JP3030328B2 - Ultrafine noble metal dispersed titanium oxide thin film and its manufacturing method - Google Patents
Ultrafine noble metal dispersed titanium oxide thin film and its manufacturing methodInfo
- Publication number
- JP3030328B2 JP3030328B2 JP8286055A JP28605596A JP3030328B2 JP 3030328 B2 JP3030328 B2 JP 3030328B2 JP 8286055 A JP8286055 A JP 8286055A JP 28605596 A JP28605596 A JP 28605596A JP 3030328 B2 JP3030328 B2 JP 3030328B2
- Authority
- JP
- Japan
- Prior art keywords
- noble metal
- titanium oxide
- thin film
- oxide thin
- ultrafine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、超微粒の貴金属粒
子を酸化チタン粒子の粒界表面近傍に選択的に固定化し
た超微粒貴金属分散酸化チタン薄膜およびその製造方法
に関するものである。The present invention relates to an ultrafine noble metal-dispersed titanium oxide thin film in which ultrafine noble metal particles are selectively fixed near the grain boundary surface of titanium oxide particles, and a method for producing the same.
【０００２】[0002]
【従来の技術】酸化チタンは、一般にｎ型の半導体であ
り、また光照射によって触媒効果を有することから、ガ
スセンサーや光触媒への利用が検討されている。一方、
貴金属は、種々のガス反応の触媒として知られており、
また、一般に、電気の良導体である。この貴金属を分散
した酸化チタンは、より高性能な触媒あるいはより高感
度のガスセンサーとして利用できることが知られてい
る。この場合、一般に、貴金属粒子の粒子径が小さいほ
ど触媒活性あるいはセンサー特性が向上することが知ら
れている。従来、貴金属粒子を分散した酸化チタンは、
微粒な酸化チタンの粉末またはそれを加熱して得られる
焼結体に、貴金属を含む塩を水等の溶媒に溶解した溶液
をコーティングまたは含浸して加熱分解または光による
分解を行って貴金属を析出させたものが知られている
（触媒，Ｖｏｌ．１９，Ｎｏ．５，ｐ３３４−３５０
（１９７７）。2. Description of the Related Art Titanium oxide is generally an n-type semiconductor and has a catalytic effect when irradiated with light. Therefore, its use in gas sensors and photocatalysts has been studied. on the other hand,
Noble metals are known as catalysts for various gas reactions,
In general, it is a good conductor of electricity. It is known that this noble metal-dispersed titanium oxide can be used as a higher-performance catalyst or a more sensitive gas sensor. In this case, it is generally known that the smaller the size of the noble metal particles, the higher the catalytic activity or sensor characteristics. Conventionally, titanium oxide in which noble metal particles are dispersed
Precipitate precious metal by coating or impregnating fine titanium oxide powder or a sintered body obtained by heating it with a solution in which a salt containing a noble metal is dissolved in a solvent such as water, and performing thermal decomposition or photolysis. What has been made known is known (catalyst, Vol. 19, No. 5, p334-350).
(1977).
【０００３】しかしながら、このものは、析出する貴金
属粒子の粒子径が大きく貴金属粒子が酸化チタン表面に
均質に析出するため、酸化チタンの粒子径が小さい場
合、貴金属の効果が有効に発揮されず、また、高温に加
熱されたとき酸化チタン粒子の焼結と同時に酸化チタン
および貴金属粒子の粒成長も招くため、センサー特性や
触媒活性が低下する問題点がある。However, in this method, the noble metal particles to be deposited have a large particle size and the noble metal particles are uniformly deposited on the surface of the titanium oxide. Therefore, when the particle size of the titanium oxide is small, the effect of the noble metal is not effectively exhibited. In addition, when heated to a high temperature, sintering of the titanium oxide particles and grain growth of the titanium oxide and noble metal particles are caused at the same time, so that there is a problem that sensor characteristics and catalytic activity are reduced.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、チタンと貴
金属を含む前駆体を出発原料に用い、かつ薄膜状にする
ことでこれらの問題点が解決できたことに基づくもので
ある。すなわち、チタンと貴金属を含む前駆体を出発原
料に用いることにより、チタンと貴金属が分子レベルで
均質に分散されたものとなるため、酸化チタンの粉末を
出発原料に用いるものに比べて、チタンと貴金属の均質
性が極めて高い状態を出発とする事が可能となる。さら
に、薄膜状とすることにより、加熱時に酸化チタンの粒
成長が抑制され、その結果、貴金属粒子を高温でも微細
な状態で酸化チタン粒子に固定化でき、また、貴金属粒
子を酸化チタン粒子の粒界表面近傍に選択的に固定化で
きることが始めて見いだされた。The present invention is based on the fact that these problems can be solved by using a precursor containing titanium and a noble metal as a starting material and forming a thin film. In other words, by using a precursor containing titanium and a noble metal as a starting material, titanium and a noble metal are homogeneously dispersed at a molecular level. It is possible to start from a state where the homogeneity of the noble metal is extremely high. Further, by forming a thin film, the growth of the titanium oxide particles during heating is suppressed, and as a result, the noble metal particles can be fixed to the titanium oxide particles in a fine state even at a high temperature. It has been found for the first time that it can be selectively immobilized near the boundary surface.
【０００５】すなわち、本発明は、超微粒の貴金属粒子
を酸化チタン粒子の粒界表面近傍に選択的に固定化した
超微粒貴金属分散酸化チタン薄膜およびその製造方法を
提供することを目的とする。また、本発明は、ガス成分
に対して高い感応性、触媒作用を有しており、高温での
経時変化のない高性能ガスセンサー、触媒材料等として
有用な、新規な超微粒貴金属分散酸化チタン薄膜を提供
することを目的とする。That is, an object of the present invention is to provide an ultrafine noble metal-dispersed titanium oxide thin film in which ultrafine noble metal particles are selectively fixed near the grain boundary surface of titanium oxide particles, and a method for producing the same. The present invention also provides a novel ultrafine noble metal-dispersed titanium oxide that has high sensitivity to gas components and catalytic action, and is useful as a high-performance gas sensor and catalyst material that does not change over time at high temperatures. It is intended to provide a thin film.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決する本発
明は、平均粒子径が１０ｎｍよりも小さい貴金属粒子の
５０％以上が酸化チタン粒子の粒界表面近傍に選択的に
固定化されていることを特徴とする超微粒貴金属分散酸
化チタン薄膜、に関する。また、本発明は、前記超微粒
貴金属分散酸化チタン薄膜において、前記酸化チタンの
薄膜の気孔率が１０％以上であることを特徴とする前記
の超微粒貴金属分散酸化チタン薄膜、前記超微粒貴金属
分散酸化チタン薄膜において、前記貴金属が白金である
ことを特徴とする前記の超微粒貴金属分散酸化チタン薄
膜、を望ましい態様とする。また、上記課題を解決する
本発明は、チタンと貴金属元素を含む前駆体の溶液を基
板上にコートしたのち、乾燥し酸化雰囲気中で予備処理
後、還元雰囲気中で加熱することを特徴とする超微粒貴
金属分散酸化チタン薄膜の製造方法、に関する。さら
に、本発明は、前記超微粒貴金属分散酸化チタン薄膜の
製造方法において、前記貴金属が白金であることを特徴
とする前記の超微粒貴金属分散酸化チタン薄膜の製造方
法、前記超微粒貴金属分散酸化チタン薄膜の製造方法に
おいて、前記基板が石英ガラスであることを特徴とする
前記の超微粒貴金属分散酸化チタン薄膜の製造方法、前
記超微粒貴金属分散酸化チタン薄膜の製造方法におい
て、前記前駆体がチタンのアルコキシドまたはその誘導
体、アミノ酸、および白金塩より合成されたものである
ことを特徴とする前記の超微粒貴金属分散酸化チタン薄
膜の製造方法、前記超微粒貴金属分散酸化チタン薄膜の
製造方法において、前駆体溶液に加熱によって揮散する
有機物を添加することを特徴とする前記の超微粒貴金属
分散酸化チタン薄膜の製造方法、を望ましい態様とす
る。SUMMARY OF THE INVENTION The present invention for solving the above-mentioned problems is based on the precious metal particles having an average particle diameter of less than 10 nm .
An ultrafine noble metal-dispersed titanium oxide thin film, characterized in that at least 50% is selectively fixed near the grain boundary surface of titanium oxide particles. The present invention also provides the ultrafine noble metal-dispersed titanium oxide thin film, wherein the porosity of the titanium oxide thin film is 10% or more. In a titanium oxide thin film, the above-mentioned noble metal-dispersed titanium oxide thin film is characterized in that the noble metal is platinum. Further, the present invention for solving the above-mentioned problem is characterized in that after coating a solution of a precursor containing titanium and a noble metal element on a substrate, drying, pretreatment in an oxidizing atmosphere, and heating in a reducing atmosphere. The present invention relates to a method for producing an ultra-fine noble metal-dispersed titanium oxide thin film. Further, the present invention provides the method for producing an ultrafine noble metal-dispersed titanium oxide thin film, wherein the noble metal is platinum, the method for producing an ultrafine noble metal-dispersed titanium oxide thin film, and the ultrafine noble metal-dispersed titanium oxide thin film. In the method for producing a thin film, the method for producing an ultrafine noble metal-dispersed titanium oxide thin film, wherein the substrate is quartz glass; and the method for producing the ultrafine noble metal-dispersed titanium oxide thin film, wherein the precursor is titanium. The method for producing an ultrafine noble metal-dispersed titanium oxide thin film, the method for producing an ultrafine noble metal-dispersed titanium oxide thin film, which is characterized by being synthesized from an alkoxide or a derivative thereof, an amino acid, and a platinum salt. The above-mentioned ultrafine noble metal-dispersed titanium oxide, characterized by adding an organic substance which volatilizes by heating to a solution. Method of manufacturing a film, and a desirable manner.
【０００７】本発明では、貴金属として、金、白金、
銀、パラジュウム、ロジュウム、オスミウム、イリジュ
ウム、ルテニュウムから選ばれたものを用いることが出
来る。これらの中から２種以上のものを組み合わせて用
いることも出来る。貴金属は、どの割合でも添加可能で
あるが、ＴｉＯ2 １００部に対し、０．１〜２０部程度
になるのが好ましい。これは、０．１部よりも少ないと
貴金属の添加効果が発揮されにくくなり、また、２０部
よりも大きいと添加効果が飽和となりコストアップにな
るためである。これらの貴金属のうち、白金は他のもの
に比べて優れた特性が得られるので好ましい。貴金属粒
子の平均粒子径を１０ｎｍより小さい数値に限定した理
由は、１０ｎｍ以上であると量子効果が得られにくくな
り、優れた特性が得られないためである。In the present invention, gold, platinum,
A material selected from silver, palladium, rhodium, osmium, iridium, and ruthenium can be used. Two or more of these can be used in combination. Precious metals, but it can be added in any proportion, with respect to TiO 2 100 parts, preferably on the order of 0.1 to 20 parts. This is because if the amount is less than 0.1 part, the effect of adding the noble metal is hardly exhibited, and if the amount is more than 20 parts, the effect of adding the noble metal is saturated and the cost increases. Among these noble metals, platinum is preferable because excellent characteristics can be obtained as compared with other metals. The reason why the average particle diameter of the noble metal particles is limited to a value smaller than 10 nm is that if it is 10 nm or more, it is difficult to obtain a quantum effect, and excellent characteristics cannot be obtained.
【０００８】本発明では貴金属粒子は、酸化チタン粒子
の粒界表面近傍に選択的に固定化されている。貴金属粒
子の存在形態を図１に模式的に示した。粒界表面近傍と
は、図中、球状粒子同士が焼結、癒着して形成される２
粒子間の凹部表面部分を指し、粒界から粒界の垂直方向
に２ｎｍづつ離れた範囲内を言う。但し、３粒子が形成
する３重点も粒界表面近傍に含むものとする。この粒界
表面近傍は２粒子間の粒界を含んでいるため、ガス分子
の反応場となり、そこに貴金属粒子が固定化されること
により、より一層反応が活性化される。すなわち、触媒
的には、非常に活性な反応場を提供することになる。酸
化チタン粒子の粒子径が小さくなるほど、反応場の数、
面積が向上するため、酸化チタン粒子の平均粒子径は小
さい程好ましく、５０ｎｍ以下であるのが望ましい。[0008] In the present invention, the noble metal particles are selectively immobilized near the grain boundary surface of the titanium oxide particles. FIG. 1 schematically shows the presence form of the noble metal particles. In the figure, the vicinity of the grain boundary surface is defined by sintering and coalescence of spherical particles in the figure.
It refers to the surface portion of the concave portion between the grains, and refers to a range separated by 2 nm from the grain boundary in the vertical direction of the grain boundary. However, the triple point formed by the three particles is also included in the vicinity of the grain boundary surface. Since the vicinity of the grain boundary surface includes a grain boundary between two particles, it becomes a reaction field for gas molecules, and the reaction is further activated by fixing the noble metal particles there. That is, a catalytically very active reaction field is provided. As the particle diameter of the titanium oxide particles becomes smaller, the number of reaction fields,
To improve the area, the average particle diameter of the titanium oxide particles is preferably as small as possible, and is desirably 50 nm or less.
【０００９】また、酸化チタンは、還元雰囲気で加熱処
理されると、３価のチタンイオンが結晶格子内に形成さ
れ、これが４価のイオンになるとき電子を放出するた
め、ｎ型の半導体となる。本発明の酸化チタンは、より
電子伝導性が大きくまたその電子伝導性を高温で維持す
るため、４価よりも価数の大きな金属イオンを含んでい
ても良い。このような金属イオンの例として、例えば、
ニオブ、タンタルイオンが挙げられ、このようなイオン
を数モル％まで含んでいても良い。酸化チタンの電気抵
抗は、酸化チタン粒子内のバルクとしての抵抗と酸化チ
タン粒子間の粒界部分の抵抗の和で表されるが、酸化チ
タン粒子の粒子径がデバイ長の２倍以下、すなわち、お
およそ５０ｎｍ以下になると粒界部分の抵抗の寄与が大
きくなり、この抵抗が全体の抵抗を支配するようにな
る。粒界部分の抵抗は、吸着ガスの種類、量に大きく影
響される。すなわち、酸化チタンの表面には、通常、酸
素分子が酸化チタンより電子を吸収して負のイオンとし
て吸着しているが、そこに還元性のガスがくると酸素分
子との間で反応がおこり吸着酸素が除去されるため、電
子が酸化チタン側に流入する。そのため還元ガスがある
場合とない場合では、酸化チタンの抵抗が大きく変動す
る。この原理を応用したものがガスセンサーである。Further, when the titanium oxide is heat-treated in a reducing atmosphere, trivalent titanium ions are formed in the crystal lattice and emit electrons when they become tetravalent ions. Become. The titanium oxide of the present invention may contain metal ions having a higher valence than tetravalent in order to have higher electron conductivity and maintain the electron conductivity at a high temperature. Examples of such metal ions include, for example,
Examples include niobium and tantalum ions, and such ions may be contained up to several mol%. The electrical resistance of titanium oxide is represented by the sum of the resistance as a bulk within the titanium oxide particles and the resistance at the grain boundary between the titanium oxide particles, and the particle diameter of the titanium oxide particles is not more than twice the Debye length, that is, When the thickness is approximately 50 nm or less, the contribution of the resistance of the grain boundary portion increases, and this resistance governs the overall resistance. The resistance at the grain boundary is greatly affected by the type and amount of the adsorbed gas. In other words, oxygen molecules usually absorb electrons from titanium oxide and adsorb as negative ions on the surface of titanium oxide, but when a reducing gas comes there, a reaction occurs with oxygen molecules. Since the adsorbed oxygen is removed, electrons flow to the titanium oxide side. For this reason, the resistance of the titanium oxide varies greatly with and without the reducing gas. The gas sensor applies this principle.
【００１０】粒界表面近傍に貴金属粒子が固定化されて
いる場合、表面につながっている粒界および貴金属の作
用によって、ガス分子の反応が非常に活性化されるた
め、還元性のガスが存在すると非常に大きな抵抗変化を
もたらし、その結果、センサー感度が著しく向上する。
すなわち、粒界表面近傍に貴金属粒子が存在することに
よって、触媒反応の活性化あるいはセンサー感度の向上
がもたらされる。また、選択的に貴金属粒子が粒界表面
近傍に存在することによって、粒子表面に均質に貴金属
粒子が固定化される場合に比べて、貴金属の添加量を減
らすことが出来るため、低コストに繋がる利点がある。
これらの現象は、酸化チタン粒子の平均粒子径が５０ｎ
ｍ以下になると顕著になるため、酸化チタン粒子の平均
粒子径は、５０ｎｍ以下であるのが好ましい。ここで酸
化チタンおよび貴金属粒子の平均粒子径は、電子顕微鏡
写真の画像解析により求めるものとする。When noble metal particles are immobilized near the grain boundary surface, the reaction of gas molecules is greatly activated by the action of the grain boundary and the noble metal connected to the surface. This results in a very large resistance change, resulting in a significant increase in sensor sensitivity.
That is, the presence of the noble metal particles near the grain boundary surface activates the catalytic reaction or improves the sensor sensitivity. In addition, since the noble metal particles are selectively present in the vicinity of the grain boundary surface, the amount of the noble metal added can be reduced as compared with the case where the noble metal particles are uniformly fixed on the particle surface, leading to low cost. There are advantages.
These phenomena occur when the average particle diameter of the titanium oxide particles is 50 n.
m or less, the average particle diameter of the titanium oxide particles is preferably 50 nm or less. Here, the average particle diameter of the titanium oxide and the noble metal particles is determined by image analysis of an electron micrograph.
【００１１】また、酸化チタン上に存在する貴金属粒子
の５０％以上が粒界表面近傍に存在すると、上記の効果
がみられるため、全貴金属粒子の５０％以上が粒界表面
近傍に存在する必要がある。本発明で言う、選択的に貴
金属粒子が粒界表面近傍に存在することの定量的な意味
は、全貴金属粒子の５０％以上が粒界表面近傍に存在す
ることを意味する。ここで貴金属粒子の存在場所の確認
は、組織の透過電子顕微鏡写真により行い、粒界表面近
傍に存在する貴金属粒子の割合は、粒界近傍に存在する
貴金属粒子の数／全貴金属粒子の数で求める。気孔率
は、組織の電子顕微鏡写真の画像解析から求めるものと
する。気孔率が１０％以上であると、雰囲気ガス分子と
薄膜との反応が早く行われるため好ましい。チタンと貴
金属を含む前駆体とは、例えば、ＲＴｉＯＣＯＲ′ＮＨ
2 ＰｔＸ（Ｒ，Ｒ′，Ｘは複数の元素からなる置換基）
等の、チタン元素と貴金属元素が１つの分子内に化学結
合を介して繋がっているものをさす。チタンイオンと貴
金属イオンが溶媒に溶解しているものとの違いは、前者
では、チタンと貴金属との相対的な位置関係があらかじ
め決まっているのに対して、後者の場合、チタンイオン
と貴金属イオンが自由に運動できるため相対的な位置関
係が時間とともに大きく変化する事である。[0011] When 50% or more of the noble metal particles present on the titanium oxide are present in the vicinity of the grain boundary surface, the above effect is observed. Therefore, it is necessary that 50% or more of all the noble metal particles be present in the vicinity of the grain boundary surface. There is. The quantitative meaning in the present invention that the noble metal particles selectively exist near the grain boundary surface means that 50% or more of all the noble metal particles exist near the grain boundary surface. Here, the location of the noble metal particles is confirmed by a transmission electron micrograph of the structure, and the ratio of the noble metal particles present near the grain boundary surface is represented by the number of noble metal particles present near the grain boundary / the total number of noble metal particles. Ask. The porosity is determined from image analysis of an electron micrograph of the tissue. When the porosity is 10% or more, the reaction between the atmospheric gas molecules and the thin film is performed quickly, which is preferable. The precursor containing titanium and a noble metal is, for example, RTiOCOR'NH
2 PtX (R, R ', X are substituents composed of a plurality of elements)
And the like, in which a titanium element and a noble metal element are connected in one molecule via a chemical bond. The difference between titanium ions and noble metal ions dissolved in a solvent is that the relative position between titanium and noble metal is determined in advance in the former, while the titanium ion and noble metal ion are Can move freely, so the relative positional relationship changes greatly with time.
【００１２】前駆体の合成にあたっては、有機金属試薬
を用いて、有機合成に用いる手法を利用して合成可能で
ある。すなわち、チタン元素および反応可能な有機官能
基を含む有機チタン化合物に対し、貴金属元素および反
応可能な有機官能基を含む有機貴金属化合物または反応
可能な貴金属化合物とを反応によって結合させる方法を
用いることが出来る。あるいは複数の官能基を有する化
合物を媒体として用い両者を結合させる方法を用いるこ
ともできる。例えば、チタンの有機金属化合物として、
チタンのアルコキシドまたはアルコキシドの一部をアセ
チルアセトナート基で置換したアルコキシド誘導体、ジ
−ｉ−プロポキシビスアセチルアセトナトチタン，ジ−
ｎ−ブトキシビストリエタノールアミナトチタンなど
を、また、白金の化合物として白金の塩化物、Ｈ2 Ｐｔ
Ｃｌ6 ・６Ｈ2 Ｏ，ＰｔＣｌ2 ，ＰｔＣｌ4 ，（Ｎ
Ｈ4 ）2 ＰｔＣｌ6 ，Ｈ2 ＰｔＣｌ6 などを、また、こ
れらを結合する媒体としてアミノ酸を用いる例があげら
れる。この場合、アミノ酸のカルボキシル基とアルコキ
シドまたはアルコキシド誘導体のアルコキシル基を反応
させて両者を結合させた後、アミノ酸のアミノ基と白金
イオンを反応、結合させることにより、白金元素とチタ
ン元素を一つの分子内に含む前駆体を得ることが出来
る。反応に用いるアミノ酸として、どんなアミノ酸でも
用いることができるが、プロリンは溶媒に多量に溶解で
きるため好ましい。必要により酸化チタンに固溶する４
価よりも大きな価数をもつ金属成分をチタンと一緒に数
モル％まで加えても良い。反応はこれらの化合物を溶解
する溶媒中で行うため、反応後は前駆体を含む溶液が得
られる。この溶液は直接基板にコートするためのコート
剤として用いることが出来る。前駆体を含む前駆体溶液
の濃度は、１モル／リットル以下である方が好ましい。
これはこの濃度よりも大きいと、薄膜形成時に膜にクラ
ックが入りやすいからである。In the synthesis of the precursor, the precursor can be synthesized by using an organic metal reagent and a technique used for organic synthesis. That is, it is possible to use a method in which a noble metal element and an organic noble metal compound containing a reactive organic functional group or a reactive noble metal compound are bonded to the organic titanium compound containing the titanium element and the reactive organic functional group by reaction. I can do it. Alternatively, a method in which a compound having a plurality of functional groups is bonded to each other using a medium as a medium can also be used. For example, as an organometallic compound of titanium,
Titanium alkoxide or an alkoxide derivative in which a part of the alkoxide is substituted with an acetylacetonate group, di-i-propoxybisacetylacetonatotitanium,
n-butoxybistriethanolaminatotitanium and the like; and platinum compounds such as platinum chloride, H 2 Pt
Cl 6 · 6H 2 O, PtCl 2, PtCl 4, (N
Examples include the use of H 4 ) 2 PtCl 6 , H 2 PtCl 6 and the like, and the use of amino acids as a medium for binding them. In this case, after reacting the carboxyl group of the amino acid with the alkoxyl group of the alkoxide or alkoxide derivative to bind them together, the amino group of the amino acid and the platinum ion are reacted and combined to form a platinum element and a titanium element into one molecule. Can be obtained. Although any amino acid can be used as the amino acid used in the reaction, proline is preferable because it can be dissolved in a large amount in a solvent. If necessary, solid solution in titanium oxide 4
A metal component having a valence larger than the valence may be added up to several mol% together with titanium. Since the reaction is carried out in a solvent in which these compounds are dissolved, a solution containing the precursor is obtained after the reaction. This solution can be used as a coating agent for directly coating the substrate. The concentration of the precursor solution containing the precursor is preferably 1 mol / liter or less.
This is because if the concentration is higher than this concentration, cracks tend to be formed in the film during the formation of the thin film.
【００１３】溶媒としては、メタノール、エタノール、
イソプロパノール等のアルコール、ヘプタン、ヘキサン
等の炭化水素化合物が例示される。薄膜を形成するため
に、まずこの前駆体溶液を、基板にコートする。基板と
しては、石英ガラス、ローソーダシリカガラスなどの非
晶質ガラス、石英、単結晶アルミナ、シリコン結晶など
の単結晶、アルミナなどの多結晶体のいずれもが使用可
能である。その中で石英ガラスを用いると、石英ガラス
と酸化チタンの相互作用が顕著になり、貴金属粒子の粒
子径が減少するため、好ましい。基板へのコートは、種
々の方法を用いて行うことが出来るが、スピンコート、
ディップコートは薄い膜を均質にかつ簡便に形成できる
ため好ましい。As the solvent, methanol, ethanol,
Examples include alcohols such as isopropanol, and hydrocarbon compounds such as heptane and hexane. In order to form a thin film, the precursor solution is first coated on a substrate. As the substrate, any of amorphous glass such as quartz glass and low soda silica glass, quartz, single crystal such as single crystal alumina and silicon crystal, and polycrystal such as alumina can be used. Among them, the use of quartz glass is preferable because the interaction between the quartz glass and titanium oxide becomes remarkable and the particle size of the noble metal particles decreases. Coating on the substrate can be performed using various methods, such as spin coating,
Dip coating is preferable because a thin film can be formed uniformly and easily.
【００１４】前駆体溶液を基板にコート後、溶媒の除去
を行う。溶媒の除去は、減圧下または加熱下で行うこと
もできるが、室温で自然乾燥を行うと、均質に乾燥が行
えるため好ましい。乾燥後は、前駆体に含まれる有機成
分およびチタン、貴金属、酸素以外の無機成分を除去す
るため、酸化雰囲気中で予備処理を行う。酸化雰囲気と
して空気、酸素、酸化ガス含有雰囲気などを用いること
が出来る。また、酸化雰囲気中に適度の水蒸気を含ませ
ると、加水分解および有機成分の除去を十分に行うこと
ができるため望ましい。また、予備処理は、３００〜５
００℃の温度範囲で行うのが好ましい。これは３００℃
よりも低いと、有機成分の十分な除去がしにくくなりそ
の後の還元処理でカーボンが残りやすいからである。ま
た、５００℃よりも高いと、貴金属の粒成長が生じやす
くなって、微粒な貴金属粒子が得られにくくなるためで
ある。After coating the substrate with the precursor solution, the solvent is removed. Although the removal of the solvent can be performed under reduced pressure or under heating, it is preferable to perform natural drying at room temperature because drying can be performed uniformly. After drying, a pretreatment is performed in an oxidizing atmosphere to remove the organic components and the inorganic components other than titanium, noble metal, and oxygen contained in the precursor. As the oxidizing atmosphere, an atmosphere containing air, oxygen, or an oxidizing gas can be used. In addition, it is desirable that an appropriate amount of water vapor be contained in the oxidizing atmosphere because hydrolysis and removal of organic components can be sufficiently performed. In addition, the preliminary processing is 300 to 5
It is preferable to carry out in a temperature range of 00 ° C. This is 300 ° C
If it is lower than this, it is difficult to sufficiently remove the organic components, and carbon tends to remain in the subsequent reduction treatment. On the other hand, if the temperature is higher than 500 ° C., grain growth of the noble metal tends to occur, and it is difficult to obtain fine noble metal particles.
【００１５】予備処理後、予備処理温度よりも高い温度
の還元雰囲気下で加熱を行う。この目的は貴金属に十分
還元する事、および貴金属の粒成長を抑制するためであ
る。還元雰囲気として水素等の還元ガスを含む雰囲気が
使用出来る。加熱温度は４５０℃以上が好ましい。これ
はこの温度よりも低いとカーボンが残りやすく、製品の
特性を低下させやすいからである。After the pretreatment, heating is performed in a reducing atmosphere at a temperature higher than the pretreatment temperature. The purpose is to sufficiently reduce the noble metal and to suppress the grain growth of the noble metal. An atmosphere containing a reducing gas such as hydrogen can be used as the reducing atmosphere. The heating temperature is preferably 450 ° C. or higher. This is because if the temperature is lower than this temperature, carbon tends to remain, and the characteristics of the product are likely to deteriorate.
【００１６】加熱後に得られる薄膜の膜厚は、前駆体溶
液の濃度、コート条件、例えば、コート回数やディップ
コートの場合は引き上げ速度、スピンコートの場合はス
ピン回転数などによって調整可能である。また、コート
を行った後、予備処理を行い、これを繰り返すことによ
って、膜厚の調整を行うことも可能である。膜厚が５０
０ｎｍより小さいと、酸化チタン粒子の焼結および粒成
長が抑制され、貴金属粒子の粒成長が抑制されやすくな
り、さらに１００ｎｍよりも小さいと高温度まで微粒貴
金属粒子のままでの保持が可能となるためさらに好まし
い。The thickness of the thin film obtained after heating can be adjusted by the concentration of the precursor solution and the coating conditions, for example, the number of coatings, the pulling speed in the case of dip coating, and the number of spins in the case of spin coating. In addition, after coating, pretreatment is performed, and by repeating this, the film thickness can be adjusted. Film thickness is 50
If it is less than 0 nm, sintering and grain growth of titanium oxide particles are suppressed, and grain growth of noble metal particles is easily suppressed. If it is less than 100 nm, fine noble metal particles can be maintained as high as high temperatures. Therefore, it is more preferable.
【００１７】本方法により加熱後に気孔を含む酸化チタ
ン薄膜が得られる。基板に前駆体溶液をコートせずに、
前駆体溶液から溶媒を除去して粉末状として、本発明の
予備処理および６００℃以上の温度で加熱を行ったもの
は、酸化チタンの緻密化および著しい酸化チタンの粒成
長が見られる。それに対し、本発明の方法に従い、基板
上にコートして処理を行ったものでは、緻密化は見られ
ずむしろ気孔の形成が認められ、また、大きな粒子成長
は見られない。According to the present method, a titanium oxide thin film containing pores is obtained after heating. Without coating the substrate with the precursor solution,
In the case where the precursor solution was subjected to pretreatment and heating at a temperature of 600 ° C. or higher after removing the solvent from the precursor solution to form a powder, the densification of titanium oxide and the remarkable grain growth of titanium oxide were observed. On the other hand, in the case where the coating is performed on the substrate in accordance with the method of the present invention and the treatment is performed, the formation of pores is recognized rather than the densification, and no large grain growth is observed.
【００１８】この理由として、基板上にコートして膜厚
が小さい状態で加熱することにより、膜厚の効果および
基材との作用により、酸化チタンの緻密化および粒子成
長が抑制されること、また、このような状態で加熱され
ることにより、酸化チタンの結晶化およびアナターゼか
らルチルへの転移に伴う密度上昇によって生じる空隙
が、緻密化によって消失することなく直接組織に現れる
ものと考えられる。その結果、多孔性の酸化チタン薄膜
が得られるが、前駆体合成時に加熱によって揮散する有
機物を共存させることにより、より効果的に気孔を形成
出来る。このような有機物として、ポリオキシエチレン
ソルビタンモノステアレート、ポリオキシエチレンジグ
リコリックアシド、ホルムアミド、ポリエチレングリコ
ールなどを用いることが出来る。[0018] The reason for this is that, by coating on a substrate and heating in a state where the film thickness is small, the effect of the film thickness and the action with the substrate suppress the densification and particle growth of titanium oxide. Further, it is considered that, by heating in such a state, voids generated by crystallization of titanium oxide and an increase in density accompanying the transition from anatase to rutile appear directly in the structure without disappearing due to densification. As a result, a porous titanium oxide thin film can be obtained, but pores can be formed more effectively by coexisting an organic substance that volatilizes by heating during the synthesis of the precursor. As such organic substances, polyoxyethylene sorbitan monostearate, polyoxyethylene diglycolic acid, formamide, polyethylene glycol and the like can be used.
【００１９】以下に実施例に基づいて本発明を具体的に
説明するが、本発明は当該実施例によって何ら限定され
るものではない。Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to the examples.
実施例１ Ｔｉ（ＯｉＰｒ）2 （ＡｃＡｃ）2 の７５％イソプロパ
ノール溶液８．６５グラムとＮＨ2 （ＣＨ2 ）4 ＣＨＮ
Ｈ2 （ＣＯＯＨ）０．１１３グラムをメタノール中で反
応させたのち、Ｈ2 ＰｔＣｌ6 ・６Ｈ2 Ｏで示される塩
化白金０．０７５グラムを加え、さらに反応させた。次
に、反応が起こらなかった残留アルコキシド基を加水分
解するため水を加えた。これによりチタンと白金元素を
分子内に含む前駆体の０．１モル／リットルメタノール
溶液が得られた。この溶液を石英ガラスの上に、ティッ
プコートを行い、室温で乾燥した後、４００℃で加湿空
気中で予備処理を行った。そののち、５００℃〜８００
℃において、３％水素を含むアルゴン中で１時間加熱を
行った。一方、比較のために粒径が２０ｎｍの酸化チタ
ン粉末をメタノール中に分散させた後、チタンと白金の
比が上記と同じになるように、上記と同じ塩化白金を加
えて混合し、その分散液を石英ガラス上にデッィップコ
ートして、上記と同じ条件で、乾燥、予備処理および加
熱を行った。Example 1 8.65 grams of a 75% solution of Ti (OiPr) 2 (AcAc) 2 in isopropanol and NH 2 (CH 2 ) 4 CHN
H 2 (COOH) and 0.113 g mixture was reacted in methanol, H 2 PtCl 6 · 6H chloroplatinic 0.075 g addition represented by 2 O, and reacted further. Next, water was added to hydrolyze the remaining alkoxide groups where no reaction occurred. As a result, a 0.1 mol / liter methanol solution of a precursor containing titanium and platinum elements in the molecule was obtained. This solution was tip-coated on quartz glass, dried at room temperature, and then pretreated at 400 ° C. in humidified air. After that, 500 ℃ ～ 800
Heating was performed at 0 ° C. in argon containing 3% hydrogen for 1 hour. On the other hand, for comparison, titanium oxide powder having a particle size of 20 nm was dispersed in methanol, and then the same platinum chloride as described above was added and mixed so that the ratio of titanium to platinum was the same as above, and the dispersion was performed. The solution was dip-coated on quartz glass and dried, pre-treated and heated under the same conditions as above.
【００２０】得られた膜を電子顕微鏡にて観察を行い、
その結果を表１に示した。なお、白金粒子の粒子径およ
び酸化チタンの粒径は電子顕微鏡写真の画像解析により
求めた。粒界表面近傍への白金の付着率は粒界近傍に存
在する白金粒子の数／全白金粒子の数で求めた。また、
膜厚を測定した結果、本発明のものでは８０〜１００ｎ
ｍであるのに対し、比較例のものでは６００ｎｍであっ
た。本発明の方法によって得られたものは、８００℃の
高温でも白金粒子の粒径は２．０ｎｍと小さく、また、
粒界表面近傍への白金の付着率でも９０％と選択的に白
金が、粒界表面近傍に固定化されているのが分かった。
また、酸化チタンの粒径においても、８００℃で５０ｎ
ｍと微粒であった。それに対し、比較例の試料では、白
金粒子の粒子径は１２ｎｍ以上と大きく、また、粒界表
面近傍への白金の付着率も３５％以下と小さかった。ま
た、８００℃において酸化チタンの大きな粒成長が認め
られた。The obtained film is observed with an electron microscope,
The results are shown in Table 1. In addition, the particle diameter of the platinum particles and the particle diameter of the titanium oxide were determined by image analysis of an electron micrograph. The adhesion ratio of platinum to the vicinity of the grain boundary surface was determined by the ratio of the number of platinum particles existing near the grain boundary / the total number of platinum particles. Also,
As a result of measuring the film thickness, it was found that the thickness was 80 to 100 n in the case of the present invention.
m, whereas that of the comparative example was 600 nm. The particles obtained by the method of the present invention have a small platinum particle size of 2.0 nm even at a high temperature of 800 ° C.
It was also found that platinum was selectively immobilized in the vicinity of the grain boundary surface, with the deposition rate of platinum in the vicinity of the grain boundary surface being 90%.
Also, the particle size of titanium oxide is 50 n at 800 ° C.
m and fine particles. On the other hand, in the sample of the comparative example, the particle diameter of the platinum particles was as large as 12 nm or more, and the adhesion rate of platinum to the vicinity of the grain boundary surface was as small as 35% or less. At 800 ° C., large grain growth of titanium oxide was observed.
【００２１】[0021]
【表１】 [Table 1]
【００２２】実施例２ チタンイソプロポキシド８．８×１０-3モルとアミノ酸
の一種であるＬ−プロリン８．８×１０-3モルをエタノ
ールに溶解し、反応させた後、塩化金３．６×１０-5モ
ルを添加、反応させ、チタンと金を分子内に含む０．５
モル／リットルの前駆体溶液を作成した。また、塩化金
を塩化白金、塩化パラジュウムに代えて同様な操作を行
い、チタンと白金およびチタンとパラジュウムを分子内
に含む０．５モル／リットルの前駆体溶液２種を作成し
た。また、比較のためにアミノ酸を用いないで、チタン
イソプロポキシド８．８×１０-3モルと塩化金３．６×
１０-5モルの混合物からなる０．５モル／リットルのエ
タノール溶液を用意した。[0022] was dissolved L- proline 8.8 × 10 -3 mol, a kind of embodiment 2 Titanium isopropoxide 8.8 × 10 -3 mol and an amino acid in ethanol, after reacting, gold chloride 3. 6 × 10 −5 mol was added and reacted, and 0.5 containing titanium and gold in the molecule was added.
A mole / liter precursor solution was made. In addition, the same operation was performed except that gold chloride was replaced with platinum chloride and palladium chloride, and two kinds of 0.5 mol / liter precursor solutions containing titanium and platinum and titanium and palladium in the molecule were prepared. For comparison, 8.8 × 10 -3 mol of titanium isopropoxide and 3.6 × gold chloride were used without using an amino acid.
A 0.5 mol / liter ethanol solution consisting of a 10 -5 mol mixture was prepared.
【００２３】これらの溶液を、石英ガラス、アルミナ多
結晶基板、コーニングガラス（＃７０５９）上にスピン
コートしたのち、室温で乾燥し、３７５℃で乾燥空気中
で予備処理を行って、１００％水素中で６００℃で加熱
した。膜厚を測定の結果、いずれの試料も１００〜２０
０ｎｍの範囲にあった。また、比較のため、空気中でも
６００℃で加熱を行った。得られた薄膜を実施例１と同
様にして電子顕微鏡で観察測定した結果を表２に示す。
本発明品では、貴金属粒子の粒子径は８．５ｎｍ以下と
小さく、また、粒界表面近傍への白金の付着率も８２％
以上と大きいのに対し、比較例では貴金属粒子の粒子径
は２３ｎｍ以上と大きく、また、粒界表面近傍への付着
率も３５％以下と小さかった。These solutions are spin-coated on quartz glass, polycrystalline alumina substrate, and Corning glass (# 7059), dried at room temperature, and pretreated at 375 ° C. in dry air to obtain 100% hydrogen. At 600 ° C. As a result of measuring the film thickness, all the samples were 100 to 20.
It was in the range of 0 nm. For comparison, heating was performed at 600 ° C. in air. Table 2 shows the results of observing and measuring the obtained thin film with an electron microscope in the same manner as in Example 1.
In the product of the present invention, the particle size of the noble metal particles is as small as 8.5 nm or less, and the adhesion rate of platinum to the vicinity of the grain boundary surface is 82%.
On the contrary, in the comparative example, the particle diameter of the noble metal particles was as large as 23 nm or more, and the adhesion rate near the grain boundary surface was as small as 35% or less.
【００２４】[0024]
【表２】 [Table 2]
【００２５】実施例３ 実施例１と同様な原料を用いて、チタンと白金元素を分
子内に含む前駆体の０．１モル／リットルメタノール溶
液を作成した。この溶液を石英ガラス上に２０００ＲＰ
Ｍの回転数でスピンコートを行った（試料 No.１６）。
また、回転数を１０００ＲＰＭにして同様にスピンコー
トを行った試料を準備した（試料 No.１７）。さらに、
大きい膜厚を得るため、溶液を３倍に濃縮し、回転数を
１０００ＲＰＭにして同様にスピンコートを行った試料
も準備した（試料 No.１８）。また、薄膜の気孔率を変
えるため、前駆体作成時にポリオキシエチレンジグリコ
リックアシッドを、前駆体に含まれるチタンを酸化チタ
ンに換算したとき、換算重量の１／２および換算量の１
／１を加えて、２０００ＲＰＭの回転数でスピンコート
を行った試料を準備した（それぞれ試料 No.１９、２
０）。Example 3 Using the same raw materials as in Example 1, a 0.1 mol / L methanol solution of a precursor containing titanium and platinum elements in the molecule was prepared. Put this solution on quartz glass at 2000RP
Spin coating was performed at a rotation speed of M (Sample No. 16).
In addition, a sample that was similarly spin-coated at a rotation speed of 1000 RPM was prepared (Sample No. 17). further,
In order to obtain a large film thickness, a sample was prepared by concentrating the solution three times, spinning at 1,000 RPM, and performing the same spin coating (Sample No. 18). Further, in order to change the porosity of the thin film, when polyoxyethylene diglycolic acid was converted to titanium oxide at the time of preparing the precursor, and the titanium contained in the precursor was converted to titanium oxide, 1/2 of the reduced weight and 1 of the reduced amount were obtained.
/ 1 and spin-coated at a rotation speed of 2000 RPM to prepare samples (Sample Nos. 19 and 2, respectively).
0).
【００２６】これらの試料を、加湿空気中で４００℃で
予備処理を行った後、８００℃で２０％の水素を含む窒
素ガス中で加熱を行い、白金を含むＴｉＯ2 薄膜を得
た。また、比較のために試料 No.１６について、予備処
理を行わないで同様な加熱処理のみ行ったもの（試料 N
o.２１）、および８００℃で空気中で加熱を行ったもの
（試料 No.２２）も用意した。加熱後の薄膜について電
子顕微鏡観察を行った結果を表３に示した。気孔率は組
織の電子顕微鏡写真の画像解析により求めた。また、得
られた薄膜のセンサー特性を評価するために、薄膜にリ
ード線をつけ、５００℃で高純度のアルゴンガスおよび
そのアルゴンガスに１ＰＰＭの一酸化炭素ガスを添加し
た雰囲気中で電気抵抗を測定した。前者の抵抗値を後者
で割った値（感度）を表３に併記した。These samples were pretreated at 400 ° C. in humidified air, and then heated at 800 ° C. in a nitrogen gas containing 20% hydrogen to obtain a TiO 2 thin film containing platinum. For comparison, the same heat treatment was performed on sample No. 16 without performing pre-treatment (sample N
o.21) and one heated at 800 ° C. in air (Sample No. 22). Table 3 shows the results of electron microscopic observation of the thin film after heating. Porosity was determined by image analysis of electron micrographs of the tissue. Further, in order to evaluate the sensor characteristics of the obtained thin film, a lead wire was attached to the thin film, and the electric resistance was measured at 500 ° C. in an atmosphere in which high-purity argon gas and 1 ppm of carbon monoxide gas were added to the argon gas. It was measured. The value (sensitivity) obtained by dividing the former resistance value by the latter is also shown in Table 3.
【００２７】[0027]
【表３】 [Table 3]
【００２８】表３で見られるように、本発明の方法に従
ったものは、１０５０以上の高いガス感度が得られるの
に対し、比較例のものではガス感度はその１／２０以下
の小さな値を示した。As can be seen from Table 3, the gas according to the method of the present invention has a high gas sensitivity of 1050 or more, whereas the gas sensitivity of the comparative example is as small as 1/20 or less. showed that.
【００２９】[0029]
【発明の効果】以上詳述したように、本発明によれば、
貴金属粒子を酸化チタン粒子の粒界表面近傍に選択的に
固定化することが出来ると共に、酸化チタンの緻密化お
よび粒子成長が抑制され、より効果的に気孔を形成する
ことが出来る。これにより、触媒反応を活性化し、セン
サー感度を向上させることが出来る。また、粒子表面に
均質に貴金属粒子が固定化される場合に比べて、貴金属
の添加量を減らすことが出来る、等の格別の効果が得ら
れる。As described in detail above, according to the present invention,
The noble metal particles can be selectively fixed near the grain boundary surface of the titanium oxide particles, and densification and particle growth of the titanium oxide can be suppressed, so that pores can be formed more effectively. Thereby, the catalytic reaction can be activated and the sensor sensitivity can be improved. Further, a remarkable effect is obtained, such as that the amount of the noble metal added can be reduced as compared with the case where the noble metal particles are uniformly fixed on the particle surface.
【図１】本発明の酸化チタン薄膜における貴金属粒子の
存在形態を示す説明図である。FIG. 1 is an explanatory diagram showing the form of noble metal particles present in a titanium oxide thin film of the present invention.
フロントページの続き (72)発明者 平野 眞一 愛知県名古屋市千種区不老町 名古屋大 学内 審査官 大工原 大二 (56)参考文献 特開 平８−66635（ＪＰ，Ａ) 特開 昭63−225532（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 23/04 ＣＡ（ＳＴＮ)Continuation of the front page (72) Inventor Shinichi Hirano Examiner Daikohara, Nagoya University, Nagoya-shi, Aichi Pref. JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) C01G 23/04 CA (STN)
Claims (8)
を基板上にコートしたのち、乾燥し酸化雰囲気中で予備
処理後、還元雰囲気中で加熱することにより製造してな
る超微粒貴金属分散酸化チタン薄膜であって、平均粒子
径が１０ｎｍよりも小さい貴金属粒子の５０％以上が酸
化チタン粒子の粒界表面近傍に選択的に固定化されてい
ることを特徴とする超微粒貴金属分散酸化チタン薄膜。1. A solution of a precursor containing titanium and a noble metal element
After coating on the substrate, dry and reserve in an oxidizing atmosphere
After the treatment, do not manufacture by heating in a reducing atmosphere.
An ultrafine noble metal-dispersed titanium oxide thin film, wherein at least 50% of noble metal particles having an average particle diameter smaller than 10 nm are selectively fixed near the grain boundary surface of the titanium oxide particles. Fine noble metal dispersed titanium oxide thin film.
おいて、前記酸化チタンの薄膜の気孔率が１０％以上で
あることを特徴とする請求項１に記載の超微粒貴金属分
散酸化チタン薄膜。2. The ultrafine noble metal-dispersed titanium oxide thin film according to claim 1, wherein in the ultrafine noble metal-dispersed titanium oxide thin film, the porosity of the titanium oxide thin film is 10% or more.
おいて、前記貴金属が白金であることを特徴とする請求
項１または請求項２に記載の超微粒貴金属分散酸化チタ
ン薄膜。3. The ultrafine noble metal dispersed titanium oxide thin film according to claim 1, wherein the noble metal is platinum in the ultrafine noble metal dispersed titanium oxide thin film.
を基板上にコートしたのち、乾燥し酸化雰囲気中で予備
処理後、還元雰囲気中で加熱することを特徴とする超微
粒貴金属分散酸化チタン薄膜の製造方法。4. An ultrafine noble metal-dispersed titanium oxide dispersion, comprising coating a substrate with a solution of a precursor containing titanium and a noble metal element, drying, pretreating in a oxidizing atmosphere, and heating in a reducing atmosphere. Manufacturing method of thin film.
製造方法において、前記貴金属が白金であることを特徴
とする請求項４に記載の超微粒貴金属分散酸化チタン薄
膜の製造方法。5. The method for producing an ultrafine noble metal-dispersed titanium oxide thin film according to claim 4, wherein in the method for producing an ultrafine noble metal-dispersed titanium oxide thin film, the noble metal is platinum.
製造方法において、前記基板が石英ガラスであることを
特徴とする請求項４に記載の超微粒貴金属分散酸化チタ
ン薄膜の製造方法。6. The method for producing an ultrafine noble metal-dispersed titanium oxide thin film according to claim 4, wherein in the method for producing an ultrafine noble metal-dispersed titanium oxide thin film, the substrate is quartz glass.
製造方法において、前記前駆体がチタンのアルコキシド
またはその誘導体、アミノ酸、および白金塩より合成さ
れたものであることを特徴とする請求項４乃至請求項６
に記載の超微粒貴金属分散酸化チタン薄膜の製造方法。7. The method for producing an ultrafine noble metal-dispersed titanium oxide thin film, wherein the precursor is synthesized from an alkoxide of titanium or a derivative thereof, an amino acid, and a platinum salt. Claim 6
3. The method for producing an ultrafine noble metal-dispersed titanium oxide thin film according to item 1.
製造方法において、前駆体溶液に加熱によって揮散する
有機物を添加することを特徴とする請求項４乃至請求項
７に記載の超微粒貴金属分散酸化チタン薄膜の製造方
法。8. The ultrafine noble metal dispersed oxidation according to claim 4, wherein in the method for producing the ultrafine noble metal dispersed titanium oxide thin film, an organic substance that volatilizes by heating is added to the precursor solution. A method for producing a titanium thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8286055A JP3030328B2 (en) | 1996-10-07 | 1996-10-07 | Ultrafine noble metal dispersed titanium oxide thin film and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8286055A JP3030328B2 (en) | 1996-10-07 | 1996-10-07 | Ultrafine noble metal dispersed titanium oxide thin film and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10114521A JPH10114521A (en) | 1998-05-06 |
| JP3030328B2 true JP3030328B2 (en) | 2000-04-10 |
Family
ID=17699380
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8286055A Expired - Lifetime JP3030328B2 (en) | 1996-10-07 | 1996-10-07 | Ultrafine noble metal dispersed titanium oxide thin film and its manufacturing method |
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| Country | Link |
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| JP (1) | JP3030328B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11335187A (en) * | 1998-05-25 | 1999-12-07 | Toshiba Corp | Photocatalyst module and equipment for photocatalyst |
| JP4508459B2 (en) * | 2000-04-20 | 2010-07-21 | メタウォーター株式会社 | Method for producing organohalogen compound decomposition catalyst and method for producing organohalogen compound decomposition filter |
| EP1205242B1 (en) | 2000-04-20 | 2007-01-24 | Ngk Insulators, Ltd. | Method for preparing decomposition catalyst for organic halide and method for manufacturing filter for use in decomposing organic halide |
| CN1165374C (en) * | 2000-05-15 | 2004-09-08 | 日本碍子株式会社 | Adsorbent having capability of decomposing organic halogen compound and method for producing the same |
| JP4602000B2 (en) * | 2004-06-16 | 2010-12-22 | 株式会社鷺宮製作所 | Hydrogen gas detection element, hydrogen gas sensor, and hydrogen gas detection method |
| DE102006020253B3 (en) * | 2006-04-27 | 2007-11-29 | Fachhochschule Kiel | Titanium dioxide sensor for measuring e.g. ammonia, has electrodes that are arranged on coating to measure resistance as measure for gas concentration, and other coating directly arranged under former coating to form heterostructure |
| US8815335B2 (en) | 2008-12-16 | 2014-08-26 | GM Global Technology Operations LLC | Method of coating a substrate with nanoparticles including a metal oxide |
| US8871294B2 (en) * | 2008-12-16 | 2014-10-28 | GM Global Technology Operations LLC | Method of coating a substrate with nanoparticles including a metal oxide |
| JP7065378B2 (en) * | 2017-03-29 | 2022-05-12 | 文修 斎藤 | Porous sintered body and air purification equipment |
| CN112079380A (en) * | 2020-09-11 | 2020-12-15 | 安徽景成新材料有限公司 | Method for preparing titanium dioxide |
-
1996
- 1996-10-07 JP JP8286055A patent/JP3030328B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH10114521A (en) | 1998-05-06 |
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