing a molybdenum oxide thin film shown in Patent Document 2 has been proposed. In this prior art method of manufacturing a molybdenum oxide thin film, a precipitate made of molybdenum oxide is dispersed in an alcohol, and then the alcohol containing the precipitate is supplied to a substrate, followed by drying and firing, thereby obtaining molybdenum trioxide. A thin film having a high orientation in which the layer direction of the film is oriented parallel to the surface of the substrate (referring to a high orientation in the b-axis direction. In the following description, high orientation refers to an orientation in the b-axis direction) Is formed.
特許文献１に開示された従来技術の有機無機ハイブリッド薄膜の作成方法は、上述したように装置が大きくなって高価になるだけでなく、下地に格子定数の近い膜を作成した後でゆっくりエピタキシャル成長をさせなければ、配向性の高い膜を得ることができないので、三酸化モリブデン膜の形成に時間がかかることが問題になっている。 As described above, the method for producing the organic-inorganic hybrid thin film disclosed in Patent Document 1 is not only large and expensive as described above, but also slowly epitaxially grows after forming a film having a lattice constant close to the base. Otherwise, a highly oriented film cannot be obtained, so that it takes time to form the molybdenum trioxide film.
また、特許文献２に開示された従来技術の酸化モリブデン薄膜の製造方法は、モリブデン酸化物から成る析出物をアルコールに分散して、含有するアルコールを基板の表面に塗布する方法として、ディップコート、滴下、スピンコート等が好ましいとされている。しかし、一般的にこのような方法から得られる膜厚は非常に小さいため、所望の膜厚を得るには同じ工程を繰り返すなどの工夫が必要となる。 Moreover, the manufacturing method of the molybdenum oxide thin film of the prior art disclosed by patent document 2 disperse | distributes the deposit which consists of molybdenum oxides in alcohol, and dip-coating as a method of apply | coating the containing alcohol to the surface of a board | substrate, Dropping, spin coating and the like are preferred. However, since the film thickness obtained by such a method is generally very small, it is necessary to devise measures such as repeating the same process in order to obtain a desired film thickness.
従って、所望の膜厚を得るまでに、上述した従来技術の有機無機ハイブリッド薄膜の作成方法と同様に三酸化モリブデン膜の形成に時間がかかることが問題になっている。特に、酸化モリブデン薄膜の製造方法で三酸化モリブデン膜を基板上に厚く形成させた場合には、三酸化モリブデン膜が割れる虞があるので、目的とする配向の三酸化モリブデン膜が得られないことが懸念されている。 Accordingly, there is a problem that it takes time to form a molybdenum trioxide film in the same manner as the above-described conventional method for producing an organic-inorganic hybrid thin film until a desired film thickness is obtained. In particular, when a molybdenum trioxide film is formed thick on a substrate by a method of manufacturing a molybdenum oxide thin film, the molybdenum trioxide film may break, so a molybdenum trioxide film with the desired orientation cannot be obtained. There are concerns.
そして、これらの従来技術の有機無機ハイブリッド薄膜の作成方法及び酸化モリブデン薄膜の製造方法は、基板上に形成される三酸化モリブデン膜の層方向を基板の表面に対して平行に配向させるために、例えば三酸化モリブデンと格子定数の近い材料の基板を用いるか、あるいは三酸化モリブデンと格子定数の近い材料を下地として基板にコーティングする必要がある。 And, in order to align the layer direction of the molybdenum trioxide film formed on the substrate in parallel with the surface of the substrate, the method for producing the organic-inorganic hybrid thin film and the manufacturing method of the molybdenum oxide thin film of these prior arts, For example, it is necessary to use a substrate having a material with a lattice constant close to that of molybdenum trioxide or to coat the substrate with a material having a lattice constant close to that of molybdenum trioxide.
しかしながら、このような三酸化モリブデンと格子定数の近い材料としてアルミニウム酸ランタン（ＬａＡｌＯ３）や酸化セシウム（ＣｅＯ２）が挙げられるが、このような下地用コート剤は、一般的に高価であり（例えば６万円／１００ｍｌ）、高温焼成が不可欠であるので（高温焼成の温度は、例えば９００℃以上）、工程が煩雑になると共に、基板や下地の種類が限定されることになる。すなわち、一般ガラスに代表される耐熱性の低い基板材料には適用することができず、汎用性が低いことが問題になっている。 However, such a material having a lattice constant close to that of molybdenum trioxide includes lanthanum aluminate (LaAlO 3 ) and cesium oxide (CeO 2 ), but such a base coating agent is generally expensive ( For example, 60,000 yen / 100 ml), high-temperature baking is indispensable (high-temperature baking temperature is, for example, 900 ° C. or more), which complicates the process and limits the types of substrates and substrates. That is, it cannot be applied to a substrate material with low heat resistance typified by general glass, and there is a problem that versatility is low.
ここで、ガスセンサや導電性薄膜に使用される三酸化モリブデン膜は、上述したＣＶＤ法や滴下焼成法で製造されるのが一般的であるが、これら以外にも無電解めっきを用いることが考えられており、この無電解めっきは、膜の形成に通電する必要がないことから、独立パターンのある電気回路や粒子状の被めっき物等にも広く利用されている。一方、還元されるべき金属イオンと還元剤が無電解めっき浴として共存しているので、温度、ｐＨ等が適正範囲から外れたり、あるいは浴負荷が大きくなった場合等には、無電解めっき浴に浴分解が生じることがある。 Here, the molybdenum trioxide film used for the gas sensor and the conductive thin film is generally manufactured by the above-described CVD method or the dropping baking method, but it is possible to use electroless plating in addition to these. Since this electroless plating does not require energization to form a film, it is widely used for an electric circuit having an independent pattern, a particulate object to be plated, and the like. On the other hand, since the metal ions to be reduced and the reducing agent coexist as an electroless plating bath, when the temperature, pH, etc. are out of the proper range or the bath load becomes large, the electroless plating bath May cause bath decomposition.
そのため、無電解めっき浴が開発されて以来、錯化剤の種類や濃度及び各種の安定化剤等が検討されており、無電解めっき浴の安定性は徐々に改善されてはいるが、それでも無電解めっき浴の浴分解は完全に解決されていない。このように、無電解めっき浴は、還元されるべき金属イオンと還元剤の共存によって潜在的な不安定さを有しているので、三酸化モリブデンのような金属酸化物の着膜に使用される例が少なく、三酸化モリブデン膜の形成に適用できるように改良されることが望まれている。 Therefore, since the development of electroless plating baths, the types and concentrations of complexing agents and various stabilizers have been studied, and the stability of electroless plating baths has been gradually improved. Bath decomposition of electroless plating baths has not been completely solved. Thus, the electroless plating bath has potential instability due to the coexistence of the metal ion to be reduced and the reducing agent, so it is used for depositing a metal oxide such as molybdenum trioxide. There are few examples, and it is desired to be improved so that it can be applied to formation of a molybdenum trioxide film.
本発明は、このような従来技術の実情からなされたもので、その目的は、三酸化モリブデン膜を基板に簡便かつ迅速に形成でき、汎用性が高い無電解めっき浴、三酸化モリブデン膜の製造方法、及び化学センサを提供することにある。 The present invention has been made based on the actual situation of the prior art as described above. The purpose of the present invention is to produce a molybdenum trioxide film easily and quickly on a substrate and to produce a versatile electroless plating bath and molybdenum trioxide film. It is to provide a method and a chemical sensor.
上記の目的を達成するために、本発明の無電解めっき浴は、触媒が付された基板を浸漬させて、この基板に三酸化モリブデン膜を被覆するための無電解めっき浴であって、モリブデン酸リチウム及びモリブデン酸ナトリウムの少なくとも一方と、ジメチルアミンボランと、硝酸と、アルコールと、を含有することを特徴としている。 In order to achieve the above object, an electroless plating bath of the present invention is an electroless plating bath for immersing a substrate provided with a catalyst and coating the substrate with a molybdenum trioxide film. It contains at least one of lithium acid and sodium molybdate, dimethylamine borane, nitric acid, and alcohol.
このように構成した本発明は、無電解めっき浴の組成にアルコールを含有することにより、無電解めっき浴の安定性を向上させることができるので、この無電解めっき浴から得られる三酸化モリブデン膜の状態を良好に保つことができる。また、基板が無電解めっき浴に浸漬している間、基板に付した触媒が下地として機能することにより、三酸化モリブデンと格子定数の近い材料の基板を用いたり、あるいは三酸化モリブデンと格子定数の近い材料を下地として基板にコーティングしなくても、配向性の高い三酸化モリブデン膜を基板に容易に形成させることができる。これにより、基板に形成される三酸化モリブデンを配向させるために高温焼成を必要とせず、より低い加熱温度で済むので、耐熱性の高い基板材料だけでなく耐熱性の低い基板材料にも適用することができる。このように、三酸化モリブデン膜を基板に簡便かつ迅速に形成でき、高い汎用性を得ることができる。 Since the present invention configured as described above can improve the stability of the electroless plating bath by containing alcohol in the composition of the electroless plating bath, the molybdenum trioxide film obtained from the electroless plating bath This state can be kept good. In addition, while the substrate is immersed in the electroless plating bath, the catalyst attached to the substrate functions as a base, so that a substrate of a material having a lattice constant close to that of molybdenum trioxide can be used, or molybdenum trioxide and the lattice constant can be used. A highly oriented molybdenum trioxide film can be easily formed on a substrate without coating the substrate with a material close to the substrate. As a result, high temperature firing is not required to align the molybdenum trioxide formed on the substrate, and a lower heating temperature is required. Therefore, the present invention can be applied not only to a substrate material having high heat resistance but also to a substrate material having low heat resistance. be able to. Thus, the molybdenum trioxide film can be easily and quickly formed on the substrate, and high versatility can be obtained.
また、本発明に係る無電解めっき浴は、前記発明において、前記アルコールは、全容量に対して７０容量％以上９０容量％以下であることを特徴としている。このように構成すると、無電解めっき浴の全容量に対するアルコールの体積比が大きくなるほど、三酸化モリブデン膜の成膜レートが減少するので、無電解めっき浴の全容量に対するアルコールの体積比を７０容量％以上９０容量％以下に設定することにより、三酸化モリブデン膜の膜厚の調整を容易に行うことができる。 The electroless plating bath according to the present invention is characterized in that, in the above invention, the alcohol is 70% by volume or more and 90% by volume or less with respect to the total volume. With this configuration, as the volume ratio of alcohol to the total capacity of the electroless plating bath increases, the film formation rate of the molybdenum trioxide film decreases, so the volume ratio of alcohol to the total capacity of the electroless plating bath is set to 70 volumes. Setting the film thickness to not less than 90% and not more than 90% by volume makes it easy to adjust the film thickness of the molybdenum trioxide film.
また、本発明に係る無電解めっき浴は、前記発明において、蒸留水をさらに含有し、前記モリブデン酸リチウム及び前記モリブデン酸ナトリウムの少なくとも一方は、０．０１モル／Ｌ以上０．５モル／Ｌ以下で、前記ジメチルアミンボランは、０．００１モル／Ｌ以上０．１モル／Ｌ以下で、前記硝酸は、０．０５モル／Ｌ以上０．１モル／Ｌ以下で、前記蒸留水は、１０容量％以上３０容量％以下であることを特徴としている。このように構成すると、無電解めっき浴を最適な条件に設定して建浴することにより、無電解めっき浴におけるｐＨ等が適正範囲から外れたり、あるいは浴負荷が大きくなることを抑制することができる。これにより、無電解めっき浴をより安定化できるので、浴分解の発生頻度を減少させることができる。 The electroless plating bath according to the present invention further includes distilled water in the above invention, and at least one of the lithium molybdate and the sodium molybdate is 0.01 mol / L or more and 0.5 mol / L. In the following, the dimethylamine borane is 0.001 mol / L or more and 0.1 mol / L or less, the nitric acid is 0.05 mol / L or more and 0.1 mol / L or less, and the distilled water is It is characterized by being 10 volume% or more and 30 volume% or less. When configured in this way, by setting the electroless plating bath to an optimum condition, it is possible to prevent the pH, etc. in the electroless plating bath from deviating from the appropriate range, or to increase the bath load. it can. Thereby, since the electroless plating bath can be further stabilized, the occurrence frequency of bath decomposition can be reduced.
また、本発明に係る無電解めっき浴は、前記発明において、前記アルコールは、エタノール及びメタノールの少なくとも一方から成ることを特徴としている。このように構成すると、エタノール及びメタノールは容易に入手可能であるので、無電解めっき浴の建浴にかかるコストを抑えることができる。 Moreover, the electroless plating bath according to the present invention is characterized in that, in the above invention, the alcohol is composed of at least one of ethanol and methanol. If comprised in this way, since ethanol and methanol can be obtained easily, the cost concerning the construction bath of an electroless-plating bath can be held down.
また、本発明の三酸化モリブデン膜の製造方法は、前記発明の無電解めっき浴に、触媒が付された基板を浸漬してこの基板に三酸化モリブデン膜を析出した後、この三酸化モリブデン膜を焼成して結晶化することを特徴としている。このように構成すると、無電解めっき浴から析出した三酸化モリブデン膜の膜質が無電解めっき浴に含有されたアルコールによって向上しており、しかもこの無電解めっき浴を用いることで三酸化モリブデン膜の製造時間が短縮されるので、析出した三酸化モリブデン膜を焼成しても、得られる三酸化モリブデン膜が割れてクラックが形成されることを抑制することができる。これにより、良質な三酸化モリブデン膜を製造することができる。 The method for producing a molybdenum trioxide film according to the present invention includes immersing a substrate provided with a catalyst in the electroless plating bath according to the present invention to deposit a molybdenum trioxide film on the substrate, and then depositing the molybdenum trioxide film. It is characterized by firing and crystallizing. With this configuration, the film quality of the molybdenum trioxide film deposited from the electroless plating bath is improved by the alcohol contained in the electroless plating bath, and by using this electroless plating bath, the molybdenum trioxide film is improved. Since the manufacturing time is shortened, even when the deposited molybdenum trioxide film is baked, the resulting molybdenum trioxide film can be prevented from cracking and forming cracks. Thereby, a high-quality molybdenum trioxide film can be manufactured.
また、本発明に係る三酸化モリブデン膜の製造方法は、前記発明において、前記基板を浸漬させるときの前記無電解めっき浴の温度は、２０℃以上４０℃以下であることを特徴としている。このように構成すると、基板を浸漬させるときの無電解めっき浴の温度が室温を考慮して調整されているので、三酸化モリブデン膜の製造過程において無電解めっき浴の温度が適正範囲から外れることを防止することができる。 In the method for manufacturing a molybdenum trioxide film according to the present invention, the temperature of the electroless plating bath when the substrate is immersed is 20 ° C. or more and 40 ° C. or less. With this configuration, the temperature of the electroless plating bath when the substrate is immersed is adjusted in consideration of the room temperature, so that the temperature of the electroless plating bath deviates from the appropriate range in the manufacturing process of the molybdenum trioxide film. Can be prevented.
また、本発明に係る三酸化モリブデン膜の製造方法は、前記発明において、前記三酸化モリブデン膜の焼成温度は、４００℃以上５００℃以下であることを特徴としている。このように構成すると、基板に形成される三酸化モリブデン膜を配向させるためには、無電解めっき浴から基板に析出された三酸化モリブデン膜を加熱して結晶粒を育てる必要があるが、その加熱温度は４００℃以上５００℃以下に設定されているので、耐熱性が低い一般ガラスであっても基板として十分に適用することができる。 In the method for manufacturing a molybdenum trioxide film according to the present invention, the firing temperature of the molybdenum trioxide film is 400 ° C. or more and 500 ° C. or less. With this configuration, in order to orient the molybdenum trioxide film formed on the substrate, it is necessary to grow the crystal grains by heating the molybdenum trioxide film deposited on the substrate from the electroless plating bath. Since the heating temperature is set to 400 ° C. or more and 500 ° C. or less, even general glass having low heat resistance can be sufficiently applied as a substrate.
また、本発明に係る三酸化モリブデン膜の製造方法は、前記基板を前記無電解めっき浴に浸漬させる前に、前記基板に前記触媒から成る下地膜を形成することを特徴としている。このように構成すると、三酸化モリブデン膜が下地膜上に析出し、この下地膜が三酸化モリブデン膜と基板との間に介在することにより、三酸化モリブデン膜と基板との密着性を高めることができる。これにより、製造された三酸化モリブデン膜が基板から剥がれるのを抑えることができる。 The method for producing a molybdenum trioxide film according to the present invention is characterized in that a base film made of the catalyst is formed on the substrate before the substrate is immersed in the electroless plating bath. With this configuration, the molybdenum trioxide film is deposited on the base film, and the base film is interposed between the molybdenum trioxide film and the substrate, thereby improving the adhesion between the molybdenum trioxide film and the substrate. Can do. Thereby, it can suppress that the manufactured molybdenum trioxide film | membrane peels from a board | substrate.
また、本発明に係る化学センサは、前記発明で製造された三酸化モリブデン膜を用いて形成されたことを特徴としている。このように構成すると、化学センサの感受性を高めることができるので、高感度に応答する化学センサを得ることができる。これにより、化学センサの実用性を向上させることができる。 In addition, the chemical sensor according to the present invention is characterized by being formed using the molybdenum trioxide film manufactured in the above invention. If comprised in this way, since the sensitivity of a chemical sensor can be raised, the chemical sensor which responds to high sensitivity can be obtained. Thereby, the practicality of a chemical sensor can be improved.
本発明によれば、三酸化モリブデン膜を基板に簡便かつ迅速に形成でき、汎用性が高いので、従来よりも無電解めっきによる三酸化モリブデン膜の優れた生産性を実現することができる。前述した以外の課題、構成及び効果は、以下の実施形態の説明により明らかにされる。 According to the present invention, a molybdenum trioxide film can be easily and quickly formed on a substrate and has high versatility. Therefore, it is possible to realize a superior productivity of a molybdenum trioxide film by electroless plating as compared with the prior art. Problems, configurations, and effects other than those described above will become apparent from the following description of embodiments.
以下、本発明に係る無電解めっき浴、及び三酸化モリブデン膜の製造方法を実施するための形態を図に基づいて説明する。 Hereinafter, an embodiment for carrying out an electroless plating bath and a method for producing a molybdenum trioxide film according to the present invention will be described with reference to the drawings.
本発明の一実施形態に係る無電解めっき浴は、例えばモリブデン酸リチウム（Ｌｉ２ＭｏＯ４）及びモリブデン酸ナトリウム（Ｎａ２ＭｏＯ４）の少なくとも一方と、ジメチルアミンボラン（ＤＭＡＢ）と、硝酸（ＨＮＯ３）と、アルコールと、蒸留水（Ｈ２Ｏ）とを含有し、触媒が付された基板を浸漬させて、この基板に三酸化モリブデン膜（ＭｏＯ３）を被覆するためのものである。なお、基板には、例えば石英ガラスや並ガラス（ソーダガラス）等の一般ガラス（三酸化モリブデンの結晶を配向させる際に行われる加熱処理（例えば４００℃以上５００℃以下）に耐え得るもの）等の絶縁基板が用いられている。 An electroless plating bath according to an embodiment of the present invention includes, for example, at least one of lithium molybdate (Li 2 MoO 4 ) and sodium molybdate (Na 2 MoO 4 ), dimethylamine borane (DMAB), and nitric acid (HNO). 3 ), alcohol, and distilled water (H 2 O), and a substrate provided with a catalyst is dipped to coat the substrate with a molybdenum trioxide film (MoO 3 ). For the substrate, for example, general glass such as quartz glass or ordinary glass (soda glass) (which can withstand heat treatment (for example, 400 ° C. or higher and 500 ° C. or lower) performed when orienting the crystals of molybdenum trioxide), etc. Insulating substrate is used.
ここで、基板に触媒を付与する方法として、例えば印刷焼成法（例えば基板にキャタペースト（ＣＣＰ−４０１０ＦＫＢ：奥野製薬工業株式会社製キャタペースト（有機パラジウム化合物を含む有機溶媒））をスクリーン印刷法により塗布した後、１２０℃で１０分間仮焼きしてから５００℃で２０分間本焼きする焼成により作成する方法）やセンシベーティング−アクチベーティング法（例えば基板を塩化第一錫水溶液（０．５ｇ／Ｌ）中に５分間浸漬して水洗した後、塩化パラジウム水溶液（０．３３ｇ／Ｌ）中に５分間浸漬して水洗する作業を２回繰返し、基板を７０℃で３０分間乾燥させる方法）が知られている。特に、印刷焼成法を用いればパターニングが容易になり、センシベーティング−アクチベーティング法を用いれば大量処理及び大面積への処理が容易になるが、本実施形態は基板に触媒を付与できる方法であれば、特にこれらの方法に限定されるものではない。 Here, as a method for imparting a catalyst to a substrate, for example, a printing baking method (for example, a cata paste (CCP-4010FKB: cata paste manufactured by Okuno Pharmaceutical Co., Ltd. (an organic solvent containing an organic palladium compound)) on a substrate by a screen printing method is used. After the coating, it is calcined at 120 ° C. for 10 minutes and then burned at 500 ° C. for 20 minutes, or a sensitizing-activating method (for example, stannous chloride aqueous solution (0.5 g) / L) 5 minutes immersion in water, followed by washing with water and then immersion in an aqueous palladium chloride solution (0.33 g / L) for 5 minutes, followed by washing with water twice and drying the substrate at 70 ° C. for 30 minutes) It has been known. In particular, patterning is facilitated by using a printing and firing method, and mass processing and processing to a large area are facilitated by using a sensitizing-activating method, but this embodiment is a method capable of imparting a catalyst to a substrate. If it is, it will not be limited to these methods in particular.
また、無電解めっき浴に含有されるモリブデン酸リチウム及びモリブデン酸ナトリウムの少なくとも一方は、金属源として用いられており、例えば０．０１モル／Ｌ以上０．５モル／Ｌ以下である。また、無電解めっき浴に含有されるジメチルアミンボランは、還元剤として用いられており、例えば０．００１モル／Ｌ以上０．１モル／Ｌ以下である。 Further, at least one of lithium molybdate and sodium molybdate contained in the electroless plating bath is used as a metal source, for example, 0.01 mol / L or more and 0.5 mol / L or less. Further, dimethylamine borane contained in the electroless plating bath is used as a reducing agent, and is, for example, 0.001 mol / L or more and 0.1 mol / L or less.
さらに、無電解めっき浴に含有される硝酸は、ｐＨ調整剤として用いられており、例えば０．０５モル／Ｌ以上０．１モル／Ｌ以下であり、無電解めっき浴に含有される蒸留水は、例えば１０容量％以上３０容量％以下である。 Furthermore, nitric acid contained in the electroless plating bath is used as a pH adjuster, for example, 0.05 mol / L or more and 0.1 mol / L or less, and distilled water contained in the electroless plating bath. Is, for example, 10 volume% or more and 30 volume% or less.
そして、無電解めっき浴に含有されるアルコールは、後述するように三酸化モリブデン膜の膜質を向上させる膜質向上剤として用いられており、例えば全容量に対して７０容量％以上９０容量％以下である。また、アルコールは、例えばエタノール及びメタノールの少なくとも一方から成っている。 The alcohol contained in the electroless plating bath is used as a film quality improver for improving the film quality of the molybdenum trioxide film as will be described later. For example, the alcohol content is 70% by volume to 90% by volume with respect to the total capacity. is there. The alcohol is made of at least one of ethanol and methanol, for example.
次に、本実施形態に係る無電解めっき浴を用いた三酸化モリブデン膜の製造方法について説明する。 Next, a method for manufacturing a molybdenum trioxide film using the electroless plating bath according to the present embodiment will be described.
まず、上述のように設定した含有量のモリブデン酸リチウム及びモリブデン酸ナトリウムの少なくとも一方、ジメチルアミンボラン、硝酸、エタノール及びメタノールの少なくとも一方、及び蒸留水を用意し、これらを建浴して無電解めっき浴を作成する。一方、三酸化モリブデン膜を被覆させる基板上に予め触媒を付しておく。 First, prepare at least one of lithium molybdate and sodium molybdate with the content set as described above, at least one of dimethylamine borane, nitric acid, ethanol and methanol, and distilled water, and build these to electroless Create a plating bath. On the other hand, a catalyst is previously applied on the substrate to be coated with the molybdenum trioxide film.
次に、作成した無電解めっき浴に、触媒が付された基板を浸漬し、この基板に触媒を下地膜として三酸化モリブデン膜を析出させる。このとき、基板を無電解めっき浴に浸漬させている間、無電解めっき浴の温度は、例えば２０℃以上４０℃以下に設定されている。 Next, the substrate provided with the catalyst is immersed in the electroless plating bath thus prepared, and a molybdenum trioxide film is deposited on the substrate using the catalyst as a base film. At this time, while the substrate is immersed in the electroless plating bath, the temperature of the electroless plating bath is set to, for example, 20 ° C. or higher and 40 ° C. or lower.
そして、三酸化モリブデン膜が基板に析出すると、基板上の三酸化モリブデン膜を、例えば４００℃以上５００℃以下の温度で焼成して結晶化し、三酸化モリブデン膜を基板に形成させる。このようにして、本実施形態に係る無電解めっき浴を用いて三酸化モリブデン膜が製造される。 When the molybdenum trioxide film is deposited on the substrate, the molybdenum trioxide film on the substrate is baked and crystallized at a temperature of, for example, 400 ° C. to 500 ° C. to form the molybdenum trioxide film on the substrate. In this manner, a molybdenum trioxide film is manufactured using the electroless plating bath according to the present embodiment.
このように構成した本実施形態に係る無電解めっき浴、及び三酸化モリブデン膜の製造方法によれば、三酸化モリブデン膜の製造に無電解めっきを用いているので、装置を小型化することができ、製造コストを抑えることができる。しかも、無電解めっきを用いても、無電解めっき浴の組成にエタノール及びメタノールの少なくとも一方を含有することにより、無電解めっき浴から得られる三酸化モリブデン膜の膜質が良くなると共に、基板には触媒を付すだけで良いので、三酸化モリブデン膜の製造工程も簡単になり、配向性の高い三酸化モリブデン膜を短時間で製造することができる。 According to the electroless plating bath and the method for manufacturing a molybdenum trioxide film according to the present embodiment configured as described above, since the electroless plating is used for manufacturing the molybdenum trioxide film, the apparatus can be downsized. Manufacturing cost can be reduced. Moreover, even when electroless plating is used, the composition of the electroless plating bath contains at least one of ethanol and methanol, so that the film quality of the molybdenum trioxide film obtained from the electroless plating bath is improved and the substrate has Since only a catalyst is required, the manufacturing process of the molybdenum trioxide film is simplified, and a highly oriented molybdenum trioxide film can be manufactured in a short time.
そして、基板に形成される三酸化モリブデン膜を配向させる際に、無電解めっき浴から基板上に析出した三酸化モリブデン膜を４００℃以上５００℃以下の温度で焼成しているので、一般ガラス等の耐熱性の低い基板材料にも十分に適用することができる。このように、三酸化モリブデン膜を基板に簡便かつ迅速に形成でき、汎用性を高めることができるので、無電解めっきによる三酸化モリブデン膜の優れた生産性を実現することができる。 And when orienting the molybdenum trioxide film formed on the substrate, the molybdenum trioxide film deposited on the substrate from the electroless plating bath is baked at a temperature of 400 ° C. to 500 ° C. It can be sufficiently applied to a substrate material having low heat resistance. As described above, since the molybdenum trioxide film can be easily and quickly formed on the substrate and versatility can be improved, excellent productivity of the molybdenum trioxide film by electroless plating can be realized.
また、本実施形態に係る無電解めっき浴、及び三酸化モリブデン膜の製造方法は、無電解めっき浴の全容量に対するアルコールの体積比が大きくなるほど、三酸化モリブデン膜の成膜レートが減少することから、無電解めっき浴の全容量に対するアルコールの体積比を変更することにより、三酸化モリブデン膜の成膜レートを自由に調整することができる。 In addition, in the electroless plating bath and the method of manufacturing a molybdenum trioxide film according to this embodiment, the film formation rate of the molybdenum trioxide film decreases as the volume ratio of alcohol to the total capacity of the electroless plating bath increases. Thus, the film formation rate of the molybdenum trioxide film can be freely adjusted by changing the volume ratio of alcohol to the total capacity of the electroless plating bath.
従って、本実施形態に係る無電解めっき浴、及び三酸化モリブデン膜の製造方法は、無電解めっき浴の全容量に対するアルコールの体積比を７０容量％以上９０容量％以下に設定し、三酸化モリブデン膜の膜厚を調整し易い成膜レートまで低下させているので、所望の膜厚の三酸化モリブデン膜を基板に的確に形成させることができる。なお、無電解めっき浴の全容量に対するアルコールの体積比が６０容量％未満では、クラック発生のない高品位の膜形成、無電解めっき浴の安定化、及び成膜速度のコントロール等の点で劣るので、本実施形態のように無電解めっき浴の全容量に対するアルコールの体積比を７０容量％以上９０容量％以下に設定するのがより好ましい。 Therefore, in the electroless plating bath and the method of manufacturing the molybdenum trioxide film according to the present embodiment, the volume ratio of alcohol to the total capacity of the electroless plating bath is set to 70% by volume or more and 90% by volume or less, and molybdenum trioxide is obtained. Since the film thickness is reduced to a film formation rate that allows easy adjustment, a molybdenum trioxide film having a desired film thickness can be accurately formed on the substrate. If the volume ratio of alcohol to the total volume of the electroless plating bath is less than 60% by volume, it is inferior in terms of forming a high-quality film without cracking, stabilizing the electroless plating bath, and controlling the film formation rate. Therefore, it is more preferable to set the volume ratio of the alcohol with respect to the total capacity of the electroless plating bath to 70% by volume or more and 90% by volume or less as in the present embodiment.
なお、上述した本実施形態は、本発明を分かり易く説明するために詳細に説明したものであり、必ずしも説明した全ての構成を備えるものに限定されるものではない。また、ある実施形態の構成の一部を他の実施形態の構成に置き換えることが可能であり、また、ある実施形態の構成に他の実施形態の構成を加えることも可能である。 In addition, this embodiment mentioned above was described in detail in order to demonstrate this invention easily, and is not necessarily limited to what is provided with all the demonstrated structures. Further, a part of the configuration of an embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of an embodiment.
次に、上記無電解めっき浴を用いて異なる２種類の基板に三酸化モリブデン膜を形成させた実施例１、２、及びこれらの実施例１、２と比較する比較例１について説明する。 Next, Examples 1 and 2 in which molybdenum trioxide films are formed on two different types of substrates using the electroless plating bath, and Comparative Example 1 compared with Examples 1 and 2 will be described.
［実施例１］
本実施例１は、上記無電解めっき浴の組成をさらに以下のように規定した。すなわち、金属源として０．１モル／Ｌのモリブデン酸ナトリウム、還元剤として０．０５モル／Ｌのジメチルアミンボラン、ｐＨ調整剤として０．０７モル／Ｌの硝酸、膜質向上剤として７０容量％のエタノール、その他全量調整用に３０容量％以下の蒸留水を使用した。建浴は、モリブデン酸ナトリウム、硝酸、ジメチルアミンボランを８割程度の蒸留水に溶解し、その後エタノールを添加し、最後に残った蒸留水で全量の調整をおこなった。無電解めっき浴のｐＨを０．８〜１．２に調整し、基板には石英ガラス基板（ＳｉＯ２）を用いた。
[Example 1]
In Example 1, the composition of the electroless plating bath was further defined as follows. That is, 0.1 mol / L sodium molybdate as a metal source, 0.05 mol / L dimethylamine borane as a reducing agent, 0.07 mol / L nitric acid as a pH adjuster, and 70% by volume as a film quality improver. 30% by volume or less of distilled water was used to adjust ethanol and other total amounts. For the bath, sodium molybdate, nitric acid, and dimethylamine borane were dissolved in about 80% distilled water, ethanol was added, and the remaining amount was finally adjusted with distilled water. The pH of the electroless plating bath was adjusted to 0.8 to 1.2, and a quartz glass substrate (SiO 2 ) was used as the substrate.
そして、上述した三酸化モリブデン膜の製造方法の製造工程を前提として、まず上述の組成で無電解めっき浴を建浴する。一方、石英ガラス基板を超音波洗浄してから石英ガラス基板に印刷法にて触媒を付す。その後、建浴した無電解めっき浴に石英ガラス基板を３０秒から６分程度浸漬する。このとき、無電解めっき浴の温度は２０℃に保たれている。 And on the premise of the manufacturing process of the manufacturing method of the molybdenum trioxide film | membrane mentioned above, an electroless-plating bath is first constructed with the above-mentioned composition. On the other hand, after the quartz glass substrate is ultrasonically cleaned, a catalyst is attached to the quartz glass substrate by a printing method. Thereafter, the quartz glass substrate is dipped in the built electroless plating bath for about 30 seconds to 6 minutes. At this time, the temperature of the electroless plating bath is kept at 20 ° C.
次に、石英ガラス基板を無電解めっき浴から取り出し、石英ガラス基板を蒸留水で水洗した後、８０℃で３０分間乾燥する。石英ガラス基板の乾燥が終了した後、石英ガラス基板を大気雰囲気の処理炉に入れて４００℃で５時間熱処理を行い、処理炉から取り出した石英ガラス基板に対してＸＲＤ分析を行った。 Next, the quartz glass substrate is taken out from the electroless plating bath, washed with distilled water, and then dried at 80 ° C. for 30 minutes. After the drying of the quartz glass substrate was completed, the quartz glass substrate was put into a processing furnace in the air atmosphere and subjected to heat treatment at 400 ° C. for 5 hours, and XRD analysis was performed on the quartz glass substrate taken out from the processing furnace.
［実施例２］
本実施例２は、上述した実施例１が基板に石英ガラス基板を用いたのに対して、基板にアルミナ基板（Ａｌ２Ｏ３）を用いており、その他は実施例１と同様である。
[Example 2]
The second embodiment is the same as the first embodiment except that the quartz glass substrate is used as the substrate in the above-described first embodiment and an alumina substrate (Al 2 O 3 ) is used as the substrate.
［比較例１］
一方、比較例１は、上述した実施例１の無電解めっき浴に７０容量％のエタノールが含有されていたのに対して、無電解めっき浴にエタノール等のアルコールが含有されておらず、アルコールの代わりに蒸留水を用いて全量を調整している。その他は実施例１と同様である。
[Comparative Example 1]
On the other hand, in Comparative Example 1, 70% by volume of ethanol was contained in the electroless plating bath of Example 1 described above, whereas no alcohol such as ethanol was contained in the electroless plating bath. Instead of using distilled water, the total amount is adjusted. Others are the same as in the first embodiment.
以上の結果、図１に示すように、実施例１における石英ガラス基板から三酸化モリブデン膜に起因する２θ＝０２０、０４０、０６０のピークの検出が確認されたので、基板が下地に格子定数を合わせた配向膜を用いない石英ガラス基板であっても高配向の三酸化モリブデン膜が得られたことが分かる。特に、図２に示すように、実施例１における石英ガラス基板上に形成された三酸化モリブデン膜の表面にはクラックがあまり見られず、三酸化モリブデン膜の状態が良好であることが分かる。 As a result, as shown in FIG. 1, detection of peaks of 2θ = 020, 040, 060 due to the molybdenum trioxide film from the quartz glass substrate in Example 1 was confirmed, so that the substrate had a lattice constant on the base. It can be seen that a highly oriented molybdenum trioxide film was obtained even on a quartz glass substrate that did not use a combined alignment film. In particular, as shown in FIG. 2, it can be seen that the surface of the molybdenum trioxide film formed on the quartz glass substrate in Example 1 does not show much cracks, and the state of the molybdenum trioxide film is good.
また、図３に示すように、実施例２におけるアルミナ基板からこの基板に起因するピークが確認されたものの、実施例１と同様に三酸化モリブデン膜に起因する２θ＝０２０、０４０、０６０のピークの検出が確認されたので、基板が下地に格子定数を合わせた配向膜を用いないアルミナ基板であっても高配向の三酸化モリブデン膜が得られたことが分かる。 Further, as shown in FIG. 3, although the peak due to this substrate was confirmed from the alumina substrate in Example 2, the peaks of 2θ = 020, 040, 060 due to the molybdenum trioxide film as in Example 1 were confirmed. Therefore, it can be seen that a highly oriented molybdenum trioxide film was obtained even if the substrate was an alumina substrate that did not use an alignment film having a lattice constant matched to the base.
一方、図４に示すように、比較例１における石英ガラス基板から三酸化モリブデン膜に起因する２θ＝０２０、０４０、０６０のピークの検出が確認されたので、無電解めっき浴にアルコールを含んでいなくても、高配向の三酸化モリブデン膜が得られたが、図５に示すように比較例１における石英ガラス基板上に形成された三酸化モリブデン膜の表面には多数のクラックが見られ、三酸化モリブデン膜の状態が実施例１に比べて劣り、この三酸化モリブデン膜は使用される状態として適していないことが分かる。 On the other hand, as shown in FIG. 4, since detection of peaks of 2θ = 020, 040, 060 due to the molybdenum trioxide film was confirmed from the quartz glass substrate in Comparative Example 1, alcohol was contained in the electroless plating bath. Although a highly oriented molybdenum trioxide film was obtained even if not, many cracks were observed on the surface of the molybdenum trioxide film formed on the quartz glass substrate in Comparative Example 1 as shown in FIG. It can be seen that the state of the molybdenum trioxide film is inferior to that of Example 1, and this molybdenum trioxide film is not suitable for use.
従って、実施例１の無電解めっき浴に含有されている７０容量％のアルコールが基板上の三酸化モリブデン膜の状態を安定化させ、得られた三酸化モリブデン膜の膜質が向上することが把握できる。この実施例１のように水とアルコールとの混合溶媒を用いた場合に、生成する三酸化モリブデン膜のクラックの発生が抑制される現象については、次のようなメカニズムが考えられる。 Therefore, it is understood that 70% by volume of alcohol contained in the electroless plating bath of Example 1 stabilizes the state of the molybdenum trioxide film on the substrate and improves the film quality of the obtained molybdenum trioxide film. it can. The following mechanism can be considered for the phenomenon in which the generation of cracks in the generated molybdenum trioxide film is suppressed when a mixed solvent of water and alcohol is used as in Example 1.
すなわち、モリブデン酸化合物は、水にのみ溶解し水和物となるが、アルコールには溶解しない。アルコールの濃度が高い液中において、モリブデン酸リチウム又はモリブデン酸ナトリウム中のモリブデン酸が溶媒中の水と反応して水和物となる確率が低下するため、三酸化モリブデン膜の生成速度が低下し緻密な膜が形成され、この得られた緻密な膜は、脱水縮合時の収縮率を小さくできるので、クラックの発生を抑制することができる。 That is, the molybdate compound dissolves only in water to form a hydrate, but does not dissolve in alcohol. In a liquid with a high alcohol concentration, the rate of formation of molybdenum trioxide film decreases because the probability that molybdic acid in lithium molybdate or sodium molybdate reacts with water in the solvent to form a hydrate decreases. A dense film is formed, and the obtained dense film can reduce the shrinkage rate at the time of dehydration condensation, so that generation of cracks can be suppressed.
さらに、水単体と比較して水とアルコールとの混合溶媒は、表面張力が小さくなるため、乾燥する際の収縮応力が低減されてクラックの発生が抑制される。しかしながら、単に、めっき液中の薬品濃度を下げるだけでは、反応の確率を低下できても加水分解の進行を抑制できないので緻密な皮膜とならず、クラックの発生を抑制することができない。以上のことにより、実施例１、２の無電解めっき浴から上述の三酸化モリブデン膜の製造方法を実施することで良質な三酸化モリブデン膜を製造することができる。 Furthermore, since the surface tension of the mixed solvent of water and alcohol is smaller than that of water alone, the shrinkage stress during drying is reduced, and the generation of cracks is suppressed. However, simply reducing the chemical concentration in the plating solution does not suppress the progress of hydrolysis even if the probability of reaction can be reduced, so that a dense film is not formed, and the occurrence of cracks cannot be suppressed. As described above, a high-quality molybdenum trioxide film can be manufactured by performing the above-described method for manufacturing a molybdenum trioxide film from the electroless plating baths of Examples 1 and 2.
次に、上述した実施例１の無電解めっき浴の全容量に対するエタノールの体積を変更して実施した実施例３、及びこの実施例３と比較する比較例２について説明する。 Next, Example 3 performed by changing the volume of ethanol with respect to the total capacity of the electroless plating bath of Example 1 described above and Comparative Example 2 compared with Example 3 will be described.
［実施例３］
本実施例３は、上述した実施例１の無電解めっき浴の全容量に対するエタノールの体積を３０容量％、５０容量％、７０容量％、及び９０容量％にそれぞれ変更し、実施例１と同様の手順を順次実施した。その際、石英ガラス基板に析出される三酸化モリブデン膜の成膜レート（無電解めっきを行った時間に対して析出した膜厚の比）をそれぞれ測定した。
[Example 3]
In Example 3, the volume of ethanol with respect to the total capacity of the electroless plating bath of Example 1 described above was changed to 30% by volume, 50% by volume, 70% by volume, and 90% by volume, respectively. The procedure was sequentially performed. At that time, the film formation rate of the molybdenum trioxide film deposited on the quartz glass substrate (ratio of the deposited film thickness to the electroless plating time) was measured.
［比較例２］
一方、比較例２は、上述の無電解めっき浴の全容量に対するエタノールの体積が０容量％、すなわち上述の比較例１を実施する際に、比較例１における石英ガラス基板に析出される三酸化モリブデン膜の成膜レートを測定した。
[Comparative Example 2]
On the other hand, in Comparative Example 2, the volume of ethanol with respect to the total capacity of the above-described electroless plating bath is 0% by volume, that is, trioxide deposited on the quartz glass substrate in Comparative Example 1 when carrying out Comparative Example 1 above. The deposition rate of the molybdenum film was measured.
以上の結果、図６に示すように、実施例３の無電解めっき浴の全容量に対するエタノールの体積が増加するほど三酸化モリブデン膜の成膜レートが低下しているので、無電解めっき浴の全容量に対するエタノールの体積比を変更することで三酸化モリブデン膜の成膜レートの制御が可能であることが分かる。 As a result, as shown in FIG. 6, the film formation rate of the molybdenum trioxide film decreases as the volume of ethanol increases with respect to the total capacity of the electroless plating bath of Example 3. It can be seen that the deposition rate of the molybdenum trioxide film can be controlled by changing the volume ratio of ethanol to the total capacity.
特に、無電解めっき浴の全容量に対するエタノールの体積が７０容量％の無電解めっき浴を用いたときの１μｍの三酸化モリブデン膜の膜厚を得るのに１０分の時間がかかり、無電解めっき浴の全容量に対するエタノールの体積が９０容量％の無電解めっき浴を用いたときの１μｍの三酸化モリブデン膜の膜厚を得るのに２０分の時間がかかった。これにより、無電解めっき浴の全容量に対するエタノールの体積比が７０容量％以上９０容量％以下の範囲が三酸化モリブデン膜の成膜レートの低下率が大きく、三酸化モリブデン膜の膜厚を調整し易くなることが分かる。 In particular, it takes 10 minutes to obtain a film thickness of 1 μm molybdenum trioxide film when using an electroless plating bath whose volume of ethanol is 70% by volume with respect to the total capacity of the electroless plating bath. It took 20 minutes to obtain a film thickness of 1 μm molybdenum trioxide film when using an electroless plating bath whose volume of ethanol was 90% by volume with respect to the total volume of the bath. As a result, the rate of decrease in the deposition rate of the molybdenum trioxide film is large when the volume ratio of ethanol to the total volume of the electroless plating bath is 70 volume% or more and 90 volume% or less, and the film thickness of the molybdenum trioxide film is adjusted. It turns out that it becomes easy to do.
一方、比較例２の無電解めっき浴の全容量に対するエタノールの体積が０容量％のときの三酸化モリブデン膜の成膜レートが最も高くなっている。このときの１μｍの三酸化モリブデン膜の膜厚を得るのに２分程の時間で完了し、三酸化モリブデン膜の成膜レートが大きいので、三酸化モリブデン膜の膜厚を調整し難いことが分かる。従って、無電解めっき浴がエタノールを含有することにより、三酸化モリブデン膜の成膜レートを制御できるので、製造工程における三酸化モリブデン膜の膜厚の精度を高めることができる。 On the other hand, the deposition rate of the molybdenum trioxide film is highest when the volume of ethanol is 0% by volume with respect to the total capacity of the electroless plating bath of Comparative Example 2. At this time, the film thickness of 1 μm of the molybdenum trioxide film is completed in about 2 minutes, and the film formation rate of the molybdenum trioxide film is high, so it is difficult to adjust the film thickness of the molybdenum trioxide film. I understand. Therefore, since the film formation rate of the molybdenum trioxide film can be controlled when the electroless plating bath contains ethanol, the accuracy of the film thickness of the molybdenum trioxide film in the manufacturing process can be increased.
次に、上述した実施例２の手順にて形成された三酸化モリブデン膜を用いて作製した化学センサ、及びこの化学センサのアセトアルデヒドに対する感度評価を実施例４として説明する。 Next, a chemical sensor manufactured using the molybdenum trioxide film formed by the procedure of Example 2 described above, and sensitivity evaluation of this chemical sensor with respect to acetaldehyde will be described as Example 4.
［実施例４］
純度９９．６％のアルミナ基板上にスクリーン印刷にてＡｕの印刷を行い、乾燥炉において１２０℃で１０分間乾燥した後、８００℃で焼成した。次に、フォトリソ・エッチング法を用いてLine/Spaceが５０μm、面積が５×５ｍｍとなる櫛電極のパターンを作製した。基板の櫛電極上にキャタペースト（ＣＣＰ−４０１０ＦＫＢ：奥野製薬工業株式会社製キャタペースト（有機パラジウム化合物を含む有機溶媒））をスクリーン印刷法により塗布した後、１２０℃で１０分間仮焼きしてから５００℃で２０分間焼成して下地としての触媒を付与した。その後、実施例２に示した方法と同様の手順にて三酸化モリブデン膜を形成した。
[Example 4]
Au was printed on a 99.6% purity alumina substrate by screen printing, dried at 120 ° C. for 10 minutes in a drying furnace, and then fired at 800 ° C. Next, a comb electrode pattern having a Line / Space of 50 μm and an area of 5 × 5 mm was prepared by using a photolithographic etching method. After applying a cata paste (CCP-4010FKB: Cathode paste (organic solvent containing an organic palladium compound) manufactured by Okuno Seiyaku Kogyo Co., Ltd.) on the comb electrode of the substrate by a screen printing method, calcining at 120 ° C. for 10 minutes. Baking at 500 ° C. for 20 minutes gave a catalyst as a base. Thereafter, a molybdenum trioxide film was formed by the same procedure as the method shown in Example 2.
次に、三酸化モリブデン膜を形成した基板をナトリウムイオン水溶液に浸漬して、三酸化モリブデン膜の層間に、水和ナトリウムイオン（［Ｎａ（Ｈ２Ｏ）Ｚ］＋）がインターカレートした［Ｎａ（Ｈ２Ｏ）Ｚ］ＸＭｏＯ３を合成した。そして、前記の基板をポリアニリン水溶液に浸漬して、水和ナトリウムイオンとのカチオン交換反応を行い、ポリアニリン（ＰＡＮＩ）を三酸化モリブデン膜の層間に挿入した（ＰＡＮＩ）ＸＭｏＯ３を合成した。その後、基板を分割してＶＯＣガス等を対象とした化学センサ素子を作製した。 Next, the substrate on which the molybdenum trioxide film was formed was immersed in a sodium ion aqueous solution, and hydrated sodium ions ([Na (H 2 O) Z ] + ) were intercalated between the layers of the molybdenum trioxide film [ Na (H 2 O) Z ] X MoO 3 was synthesized. Then, the substrate was immersed in polyaniline aqueous solution, subjected to cation exchange reaction between the hydrated sodium ions, was synthesized polyaniline (PANI) was inserted between layers of molybdenum trioxide film (PANI) X MoO 3. Thereafter, the substrate was divided to produce a chemical sensor element targeting VOC gas or the like.
作製した化学センサ素子に対して、アセトアルデヒドの濃度を５ｐｐｍ、２ｐｐｍ、１ｐｐｍ、０．５ｐｐｍにそれぞれ設定し、キャリアガスを窒素としたガスセンサ評価装置にて感度測定を行った。なお、この感度測定は抵抗値をモニタリングすることにより実施された。 With respect to the produced chemical sensor element, the concentration of acetaldehyde was set to 5 ppm, 2 ppm, 1 ppm, and 0.5 ppm, respectively, and sensitivity measurement was performed with a gas sensor evaluation apparatus using nitrogen as the carrier gas. This sensitivity measurement was performed by monitoring the resistance value.
以上の結果、図７に示すように、アセトアルデヒドの各濃度に対してリニアな抵抗値変化が得られた。また、アセトアルデヒドの濃度が１ｐｐｍ以下の極低濃度においても実施例４で作製した化学センサ素子はセンシング可能であり、このように高感度に応答する化学センサが得られることが確認された。 As a result, as shown in FIG. 7, a linear change in resistance value was obtained for each concentration of acetaldehyde. Moreover, it was confirmed that the chemical sensor element produced in Example 4 can sense even at an extremely low concentration of acetaldehyde of 1 ppm or less, and thus a chemical sensor that responds with high sensitivity can be obtained.
Claims (9)
モリブデン酸リチウム及びモリブデン酸ナトリウムの少なくとも一方と、
ジメチルアミンボランと、
硝酸と、
アルコールと、
を含有することを特徴とする無電解めっき浴。 An electroless plating bath for immersing a substrate with a catalyst and coating the substrate with a molybdenum trioxide film,
At least one of lithium molybdate and sodium molybdate,
Dimethylamine borane,
Nitric acid,
Alcohol and
An electroless plating bath comprising:
前記アルコールは、全容量に対して７０容量％以上９０容量％以下であることを特徴とする無電解めっき浴。 In the electroless plating bath according to claim 1,
The electroless plating bath, wherein the alcohol is 70% by volume or more and 90% by volume or less with respect to the total volume.
蒸留水をさらに含有し、
前記モリブデン酸リチウム及び前記モリブデン酸ナトリウムの少なくとも一方は、０．０１モル／Ｌ以上０．５モル／Ｌ以下で、
前記ジメチルアミンボランは、０．００１モル／Ｌ以上０．１モル／Ｌ以下で、
前記硝酸は、０．０５モル／Ｌ以上０．１モル／Ｌ以下で、
前記蒸留水は、１０容量％以上３０容量％以下であることを特徴とする無電解めっき浴。 In the electroless plating bath according to claim 2,
Further containing distilled water,
At least one of the lithium molybdate and the sodium molybdate is 0.01 mol / L or more and 0.5 mol / L or less,
The dimethylamine borane is 0.001 mol / L or more and 0.1 mol / L or less,
The nitric acid is 0.05 mol / L or more and 0.1 mol / L or less,
The electroless plating bath, wherein the distilled water is 10% by volume or more and 30% by volume or less.
前記アルコールは、エタノール及びメタノールの少なくとも一方から成ることを特徴とする無電解めっき浴。 In the electroless plating bath according to any one of claims 1 to 3,
The electroless plating bath, wherein the alcohol comprises at least one of ethanol and methanol.
前記基板を浸漬させるときの前記無電解めっき浴の温度は、２０℃以上４０℃以下であることを特徴とする三酸化モリブデン膜の製造方法。 In the manufacturing method of the molybdenum trioxide film according to claim 5,
The method of manufacturing a molybdenum trioxide film, wherein the temperature of the electroless plating bath when the substrate is immersed is 20 ° C. or higher and 40 ° C. or lower.
前記三酸化モリブデン膜の焼成温度は、４００℃以上５００℃以下であることを特徴とする三酸化モリブデン膜の製造方法。 In the manufacturing method of the molybdenum trioxide film according to claim 5 or 6,
The method for producing a molybdenum trioxide film, wherein the firing temperature of the molybdenum trioxide film is 400 ° C. or higher and 500 ° C. or lower.
前記基板を前記無電解めっき浴に浸漬させる前に、前記基板に前記触媒から成る下地膜を形成することを特徴とする三酸化モリブデン膜の製造方法。 In the manufacturing method of the molybdenum trioxide film according to claim 7,
Before dipping the substrate in the electroless plating bath, a base film made of the catalyst is formed on the substrate.
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