JP5282289B2 - Method and device for forming concavo-convex structure on compound containing Si-O-Si bond - Google Patents
Method and device for forming concavo-convex structure on compound containing Si-O-Si bond Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 90
- 229910002808 Si–O–Si Inorganic materials 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000012780 transparent material Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 229920006254 polymer film Polymers 0.000 claims description 12
- 230000001678 irradiating effect Effects 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000003486 chemical etching Methods 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 3
- 229910018557 Si O Inorganic materials 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 31
- 229920000642 polymer Polymers 0.000 abstract description 8
- 230000001939 inductive effect Effects 0.000 abstract description 2
- 229920002050 silicone resin Polymers 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000000608 laser ablation Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000000018 DNA microarray Methods 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
本発明は、材料の微細加工法に係り、とくに任意の基体上に高分子膜を介してＳｉ−Ｏ−Ｓｉ結合を含む化合物膜を形成した場合の凹凸構造の形成法及びそれを用いたデバイスに関する。 The present invention relates to a material microfabrication method, and more particularly to a method for forming a concavo-convex structure when a compound film containing a Si-O-Si bond is formed on a given substrate via a polymer film, and a device using the same About.
電気電子工学、光工学あるいは医用・生体工学の分野において、Ｓｉ−Ｏ−Ｓｉ結合を含む化合物への微細加工法の確立は重要である。現在、Ｓｉ−Ｏ−Ｓｉ結合を含む化合物の微細加工は、モールディング法に依ることが多い。しかし、Ｓｉ−Ｏ−Ｓｉ結合を含む化合物膜の膜厚が薄く、加工サイズも小さくなるにつれて、あるいはＳｉ−Ｏ−Ｓｉ結合を含む化合物上に透明性材料が形成されている場合など、モールディング法では困難な場面もあり、他の新規微細加工法の確立が必要とされている。 In the fields of electrical and electronic engineering, optical engineering, and medical / bioengineering, it is important to establish a microfabrication method for a compound containing a Si—O—Si bond. At present, fine processing of a compound containing a Si—O—Si bond often depends on a molding method. However, as the film thickness of the compound film containing Si—O—Si bond is thin and the processing size is reduced, or when a transparent material is formed on the compound containing Si—O—Si bond, the molding method is used. However, there are some difficult situations, and it is necessary to establish other new microfabrication methods.
Ｓｉ−Ｏ−Ｓｉ結合を含む化合物表面乃至は、シリカガラス（ＳｉＯ２）を代表とする透明性材料が予め形成されたＳｉ−Ｏ−Ｓｉ結合を含む化合物表面に、膜厚変化を誘起せず、モールディング法では困難な微細凹凸構造を形成する手法の確立を課題とする。 No change in film thickness is induced on the compound surface containing Si—O—Si bonds or on the compound surface containing Si—O—Si bonds, in which a transparent material typified by silica glass (SiO 2 ) is formed in advance. Therefore, it is an object to establish a technique for forming a fine concavo-convex structure, which is difficult with the molding method.
そこで、本発明は、上記の点に鑑み、Ｓｉ−Ｏ−Ｓｉ結合を含む化合物表面乃至は、予めシリカガラス（ＳｉＯ２）を代表とする透明性材料が形成されたＳｉ−Ｏ−Ｓｉ結合を含む化合物表面に、膜厚変化を誘起せずに、微細な凹凸構造を得ることが可能な、凹凸構造の形成法及びその形成法を用いたデバイスを提供することを目的とする。 Therefore, in view of the above points, the present invention provides a compound surface containing a Si—O—Si bond or a Si—O—Si bond on which a transparent material typified by silica glass (SiO 2 ) is formed in advance. It is an object of the present invention to provide a method for forming a concavo-convex structure and a device using the formation method capable of obtaining a fine concavo-convex structure without inducing a change in film thickness on the surface of the compound.
本発明のその他の目的や新規の特徴は後述の実施の形態において明らかにする。 Other objects and novel features of the present invention will be clarified in embodiments described later.
上記目的を達成するために、本発明に係る第１の態様のＳｉ−Ｏ−Ｓｉ結合を含む化合物への凹凸構造の形成法は、基体上に高分子膜を介してＳｉ−Ｏ−Ｓｉ結合を含む化合物膜を形成し、その表面から波長１９０ｎｍより長く４００ｎｍ以下の光を照射することにより、前記Ｓｉ−Ｏ−Ｓｉ結合を含む化合物膜に、膜厚変化を与えることなく、露光部分のみを沈下させることを特徴としている。 In order to achieve the above object, a method for forming a concavo-convex structure on a compound containing a Si—O—Si bond according to the first aspect of the present invention comprises a Si—O—Si bond via a polymer film on a substrate. The compound film containing the Si—O—Si bond is irradiated to the compound film containing the Si—O—Si bond by irradiating light having a wavelength longer than 190 nm and not longer than 400 nm from the surface thereof, so that only the exposed portion is exposed. It is characterized by being subsided.
本発明に係る第２の態様のＳｉ−Ｏ−Ｓｉ結合を含む化合物への凹凸構造の形成法は、基体上に高分子膜を介して透明性材料膜とＳｉ−Ｏ−Ｓｉ結合を含む化合物膜の積層構造を形成し、その表面から波長１９０ｎｍより長く４００ｎｍ以下の光を照射することにより、前記透明性材料膜とＳｉ−Ｏ−Ｓｉ結合を含む化合物膜の積層構造に、膜厚変化を与えることなく、露光部分のみを沈下させることを特徴としている。 The method for forming a concavo-convex structure on a compound containing a Si—O—Si bond according to the second aspect of the present invention is a compound containing a transparent material film and a Si—O—Si bond via a polymer film on a substrate. By forming a laminated structure of the film and irradiating light having a wavelength longer than 190 nm and shorter than or equal to 400 nm from the surface, the film thickness change is made to the laminated structure of the transparent material film and the compound film containing the Si—O—Si bond. It is characterized by sinking only the exposed portion without giving.
本発明に係る第３の態様のＳｉ−Ｏ−Ｓｉ結合を含む化合物への凹凸構造の形成法は、基体上に高分子膜を介してＳｉ−Ｏ−Ｓｉ結合を含む化合物膜を形成し、その表面から予め波長１９０ｎｍ以下の光を照射してシリカガラス層を形成した後、波長１９０ｎｍより長く４００ｎｍ以下の光を照射することにより、前記シリカガラス層が形成されたＳｉ−Ｏ−Ｓｉ結合を含む化合物膜に、膜厚変化を与えることなく、露光部分のみを沈下させることを特徴としている。 According to the third aspect of the present invention, in the method for forming a concavo-convex structure on a compound containing a Si—O—Si bond, a compound film containing a Si—O—Si bond is formed on a substrate via a polymer film, After the surface is irradiated with light having a wavelength of 190 nm or less in advance to form a silica glass layer, the silica glass layer is formed by irradiating with light having a wavelength longer than 190 nm and not longer than 400 nm, thereby forming the Si—O—Si bond. It is characterized in that only the exposed portion is allowed to sink without giving a film thickness change to the compound film.
本発明に係る第４の態様のＳｉ−Ｏ−Ｓｉ結合を含む化合物への凹凸構造の形成法は、基体上に高分子膜を介して透明性材料膜とＳｉ−Ｏ−Ｓｉ結合を含む化合物膜の積層構造を形成し、その表面から波長１９０ｎｍより長く４００ｎｍ以下の光を照射することにより、前記透明性材料膜とＳｉ−Ｏ−Ｓｉ結合を含む化合物膜の積層構造に、膜厚変化を与えることなく、露光部分のみを沈下させ、その後、前記透明性材料膜のみをエッチングすることを特徴としている。 According to the fourth aspect of the present invention, there is provided a method for forming a concavo-convex structure on a compound containing a Si—O—Si bond, wherein the compound contains a transparent material film and a Si—O—Si bond via a polymer film on a substrate. By forming a laminated structure of the film and irradiating light having a wavelength longer than 190 nm and shorter than or equal to 400 nm from the surface, the film thickness change is made to the laminated structure of the transparent material film and the compound film containing the Si—O—Si bond. It is characterized in that only the exposed portion is sunk without giving, and then only the transparent material film is etched.
本発明に係る第５の態様のＳｉ−Ｏ−Ｓｉ結合を含む化合物への凹凸構造の形成法は、基体上に高分子膜を介してＳｉ−Ｏ−Ｓｉ結合を含む化合物膜を形成し、その表面から予め波長１９０ｎｍ以下の光を照射してシリカガラス層を形成した後、波長１９０ｎｍより長く４００ｎｍ以下の光を照射することにより、前記シリカガラス層が形成されたＳｉ−Ｏ−Ｓｉ結合を含む化合物膜に、膜厚変化を与えることなく、露光部分のみを沈下させ、さらにその後、前記シリカガラス層のみを化学エッチングすることを特徴としている。 According to the fifth aspect of the present invention, in the method for forming a concavo-convex structure on a compound containing a Si—O—Si bond, a compound film containing a Si—O—Si bond is formed on a substrate via a polymer film, After the surface is irradiated with light having a wavelength of 190 nm or less in advance to form a silica glass layer, the silica glass layer is formed by irradiating with light having a wavelength longer than 190 nm and not longer than 400 nm, thereby forming the Si—O—Si bond. It is characterized in that only the exposed portion is allowed to sink without giving a change in film thickness to the compound film, and then only the silica glass layer is chemically etched.
本発明に係る第６の態様のデバイスは、前記第１，２，３，４又は５の態様による凹凸構造を備えることを特徴としている。 A device according to a sixth aspect of the present invention is characterized by comprising the uneven structure according to the first, second, third, fourth or fifth aspect.
なお、以上の構成要素の任意の組合せ、本発明の表現を方法やシステムなどの間で変換したものもまた、本発明の態様として有効である。 It should be noted that any combination of the above-described constituent elements, and those obtained by converting the expression of the present invention between methods and systems are also effective as aspects of the present invention.
本発明によれば、Ｓｉ−Ｏ−Ｓｉ結合を含む化合物表面乃至は、シリカガラスを代表とする透明性材料が予め形成されたＳｉ−Ｏ−Ｓｉ結合を含む化合物表面に、膜厚変化を誘起せず、微細凹凸構造を形成することにより、Ｓｉ−Ｏ−Ｓｉ結合を含む化合物を基礎とした新規デバイスが確立でき、電気電子工学、光工学あるいは医用・生体工学分野での材料開発ならびにデバイス作製の基盤技術として必要不可欠な技術となる。また本発明は、これら分野にとどまらず、今後Ｓｉ−Ｏ−Ｓｉ結合を含む化合物を基にして発展する材料科学の分野に多大に利用可能である。 According to the present invention, a change in film thickness is induced on the surface of a compound containing Si—O—Si bonds or on the surface of a compound containing Si—O—Si bonds in which a transparent material typified by silica glass is formed in advance. Without forming a fine concavo-convex structure, a new device based on a compound containing a Si-O-Si bond can be established. Material development and device fabrication in the fields of electrical and electronic engineering, optical engineering, or medical / bioengineering It becomes an indispensable technology as a basic technology of The present invention is not limited to these fields, and can be used greatly in the field of material science that will develop based on compounds containing Si-O-Si bonds.
以下、図面を参照しながら本発明の好適な実施の形態を詳述する。なお、各図面に示される同一または同等の構成要素、部材、処理等には同一の符号を付し、適宜重複した説明は省略する。また、実施の形態は発明を限定するものではなく例示であり、実施の形態に記述されるすべての特徴やその組み合わせは必ずしも発明の本質的なものであるとは限らない。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In addition, the same code | symbol is attached | subjected to the same or equivalent component, member, process, etc. which are shown by each drawing, and the overlapping description is abbreviate | omitted suitably. In addition, the embodiments do not limit the invention but are exemplifications, and all features and combinations thereof described in the embodiments are not necessarily essential to the invention.
図１は本発明に係るＳｉ−Ｏ−Ｓｉ結合を含む化合物への凹凸構造の形成法の第１の実施の形態であって、実験概略構成を示す。この第１の実施の形態においては、任意の基体１上に高分子プライマー２を介してＳｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３を形成した試料を用意し、波長１９０ｎｍより長く４００ｎｍ以下のレーザー光４をＳｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３表面から照射する。図１（Ａ）はレーザー光照射前、同図（Ｂ）はレーザー光照射後であり、同図（Ｂ）のようにレーザー光照射によってＳｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３自体には、膜厚変化を与えることなく、露光部分のみをマイクロ/ナノオーダーで沈下させることができる。 FIG. 1 is a first embodiment of a method for forming a concavo-convex structure on a compound containing a Si—O—Si bond according to the present invention, and shows a schematic configuration of an experiment. In the first embodiment, a sample is prepared in which a solid compound film 3 including Si—O—Si bonds is formed on an arbitrary substrate 1 via a polymer primer 2 and has a wavelength longer than 190 nm and not longer than 400 nm. Laser light 4 is irradiated from the surface of the solid compound film 3 containing Si—O—Si bonds. FIG. 1 (A) is before laser beam irradiation, and FIG. 1 (B) is after laser beam irradiation. As shown in FIG. 1 (B), the solid compound film 3 itself containing Si—O—Si bonds is irradiated by laser beam irradiation. Can sink only the exposed portion in micro / nano order without changing the film thickness.
その際、Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３上に予めマスクを置いてレーザー光４を位置選択的に照射しても良い。また、Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３上でレーザー光を結像させたり、あるいは干渉させたりして位置選択的に照射を行っても良い。 At that time, a laser beam 4 may be selectively irradiated by placing a mask on the solid compound film 3 including Si—O—Si bonds. Further, irradiation may be performed in a position-selective manner by forming an image of laser light or causing interference on the solid compound film 3 containing Si—O—Si bonds.
ここで、基体１は任意の材質であり、ポリカーボネート等の有機材料やガラス等の無機材料が使用可能である。高分子製プライマー２はＳｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３の付着性を良好とするために基体１上に形成される高分子膜であり、その膜厚は例えば１００μｍから数μｍである。高分子製プライマー２は汎用プラスチック又はエンジニアリング・プラスチックのいずれでもよく、例えばアクリル系樹脂、ポリイミド樹脂等である。Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３は例えばシリコーン樹脂、シリコーンゴム等である。Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３の表面に照射するレーザ光の波長は、波長１９０ｎｍより短い場合にはＳｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３がＳｉＯ２に改質される現象が発生しやすくなるため、好ましくない。また、波長４００ｎｍより長い場合には沈下させる作用が無くなってしまう。 Here, the substrate 1 is an arbitrary material, and an organic material such as polycarbonate or an inorganic material such as glass can be used. The polymer primer 2 is a polymer film formed on the substrate 1 in order to improve the adhesion of the solid compound film 3 containing Si—O—Si bonds, and the film thickness is, for example, 100 μm to several μm. is there. The polymer primer 2 may be a general-purpose plastic or an engineering plastic, such as an acrylic resin or a polyimide resin. The solid compound film 3 containing a Si—O—Si bond is, for example, a silicone resin, silicone rubber, or the like. When the wavelength of the laser beam applied to the surface of the solid compound film 3 containing Si—O—Si bonds is shorter than 190 nm, the solid compound film 3 containing Si—O—Si bonds is modified to SiO 2. This is not preferable because the phenomenon tends to occur. Further, when the wavelength is longer than 400 nm, the action of sinking is lost.
前記露光部分の沈下量は、例えば高分子製プライマー２の膜厚が１００μｍ程度であるとき、最大５０μｍである。 For example, when the film thickness of the polymer primer 2 is about 100 μm, the sinking amount of the exposed portion is 50 μm at the maximum.
この第１の実施の形態によれば、Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３に膜厚変化を与えることなく、レーザー光４の露光部分のみをマイクロ/ナノオーダー（例えば５０μｍから数ｎｍ）で沈下させることができる。 According to the first embodiment, only the exposed portion of the laser beam 4 is micro / nano order (for example, 50 μm to several nm) without changing the film thickness of the solid compound film 3 containing Si—O—Si bonds. ).
図２は本発明に係るＳｉ−Ｏ−Ｓｉ結合を含む化合物への凹凸構造の形成法の第２の実施の形態である。第２の実施の形態においては、任意の基体１上に高分子プライマー２を介して、Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３及び透明性材料膜５の積層構造を形成した試料を用意し、波長１９０ｎｍより長く４００ｎｍ以下のレーザー光４を透明性材料膜５の表面から照射する。図２（Ａ）はレーザー光照射前、同図（Ｂ）はレーザー光照射後であり、同図（Ｂ）のようにレーザー光照射によってＳｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３及び透明性材料膜５の積層構造自体には、膜厚変化を与えることなく、露光部分のみをマイクロ/ナノオーダーで沈下させることができる。 FIG. 2 shows a second embodiment of the method for forming a concavo-convex structure on a compound containing a Si—O—Si bond according to the present invention. In the second embodiment, a sample in which a laminated structure of a solid compound film 3 containing a Si—O—Si bond and a transparent material film 5 is formed on an arbitrary substrate 1 via a polymer primer 2 is prepared. Then, the laser beam 4 having a wavelength longer than 190 nm and not longer than 400 nm is irradiated from the surface of the transparent material film 5. 2A is before laser light irradiation, and FIG. 2B is after laser light irradiation. As shown in FIG. 2B, the solid compound film 3 containing a Si—O—Si bond and transparent by laser light irradiation. In the laminated structure itself of the conductive material film 5, only the exposed portion can be sunk in the micro / nano order without changing the film thickness.
その際、前記積層構造の透明性材料膜５上に予めマスクを置いてレーザー光４を位置選択的に照射しても良い。また、透明性材料膜５上でレーザー光を結像させたり、あるいは干渉させたりして位置選択的に照射を行っても良い。 At that time, a mask may be previously placed on the transparent material film 5 having the laminated structure, and the laser beam 4 may be selectively irradiated. Alternatively, the laser beam may be imaged on the transparent material film 5 or may be irradiated in a position-selective manner by causing interference.
前記透明性材料膜５の材質は、ガラス、酸化アルミニウムの透明膜等の無機材料のほか、レーザ光照射により変質しないものであれは、透明な有機材料の使用も可能である。 As the material of the transparent material film 5, a transparent organic material can be used as long as it is an inorganic material such as glass and a transparent film of aluminum oxide, or the like, as long as the material is not altered by laser light irradiation.
さらに、基体１上に高分子プライマー２を介してＳｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３を形成し、この表面に予め波長１９０ｎｍ以下の光（例えば波長１５７ｎｍのＦ２レーザー光）を照射して固体化合物膜３の表面をシリカガラス層に改質し、このシリカガラス層を透明性材料膜５として利用することも可能である。Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物のシリカガラスへの改質については特開２００４−１２３８１６の技術が利用可能である。 Further, a solid compound film 3 including a Si—O—Si bond is formed on the substrate 1 via the polymer primer 2, and light having a wavelength of 190 nm or less (for example, F 2 laser light having a wavelength of 157 nm) is irradiated on the surface in advance. Then, the surface of the solid compound film 3 can be modified to a silica glass layer, and this silica glass layer can be used as the transparent material film 5. Japanese Patent Application Laid-Open No. 2004-123816 can be used to modify a solid compound containing a Si—O—Si bond into silica glass.
この第２の実施の形態によれば、Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３及び透明性材料膜５の積層構造に、膜厚変化を与えることなく、レーザー光４の露光部分のみをマイクロ/ナノオーダーで沈下させることができる。 According to the second embodiment, only the exposed portion of the laser beam 4 is applied to the laminated structure of the solid compound film 3 including the Si—O—Si bond and the transparent material film 5 without changing the film thickness. It can be sunk in micro / nano order.
図３は本発明に係るＳｉ−Ｏ−Ｓｉ結合を含む化合物への凹凸構造の形成法の第３の実施の形態である。この場合、図３（Ａ）は第２の実施の形態の図２（Ｂ）のレーザー光照射後の状態であり、Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３及び透明性材料膜５の積層構造自体には、膜厚変化を与えることなく、露光部分のみをマイクロ/ナノオーダーで沈下させている。その後、図３（Ａ）の透明性材料膜５のみをエッチングし、Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３を表面とする凹凸構造を形成している。 FIG. 3 shows a third embodiment of the method for forming a concavo-convex structure on a compound containing a Si—O—Si bond according to the present invention. In this case, FIG. 3A shows a state after the laser light irradiation of FIG. 2B of the second embodiment, and the solid compound film 3 and the transparent material film 5 including the Si—O—Si bond. In the laminated structure itself, only the exposed part is sunk in the micro / nano order without changing the film thickness. Thereafter, only the transparent material film 5 in FIG. 3A is etched to form a concavo-convex structure having the surface of the solid compound film 3 containing Si—O—Si bonds.
このとき、透明性材料膜５のエッチングはマスキングにより部分的に行っても良く、凹凸構造の表面が透明性材料膜５の部分とＳｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３の部分とが共存する場合もある。 At this time, the etching of the transparent material film 5 may be partially performed by masking, and the surface of the concavo-convex structure has a part of the transparent material film 5 and a part of the solid compound film 3 containing Si—O—Si bonds. May coexist.
なお、固体化合物膜３の表面に、予め波長１９０ｎｍ以下の光を照射してシリカガラス層に改質し、このシリカガラス層を透明性材料膜５とした場合、シリカガラス層を化学エッチングで除去可能である。 In addition, when the surface of the solid compound film 3 is previously irradiated with light having a wavelength of 190 nm or less to be modified into a silica glass layer, and this silica glass layer is used as the transparent material film 5, the silica glass layer is removed by chemical etching. Is possible.
この第３の実施の形態によれば、透明性材料膜５のみがエッチングされ、Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３を表面とする微細な凹凸構造が形成できる。また凹凸構造の表面を、透明性材料膜５の部分とＳｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３の部分とが共存した形にすることもできる。 According to the third embodiment, only the transparent material film 5 is etched, and a fine concavo-convex structure having the surface of the solid compound film 3 containing Si—O—Si bonds can be formed. In addition, the surface of the concavo-convex structure can be formed such that the portion of the transparent material film 5 and the portion of the solid compound film 3 containing Si—O—Si bonds coexist.
上記第１、第２又は第３の実施の形態に係るＳｉ−Ｏ−Ｓｉ結合を含む化合物への凹凸構造の形成法で得られた微細な凹凸構造を有するデバイスは、例えば基体１及びその上の積層膜（Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜３のみ、あるいは固体化合物膜３及び透明性材料膜５の両者）を所要の大きさに切断することにより作製され、凹凸構造を利用したバイオチップ等の用途に使用できる。また、微細凹凸構造の撥水性を利用した撥水性デバイスとしての応用も可能である。 A device having a fine concavo-convex structure obtained by the method of forming a concavo-convex structure on the compound containing the Si—O—Si bond according to the first, second, or third embodiment includes, for example, the substrate 1 and the top thereof. The laminated film (only the solid compound film 3 containing Si—O—Si bond, or both the solid compound film 3 and the transparent material film 5) is cut into a required size, and uses an uneven structure. It can be used for applications such as biochips. Moreover, application as a water-repellent device using the water-repellent property of the fine uneven structure is also possible.
以下、本発明に係るＳｉ−Ｏ−Ｓｉ結合を含む化合物への凹凸構造の形成法を実施例で詳述する。 Hereinafter, a method for forming a concavo-convex structure on a compound containing a Si—O—Si bond according to the present invention will be described in detail in Examples.
ポリカーボネート基体上に、アクリル系プライマー（膜厚４μｍ）を介して、Ｓｉ−Ｏ−Ｓｉ結合を含む化合物（シリコーン樹脂）膜（膜厚３．７μｍ）を形成した。その後、波長１９３ｎｍのＡｒＦエキシマレーザー光を、エネルギー密度１０ｍＪ／ｃｍ２、繰り返し周波数１０Ｈｚ、照射時間６０秒で照射した。その際、シリコーン樹脂膜上にＮｉ製マスク（開口５０μｍ角メッシュ）を設置し、レーザー光照射を位置選択的に行った。その結果、シリコーン樹脂表面に７０ｎｍの深さで凹凸構造を形成することができた。この凹凸構造の深さは、レーザーアブレーションが発生しない範囲でレーザー光のエネルギー密度及び照射時間を変えることで、変化させることができた。 A compound (silicone resin) film (film thickness 3.7 μm) containing Si—O—Si bonds was formed on a polycarbonate substrate via an acrylic primer (film thickness 4 μm). Thereafter, ArF excimer laser light having a wavelength of 193 nm was irradiated at an energy density of 10 mJ / cm 2 , a repetition frequency of 10 Hz, and an irradiation time of 60 seconds. At that time, a Ni mask (opening 50 μm square mesh) was placed on the silicone resin film, and laser beam irradiation was performed selectively. As a result, a concavo-convex structure could be formed at a depth of 70 nm on the surface of the silicone resin. The depth of the concavo-convex structure could be changed by changing the energy density and irradiation time of the laser beam within a range where laser ablation does not occur.
上記の凹凸構造は、ポリカーボネート基体上にＳｉ−Ｏ−Ｓｉ結合を含む化合物（シリコーン樹脂）膜を直接形成した場合には認められなかった。また、ポリカーボネート基体上にアクリル系プライマー（膜厚４μｍ）を介してＳｉ−Ｏ−Ｓｉ結合を含む化合物（シリコーン樹脂）膜（膜厚３．７μｍ）を形成した試料において、アクリル系プライマーをレーザーアブレーションにより除去した場合、Ｓｉ−Ｏ−Ｓｉ結合を含む化合物（シリコーン樹脂）膜の剥離が起こり、上記凹凸構造は形成されなかった。 The above uneven structure was not observed when a compound (silicone resin) film containing a Si—O—Si bond was directly formed on a polycarbonate substrate. In addition, laser ablation of an acrylic primer was performed on a sample in which a compound (silicone resin) film (silicon film) containing a Si—O—Si bond (film thickness 3.7 μm) was formed on a polycarbonate substrate via an acrylic primer (film thickness 4 μm). When removed by this, the compound (silicone resin) film containing the Si—O—Si bond was peeled off, and the uneven structure was not formed.
ポリカーボネート基体上にアクリル系プライマーを介してＳｉ−Ｏ−Ｓｉ結合を含む化合物（シリコーン樹脂）膜（膜厚３．７μｍ）を形成し、その表面から予め波長１５７ｎｍのフッ素レーザー光を、エネルギー密度１４ｍＪ／ｃｍ２、繰り返し周波数１０Ｈｚ、照射時間３０秒で照射しシリカガラス（ＳｉＯ２）層（膜厚０．５μｍ）を形成した。その後、波長１９３ｎｍのＡｒＦエキシマレーザー光を、エネルギー密度１０ｍＪ／ｃｍ２、繰り返し周波数１０Ｈｚ、照射時間６０秒で照射した。その際、シリコーン樹脂膜上にＮｉ製マスク（開口５０μｍ角メッシュ）を設置し、レーザー光照射を位置選択的に行った。その結果、シリコーン樹脂表面に７０ｎｍの深さで凹凸構造を形成することができた（図４の写真図参照）。この凹凸構造の深さは、レーザーアブレーションが発生しない範囲でレーザー光のエネルギー密度及び照射時間を変えることで、変化させることができた。 A compound (silicone resin) film (thickness 3.7 μm) containing a Si—O—Si bond is formed on a polycarbonate substrate via an acrylic primer, and a fluorine laser beam having a wavelength of 157 nm is applied in advance from the surface to an energy density of 14 mJ. Irradiation was performed at / cm 2 , a repetition frequency of 10 Hz, and an irradiation time of 30 seconds to form a silica glass (SiO 2 ) layer (film thickness 0.5 μm). Thereafter, ArF excimer laser light having a wavelength of 193 nm was irradiated at an energy density of 10 mJ / cm 2 , a repetition frequency of 10 Hz, and an irradiation time of 60 seconds. At that time, a Ni mask (opening 50 μm square mesh) was placed on the silicone resin film, and laser beam irradiation was performed selectively. As a result, a concavo-convex structure could be formed on the surface of the silicone resin at a depth of 70 nm (see the photographic diagram in FIG. 4). The depth of the concavo-convex structure could be changed by changing the energy density and irradiation time of the laser beam within a range where laser ablation does not occur.
上記で形成した凹凸構造は、予め形成したシリカガラス（ＳｉＯ２）層が、レーザー光によりアブレーションされたことによるものではないことが赤外分光分析により判明した。また、この凹凸構造形成において、シリカガラス（ＳｉＯ２）層にクラックが発生することはなかった（図４の写真図参照）。 It was found by infrared spectroscopic analysis that the concavo-convex structure formed above was not due to the ablation of a previously formed silica glass (SiO 2 ) layer by laser light. Furthermore, in this uneven structure formed, the silica glass cracks (SiO 2) layer did not occur (see photograph of FIG. 4).
上記試料を、１重量％のフッ酸水溶液で６０秒間化学エッチングを行うと、予め形成したシリカガラス（ＳｉＯ２）層（膜厚０．５μｍ）のみが除去され、シリコーン樹脂を表面とした凹凸構造が形成できた。また、マスキングにより化学エッチング部分を限定することにより、シリカガラス（ＳｉＯ２）の部分とシリコーン樹脂の部分とが共存した形とすることもできた。 When the sample is subjected to chemical etching with a 1% by weight hydrofluoric acid aqueous solution for 60 seconds, only the preformed silica glass (SiO 2 ) layer (thickness 0.5 μm) is removed, and the concavo-convex structure with the silicone resin as the surface Was formed. Further, by limiting the chemical etching portion by masking, the silica glass (SiO 2 ) portion and the silicone resin portion could coexist.
上記各実施例で述べたように、本発明によれば、Ｓｉ−Ｏ−Ｓｉ結合を含む化合物膜あるいは、透明性材料膜とＳｉ−Ｏ−Ｓｉ結合を含む化合物膜の積層構造に、膜厚変化を与えることなく、露光部分のみをマイクロ/ナノオーダーで凹凸構造を形成することにより、モールディング法では困難な場合の新規微細加工法が確立できるようになる。この結果は、電気電子工学、光工学あるいは医用・生体工学分野での材料開発ならびにデバイス作製に適用可能になるなど、その用途はあらゆる分野で有用である。 As described in each of the above embodiments, according to the present invention, the thickness of the compound film containing Si—O—Si bonds or the laminated structure of the transparent material film and the compound film containing Si—O—Si bonds is increased. By forming a concavo-convex structure in the micro / nano order only in the exposed portion without giving any change, a new fine processing method can be established when difficult by the molding method. The results are useful in all fields, such as being applicable to material development and device fabrication in the fields of electrical and electronic engineering, optical engineering, or medical / bioengineering.
以上、本発明の実施の形態及び実施例について説明してきたが、本発明はこれに限定されることなく請求項の記載の範囲内において各種の変形、変更が可能なことは当業者には自明であろう。 Although the embodiments and examples of the present invention have been described above, it is obvious to those skilled in the art that the present invention is not limited thereto and various modifications and changes can be made within the scope of the claims. Will.
１ 基体
２ 高分子製プライマー
３ Ｓｉ−Ｏ−Ｓｉ結合を含む固体化合物膜
４ レーザー光
５ 透明性材料膜
1 Base 2 Polymer Primer 3 Solid Compound Film Containing Si—O—Si Bond 4 Laser Light 5 Transparent Material Film
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