JP2015141986A - Method of manufacturing structure - Google Patents

Method of manufacturing structure Download PDF

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JP2015141986A
JP2015141986A JP2014013590A JP2014013590A JP2015141986A JP 2015141986 A JP2015141986 A JP 2015141986A JP 2014013590 A JP2014013590 A JP 2014013590A JP 2014013590 A JP2014013590 A JP 2014013590A JP 2015141986 A JP2015141986 A JP 2015141986A
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coating film
solvent
mold
coating
base material
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JP6427885B2 (en
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祐樹 有塚
Yuki Aritsuka
祐樹 有塚
尚子 中田
Naoko Nakada
尚子 中田
伊藤　公夫
Kimio Ito
公夫 伊藤
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Dai Nippon Printing Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To shorten the time required for reducing a solvent contained in a coating film in the room temperature imprint.SOLUTION: A method of manufacturing a structure includes the steps of: forming a coating film by coating a coating agent containing an inorganic material and a solvent on a base material; bringing the coating film into contact with a mold in which the side opposite to at least the coating film has solvent absorbency; and reducing the solvent to cure the coating film while interposing the coating film between the base material and the mold under reduced pressure.

Description

本発明は、構造体の製造方法に関する。   The present invention relates to a method for manufacturing a structure.

微細パターン形成技術として注目されている、室温ナノインプリントリソグラフィー技術については、特許文献１に開示されている。ＳＯＧ（Spin-On-Glass）等の材料と溶剤を含む塗布剤を基板表面に塗布して塗布膜を形成した後、溶剤が揮発し硬化が完了する前に塗布膜にモールドでインプリントし、その後、モールドを塗布膜から離間することでナノ精度のＳｉＯ２微細パターンを形成することができる。 A room temperature nanoimprint lithography technique that is attracting attention as a fine pattern formation technique is disclosed in Patent Document 1. After applying a coating agent containing a material such as SOG (Spin-On-Glass) and a solvent to the substrate surface to form a coating film, the solvent is volatilized and imprinted on the coating film with a mold before curing is completed. Thereafter, a nano-accurate SiO 2 fine pattern can be formed by separating the mold from the coating film.

また、溶剤吸収性を有するポリジメチルシロキサン（以下、「ＰＤＭＳ」と称する。）製のモールドを用いてＳＯＧ材料にインプリントを行い、モールド側に塗布膜に含まれる溶剤を吸収させて、パターンを形成する技術も、非特許文献１に開示されている。   In addition, the SOG material is imprinted using a mold made of polydimethylsiloxane having solvent absorbability (hereinafter referred to as “PDMS”), and the solvent contained in the coating film is absorbed on the mold side to form a pattern. The forming technique is also disclosed in Non-Patent Document 1.

特開２００３−１００６０９号公報Japanese Patent Laid-Open No. 2003-100609

“Room-Temperature Nanoimpringing Using Liquid-Phase Hydrogen Silsesquioxane with Hard Poly (dimethylsiloxane) Mold, Jpn. J. Appl. Phys. 49 (2010) 06GL 13 (5 pages).“Room-Temperature Nanoimpringing Using Liquid-Phase Hydrogen Silsesquioxane with Hard Poly (dimethylsiloxane) Mold, Jpn. J. Appl. Phys. 49 (2010) 06GL 13 (5 pages).

しかしながら、溶剤をモールド側に吸収させるには時間がかかるという問題があった。   However, there is a problem that it takes time to absorb the solvent on the mold side.

本発明は、室温インプリントにおいて、塗布膜に含まれる溶剤を減少させる時間を短縮することを目的とする。   An object of the present invention is to shorten the time for reducing the solvent contained in a coating film in room temperature imprinting.

本発明の一実施の形態は、基材に、無機材料と溶剤とを含有する塗布剤を塗布することにより塗布膜を形成する工程と、前記塗布膜と、少なくとも前記塗布膜に対向する側が溶剤吸収性を有するモールドとを接触させる工程と、減圧下で前記塗布膜を前記基材と前記モールドとの間に介在させた状態とし、前記溶剤を減少させて前記塗布膜を硬化させる工程と、を有することを特徴とする構造体の製造方法である。   In one embodiment of the present invention, a step of forming a coating film by applying a coating agent containing an inorganic material and a solvent to a substrate, the coating film, and at least the side facing the coating film is a solvent A step of contacting an absorptive mold, a state in which the coating film is interposed between the base material and the mold under reduced pressure, and a step of curing the coating film by reducing the solvent; It is a manufacturing method of the structure characterized by having.

本発明の一実施の形態の別の態様として、前記基材が溶剤吸収性を有していてもよい。   As another aspect of one embodiment of this invention, the said base material may have solvent absorptivity.

本発明の一実施の形態の別の態様として、前記無機材料は、シロキサンポリマーであっても良い。   As another aspect of an embodiment of the present invention, the inorganic material may be a siloxane polymer.

本発明の一実施の形態の別の態様として、前記モールドは、ポーラス構造を有する樹脂であることが好ましい。   As another aspect of an embodiment of the present invention, the mold is preferably a resin having a porous structure.

本発明によれば、室温インプリントにおいて、塗布膜に含まれる溶剤を減少させる時間を短縮することができる。   ADVANTAGE OF THE INVENTION According to this invention, the time which reduces the solvent contained in a coating film can be shortened in room temperature imprint.

本発明の一実施の形態による構造体の製造工程を示す図である。It is a figure which shows the manufacturing process of the structure by one embodiment of this invention.

以下、本発明の一実施の形態による構造体の製造方法について、図面を参照しながら詳細に説明する。以下では、無機材料と溶剤を含む塗布剤を塗布膜として基板に塗布し、溶剤吸収性のあるモールドを用いて塗布膜を成形する工程を例にして説明する。   Hereinafter, a structure manufacturing method according to an embodiment of the present invention will be described in detail with reference to the drawings. In the following, a process of applying a coating agent containing an inorganic material and a solvent as a coating film to a substrate and forming the coating film using a solvent-absorbing mold will be described as an example.

図１は、本実施の形態による構造体の製造方法の要部工程を示す工程図である。
図１（ａ）に示すように、基材１上に無機材料と溶剤を含む塗布剤を塗布することにより、塗布膜３を形成する（塗布膜形成工程）。塗布膜３の形成は、公知の塗布法により行うことができ、典型的にはスピンコート法を用いることができる。スピンコート法により塗布膜３を形成する場合には、塗布剤の溶剤量を多くし、塗布剤の粘度を低下させておくことで均一な薄膜が形成可能となる。塗布膜３の厚みは、特に制限はないが、例えば、０．０１μｍ〜０．５μｍの範囲で形成することができる。 FIG. 1 is a process diagram showing a main process of the structure manufacturing method according to the present embodiment.
As shown to Fig.1 (a), the coating film 3 is formed by apply | coating the coating agent containing an inorganic material and a solvent on the base material 1 (coating film formation process). The coating film 3 can be formed by a known coating method, and typically a spin coating method can be used. When the coating film 3 is formed by spin coating, a uniform thin film can be formed by increasing the solvent amount of the coating agent and decreasing the viscosity of the coating agent. Although there is no restriction | limiting in particular in the thickness of the coating film 3, For example, it can form in 0.01 micrometer-0.5 micrometer.

基材１は、特に制限はないが、例えば、シリコン、金属、石英ガラス、ソーダガラス、蛍石、フッ化カルシウム、フッ化マグネシウム、アクリルガラス、ホウケイ酸ガラス等のガラス材料、ポリカーボネート、ポリプロピレン、ポリエチレン、その他ポリオレフィン類等の樹脂材料のほか、低膨張セラミックス等のセラミックス材料等が挙げられる。また、基材１に溶剤吸収性を持たせてもよく、この場合、例えば、多孔質シリコン、多孔質シリカ、セラミックス、ＰＤＭＳ等のポーラス構造を有する材料、紙や繊維等の溶剤を含浸可能な３次元網目構造を有する材料などを用いることができる。   The substrate 1 is not particularly limited. For example, glass materials such as silicon, metal, quartz glass, soda glass, fluorite, calcium fluoride, magnesium fluoride, acrylic glass, borosilicate glass, polycarbonate, polypropylene, polyethylene In addition to resin materials such as polyolefins, ceramic materials such as low expansion ceramics can be used. In addition, the substrate 1 may be provided with solvent absorbability. In this case, for example, a porous structure such as porous silicon, porous silica, ceramics, PDMS, or a solvent such as paper or fiber can be impregnated. A material having a three-dimensional network structure can be used.

塗布剤に含まれる無機材料としては、共存する溶剤が減少したときに硬質無機膜が得られる材料であればよく、例えば、シリコン等の半導体、チタン、ニッケル、コバルト、金、銀、銅、パラジウム、白金、スズ、ロジウム、インジウム、 ルテニウム、亜鉛、アルミニウム、モリブデン、クロム等の金属に代表される材料、及び、それらの酸化物、窒化物を有する無機コロイドや無機ポリマーあるいは、これらのコロイド物を挙げることができる。なかでも、シリコン含有の無機ポリマーである、シロキサンポリマーを用いることが好ましい。さらに、シロキサンポリマーのうち、水素化シルセスキオキサンポリマー（ＨＳＱ）を用いることが好ましい。   The inorganic material contained in the coating agent may be any material that can provide a hard inorganic film when the coexisting solvent decreases. For example, semiconductors such as silicon, titanium, nickel, cobalt, gold, silver, copper, palladium Materials such as platinum, tin, rhodium, indium, ruthenium, zinc, aluminum, molybdenum, chromium, etc., as well as inorganic colloids and polymers containing these oxides and nitrides, or colloids of these. Can be mentioned. Among these, it is preferable to use a siloxane polymer which is a silicon-containing inorganic polymer. Furthermore, it is preferable to use a hydrogenated silsesquioxane polymer (HSQ) among siloxane polymers.

塗布剤に含まれる溶剤としては、上記無機材料に応じて適宜選択することができるが、例えば、メタノール、エタノール、キシレン、トルエン、酢酸ブチル、シクロヘキサン、エチルベンゼン、イソプロピルアルコール、１−プロパノール、２−プロパノール、メトキシプロピルアセテート、プロピレングリコールモノエチルエーテルアセチレート等を挙げることができる。   The solvent contained in the coating agent can be appropriately selected according to the inorganic material. For example, methanol, ethanol, xylene, toluene, butyl acetate, cyclohexane, ethylbenzene, isopropyl alcohol, 1-propanol, 2-propanol , Methoxypropyl acetate, propylene glycol monoethyl ether acetylate and the like.

次いで、図１（ｂ）に示すように、例えば室温で大気圧Ｐ０下においてモールド５の凹凸のパターンが形成された表面を塗布膜３ａに接触させる（接触工程）。これにより、モールド５の基板１の表面側のパターンが、基板１上の塗布膜３ａの表面に転写される。モールド５は、少なくとも塗布膜３ａに対向する側が溶剤吸収性を有する。なお、モールド５全体が溶剤吸収性を有していてもよい。溶剤吸収性のあるモールド５としては、例えば、ポーラス構造を有する材料を用いることができ、ポーラス構造を有する樹脂が好ましく、具体的にはより具体的にはＰＤＭＳを利用するとよい。モールド５の厚みは、特に制限はないが、可撓性を有するように１００μｍ〜３０００μｍの範囲で設定すると良い。可撓性を有すると、剥離の際の応力を低減できたり、基材側の形状に対する追従性が向上できたりするからである。薄い場合は乾燥速度が上がり５０００ｕｍ以下が好ましい。機械的な強度が必要なため１００ｕｍ以上が好ましい。なお、モールド５のみならず、基材１又は基材１とモールド５の両方を溶剤吸収性のある材料とし、塗布膜３に含まれる溶剤の減少速度を速めてもよい。塗布膜３に含まれる溶剤が基材１にも吸収されることにより、塗布膜３の硬化が進む。 Next, as shown in FIG. 1B, for example, the surface of the mold 5 on which the concave / convex pattern is formed is brought into contact with the coating film 3a at room temperature and under atmospheric pressure P 0 (contact process). Thereby, the pattern on the surface side of the substrate 1 of the mold 5 is transferred to the surface of the coating film 3 a on the substrate 1. The mold 5 has solvent absorbability at least on the side facing the coating film 3a. In addition, the whole mold 5 may have a solvent absorptivity. As the mold 5 having a solvent absorbability, for example, a material having a porous structure can be used, and a resin having a porous structure is preferable, and more specifically, PDMS may be used more specifically. Although there is no restriction | limiting in particular in the thickness of the mold 5, It is good to set it in the range of 100 micrometers-3000 micrometers so that it may have flexibility. This is because, when having flexibility, the stress at the time of peeling can be reduced, and the followability to the shape on the substrate side can be improved. When it is thin, the drying speed is increased, and it is preferably 5000 μm or less. Since mechanical strength is required, 100 um or more is preferable. Note that not only the mold 5 but also the base material 1 or both the base material 1 and the mold 5 may be made of a solvent-absorbing material, and the reduction rate of the solvent contained in the coating film 3 may be increased. The solvent contained in the coating film 3 is also absorbed by the substrate 1, whereby the coating film 3 is cured.

次いで、図１（ｃ）に示すように、室温で大気圧Ｐ０から、Ｐ０よりも低いＰ１に減圧する。減圧下で、モールド５と基材１との間に塗布膜３ａを介在させた状態を保持する（硬化工程）。これにより、モールド５の溶剤吸収性の部位を通じて塗布膜３が減圧下に置かれることから、溶剤の揮発が促進され、溶剤量の減少速度を上げることができる。塗布膜に含まれる溶剤の種類にもよるが、例えば、Ｐ１を０．２（気圧）〜０．５（気圧）とすることにより、溶剤の揮発を効果的に促進することができる。１気圧と減圧を繰り返してもよい。減圧乾燥は細管内部まで強制的に減圧されるためＰＤＭＳ内部まで乾燥が可能となる。つまり多孔質性の溶剤吸収性のある材料の表面にある塗布膜の溶剤を高速に乾燥できる。なお、減圧状態は、塗布膜３とモールド５との接触前から開始されていてもよい。 Then, as shown in FIG. 1 (c), from the atmospheric pressure P 0 at room temperature, under reduced pressure to a lower P 1 than P 0. Under the reduced pressure, the state where the coating film 3a is interposed between the mold 5 and the substrate 1 is maintained (curing step). Thereby, since the coating film 3 is placed under reduced pressure through the solvent-absorbing part of the mold 5, the volatilization of the solvent is promoted, and the reduction rate of the solvent amount can be increased. Depending on the type of solvent contained in the coating film, for example, by the P 1 and 0.2 (pressure) 0.5 (pressure), it is possible to effectively promote the volatilization of the solvent. You may repeat 1 atmosphere and pressure reduction. In the vacuum drying, the pressure is forcibly reduced to the inside of the narrow tube, so that the inside of the PDMS can be dried. That is, the solvent of the coating film on the surface of the porous solvent-absorbing material can be dried at high speed. The reduced pressure state may be started before contact between the coating film 3 and the mold 5.

次いで、図１（ｄ）に示すように、基材１上の硬化した塗布膜３ａからモールド５を離間することにより、モールド５のパターンが塗布膜３ａ側に転写され、例えば、開口部Ｏ１が形成された塗布膜パターン３ｂを形成することができる。   Next, as shown in FIG. 1D, by separating the mold 5 from the cured coating film 3a on the substrate 1, the pattern of the mold 5 is transferred to the coating film 3a side. The formed coating film pattern 3b can be formed.

通常、インプリント時に基材１とモールド５とは所定の間隔をもって配置されることから、開口部内の塗布膜は一部が残膜として残存する。   Usually, since the substrate 1 and the mold 5 are arranged at a predetermined interval during imprinting, a part of the coating film in the opening remains as a remaining film.

さらに、この残膜３ｂを除去したい場合には、図１（ｅ）に示すように、残膜除去のためのリアクティブイオンエッチング等によりエッチバックを行い、残膜を完全に除去することができる。さらに必要に応じて、図１（ｆ）に示すように、例えば、ＣＦ４、ＣＨＦ３などを用いたリアクティブイオンエッチング法などにより、基材１である例えばＳｉ基板を、塗布膜パターン３ｂをマスクとして加工することで、基材１の微細加工を行うことができる。 Further, when it is desired to remove the residual film 3b, as shown in FIG. 1E, etch back is performed by reactive ion etching or the like for removing the residual film, and the residual film can be completely removed. . If necessary, as shown in FIG. 1F, for example, a reactive ion etching method using CF 4 , CHF 3 or the like, for example, a Si substrate as a base material 1 and a coating film pattern 3b are formed. By processing as a mask, the substrate 1 can be finely processed.

以上のように、本実施形態によれば、室温インプリントにおいて、塗布膜に含まれる溶剤を減少させる時間を短縮させることができる。   As described above, according to the present embodiment, it is possible to shorten the time for reducing the solvent contained in the coating film in the room temperature imprint.

上記の実施の形態において、添付図面に図示されている構成等については、これらに限定されるものではなく、本発明の効果を発揮する範囲内で適宜変更することが可能である。その他、本発明の目的の範囲を逸脱しない限りにおいて適宜変更して実施することが可能である。   In the above-described embodiment, the configuration and the like illustrated in the accompanying drawings are not limited to these, and can be appropriately changed within a range in which the effect of the present invention is exhibited. In addition, various modifications can be made without departing from the scope of the object of the present invention.

また、本発明の各構成要素は、任意に取捨選択することができ、取捨選択した構成を具備する発明も本発明に含まれるものである。   Each component of the present invention can be arbitrarily selected, and an invention having a selected configuration is also included in the present invention.

１…基材、３…塗布膜、５…モールド。 DESCRIPTION OF SYMBOLS 1 ... Base material, 3 ... Coating film, 5 ... Mold.

Claims (4)

基材に、無機材料と溶剤とを含有する塗布剤を塗布することにより塗布膜を形成する工程と、
前記塗布膜と、少なくとも前記塗布膜に対向する側が溶剤吸収性を有するモールドとを接触させる工程と、
減圧下で前記塗布膜を前記基材と前記モールドとの間に介在させた状態とし、前記溶剤を減少させて前記塗布膜を硬化させる工程と、を有することを特徴とする構造体の製造方法。 Forming a coating film by applying a coating agent containing an inorganic material and a solvent to the substrate;
Contacting the coating film with a mold having at least a solvent-absorbing side facing the coating film;
And a step of setting the coating film in a state of being interposed between the base material and the mold under reduced pressure, and curing the coating film by reducing the solvent. . 前記基材が溶剤吸収性を有することを特徴とする請求項１記載の構造体の製造方法。   The method for producing a structure according to claim 1, wherein the base material has solvent absorbability. 前記無機材料は、シロキサンポリマーであることを特徴とする請求項１または２に記載の構造体の製造方法。   The method for manufacturing a structure according to claim 1, wherein the inorganic material is a siloxane polymer. 前記モールドは、ポーラス構造を有する樹脂であることを特徴とする請求項１から３までのいずれか１項に記載の構造体の製造方法。   The method of manufacturing a structure according to any one of claims 1 to 3, wherein the mold is a resin having a porous structure.
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