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JP4822256B2 - Nanostructure and manufacturing method thereof - Google Patents

Nanostructure and manufacturing method thereof Download PDF

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JP4822256B2
JP4822256B2 JP2005304151A JP2005304151A JP4822256B2 JP 4822256 B2 JP4822256 B2 JP 4822256B2 JP 2005304151 A JP2005304151 A JP 2005304151A JP 2005304151 A JP2005304151 A JP 2005304151A JP 4822256 B2 JP4822256 B2 JP 4822256B2
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particles
crystal
connector
nanostructure
titanium oxide
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JP2006175582A (en
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佳弘 寺田
充 上片野
邦治 姫野
文章 大谷
隆宗 山上
司 鳥本
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Hokkaido University NUC
Fujikura Ltd
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Fujikura Ltd
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Description

本発明は、ナノ構造をもつ高次機能性材料であるナノ構造体及びその製造方法に関する。   The present invention relates to a nanostructure that is a high-order functional material having a nanostructure and a method for producing the nanostructure.

金属および半導体の薄膜、細線、細孔、ドットなどでは、ある特徴的な長さより小さいサイズとすることで、特異な電気的、光学的、化学的特性を示すことが広く知られている。こうした観点から高次機能性材料として、数十nm〜数百nmレベルの微細なサイズを持つナノ構造体の検討が盛んに行われている(例えば、特許文献1,2参照。)。   It is widely known that metal and semiconductor thin films, thin wires, pores, dots, and the like exhibit unique electrical, optical, and chemical characteristics by having a size smaller than a certain characteristic length. From such a viewpoint, nanostructures having a fine size of several tens to several hundreds of nanometers have been actively studied as high-order functional materials (see, for example, Patent Documents 1 and 2).

特許文献1には、ナノ構造体が選択的に結合する側鎖を有するアミノ酸を所定位置に組み入れたアミノ酸配列からなるペプチド結合鎖を用い、そのペプチド結合鎖の取る立体構造により1つまたは複数のナノ構造体の空間における配置を決めて機能材料とする技術が開示されている。
特許文献2には、(a)アルミニウムとシリコンを用意する工程、(b)該アルミニウムとシリコンを非平衡状態で物質を形成する成膜法を用いて、アルミニウムを含む柱状構造体と該柱状構造体を取り囲むシリコン領域とを有し、アルミニウムとシリコンの全量に対してシリコンを20〜70atomic%の割合で含有するアルミニウムシリコン混合膜を形成する工程及び(c)該アルミニウムシリコン混合膜を陽極酸化して細孔を形成する工程を有するシリコン酸化物ナノ構造体の製造方法が開示されている。
これらの技術は、化学のみならず、医学、薬学、生物学などにも広く役立つと考えられる技術である。
特開2003−332561号公報 特開2003−266400号公報
In Patent Document 1, a peptide bond chain consisting of an amino acid sequence in which amino acids having side chains to which nanostructures are selectively bonded is incorporated at a predetermined position is used. A technique for determining the arrangement of nanostructures in a space and making them functional materials is disclosed.
In Patent Document 2, (a) a step of preparing aluminum and silicon, and (b) a columnar structure including aluminum and a columnar structure using a film forming method of forming a material in a non-equilibrium state between the aluminum and silicon. And (c) anodizing the aluminum silicon mixed film, and a step of forming an aluminum silicon mixed film containing silicon at a ratio of 20 to 70 atomic% with respect to the total amount of aluminum and silicon. A method for producing a silicon oxide nanostructure having a step of forming pores is disclosed.
These technologies are considered to be useful not only in chemistry but also in medicine, pharmacy, biology, and the like.
JP 2003-332561 A JP 2003-266400 A

このようなナノ構造体の作製方法として、例えば半導体加工技術であるフォトリソグラフィー、電子線露光などの微細パターン形成技術によってナノ構造体を作製する方法がある。
しかしながら、これらの従来技術は製造コストが高く、歩留まりも悪い。また、これらの従来技術は二次元的な工作方法であり、三次元構造の材料を大量に生産する用途には不向きである。
As a method for manufacturing such a nanostructure, for example, there is a method for manufacturing a nanostructure by a fine pattern forming technique such as photolithography or electron beam exposure which is a semiconductor processing technique.
However, these conventional techniques are expensive to manufacture and have a poor yield. In addition, these conventional techniques are two-dimensional working methods, and are not suitable for use in mass production of materials having a three-dimensional structure.

そこで、ナノサイズの微粒子を用いて自然に形成される規則的な構造(自己組織化構造)により配列させた集合体をベースとし、新規なナノ構造体を実現することが考えられている。
しかしながら、通常の自己組織化では、粒子が等方的であるために、微粒子が最密に充填された構造体しか得られないことが問題となっている。
In view of this, it has been considered to realize a novel nanostructure based on an assembly arranged in a regular structure (self-organized structure) naturally formed using nano-sized fine particles.
However, in normal self-assembly, since the particles are isotropic, there is a problem that only a structure in which fine particles are packed closely can be obtained.

本発明は前記事情に鑑みてなされ、任意の三次元構造を持つナノ構造体及びそれを大量に製造することが可能な製造方法の提供を目的とする。   This invention is made | formed in view of the said situation, and aims at provision of the manufacturing method which can manufacture nanostructure which has arbitrary three-dimensional structures, and it in large quantities.

前記目的を達成するため、本発明は、異方性をもつ結晶粒子である十面体酸化チタン粒子と、該結晶粒子の(101)面を反映した結晶面に析出させた金属に一端側が結合する接続子と、該接続子の他端側に結合される、前記結晶粒子と異種の他の粒子とを準備し、前記十面体酸化チタン粒子を前記金属の塩溶液に懸濁し、紫外光を照射することにより、前記結晶面に前記金属を析出させ、前記金属に前記接続子の一端側を結合し、それと同時又は前後いずれかで、前記他の粒子の表面に前記接続子の他端側を結合することで、前記接続子を介して前記金属と前記他の粒子の表面とを結合させ、最密充填構造以外の三次元構造をもつナノ構造体を得ることを特徴とするナノ構造体の製造方法を提供する。 In order to achieve the above object, the present invention binds one end side to a decahedral titanium oxide particle , which is an anisotropic crystal particle , and a metal deposited on a crystal plane reflecting the (101) plane of the crystal particle. Prepare a connector and the crystal particles and other different particles bonded to the other end of the connector , suspend the decahedral titanium oxide particles in the metal salt solution, and irradiate with ultraviolet light By depositing the metal on the crystal plane, the one end side of the connector is bonded to the metal , and at the same time or before and after, the other end side of the connector is attached to the surface of the other particle. By bonding, the metal and the surface of the other particle are bonded through the connector, and a nanostructure having a three-dimensional structure other than a close-packed structure is obtained. A manufacturing method is provided.

本発明の製造方法において、前記他の粒子がシリカ粒子であることが好ましい。 In the production method of the present invention, the other particles are preferably silica particles .

本発明の製造方法において、前記接続子がシランカップリング剤であることが好ましい。 In the production method of the present invention, it is preferable that the connector is a silane coupling agent.

本発明の製造方法において、前記金属は、金又は白金であることが好ましい。 In the production method of the present invention, the metal is preferably a gold or platinum.

本発明の製造方法において、前記十面体酸化チタン粒子と前記シリカ粒子とを接続子を介して直鎖状に結合したナノ構造体を得ることが好ましい。 In the production method of the present invention, it is preferable to obtain a nanostructure that combines with the decahedral titanium oxide particles and the silica particles through the connectors linear.

また本発明は、異方性をもつ結晶粒子である十面体酸化チタン粒子と、該結晶粒子の(101)面を反映した結晶面に析出させた金属に一端側が結合した接続子と、該接続子の他端側が結合した他の粒子とを有し、該接続子を介して前記金属と前記他の粒子の表面とが結合されてなり、最密充填構造以外の三次元構造をもつことを特徴とするナノ構造体を提供する。 The present invention also includes decahedral titanium oxide particles, which are crystal grains having anisotropy, a connector having one end bonded to a metal deposited on a crystal plane reflecting the (101) plane of the crystal grains, and the connection The other end of the child is bonded to the other particle, the metal and the surface of the other particle are bonded through the connector, and has a three-dimensional structure other than the closest packing structure. Provided is a featured nanostructure.

本発明のナノ構造体において、前記他の粒子がシリカ粒子であることが好ましい。 In the nanostructure of the present invention, the other particles are preferably silica particles .

本発明のナノ構造体において、前記接続子がシランカップリング剤であることが好ましい。   In the nanostructure of the present invention, the connector is preferably a silane coupling agent.

また本発明は、前述した本発明に係るナノ構造体の製造方法により得られたことを特徴とするナノ構造体を提供する。   The present invention also provides a nanostructure obtained by the above-described method for producing a nanostructure according to the present invention.

本発明によれば、最密充填構造以外の任意の三次元構造を持つ新規のナノ構造体を提供できる。
また本発明の製造方法によれば、最密充填構造以外の任意の三次元構造を持つ新規のナノ構造体を安価に大量に製造することができる。
According to the present invention, a novel nanostructure having an arbitrary three-dimensional structure other than the close-packed structure can be provided.
Moreover, according to the production method of the present invention, a novel nanostructure having an arbitrary three-dimensional structure other than the close-packed structure can be produced in large quantities at a low cost.

本発明では、ナノサイズの微粒子を用いて自然に形成される規則的な構造(自己組織化構造)により配列させた集合体をベースとし、さらに結晶粒子の異方性を利用し、最密充填構造以外の任意の三次元構造をもつ新規なナノ構造体を実現する。
すなわち、本発明によるナノ構造体の製造方法は、異方性をもつ結晶粒子と、該結晶粒子の特定の結晶面に一端側が結合する接続子と、該接続子の他端側に結合される他の粒子とを準備し、前記結晶粒子の特定の結晶面に前記接続子の一端側を結合し、それと同時又は前後いずれかで、前記他の粒子の表面に前記接続子の他端側を結合し、最密充填構造以外の三次元構造をもつナノ構造体を得ることを特徴としている。
In the present invention, close-packing is based on an aggregate arranged by a regular structure (self-organized structure) that is naturally formed using nano-sized fine particles, and further utilizing the anisotropy of crystal grains. A novel nanostructure having an arbitrary three-dimensional structure other than the structure is realized.
That is, the method for producing a nanostructure according to the present invention is coupled to crystal grains having anisotropy, a connector having one end bonded to a specific crystal plane of the crystal particles, and the other end of the connector. Preparing other particles, bonding one end side of the connector to a specific crystal plane of the crystal particle, and at the same time or before and after the other end side of the connector to the surface of the other particle It is characterized by obtaining a nanostructure having a three-dimensional structure other than the close-packed structure.

本発明の製造方法において用いられる異方性をもつ結晶粒子としては、シリコンなどの金属の結晶粒子、合金の結晶粒子、無機化合物(塩、金属間化合物、酸化物、窒化物、炭化物など)又は有機化合物の結晶粒子などが挙げられ、これらの各種結晶粒子の中から1種又は2種以上を適宜選択して用いることができる。この結晶粒子の粒径は特に限定されないが、1nm〜1000nmの範囲とすることが望ましい。
結晶粒子は、属する結晶構造系に応じて四面体、六面体、八面体、十面体、十二面体などの形状をとる。これらの多面体の各面は化学的ポテンシャルが異なるため、ある反応基に対する各面の反応性が異なる。そのため、特定の反応基は結晶粒子の所定の面だけに優先的に作用する可能性が高い。
The anisotropic crystal particles used in the production method of the present invention include metal crystal particles such as silicon, alloy crystal particles, inorganic compounds (salts, intermetallic compounds, oxides, nitrides, carbides, etc.) or Examples include organic compound crystal particles, and one or more of these crystal particles can be appropriately selected and used. The particle size of the crystal particles is not particularly limited, but is preferably in the range of 1 nm to 1000 nm.
The crystal grains take a shape such as tetrahedron, hexahedron, octahedron, decahedral, dodecahedron, etc. depending on the crystal structure system to which they belong. Since each surface of these polyhedra has different chemical potentials, the reactivity of each surface with respect to a certain reactive group is different. Therefore, there is a high possibility that the specific reactive group acts preferentially only on a predetermined surface of the crystal particle.

本発明の製造方法において用いられる他の粒子としては、前記結晶粒子と同種又は異種の結晶粒子を用いることができ、さらに異方性のない結晶粒子やアモルファス粒子を用いることができ、これらの各種粒子の中から1種又は2種以上を適宜選択して用いることができる。他の粒子の粒径は特に限定されないが、1nm〜1000nmの範囲とすることが望ましい。   As other particles used in the production method of the present invention, crystal particles of the same type or different types from the crystal particles can be used, and crystal particles and amorphous particles having no anisotropy can be used. One type or two or more types can be appropriately selected from the particles and used. The particle size of the other particles is not particularly limited, but is preferably in the range of 1 nm to 1000 nm.

本発明の製造方法において用いられる接続子としては、前記結晶粒子の所定の結晶面と前記他の粒子とを結合させることができればよく、使用する結晶粒子及び他の粒子の材質等によって各種の反応基をもつ材料の中から選択して用いることができる。例えば、一端側に結晶粒子の所定の結晶面に優先的に結合する第1の反応基をもち、他端側に他の粒子の表面に結合可能な第2の反応基をもった接続子が挙げられる。   The connector used in the production method of the present invention is only required to be able to bond the predetermined crystal plane of the crystal particle and the other particle, and various reactions may be performed depending on the crystal particle to be used and the material of the other particle. A material having a group can be selected and used. For example, a connector having a first reactive group that preferentially binds to a predetermined crystal surface of a crystal particle on one end side and a second reactive group that can bind to the surface of another particle on the other end side. Can be mentioned.

このような第1、第2の反応基をもつ接続子としては、例えばシランカップリング剤などが挙げられる。シランカップリング剤の中には、通常では非常に結びつきにくい有機質材料と無機質材料を結ぶ反応基を有するものがあり、これを本発明において接続子として用いることで、これまでにないナノ構造物を作製することができる。   Examples of the connector having the first and second reactive groups include a silane coupling agent. Some silane coupling agents have a reactive group that connects an organic material and an inorganic material, which are usually very difficult to bond. By using this as a connector in the present invention, an unprecedented nanostructure can be obtained. Can be produced.

ガラス、金属、砂などの無機質材料と化学結合する反応基としては、メトキシ基、エトキシ基などが挙げられ、また各種合成樹脂などの有機質材料と化学結合する反応基としては、ビニル基、エポキシ基、アミノ基、メタクリル基、メルカプト基などが挙げられる。   Examples of reactive groups that chemically bond with inorganic materials such as glass, metal, and sand include methoxy groups and ethoxy groups, and reactive groups that chemically bond with organic materials such as various synthetic resins include vinyl groups and epoxy groups. Amino group, methacryl group, mercapto group and the like.

また、めっき、析出などを用いて結晶粒子の特定面に金属粒子などを付着させ、これを接続子もしくは接続子の一部とすることもできる。金属粒子などの析出方法や析出物は特に制限されない。例えば、光半導体である酸化チタン(TiO)結晶粒子の結晶面に白金や金を接続子として析出させる場合、塩化金酸などの金属前駆体を含む溶液に酸化チタン粒子を入れ、紫外線照射することで金属が還元され、特定の結晶面にのみ金属粒子を析出することができる。そして、他の粒子に結合したシランカップリング剤などの接続子が有する反応基と、前記金属粒子とを結合させることで、結晶粒子と他の粒子とが、前記金属粒子と接続子を介して結合されたナノ構造体を得ることができる。 Alternatively, metal particles or the like can be attached to a specific surface of the crystal particles using plating, precipitation, or the like, and this can be used as a connector or a part of the connector. There are no particular restrictions on the deposition method or deposits of metal particles or the like. For example, when depositing platinum or gold as a connector on the crystal plane of titanium oxide (TiO 2 ) crystal particles that are optical semiconductors, the titanium oxide particles are placed in a solution containing a metal precursor such as chloroauric acid and irradiated with ultraviolet rays. Thus, the metal is reduced, and the metal particles can be deposited only on a specific crystal plane. Then, by combining the metal particles with a reactive group possessed by a connector such as a silane coupling agent bonded to other particles, the crystal particles and the other particles are connected via the metal particles and the connector. A bonded nanostructure can be obtained.

本発明の製造方法において、異方性をもつ結晶粒子と、異方性のない結晶粒子やアモルファス粒子を接続子を介して結合してナノ構造体を製造する場合、それぞれの粒子の大きさを考慮して組み合わせることで、特定の三次元構造を得ることができる。   In the production method of the present invention, when a nanostructure is produced by bonding crystal particles having anisotropy and crystal particles or amorphous particles having no anisotropy via a connector, the size of each particle is set to By combining them in consideration, a specific three-dimensional structure can be obtained.

以下、図面を参照して本発明の実施形態を説明する。
図1〜図3は本発明の製造方法の第1実施形態を説明する図であり、本実施形態では、異方性をもつ結晶粒子として、図1に示す六面体結晶粒子1を用い、他の粒子として図3(a)の下部に示す十面体結晶粒子7を用い、さらに接続子として、一端側に六面体結晶粒子1の所定の結晶面5に優先的に結合する第1の反応基3と、他端側に十面体結晶粒子7の所定の結晶面に優先的に結合する第2の反応基4をもった接続子2とを用い、この接続子2を介して六面体結晶粒子1と十面体結晶粒子7を結合し、図3(b)に示すような三次元構造のナノ粒子8を製造する場合を例示している。図1(a)は六面体結晶粒子1の結晶軸方向を示す斜視図、図1(b)は六面体結晶粒子1の各結晶面を示す斜視図、また図2(a)は接続子の構造を示す構成図、図2(b)は六面体結晶粒子1の所定の結晶面5に接続子2の第1の反応基4が結合された状態を示す構成図、図3(a)は各粒子1,7に接続子2が結合した状態を示す構成図、図3(b)は得られるナノ構造体8を例示する斜視図である。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
1-3 is a figure explaining 1st Embodiment of the manufacturing method of this invention, In this embodiment, hexagonal crystal grain 1 shown in FIG. The first reactive group 3 that preferentially bonds to a predetermined crystal plane 5 of the hexahedral crystal particle 1 on one end side as a connector, using the decahedral crystal particle 7 shown in the lower part of FIG. A connector 2 having a second reactive group 4 that preferentially binds to a predetermined crystal plane of the decahedral crystal particle 7 on the other end side is used, and the hexahedral crystal particle 1 and the ten The case where the faceted crystal particles 7 are combined to produce the three-dimensional nanoparticle 8 as shown in FIG. 3B is illustrated. 1A is a perspective view showing the crystal axis direction of the hexahedral crystal particle 1, FIG. 1B is a perspective view showing each crystal face of the hexahedral crystal particle 1, and FIG. 2A shows the structure of the connector. FIG. 2B is a configuration diagram showing a state in which the first reactive group 4 of the connector 2 is bonded to a predetermined crystal plane 5 of the hexahedral crystal particle 1, and FIG. , 7 is a configuration diagram illustrating a state in which the connector 2 is coupled, and FIG. 3B is a perspective view illustrating the obtained nanostructure 8.

図1に示すような結晶系が正方晶に属する物質の直方体形状の六面体結晶粒子1において、その結晶面は(001)と(101)を反映した2種の結晶面から構成されている。各結晶面は、化学的ポテンシャルが異なるため、ある反応基に対する各結晶面の反応性が異なっている。そのため、特定の反応基は結晶粒子の所定の結晶面5だけに優先的に作用する。   In the hexahedron crystal particle 1 having a rectangular parallelepiped shape whose substance is a tetragonal crystal system as shown in FIG. 1, the crystal face is composed of two kinds of crystal faces reflecting (001) and (101). Since each crystal plane has a different chemical potential, the reactivity of each crystal plane with respect to a certain reactive group is different. Therefore, the specific reactive group acts preferentially only on the predetermined crystal plane 5 of the crystal grain.

この六面体結晶粒子1と、図2(a)に示すように、一端側に六面体結晶粒子1の所定の結晶面5に優先的に結合する第1の反応基3をもった接続子2を反応させた場合、図2(b)に示すように、六面体結晶粒子1の所定の結晶面5だけに第1の反応基3が結合し、他の結晶面6には第1の反応基3が結合していない状態とすることができる。なお、この反応基による結合を結晶粒子同士の接続子とすれば、結晶粒子の特定の結晶面だけを繋ぐナノ構造体を作ることができる。   As shown in FIG. 2 (a), this hexahedral crystal particle 1 reacts with a connector 2 having a first reactive group 3 preferentially bonded to a predetermined crystal surface 5 of the hexahedral crystal particle 1 on one end side. In this case, as shown in FIG. 2B, the first reactive group 3 is bonded only to the predetermined crystal plane 5 of the hexahedral crystal particle 1, and the first reactive group 3 is bonded to the other crystal plane 6. It can be made into the state which is not couple | bonded. If the bond by the reactive group is used as a connector between crystal grains, a nanostructure that connects only specific crystal planes of the crystal grains can be formed.

この接続子2が、図3(a)に示すように、一端側に六面体結晶粒子1の所定の結晶面5に優先的に結合する第1の反応基3と、他端側に十面体結晶粒子7の所定の結晶面に優先的に結合する第2の反応基4を有している場合、接続子2と六面体結晶粒子1及び接続子2と十面体結晶粒子7とを同時に又は順次反応させることによって、六面体結晶粒子1の所定の結晶面と十面体結晶粒子7の所定の結晶面とが、接続子2を介して結合され、図3(b)に示すように、最密充填構造以外の三次元構造をもつナノ構造体8が得られる。   As shown in FIG. 3A, the connector 2 includes a first reactive group 3 preferentially bonded to a predetermined crystal plane 5 of the hexahedral crystal particle 1 on one end side, and a decahedral crystal on the other end side. When the second reactive group 4 that preferentially bonds to a predetermined crystal plane of the particle 7 is included, the connector 2 and the hexahedral crystal particle 1 and the connector 2 and the decahedral crystal particle 7 are reacted simultaneously or sequentially. By doing so, the predetermined crystal face of the hexahedral crystal particle 1 and the predetermined crystal face of the decahedron crystal particle 7 are coupled via the connector 2, and as shown in FIG. A nanostructure 8 having a three-dimensional structure other than the above is obtained.

この製造方法によれば、接続子2の反応基を適宜選択することによって、結晶粒子のいずれの結晶面に接続子2を結合させるかを選択でき、また使用する結晶粒子又は結晶粒子と他の粒子を適宜選択することによって、最密充填構造以外の任意の三次元構造をもつ新規ナノ構造体を得ることができる。
また、この製造方法では、簡単な化学反応等によって結晶粒子同士又は結晶粒子と他の粒子とを結合することができるので、最密充填構造以外の任意の三次元構造を持つ新規のナノ構造体を安価に大量に製造することができる。
According to this manufacturing method, by appropriately selecting the reactive group of the connector 2, it is possible to select which crystal face of the crystal particle is bonded to the connector 2. By appropriately selecting the particles, a novel nanostructure having an arbitrary three-dimensional structure other than the close-packed structure can be obtained.
Further, in this manufacturing method, since the crystal particles or crystal particles and other particles can be bonded by a simple chemical reaction or the like, a novel nanostructure having an arbitrary three-dimensional structure other than the close-packed structure Can be manufactured in large quantities at low cost.

次に、本発明の第2実施形態を説明する。
本実施形態では、異方性をもつ結晶粒子として十面体酸化チタン粒子を用い、他の粒子としてシリカ粒子を用い、また接続子として十面体酸化チタン粒子の所定の結晶面に析出させた金粒子とシランカップリング剤とを用いる。このシランカップリング剤としては、金に結合するメルカプト基とシリカ粒子表面に結合するメトキシ基とを両方もつ3−メルカプトプロピルトリメトキシシランなどのシランカップリング剤を用いる。
Next, a second embodiment of the present invention will be described.
In this embodiment, decahedral titanium oxide particles are used as anisotropic crystal particles, silica particles are used as other particles, and gold particles precipitated on a predetermined crystal plane of decahedral titanium oxide particles as connectors. And a silane coupling agent. As this silane coupling agent, a silane coupling agent such as 3-mercaptopropyltrimethoxysilane having both a mercapto group bonded to gold and a methoxy group bonded to the surface of silica particles is used.

本実施形態では、まず、十面体酸化チタン粒子の結晶面のうち、(101)面を反映した結晶面に金粒子を析出させる。この工程は、例えば、十面体酸化チタン粒子を塩化金酸溶液中に懸濁し、紫外光を照射して十面体酸化チタン粒子の(101)面に金を析出させ、その後溶液から金担持十面体酸化チタン粒子を分離することにより、簡単に行うことができる。   In this embodiment, first, gold particles are deposited on a crystal plane reflecting the (101) plane among the crystal planes of the decahedral titanium oxide particles. In this step, for example, decahedral titanium oxide particles are suspended in a chloroauric acid solution, irradiated with ultraviolet light to deposit gold on the (101) plane of the decahedral titanium oxide particles, and then the gold-supported decahedron from the solution. By separating the titanium oxide particles, this can be done easily.

一方、シリカ粒子は、前記シランカップリング剤で表面修飾する。この表面修飾により、前記シランカップリング剤のメトキシ基がシリカ粒子表面に結合し、シリカ粒子の表面には結合したシランカップリング剤のメルカプト基が残存している状態になる。   On the other hand, the surface of the silica particles is modified with the silane coupling agent. By this surface modification, the methoxy group of the silane coupling agent is bonded to the surface of the silica particle, and the mercapto group of the bonded silane coupling agent remains on the surface of the silica particle.

次に、適当な溶媒中、前記金担持十面体酸化チタン粒子と前記表面修飾済みのシリカ粒子を混ぜ合わせ、シリカ粒子表面のメルカプト基と十面体酸化チタン粒子の所定の結晶面に析出した金粒子を結合させる。次に、生成物を分離し、必要に応じて乾燥することで、十面体酸化チタン粒子とシリカ粒子とが結合したナノ構造体を得ることができる。
本実施形態は、前述した第1実施形態と同様の効果が得られる。
Next, in a suitable solvent, the gold-supported decahedral titanium oxide particles and the surface-modified silica particles are mixed, and gold particles precipitated on a predetermined crystal plane of the mercapto group on the silica particle surface and the decahedral titanium oxide particles. Are combined. Next, the nanostructure in which the decahedral titanium oxide particles and the silica particles are bonded can be obtained by separating the product and drying it as necessary.
This embodiment can obtain the same effects as those of the first embodiment described above.

次に、本発明の第3実施形態を説明する。
さらに詳細な検討を続け、より効果的に、任意の三次元構造をもつナノ構造体およびそれを大量に製造する方法を発明した。具体的には、異方性をもち、かつ光活性をもつ結晶粒子に、光照射をほどこすことにより、結晶粒子の特定の結晶面に金属、無機化合物、有機化合物などを析出させ、接続子又は接続子の一部とすることを特徴とする最密充填構造以外の三次元構造をもつナノ構造体の製造方法において、照射する光の強度と、光照射を行う際の結晶粒子を分散させる溶媒種と、結晶面に析出させる金属、無機化合物、有機化合物などの前駆体溶液の濃度とを最適化することにより、異方性をもつ結晶粒子の、特定の結晶面に対してのみ接続子を析出させる効果(接続子析出の面選択性)を著しく向上させることができることを見出した。接続子析出の面選択性を著しく向上させた結果、より、均一な構造のナノ構造体を形成することが可能となった。これにより、さらに特異で強力な電気的、光学的、化学的特性を示すナノ構造体を得ることができると予想される。
Next, a third embodiment of the present invention will be described.
Further detailed investigation was continued, and a nanostructure having an arbitrary three-dimensional structure and a method for manufacturing it in large quantities were invented more effectively. Specifically, the crystal particles having anisotropy and photoactivity are irradiated with light, thereby depositing a metal, an inorganic compound, an organic compound, or the like on a specific crystal surface of the crystal particles, thereby connecting the connector. Alternatively, in the method of manufacturing a nanostructure having a three-dimensional structure other than the close-packed structure, which is a part of a connector, the intensity of light to be irradiated and crystal particles at the time of light irradiation are dispersed By optimizing the solvent species and the concentration of the precursor solution of metal, inorganic compound, organic compound, etc. deposited on the crystal plane, the connector is only connected to a specific crystal plane of anisotropic crystal grains. It has been found that the effect of precipitating (surface selectivity of connector precipitation) can be remarkably improved. As a result of remarkably improving the surface selectivity of connector precipitation, it became possible to form nanostructures with a more uniform structure. As a result, it is expected that nanostructures exhibiting more specific and powerful electrical, optical and chemical properties can be obtained.

また、接続子の一部として、金や白金などの高価な貴金属を用いる場合、接続子析出の面選択性を著しく向上させた結果、これらの貴金属の使用量を減少させることができ、低コストでナノ構造体が得られることが期待される。   In addition, when expensive noble metals such as gold and platinum are used as part of the connector, the surface selectivity of the connector deposition is significantly improved, so that the amount of these noble metals used can be reduced, resulting in low cost. It is expected that nanostructures can be obtained.

また、使用後のナノ構造体を破棄する場合、薬品などを用いて、結晶粒子と接続子の結合を分解する。異方性をもつ結晶粒子では、各結晶面における化学的ポテンシャルが異なるため、複数の結晶面に結合した接続子は、それぞれの結晶面ごとに適する薬品と処理条件で接続子との結合を解除しなければならない。そのため工程が複雑で、また処理後の結晶粒子表面は、薬品によるエッチング効果を受け、形状を大きく損なってしまうことが頻繁にある。ナノサイズの結晶粒子の選別は困難であるため、処理後の結晶粒子を再びナノ構造体材料として再利用することは不可能である。今回の発明により、接続子析出の面選択性を著しく向上させた結果、接続子と粒子の結合を解除する工程は、単一条件のみで済むため、従来技術に比較して、処理工程は大幅に単純化でき、さらに結晶粒子に与えるダメージを最小限にすることが可能になる。これにより、結晶粒子を再びナノ構造体材料として再利用することも可能となる。   In addition, when discarding the nanostructure after use, the bonds between the crystal particles and the connector are decomposed using chemicals or the like. Since an anisotropic crystal grain has a different chemical potential at each crystal plane, a connector bonded to multiple crystal planes is released from the bond with the appropriate chemical and processing conditions for each crystal plane. Must. For this reason, the process is complicated, and the surface of the crystal grain after the treatment is often subjected to an etching effect by a chemical, and the shape is often greatly lost. Since it is difficult to select nano-sized crystal particles, it is impossible to reuse the processed crystal particles as a nanostructure material again. As a result of remarkably improving the surface selectivity of connector deposition by the present invention, the process for releasing the connection between the connector and the particles only requires a single condition. In addition, the damage to the crystal grains can be minimized. As a result, the crystal particles can be reused again as the nanostructure material.

本実施形態では、異方性をもち、かつ光活性をもつ結晶粒子として、特に、十面体形状の酸化チタン粒子を選択した場合について、詳細な条件を見出したので、詳細な説明を加える。   In the present embodiment, detailed conditions have been found, particularly when decahedral titanium oxide particles are selected as crystal particles having anisotropy and photoactivity, and detailed description will be added.

四塩化チタンを原料としたCVD法により、十面体形状の酸化チタン粒子を得ることができる。この酸化チタン粒子の十面体形状は、酸化チタンが属する結晶系である正方晶系を反映した形状である。これは図7(a)、(b)に示すような形状をしており、(001)面を反映した面と、(101)面を反映した面からなる。ナノ構造体を構成するための酸化チタン粒子の粒径は特に制限はないが、粒径10〜1000nmであることが望ましい。粒径10nm未満の十面体酸化チタン粒子では、十面体形状が不明瞭となり、接続子析出の面選択性が低下するという問題が発生する。また、粒径が1000nmより大きい粒子は、均一な大きさで製造することが困難であるため実用的でない。粒径が40〜200nmの十面体チタン粒子は、最も、接続子析出の面選択性が高く、更に望ましい。   Decahedral titanium oxide particles can be obtained by a CVD method using titanium tetrachloride as a raw material. The decahedron shape of the titanium oxide particles is a shape reflecting a tetragonal system that is a crystal system to which titanium oxide belongs. This has a shape as shown in FIGS. 7A and 7B, and is composed of a plane reflecting the (001) plane and a plane reflecting the (101) plane. The particle size of the titanium oxide particles for constituting the nanostructure is not particularly limited, but is desirably 10 to 1000 nm. In the case of decahedral titanium oxide particles having a particle size of less than 10 nm, the decahedral shape becomes unclear, and there arises a problem that the surface selectivity of connector precipitation decreases. Also, particles having a particle size larger than 1000 nm are not practical because it is difficult to produce them with a uniform size. Decahedron titanium particles having a particle size of 40 to 200 nm have the highest surface selectivity for connector precipitation and are more desirable.

この十面体酸化チタン粒子は、光半導体であり、光活性を示す。十面体酸化チタン粒子を溶媒に分散させ、さらにそこに析出させる接続子の前駆体を加え、光照射を行うことで、十面体酸化チタン粒子の特定の面に接続子を析出させることができる。   The decahedral titanium oxide particles are an optical semiconductor and exhibit photoactivity. A connector can be deposited on a specific surface of the decahedral titanium oxide particles by dispersing the decahedral titanium oxide particles in a solvent, and further adding a precursor of the connector to be precipitated there, followed by light irradiation.

十面体酸化チタン粒子を分散させる溶媒は、2−プロパノールが望ましく、超音波処理を行い分散させる。例えば、水では十分に分散させることはできない。また、分散時の溶媒に対する十面体酸化チタン粒子の濃度は、1〜100mg/Lの範囲が望ましく、10〜20mg/Lの範囲がさらに望ましい。これ以上の高濃度では、光照射時に十面体酸化チタン粒子に対し、均一に光照射が行われず、接続子の析出が均一に行われないという問題が生じる。また、これ以下の濃度では、ナノ構造体の形成速度が著しく低下し、工業的に不利となるので望ましくない。   The solvent in which the decahedral titanium oxide particles are dispersed is preferably 2-propanol and is dispersed by sonication. For example, water cannot be sufficiently dispersed. The concentration of decahedral titanium oxide particles relative to the solvent during dispersion is preferably in the range of 1 to 100 mg / L, and more preferably in the range of 10 to 20 mg / L. When the concentration is higher than this, there is a problem that the light is not uniformly applied to the decahedral titanium oxide particles at the time of the light irradiation, and the connector is not uniformly deposited. In addition, if the concentration is less than this, the formation rate of the nanostructure is remarkably lowered, which is disadvantageous industrially, which is not desirable.

接続子の前駆体は、金属塩、錯体など、任意の試薬を用いることができる。例えば、金、白金、銀を析出させ接続子とする場合、それぞれ、塩化金酸、塩化白金酸、硝酸銀を用いることができる。これらの金属塩を溶媒に溶かし溶液とし、十面体酸化チタン粒子を分散させた溶媒に加え、光照射を行う。例えば、塩化金を用いる場合、加える塩化金の量は、塩化金に含まれる金の質量が、十面体酸化チタンの質量に対し、10〜30質量%となるようにすることが望ましい。これ以上に高濃度になると、接続子析出の面選択性は低下するので望ましくない。また、これ以下の低濃度では、接続子の析出速度が著しく低下し、工業的に不利なので望ましくない。   Arbitrary reagents, such as a metal salt and a complex, can be used for the precursor of a connector. For example, when gold, platinum, and silver are deposited to form a connector, chloroauric acid, chloroplatinic acid, and silver nitrate can be used, respectively. These metal salts are dissolved in a solvent to form a solution, added to a solvent in which decahedral titanium oxide particles are dispersed, and then irradiated with light. For example, when gold chloride is used, the amount of gold chloride added is preferably such that the mass of gold contained in the gold chloride is 10 to 30% by mass with respect to the mass of decahedral titanium oxide. If the concentration is higher than this, it is not desirable because the surface selectivity of connector precipitation is lowered. On the other hand, when the concentration is lower than this, the deposition rate of the connector is remarkably lowered, which is not preferable because it is industrially disadvantageous.

十面体酸化チタン粒子を用いる場合、照射する光の波長は、380nm以下であることが望ましい。これ以上の波長の光を照射しても十分な光活性が得られず、接続子の析出速度が著しく遅い、もしくは全く析出が起こらないという結果となる。照射強度は3〜30mW/cmの範囲が望ましく、さらに10〜20mW/cmの範囲とすることがより望ましい。これより高強度とすると、接続子析出の面選択性が低下するので望ましくない。また、これより低強度では、接続子の析出速度が著しく低下し、工業的に不利なので望ましくない。 When decahedral titanium oxide particles are used, the wavelength of light to be irradiated is preferably 380 nm or less. Even if light with a wavelength longer than this is irradiated, sufficient photoactivity cannot be obtained, resulting in a very slow deposition rate of the connector or no precipitation at all. The irradiation intensity is desirably range 3~30mW / cm 3, it is more desirable to further the range of 10~20mW / cm 3. If the strength is higher than this, it is not desirable because the surface selectivity of connector precipitation is lowered. On the other hand, if the strength is lower than this, the deposition rate of the connector is remarkably lowered, which is not preferable because it is industrially disadvantageous.

以上のように、照射する光の強度と、光照射を行う際の結晶粒子を分散させる溶媒種と、結晶面に析出させる金属の前駆体溶液の濃度とを最適化することにより、例えば、十面体酸化チタン粒子に、接続子として金を析出させる場合、十面体酸化チタン粒子の表面に析出した金の総量のうち、95%以上を十面体酸化チタン粒子の(101)面に析出させることが可能となる。   As described above, by optimizing the intensity of light to be irradiated, the solvent species in which crystal particles are dispersed during the light irradiation, and the concentration of the metal precursor solution deposited on the crystal plane, for example, 10 When gold is deposited as a connector on the tetrahedral titanium oxide particles, 95% or more of the total amount of gold deposited on the surface of the decahedral titanium oxide particles may be deposited on the (101) plane of the decahedral titanium oxide particles. It becomes possible.

前述した接続子若しくは接続子の一部として金を析出させた十面体酸化チタン粒子を用いて、非常に均一な構造のナノ構造体を形成することができる。   A nanostructure having a very uniform structure can be formed using the above-described connector or decahedral titanium oxide particles on which gold is deposited as a part of the connector.

ナノ構造体の形成方法は、図8に示すように、(101)面に金粒子13を析出させた十面体酸化チタン粒子11と、金粒子13に接合される他の粒子とを準備し(図8(a))、金粒子13を介して十面体酸化チタン粒子と他の粒子とを接合することで、最密充填構造以外の三次元構造をもつナノ構造体14が得られる。   As shown in FIG. 8, the nanostructure forming method is prepared by preparing decahedral titanium oxide particles 11 having gold particles 13 deposited on the (101) plane and other particles bonded to the gold particles 13 ( 8A), the nanostructure 14 having a three-dimensional structure other than the close-packed structure is obtained by joining the decahedral titanium oxide particles and other particles via the gold particles 13. FIG.

また、図9に示すように、(101)面に金粒子13を析出させた十面体酸化チタン粒子11と、他の粒子12と、金粒子13に接合する第1の反応基15と他の粒子12に接合する第2の反応基16を有する接続子17とを準備し、それぞれ結合させることで最密充填構造以外の三次元構造をもつナノ構造体14が得られる。   In addition, as shown in FIG. 9, decahedral titanium oxide particles 11 having gold particles 13 deposited on the (101) plane, other particles 12, first reactive groups 15 bonded to the gold particles 13, and other particles. A nanostructure 14 having a three-dimensional structure other than the close-packed structure is obtained by preparing a connector 17 having a second reactive group 16 to be bonded to the particle 12 and bonding them together.

ここで用いられる他の粒子12としては、前記の十面体酸化チタン粒子11又は異種の結晶粒子を用いることができ、さらに異方性のない結晶粒子やアモルファス粒子を用いることができ、これらの各種粒子の中から1種又は2種以上を適宜選択して用いることができる。他の粒子12の粒径は特に限定されないが、1nm〜1000nmの範囲とすることが望ましい。十面体酸化チタン粒子11と他の粒子12の大きさを考慮して組み合わせることで、特定の三次元構造を得ることができる。   As the other particles 12 used here, the above-mentioned decahedral titanium oxide particles 11 or different types of crystal particles can be used, and crystal particles and amorphous particles having no anisotropy can be used. One type or two or more types can be appropriately selected from the particles and used. The particle size of the other particles 12 is not particularly limited, but is desirably in the range of 1 nm to 1000 nm. A specific three-dimensional structure can be obtained by combining decahedral titanium oxide particles 11 and other particles 12 in consideration of their sizes.

また、ここで用いられる接続子17としては、十面体酸化チタン粒子の(101)面に析出させた金粒子13と、前記他の粒子12とを結合させることができればよく、他の粒子12の材質等によって各種の反応基をもつ材料の中から選択して用いることができる。例えば、一端側に金粒子に優先的に結合する第1の反応基15をもち、他端側に他の粒子12の表面に結合可能な第2の反応基16をもった接続子17が挙げられる。   Moreover, as the connector 17 used here, the gold particles 13 deposited on the (101) plane of the decahedral titanium oxide particles and the other particles 12 may be combined. It can be selected from materials having various reactive groups depending on the material. For example, a connector 17 having a first reactive group 15 that preferentially bonds to gold particles at one end and a second reactive group 16 that can be bonded to the surface of another particle 12 at the other end. It is done.

このような第1、第2の反応基をもつ接続子としては、例えばシランカップリング剤などが挙げられる。シランカップリング剤の中には、通常では非常に結びつきにくい金属材料、有機質材料、無機質材料とを結ぶ反応基を有するものがあり、これを本実施形態において接続子17として用いることで、これまでにないナノ構造物14を作製することができる。   Examples of the connector having the first and second reactive groups include a silane coupling agent. Some silane coupling agents usually have a reactive group that connects a metal material, an organic material, and an inorganic material that are very difficult to be combined, and this is used as the connector 17 in the present embodiment. Nanostructures 14 that are not present can be produced.

ガラス、金属、砂などの無機質材料と化学結合する反応基としては、メトキシ基、エトキシ基などが挙げられ、また各種合成樹脂などの有機質材料と化学反応する反応基としては、ビニル基、エポキシ基、アミノ機、メタクリル基、メルカプト基などが挙げられる。   Examples of reactive groups that chemically bond with inorganic materials such as glass, metal, and sand include methoxy groups and ethoxy groups, and reactive groups that chemically react with organic materials such as various synthetic resins include vinyl groups and epoxy groups. Amino group, methacryl group, mercapto group and the like.

次に、本実施形態の好適な具体例を説明する。
本具体例では、異方性をもつ結晶粒子として十面体酸化チタン粒子を用い、他の粒子としてシリカ粒子を用い、接続子として十面体酸化チタン粒子の所定の結晶面に析出させた金粒子とシランカップリング剤とを用いる。このシランカップリング剤としては、金に結合するメルカプト基とシリカ粒子表面に結合するメトキシ基とを両方もつ、3−メルカプトプロピルトリメトキシシランなどのシランカップリング剤を用いる。
Next, a preferred specific example of this embodiment will be described.
In this specific example, decahedral titanium oxide particles are used as anisotropic crystal particles, silica particles are used as other particles, gold particles precipitated on a predetermined crystal surface of decahedral titanium oxide particles as connectors, and A silane coupling agent is used. As this silane coupling agent, a silane coupling agent such as 3-mercaptopropyltrimethoxysilane having both a mercapto group bonded to gold and a methoxy group bonded to the surface of silica particles is used.

本具体例では、まず、十面体酸化チタン粒子の結晶面のうち、(101)面を反映した結晶面に金粒子を析出させる。この工程は、例えば、十面体酸化チタン粒子を塩化金酸溶液中に懸濁し、紫外光を照射して十面体酸化チタン粒子の(101)面に金を析出させ、その後、溶液から金担持十面体酸化チタン粒子を分離することにより、簡単に行うことができる。   In this specific example, first, gold particles are deposited on the crystal plane reflecting the (101) plane among the crystal planes of the decahedral titanium oxide particles. In this step, for example, decahedral titanium oxide particles are suspended in a chloroauric acid solution and irradiated with ultraviolet light to deposit gold on the (101) plane of the decahedral titanium oxide particles. Separation of the faceted titanium oxide particles can be performed easily.

一方、シリカ粒子は、前記シランカップリング剤で表面修飾する。この表面修飾により、前記シランカップリング剤のメルカプト基が残存している状態になる。   On the other hand, the surface of the silica particles is modified with the silane coupling agent. By this surface modification, the mercapto group of the silane coupling agent remains.

次に、適当な溶媒中、前記金担持十面体酸化チタン粒子と前記表面修飾済みのシリカ粒子を混ぜ合わせ、シリカ粒子表面のメルカプト基と十面体酸化チタン粒子の所定の結晶面に析出した金粒子を結合させる。次に、生成物を分離し、必要に応じて乾燥することで、十面体酸化チタン粒子とシリカ粒子とが結合したナノ構造体を得ることができる。   Next, in a suitable solvent, the gold-supported decahedral titanium oxide particles and the surface-modified silica particles are mixed, and gold particles precipitated on a predetermined crystal plane of the mercapto group on the silica particle surface and the decahedral titanium oxide particles. Are combined. Next, the nanostructure in which the decahedral titanium oxide particles and the silica particles are bonded can be obtained by separating the product and drying it as necessary.

[実施例1]
四塩化チタンを原料とするCVD法により、図4に示すような十面体形状の酸化チタン結晶粒子を合成した。酸化チタンは正方晶系に属しており、十面体を形成する面は、(001)を反映した正方形の面と(101)を反映した台形の面からなっている。この十面体酸化チタン粒子の粒径は平均で100nmであった。
次に、この十面体酸化チタン粒子を塩化金酸を含む2−プロパノール溶液中に分散させ、高圧水銀灯の光を照射することにより、十面体酸化チタン結晶粒子表面に金粒子を約20質量%光析出させた。溶液をスライドガラス上に数滴たらし乾燥させた後、観察したSEM像を図5に示す。
観察の結果、金粒子は主に十面体酸化チタン粒子の(101)面に光析出していることがわかった。これは、光反応の一部である還元反応が十面体酸化チタン粒子の(101)面で優先的に起きていることを示している。
[Example 1]
The decahedron-shaped titanium oxide crystal particles as shown in FIG. 4 were synthesized by a CVD method using titanium tetrachloride as a raw material. Titanium oxide belongs to the tetragonal system, and the faces forming the decahedron are a square face reflecting (001) and a trapezoidal face reflecting (101). The average particle size of the decahedral titanium oxide particles was 100 nm.
Next, the decahedral titanium oxide particles are dispersed in a 2-propanol solution containing chloroauric acid, and irradiated with light from a high-pressure mercury lamp. Precipitated. FIG. 5 shows an observed SEM image after several drops of the solution on a slide glass and dried.
As a result of observation, it was found that gold particles were mainly photodeposited on the (101) plane of decahedral titanium oxide particles. This indicates that the reduction reaction, which is part of the photoreaction, occurs preferentially on the (101) plane of the decahedral titanium oxide particles.

[実施例2]
粒径約500nmの市販の球状シリカ粒子をシランカップリング剤(3−メルカプトプロピルトリメトキシシラン)で表面修飾した。このとき、シランカップリング剤のメトキシ基側がシリカ粒子と接続すると考えられるため、修飾後のシリカ粒子はメルカプト基が表面に出ていることになる。
次に、このシリカ粒子を、実施例1において調製した金担持十面体酸化チタン粒子を分散させた溶液に加えて撹拌し、ナノ構造体を形成した。撹拌後のナノ構造体のSEM像を図6に示す。
観察の結果、球状シリカ粒子が十面体酸化チタン粒子の(101)面に結合していることが確認できた。これは、メルカプト基が十面体酸化チタン粒子の(101)面に光析出した金粒子とのみ結合してナノ構造体が形成されたものと考えられる。また、直鎖構造のナノ構造体のみが形成されていた。これはシリカ粒子のサイズが十面体酸化チタン粒子と比べて非常に大きいため、立体的な反発により、十面体酸化チタン粒子の隣り合う(101)面に二つのシリカ粒子が結合できないためと考えられる。
[Example 2]
A commercially available spherical silica particle having a particle size of about 500 nm was surface-modified with a silane coupling agent (3-mercaptopropyltrimethoxysilane). At this time, since it is considered that the methoxy group side of the silane coupling agent is connected to the silica particles, the modified silica particles have a mercapto group on the surface.
Next, the silica particles were added to the solution in which the gold-supported decahedral titanium oxide particles prepared in Example 1 were dispersed and stirred to form nanostructures. The SEM image of the nanostructure after stirring is shown in FIG.
As a result of observation, it was confirmed that the spherical silica particles were bonded to the (101) plane of the decahedral titanium oxide particles. This is probably because the mercapto group was bonded only to the gold particles photodeposited on the (101) plane of the decahedral titanium oxide particles to form a nanostructure. Moreover, only the nanostructure of a linear structure was formed. This is probably because the size of the silica particles is very large compared to the decahedral titanium oxide particles, and the two silica particles cannot be bonded to the adjacent (101) faces of the decahedral titanium oxide particles due to steric repulsion. .

[比較例1]
実施例1で用いた十面体酸化チタン粒子と、実施例2で用いた球状シリカ粒子とを、2−プロパノール溶液中に分散させた。溶液をスライドガラス上に数滴たらし乾燥させた後、SEMにて観察したところ、十面体酸化チタン粒子と球状シリカ粒子がそれぞれ別々に凝集していた。球状シリカ粒子は最密充填に凝集していたが、十面体酸化チタン粒子はランダムに凝集した。
[Comparative Example 1]
The decahedral titanium oxide particles used in Example 1 and the spherical silica particles used in Example 2 were dispersed in a 2-propanol solution. After dropping several drops of the solution on a slide glass and drying it, observation with an SEM revealed that decahedral titanium oxide particles and spherical silica particles were separately aggregated. The spherical silica particles were aggregated in the closest packing, but the decahedral titanium oxide particles were aggregated randomly.

[実施例3]
本実施例では、酸化チタン微粒子に結晶面特異的に析出させた金属と球状シリカ粒子を架橋させることにより、特定方向に結合をもつ新規ナノ構造体の調製を試みた。
四塩化チタンを原料とするCVD法で図7に示すような十面体形状の酸化チタン結晶粒子を合成した。酸化チタンは正方晶系に属しており、十面体を形成する面は、(001)を反映した正方形の面と(101)を反映した台形の面からなっている。この十面体酸化チタン粒子の粒径は、平均で100nmであった。これを2−プロパノールに20mg/Lの濃度で混合し、超音波処理を施して分散させた。ここに1g/10mLの塩化金酸水溶液を、水溶液中に含まれる金の質量で換算し、2−プロパノール中に分散する十面体酸化チタン粒子に対して20質量%になるように秤量して加え、よく混合した。これに、365nmの波長を発する高圧水銀灯の光を、10mW/cmの強度で照射することにより、十面体酸化チタン粒子の表面に光析出させた。溶液をスライドガラス状に数滴たらし乾燥させた後、観察したSEM像を図10に示す。観察の結果、金粒子の殆どは十面体酸化チタン粒子の(101)面に光析出していることがわかった。SEM観察により金粒子の体積を計測した結果、十面体酸化チタン粒子表面に析出した金の総量のうち、97%が(101)面に析出していることがわかった。
[Example 3]
In this example, an attempt was made to prepare a novel nanostructure having a bond in a specific direction by cross-linking a metal precipitated in a crystal plane specifically on titanium oxide fine particles and spherical silica particles.
Decahedral titanium oxide crystal particles as shown in FIG. 7 were synthesized by CVD using titanium tetrachloride as a raw material. Titanium oxide belongs to the tetragonal system, and the faces forming the decahedron are a square face reflecting (001) and a trapezoidal face reflecting (101). The average particle size of the decahedral titanium oxide particles was 100 nm. This was mixed with 2-propanol at a concentration of 20 mg / L, and subjected to ultrasonic treatment to be dispersed. Here, 1 g / 10 mL of chloroauric acid aqueous solution was converted to the mass of gold contained in the aqueous solution, and weighed so as to be 20% by mass with respect to decahedral titanium oxide particles dispersed in 2-propanol. Mixed well. This was irradiated with light from a high-pressure mercury lamp emitting a wavelength of 365 nm at an intensity of 10 mW / cm 2 to cause photodeposition on the surface of decahedral titanium oxide particles. FIG. 10 shows an observed SEM image after several drops of the solution in a glass slide and dried. As a result of observation, it was found that most of the gold particles were photo-deposited on the (101) plane of the decahedral titanium oxide particles. As a result of measuring the volume of the gold particles by SEM observation, it was found that 97% of the total amount of gold deposited on the surface of the decahedral titanium oxide particles was deposited on the (101) plane.

[比較例2]
四塩化チタンを原料とするCVD法で十面体形状の酸化チタン結晶粒子を合成した。この十面体酸化チタン粒子の粒径は、平均で100nmであった。これを2−プロパノールに50mg/Lの濃度で混合し、超音波処理を施して分散させた。ここに1g/10mLの塩化金酸水溶液を、水溶液中に含まれる金の質量で換算し、2−プロパノール中に分散する十面体酸化チタン粒子に対して40質量%になるように秤量して加え、よく混合した。これに、365nmの波長を発する高圧水銀灯の光を、60mW/cmの強度で照射することにより、十面体酸化チタン粒子の表面に光析出させた。溶液をスライドガラス状に数滴たらし乾燥させた後、観察した結果、金粒子は十面体酸化チタン粒子の表面に析出したが、(101)面、(001)面の両方に、ほぼ同じ割合で析出していた。
[Comparative Example 2]
Decahedral titanium oxide crystal particles were synthesized by CVD using titanium tetrachloride as a raw material. The average particle size of the decahedral titanium oxide particles was 100 nm. This was mixed with 2-propanol at a concentration of 50 mg / L, and subjected to ultrasonic treatment to be dispersed. Here, 1 g / 10 mL of chloroauric acid aqueous solution was converted to the mass of gold contained in the aqueous solution and weighed so as to be 40% by mass with respect to decahedral titanium oxide particles dispersed in 2-propanol. Mixed well. This was irradiated with light of a high-pressure mercury lamp emitting a wavelength of 365 nm at an intensity of 60 mW / cm 2 to cause photodeposition on the surface of the decahedral titanium oxide particles. As a result of observation after drying several drops of the solution in the shape of a glass slide, gold particles were deposited on the surface of the decahedral titanium oxide particles, but almost the same ratio on both the (101) plane and the (001) plane. It was precipitated.

本発明に用いられる結晶粒子の一例としての六面体結晶粒子を示し、(a)は六面体結晶粒子の結晶軸方向を示す斜視図、(b)は六面体結晶粒子の各結晶面を示す斜視図である。FIG. 2 shows hexahedral crystal particles as an example of crystal grains used in the present invention, (a) is a perspective view showing the crystal axis direction of the hexahedral crystal particles, and (b) is a perspective view showing each crystal face of the hexahedral crystal particles. . 本発明の製造方法の一例を示し、(a)は本発明に用いられる接続子の構造を例示する構成図、(b)は六面体結晶粒子の所定の結晶面に接続子の第1の反応基が結合された状態を示す構成図である。An example of the manufacturing method of this invention is shown, (a) is a block diagram which illustrates the structure of the connector used for this invention, (b) is the 1st reactive group of a connector on the predetermined crystal plane of a hexahedral crystal particle. It is a block diagram which shows the state by which was couple | bonded. 本発明の製造方法の一例を示し、(a)は各粒子に接続子が結合した状態を示す構成図、(b)は得られるナノ構造体を例示する斜視図である。An example of the manufacturing method of this invention is shown, (a) is a block diagram which shows the state which the connector couple | bonded with each particle | grain, (b) is a perspective view which illustrates the nanostructure obtained. 本発明に係る実施例において用いた結晶粒子を示すSEM像である。It is a SEM image which shows the crystal grain used in the Example which concerns on this invention. 本発明に係る実施例において作製した金担持結晶粒子を示すSEM像である。It is a SEM image which shows the gold | metal | money carrying | support crystal particle produced in the Example which concerns on this invention. 本発明に係る実施例において作製したナノ構造体を示すSEM像である。It is a SEM image which shows the nanostructure produced in the Example which concerns on this invention. 本発明に係る実施例において作製した十面体酸化チタン粒子を示し、(a)は該粒子のSEM像、(b)は斜視図である。The decahedral titanium oxide particle produced in the Example which concerns on this invention is shown, (a) is the SEM image of this particle | grain, (b) is a perspective view. 本発明の製造方法の別な例を示し、(a)は十面体酸化チタン粒子の(101)面に金粒子を析出させた状態を示す斜視図、(b)は作製されたナノ粒子を示す斜視図である。The other example of the manufacturing method of this invention is shown, (a) is a perspective view which shows the state which deposited the gold particle on the (101) surface of a decahedral titanium oxide particle, (b) shows the produced nanoparticle. It is a perspective view. 本発明の製造方法のさらに別な例を示し、(a)は金粒子を析出させた十面体酸化チタン粒子と、他の粒子と、接続子とを準備する工程を示す斜視図、(b)は作製されたナノ粒子を示す斜視図である。Another example of the manufacturing method of this invention is shown, (a) is a perspective view which shows the process of preparing the decahedral titanium oxide particle which precipitated the gold particle, another particle | grain, and a connector, (b). FIG. 3 is a perspective view showing the produced nanoparticles. 本発明に係る実施例において作製した金粒子を析出させた十面体酸化チタン粒子を示すSEM像である。It is a SEM image which shows the decahedral titanium oxide particle which precipitated the gold particle produced in the Example which concerns on this invention.

符号の説明Explanation of symbols

1…六面体結晶粒子(異方性をもつ結晶粒子)、2…接続子、3…第1の反応基、4…第2の反応基、5…特定の結晶面、6…その他の結晶面、7…十面体結晶粒子(他の粒子)、8…ナノ構造体、11…十面体酸化チタン粒子、12…他の粒子、13…金粒子、14…ナノ構造体、15…第1の反応基、16…第2の反応基、17…接続子。
DESCRIPTION OF SYMBOLS 1 ... Hexahedral crystal grain (crystal grain with anisotropy), 2 ... Connector, 3 ... 1st reaction group, 4 ... 2nd reaction group, 5 ... Specific crystal plane, 6 ... Other crystal planes, 7 ... Decahedral crystal particles (other particles), 8 ... Nanostructure, 11 ... Decahedron titanium oxide particles, 12 ... Other particles, 13 ... Gold particles, 14 ... Nanostructure, 15 ... First reactive group 16 ... second reactive group, 17 ... connector.

Claims (10)

異方性をもつ結晶粒子である十面体酸化チタン粒子と、該結晶粒子の(101)面を反映した結晶面に析出させた金属に一端側が結合する接続子と、該接続子の他端側に結合される、前記結晶粒子と異種の他の粒子とを準備し、
前記十面体酸化チタン粒子を前記金属の塩溶液に懸濁し、紫外光を照射することにより、前記結晶面に前記金属を析出させ、
前記金属に前記接続子の一端側を結合し、それと同時又は前後いずれかで、前記他の粒子の表面に前記接続子の他端側を結合することで、前記接続子を介して前記金属と前記他の粒子の表面とを結合させ、最密充填構造以外の三次元構造をもつナノ構造体を得ることを特徴とするナノ構造体の製造方法。
Decahedral titanium oxide particles which are crystal grains having anisotropy, a connector having one end coupled to a metal deposited on a crystal plane reflecting the (101) plane of the crystal particles, and the other end of the connector Preparing the crystal particles and other particles different from each other,
By suspending the decahedral titanium oxide particles in the salt solution of the metal and irradiating with ultraviolet light, the metal is deposited on the crystal plane,
One end side of the connector is coupled to the metal, and the other end side of the connector is coupled to the surface of the other particle either at the same time or before and after, thereby the metal and the metal through the connector. A method for producing a nanostructure, characterized in that a nanostructure having a three-dimensional structure other than a close-packed structure is obtained by bonding to the surface of the other particles.
前記他の粒子がシリカ粒子であることを特徴とする請求項1に記載のナノ構造体の製造方法。 The method for producing a nanostructure according to claim 1, wherein the other particles are silica particles. 前記接続子がシランカップリング剤であることを特徴とする請求項1又は2に記載のナノ構造体の製造方法。 The method for producing a nanostructure according to claim 1 or 2, wherein the connector is a silane coupling agent. 前記十面体酸化チタン粒子と前記シリカ粒子とを前記接続子を介して直鎖状に結合したナノ構造体を得ることを特徴とする請求項2に記載のナノ構造体の製造方法。 The method for producing a nanostructure according to claim 2, wherein a nanostructure in which the decahedral titanium oxide particles and the silica particles are linearly bonded via the connector is obtained. 前記接続子がシランカップリング剤であることを特徴とする請求項4に記載のナノ構造体の製造方法。The method for producing a nanostructure according to claim 4, wherein the connector is a silane coupling agent. 前記金属が、金又は白金であることを特徴とする請求項1〜のいずれか一項に記載のナノ構造体の製造方法。 The said metal is gold or platinum, The manufacturing method of the nanostructure as described in any one of Claims 1-5 characterized by the above-mentioned. 異方性をもつ結晶粒子である十面体酸化チタン粒子と、該結晶粒子の(101)面を反映した結晶面に析出させた金属に一端側が結合した接続子と、該接続子の他端側が結合した他の粒子とを有し、該接続子を介して前記金属と前記他の粒子の表面とが結合されてなり、最密充填構造以外の三次元構造をもつことを特徴とするナノ構造体。 A decahedral titanium oxide particle, which is a crystal particle having anisotropy, a connector bonded at one end to a metal deposited on a crystal plane reflecting the (101) plane of the crystal particle, and the other end of the connector A nanostructure characterized by having a three-dimensional structure other than a close-packed structure, wherein the metal and the surface of the other particle are bonded via the connector. body. 前記他の粒子がシリカ粒子であることを特徴とする請求項に記載のナノ構造体。 The nanostructure according to claim 7 , wherein the other particles are silica particles. 前記接続子がシランカップリング剤であることを特徴とする請求項又はに記載のナノ構造体。 The nanostructure according to claim 7 or 8 , wherein the connector is a silane coupling agent. 請求項1〜のいずれかに記載のナノ構造体の製造方法により得られたことを特徴とするナノ構造体。 A nanostructure obtained by the method for producing a nanostructure according to any one of claims 1 to 6 .
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