JP7457583B2 - Nanowire-containing film and method for producing nanowires - Google Patents
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- 239000002070 nanowire Substances 0.000 title claims description 83
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 56
- 239000011787 zinc oxide Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- 229920006127 amorphous resin Polymers 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001925 cycloalkenes Chemical class 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 229920006289 polycarbonate film Polymers 0.000 description 36
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004312 hexamethylene tetramine Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000369 bright-field scanning transmission electron microscopy Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- -1 zinc oxide Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Description
本発明は、基材上にナノワイヤが成長したナノワイヤ付きフィルム、及び基材上へのナノワイヤの製造方法に関する。 The present invention relates to a film with nanowires in which nanowires are grown on a substrate, and a method for producing nanowires on a substrate.
酸化亜鉛等の金属酸化物からなるナノワイヤ（ナノロッド）の製造方法として、化学気相法、レーザー堆積法、水熱合成法など、様々な方法が知られている。 Various methods are known for producing nanowires (nanorods) made of metal oxides such as zinc oxide, such as chemical vapor deposition, laser deposition, and hydrothermal synthesis.
これらのうち、水熱合成法は、比較的簡単にナノワイヤを製造することができる。例えば、特許文献１には、表面にシード層が形成された基材を、硝酸亜鉛とヘキサメチレンテトラミンとを混合した水溶液に浸漬して、３０℃～１００℃の温度で、酸化亜鉛ナノワイヤを成長させる方法が開示されている。 Of these, hydrothermal synthesis is a relatively easy method for producing nanowires. For example, Patent Document 1 discloses a method in which a substrate having a seed layer formed on its surface is immersed in an aqueous solution of zinc nitrate and hexamethylenetetramine, and zinc oxide nanowires are grown at temperatures between 30°C and 100°C.
従来のナノワイヤの製造方法は、例外なく、基材の上に、予め、ナノワイヤを成長させるためのシード層を形成する必要があった。そのため、製造コストが高くなるという問題があった。また、シード層上に成長したナノワイヤを剥離回収する際、ナノワイヤにシード層の不純物が混入するという問題があった。 In all conventional nanowire manufacturing methods, it is necessary to form a seed layer on a base material in advance for growing nanowires. Therefore, there was a problem that the manufacturing cost increased. Furthermore, when the nanowires grown on the seed layer are peeled off and recovered, there is a problem in that impurities from the seed layer are mixed into the nanowires.
然るに、今まで、基材上にシード層を形成することなく、直接ナノワイヤを成長させる方法はなかった。従来技術においては、余計な粉末層の形成、並びに粉末の落下及びスキージにおける非効率的な作動を改善する方法については何ら提言が行われていない。 However, until now, there has been no method to grow nanowires directly on a substrate without forming a seed layer. The prior art does not provide any suggestions as to how to improve the formation of extra powder layers, as well as powder fallout and inefficient operation of the squeegee.
本発明は、かかる点に鑑みてなされたもので、その主な目的は、基材上にナノワイヤが直接成長したナノワイヤ付きフィルム、及び基材上に直接ナノワイヤを成長させるナノワイヤの製造方法を提供することにある。 The present invention has been made in consideration of these points, and its main objective is to provide a film with nanowires in which the nanowires are grown directly on a substrate, and a method for manufacturing nanowires in which the nanowires are grown directly on a substrate.
本発明に係るナノワイヤ付きフィルムは、非晶質な樹脂からなる基材と、基材上に直接成長した金属酸化物からなるナノワイヤとを備え、基材の表面に、ピッチが２～１００ｎｍで、深さが５～３０ｎｍの微細な凹凸構造が形成され、この凹凸構造からナノワイヤが直接成長している。 The film with nanowires according to the present invention includes a base material made of an amorphous resin and nanowires made of a metal oxide grown directly on the base material, and the nanowires are grown on the surface of the base material at a pitch of 2 to 100 nm. A fine uneven structure with a depth of 5 to 30 nm is formed, and nanowires grow directly from this uneven structure.
本発明に係るナノワイヤの製造方法は、非晶質な樹脂からなる基材を用意する工程（ａ）と、基材の表面に、ピッチが２～１００ｎｍで、深さが５～３０ｎｍの微細な凹凸構造を形成する工程（ｂ）と、基材を水熱合成溶液に浸漬させて、金属酸化物からなるナノワイヤを、基材の表面に形成した凹凸構造の上に直接成長させる工程（ｃ）とを含む。 The method for producing nanowires according to the present invention includes the step (a) of preparing a base material made of an amorphous resin, and forming fine particles on the surface of the base material with a pitch of 2 to 100 nm and a depth of 5 to 30 nm. Step (b) of forming an uneven structure; Step (c) of immersing the base material in a hydrothermal synthesis solution and growing nanowires made of metal oxide directly on the uneven structure formed on the surface of the base material. including.
本発明によれば、基材上にナノワイヤが直接成長したナノワイヤ付きフィルム、及び基材上に直接ナノワイヤを成長させるナノワイヤの製造方法を提供することができる。 According to the present invention, it is possible to provide a film with nanowires in which nanowires are grown directly on a base material, and a method for producing nanowires in which nanowires are grown directly on a base material.
本発明を説明する前に、本発明を想到するに至った経緯を説明する。 Before explaining the present invention, the circumstances that led to the idea of the present invention will be explained.
本願発明者は、シリコンウエハを基材に用いて、この基材上にナノワイヤを成長させる技術の開発を行っていた。なお、シード層は、シリコンウエハの表面に、クロムをスパッタ蒸着して形成していた。 The inventor of the present application has been developing a technique for growing nanowires on a silicon wafer as a base material. Note that the seed layer was formed by sputter-depositing chromium on the surface of the silicon wafer.
しかしながら、シリコンウエハは高価なため、製造コストを低減する目的で、樹脂フィルム（ポリカーボネート）を基材に用いて、この基材上にナノワイヤを成長させる技術の検討を行った。 However, silicon wafers are expensive, so in order to reduce manufacturing costs, we investigated a technology to use a resin film (polycarbonate) as a substrate and grow nanowires on this substrate.
しかしながら、樹脂フィルム上に、直接、クロムをスパッタ蒸着してシード層を形成することは難しいため、樹脂フィルム上に、スパッタ蒸着でシリコン酸化膜を形成し、このシリコン酸化膜上に、クロムをスパッタ蒸着してシード層を形成する必要があった。そのため、シリコン酸化膜の形成プロセスが新たに加わるため、製造コストの低減には至らなかった。 However, it is difficult to form a seed layer by directly sputtering chromium on a resin film, so a silicon oxide film is formed on the resin film by sputter deposition, and chromium is sputtered onto this silicon oxide film. It was necessary to form a seed layer by vapor deposition. As a result, a new process for forming a silicon oxide film is added, which has not resulted in a reduction in manufacturing costs.
そこで、本願発明者等は、樹脂フィルム上に、シード層を形成することなく、直接ナノワイヤを成長させることができないかと考えた。 Therefore, the inventors of the present invention considered whether it would be possible to grow nanowires directly on a resin film without forming a seed layer.
本願発明者等は、長年、樹脂フィルムに表面処理を施して、表面状態を変えることによって、母材とは異なる機能を付与する技術（表面改質技術）の研究を行っていた。例えば、樹脂フィルムに表面処理を施すことによって、樹脂フィルム上に形成する膜との密着性を向上させる技術の開発を行っていた。 The inventors of the present application have been conducting research for many years on a technology (surface modification technology) that imparts a function different from that of the base material by subjecting a resin film to surface treatment to change the surface condition. For example, we have been developing a technology that improves the adhesion of a film formed on a resin film by subjecting the resin film to surface treatment.
本願発明者等は、この表面改質技術に着目した。すなわち、表面改質技術を利用することによって、樹脂フィルムの表面に、ナノワイヤを成長させるようなシード性を発現させることができないかと考えた。例えば、樹脂フィルムに表面処理を施して、樹脂フィルムの表面に何らかの活性化を付与することによって、この活性化した状態が、ナノワイヤ成長の核になる可能性があると考えた。 The inventors of the present application focused on this surface modification technology. In other words, we thought that by using surface modification technology, it would be possible to make the surface of a resin film exhibit seeding properties that would allow nanowires to grow. For example, we thought that by surface-treating a resin film to impart some kind of activation to the surface of the resin film, this activated state could become the nucleus for nanowire growth.
そこで、本願発明者等は、非晶質な樹脂材料であるポリカーボネートフィルムを用いて、実験を行った。具体的には、ポリカーボネートフィルム（旭硝子製「カーボグラスＣ１１０Ｃ」）に表面処理を施した後、このポリカーボネートフィルムを、硝酸亜鉛（Ｚｎ（ＮＯ３）２／６Ｈ２Ｏ）と、ヘキサメチレンテトラミン（Ｃ６Ｈ１２Ｎ４）とを混合した水溶液に浸漬して、酸化亜鉛（ＺｎＯ）のナノワイヤを成長させた。なお、ここで用いた水熱合成法によるナノワイヤの成長は、公知の方法を用いた。 Therefore, the inventors of the present application conducted an experiment using a polycarbonate film, which is an amorphous resin material. Specifically, after surface-treating a polycarbonate film (“Carboglass C110C” manufactured by Asahi Glass), this polycarbonate film was treated with zinc nitrate (Zn(NO 3 ) 2 /6H 2 O) and hexamethylenetetramine (C 6H 12 N 4 ) to grow zinc oxide (ZnO) nanowires. Note that a known method was used to grow the nanowires by the hydrothermal synthesis method used here.
表面処理の条件を種々変えて実験を行ったところ、ある条件で表面処理を施したポリカーボネートフィルムの表面に、直接、ＺｎＯナノワイヤが成長しているという驚くべき事実を発見した。 After conducting experiments with various surface treatment conditions, they discovered the surprising fact that ZnO nanowires were growing directly on the surface of a polycarbonate film that had been surface treated under certain conditions.
図１（Ａ）、（Ｂ）は、ナノワイヤが成長した試料の明視野－走査透過型電子顕微鏡（ＢＦ－ＳＴＥＭ）の平面写真である。図１（Ａ）、（Ｂ）に示すように、ポリカーボネートフィルム１０上に、柱状のナノワイヤ２０が成長しているのが確認できる。 FIGS. 1(A) and 1(B) are bright field-scanning transmission electron microscopy (BF-STEM) planar photographs of a sample on which nanowires have grown. As shown in FIGS. 1A and 1B, columnar nanowires 20 can be seen growing on the polycarbonate film 10.
また、ナノワイヤが成長した試料の断面を、エネルギー分散型Ｘ線分析（ＥＤＸ）による元素分析を行った結果、ナノワイヤ２０が存在する領域において、亜鉛（Ｚｎ）、及び酸素（Ｏ）が存在していることが確認できた。一方、ポリカーボネートフィルム１０が存在する領域においては、炭素（Ｃ）、及び窒素（Ｎ）が存在していることが確認できた。この分析結果から、ポリカーボネートフィルム１０の上に、ＺｎＯナノワイヤ２０が直接成長していることが分かる。 Furthermore, as a result of elemental analysis using energy dispersive X-ray analysis (EDX) of the cross section of the sample where the nanowires had grown, it was found that zinc (Zn) and oxygen (O) were present in the region where the nanowires 20 were present. I was able to confirm that there was. On the other hand, it was confirmed that carbon (C) and nitrogen (N) were present in the region where the polycarbonate film 10 was present. From this analysis result, it can be seen that the ZnO nanowires 20 are grown directly on the polycarbonate film 10.
ところで、表面処理を施したポリカーボネートフィルム１０には、ＺｎＯナノワイヤが成長したのに対し、表面処理を施さなかったポリカーボネートフィルム１０には、ＺｎＯナノワイヤが全く成長しなかったという事実から、次のことが考えられる。 By the way, based on the fact that ZnO nanowires grew on the surface-treated polycarbonate film 10, but no ZnO nanowires grew on the polycarbonate film 10 that was not surface-treated, the following can be concluded. Conceivable.
すなわち、ポリカーボネートフィルム１０に表面処理を施すことによって、ポリカーボネートフィルム１０の表面が、ＺｎＯナノワイヤが成長できるような状態に変化していると考えられる。 That is, it is considered that by surface-treating the polycarbonate film 10, the surface of the polycarbonate film 10 is changed into a state in which ZnO nanowires can grow.
そこで、表面処理の条件を種々変えて行った実験において、ポリカーボネートフィルム１０の上にＺｎＯナノワイヤが成長した試料の断面を、走査透過型電子顕微鏡を用いてさらに詳しく調べた。その結果、図２に示すように、ＺｎＯナノワイヤが成長した試料では、ポリカーボネートフィルム１０の表面に、微細な凹凸構造１０Ａが形成されていることが分かった。 Therefore, in an experiment conducted with various surface treatment conditions, the cross section of a sample in which ZnO nanowires were grown on the polycarbonate film 10 was examined in more detail using a scanning transmission electron microscope. As a result, as shown in FIG. 2, it was found that in the sample in which ZnO nanowires were grown, a fine uneven structure 10A was formed on the surface of the polycarbonate film 10.
一方、表面処理を行っても、ポリカーボネートフィルム１０の表面に、微細な凹凸構造１０Ａが形成されていない試料では、ＺｎＯナノワイヤが成長していないことが分かった。 On the other hand, it was found that ZnO nanowires did not grow in the sample in which the fine uneven structure 10A was not formed on the surface of the polycarbonate film 10 even after the surface treatment.
すなわち、詳しいメカニズムは明らかではないが、ポリカーボネートフィルム１０の表面に形成された微細な凹凸構造１０Ａが、従来のシード層のように、ナノワイヤが成長する核の役目を果たしていると考えられる。 That is, although the detailed mechanism is not clear, it is thought that the fine uneven structure 10A formed on the surface of the polycarbonate film 10 plays the role of a nucleus on which nanowires grow, like a conventional seed layer.
なお、従来のシード層において、シード層の形成条件や、ナノワイヤの成長条件を変えることによって、ナノワイヤの成長状態が変わるように、本発明の微細な凹凸構造１０Ａにおいても、微細な凹凸構造１０Ａの形成条件や、ナノワイヤの成長条件を変えることによって、ナノワイヤの成長状態は変わる。 In addition, in the conventional seed layer, the growth condition of the nanowires changes by changing the seed layer formation conditions and the nanowire growth conditions, so also in the fine uneven structure 10A of the present invention. The growth state of nanowires can be changed by changing the formation conditions and nanowire growth conditions.
従って、微細な凹凸構造１０Ａの形状は、要求されるナノワイヤの仕様（密度、長さ、太さ等）に応じて適宜決めればよいが、ナノワイヤを安定して成長させるためには、微細な凹凸構造１０Ａを、ピッチ（凸部（凹部）と凸部（凹部）との間隔）が２～１００ｎｍで、深さが５～３０ｎｍの形状に形成することが好ましい。 Therefore, the shape of the fine unevenness structure 10A may be determined as appropriate depending on the required nanowire specifications (density, length, thickness, etc.), but in order to grow nanowires stably, it is necessary to It is preferable that the structure 10A is formed in a shape with a pitch (distance between convex portions (concave portions) and convex portions (concave portions)) of 2 to 100 nm and a depth of 5 to 30 nm.
本実施形態において、予めポリカーボネートフィルム１０の表面に微細な凹凸構造１０Ａを形成することによって、ポリカーボネートフィルム１０上に直接ＺｎＯナノワイヤを形成することが可能となる。 In this embodiment, by forming the fine uneven structure 10A on the surface of the polycarbonate film 10 in advance, it becomes possible to form ZnO nanowires directly on the polycarbonate film 10.
以上、説明したように、本実施形態におけるナノワイヤ付きフィルムは、非晶質な樹脂からなるポリカーボネートフィルム（基材）１０と、ポリカーボネートフィルム１０の上に直接成長したＺｎＯナノワイヤとを備え、ポリカーボネートフィルム１０の表面に、ピッチが２～１００ｎｍで、深さが５～３０ｎｍの微細な凹凸構造１０Ａが形成されている。また。ポリカーボネートフィルム１０の表面に、ポリカーボネートフィルムの粒界が析出していることが好ましい。これにより、ＺｎＯナノワイヤを安定して成長させることができる。 As described above, the film with nanowires in this embodiment includes the polycarbonate film (base material) 10 made of an amorphous resin and the ZnO nanowires grown directly on the polycarbonate film 10. A fine uneven structure 10A having a pitch of 2 to 100 nm and a depth of 5 to 30 nm is formed on the surface of the substrate. Also. It is preferable that grain boundaries of the polycarbonate film are precipitated on the surface of the polycarbonate film 10. Thereby, ZnO nanowires can be stably grown.
本実施形態によれば、非晶質な樹脂からなるポリカーボネートフィルム１０の上に、直接ＺｎＯナノワイヤを成長させることができるため、製造コストの低減を図ることができる。また、ＺｎＯナノワイヤには、従来のシード層からの拡散による不純物が存在しないため、不純物のないＺｎＯナノワイヤを剥離回収することができる。 According to this embodiment, ZnO nanowires can be grown directly on the polycarbonate film 10 made of amorphous resin, which reduces manufacturing costs. In addition, since the ZnO nanowires do not contain impurities that are caused by diffusion from a conventional seed layer, the ZnO nanowires can be peeled off and collected without impurities.
本実施形態におけるＺｎＯナノワイヤは、図３（Ａ）～（Ｄ）に示す工程により製造することができる。 The ZnO nanowire in this embodiment can be manufactured by the steps shown in FIGS. 3(A) to 3(D).
まず、図３（Ａ）に示すように、非晶質な樹脂からなるポリカーボネートフィルム１０を用意する。ポリカーボネートフィルム１０の厚みは、例えば、５０～５００μｍである。 First, as shown in FIG. 3(A), a polycarbonate film 10 made of amorphous resin is prepared. The thickness of the polycarbonate film 10 is, for example, 50 to 500 μm.
次に、図３（Ｂ）に示すように、ポリカーボネートフィルム１０を表面処理する。なお、表面処理は、ポリカーボネートフィルム１０の表面に、微細な凹凸構造１０Ａが形成される条件で行えばよい。なお、図３（Ｂ）に示した凹凸構造１０Ａは、実際の寸法を示すものではない。ここで、微細な凹凸構造１０Ａは、ピッチが２～１００ｎｍで、深さが５～３０ｎｍの形状に形成されていることが好ましい。 Next, as shown in FIG. 3(B), the polycarbonate film 10 is surface-treated. Note that the surface treatment may be performed under conditions such that a fine uneven structure 10A is formed on the surface of the polycarbonate film 10. Note that the uneven structure 10A shown in FIG. 3(B) does not indicate actual dimensions. Here, the fine uneven structure 10A is preferably formed with a pitch of 2 to 100 nm and a depth of 5 to 30 nm.
次に、図３（Ｃ）に示すように、ポリカーボネートフィルム１０を、容器３０に入れられた水熱合成溶液４０に浸漬させて、ポリカーボネートフィルム１０上に、ＺｎＯナノワイヤを直接成長させる。なお、ポリカーボネートフィルム１０は非常に薄いので、治具５０に固定した状態で、水熱合成溶液４０に浸漬させることが好ましい。具体的には、図５に示すように、ポリカーボネートフィルム１０をスライドガラス５２、５２で押さえ、このスライドガラス５２、５２を、ガラス板５１、５１で挟み込んで固定し、これを、ステンレス板５３に載せた状態で、水熱合成溶液４０に浸漬させる。 Next, as shown in FIG. 3C, the polycarbonate film 10 is immersed in the hydrothermal synthesis solution 40 contained in the container 30 to grow ZnO nanowires directly on the polycarbonate film 10. Note that since the polycarbonate film 10 is very thin, it is preferable to immerse it in the hydrothermal synthesis solution 40 while it is fixed to the jig 50. Specifically, as shown in FIG. 5, the polycarbonate film 10 is held down by slide glasses 52, 52, the slide glasses 52, 52 are sandwiched and fixed between glass plates 51, 51, and this is placed on a stainless steel plate 53. The mounted state is immersed in the hydrothermal synthesis solution 40.
水熱合成溶液４０は、例えば、硝酸亜鉛（Ｚｎ（ＮＯ３）２／６Ｈ２Ｏ）と、ヘキサメチレンテトラミン（Ｃ６Ｈ１２Ｎ４）とを混合した水溶液を用いることができる。なお、水熱合成溶液４０の濃度や、混合比、温度、浸漬時間等は、要求されるＺｎＯナノワイヤの仕様に応じて、適宜決めればよい。 As the hydrothermal synthesis solution 40, for example, an aqueous solution containing a mixture of zinc nitrate (Zn( NO3 ) 2 / 6H2O ) and hexamethylenetetramine ( C6H12N4 ) can be used. Note that the concentration, mixing ratio, temperature, immersion time, etc. of the hydrothermal synthesis solution 40 may be determined as appropriate depending on the required specifications of the ZnO nanowires.
ポリカーボネートフィルム１０を水熱合成溶液４０に所定時間浸漬した後、ＺｎＯナノワイヤが成長したポリカーボネートフィルム１０を洗浄、乾燥することによって、図４（Ｄ）に示すように、ＺｎＯナノワイヤ２０付きフィルムが得られる。 After immersing the polycarbonate film 10 in the hydrothermal synthesis solution 40 for a predetermined time, the polycarbonate film 10 on which the ZnO nanowires have grown is washed and dried to obtain a film with ZnO nanowires 20, as shown in FIG. 4(D).
以上、本発明を好適な実施形態により説明してきたが、こうした記述は限定事項ではなく、もちろん、種々の改変が可能である。 The present invention has been described above using preferred embodiments, but these descriptions are not limiting and, of course, various modifications are possible.
例えば、上記実施形態では、ポリカーボネートフィルム１０を基材に用いて、この基材上にＺｎＯナノワイヤを成長させたが、これに限定されず、非晶質な樹脂からなる基材であればよい。非晶質な樹脂としては、例えば、ポリスチレン、シクロオレフィン等を用いることができる。 For example, in the above embodiment, the polycarbonate film 10 is used as a base material and ZnO nanowires are grown on this base material, but the present invention is not limited thereto, and any base material may be used as long as it is made of an amorphous resin. As the amorphous resin, for example, polystyrene, cycloolefin, etc. can be used.
また、上記実施形態では、ポリカーボネートフィルム１０上にＺｎＯナノワイヤ２０を成長させたが、これに限定されず、酸化チタン（ＴｉＯ）等の他の金属酸化物からなるナノワイヤを成長させることができる。 Further, in the above embodiment, the ZnO nanowires 20 are grown on the polycarbonate film 10, but the present invention is not limited thereto, and nanowires made of other metal oxides such as titanium oxide (TiO) can be grown.
１０ ポリカーボネートフィルム（基材）
１０Ａ 微細な凹凸構造
２０ ＺｎＯナノワイヤ
３０ 容器
４０ 水熱合成溶液
５０ 治具
10 Polycarbonate film (substrate)
10A Fine uneven structure
20 ZnO nanowires
30 Container
40 Hydrothermal synthesis solution
50 Jig
Claims (7)
前記基材上に直接成長した金属酸化物からなるナノワイヤと
を備えたナノワイヤ付きフィルムであって、
前記基材の表面に、ピッチが２～１００ｎｍで、深さが５～３０ｎｍの微細な凹凸構造が形成され、該凹凸構造から前記ナノワイヤが直接成長している、ナノワイヤ付きフィルム。 A base material made of amorphous resin,
A nanowire-attached film comprising nanowires made of a metal oxide grown directly on the base material,
A film with nanowires, wherein a fine uneven structure with a pitch of 2 to 100 nm and a depth of 5 to 30 nm is formed on the surface of the base material, and the nanowires grow directly from the uneven structure.
前記基材の表面に、ピッチが２～１００ｎｍで、深さが５～３０ｎｍの微細な凹凸構造を形成する工程（ｂ）と、
前記基材を水熱合成溶液に浸漬させて、金属酸化物からなるナノワイヤを、前記基材の表面に形成した前記凹凸構造の上に直接成長させる工程（ｃ）と
を含むナノワイヤの製造方法。 Step (a) of preparing a base material made of an amorphous resin;
Step (b) of forming a fine uneven structure with a pitch of 2 to 100 nm and a depth of 5 to 30 nm on the surface of the base material;
A method for producing nanowires, comprising a step (c) of immersing the base material in a hydrothermal synthesis solution and growing nanowires made of metal oxide directly on the uneven structure formed on the surface of the base material.
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