JP2016114716A - Pattern formation method using difference of hydrophilic and hydrophobic properties for electrode printing using light crosslinking agent - Google Patents
Pattern formation method using difference of hydrophilic and hydrophobic properties for electrode printing using light crosslinking agent Download PDFInfo
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Abstract
Description
本発明は、プリンタブルエレクトロニクスにおける微細配線技術に好適に用いることができる親撥パターン形成方法、該親撥パターンを利用した導電性パターン膜形成方法等に関する。
より具体的には、プリンタブルエレクトロニクス（Printable Electronics）等の技術分野において、電極、配線等の各種の導電性パターン膜を形成する際に好適に利用することのできる親撥パターンを簡易に形成する技術に関する。
The present invention relates to a repellent pattern forming method that can be suitably used for a fine wiring technique in printable electronics, a conductive pattern film forming method using the repellent pattern, and the like.
More specifically, in a technical field such as printable electronics, a technology for easily forming an affinity pattern that can be suitably used for forming various conductive pattern films such as electrodes and wiring. About.
プリンタブルエレクトロニクスは、印刷技術を利用して電子回路、デバイス等を形成するもので、低コスト化、生産性向上、さらには省資源など環境調和性にも期待されている。その生産・実用化の製品開発分野は、フレキシブル配線技術開発、太陽電池製品の開発、有機ＥＬディスプレイ・デジタルサイネージ・電子ペーパ開発、センサ技術、ヘルスケア技術開発、など、非常に多岐に渡っている。 Printable electronics uses printing technology to form electronic circuits, devices, and the like, and is expected to reduce costs, improve productivity, and conserve the environment. The production / practical product development fields are very diverse, such as flexible wiring technology development, solar cell product development, organic EL display / digital signage / electronic paper development, sensor technology, healthcare technology development, etc. .
そのようなプリンタブルエレクトロニクスにおいて、各種配線や電極等の導電性パターン膜の形成は、大きなウエートを占めているため、導電性パターン膜形成方法の合理化や効率化は、プリンタブルエレクトロニクスの今後の進展に大きく寄与するものと考えられる。 In such printable electronics, the formation of conductive pattern films such as various wirings and electrodes occupies a large weight. Therefore, the rationalization and efficiency improvement of conductive pattern film formation methods will greatly contribute to the future development of printable electronics. It is thought to contribute.
従来の導電性パターン膜の形成方法としては、フォトレジストを用いたフォトリソグラフィー法が知られているが、基板表面へのフォトレジスト塗布⇒フォトマスクを介してフォトレジストのパターニング露光⇒現像⇒導電性膜形成（蒸着or 印刷）⇒レジスト剥離・洗浄という多くの工程が必要となっている（特許文献１，２参照）。 As a conventional method for forming a conductive pattern film, a photolithography method using a photoresist is known, but a photoresist coating on a substrate surface ⇒ patterning exposure of a photoresist through a photomask ⇒ development ⇒ conductivity Many steps of film formation (evaporation or printing) ⇒ resist peeling and cleaning are required (see Patent Documents 1 and 2).
また、フォトレジストのパターニング露光には、一般的に短波長光（300nm未満）が使用され、波長が300〜400nmの直描レーザは使用できず、パターンの固定化されたフォトマスクを通してパターニングを行っている。そのため、フレキシブル基板やフレキシブル層のように歪みやすい基材を用いる際に、基材の歪みに応じたパターニング露光ができず、それ故、フォトレジストを用いたフォトリソグラフィー法は、フレキシブル基材を用いた積層デバイスの製造に適用するのが困難である等の問題点も存在する。 Photoresist patterning exposure generally uses short-wavelength light (less than 300 nm). Direct-drawing lasers with a wavelength of 300 to 400 nm cannot be used, and patterning is performed through a photomask with a fixed pattern. ing. Therefore, when using a flexible substrate such as a flexible substrate or a flexible layer, patterning exposure according to the distortion of the substrate cannot be performed. Therefore, a photolithography method using a photoresist uses a flexible substrate. There is also a problem that it is difficult to apply to the manufacture of the stacked device.
前述のように、フォトリソグラフィー法による配線等の導電性膜パターニング技術は、多工程であること、基材の歪みに応じたパターニングができないため歪みやすいフレキシブル基材での積層は難しい等の問題点が存在することを本発明者は認識した。 As mentioned above, conductive film patterning technology such as wiring by photolithography is a multi-step process, and it is difficult to laminate on flexible flexible substrates because patterning according to substrate distortion is not possible. The present inventor has recognized that
本発明は、そのような問題点を有する従来技術を背景としたものであり、フォトレジストを用いたフォトリソグラフィー法による場合に比べ少ない工程で導電性パターン膜を形成する際に有用な親撥パターン形成方法を提供することを課題とする。
また、本発明は、フレキシブル基材のように歪みやすい基材であっても、歪み補正を行うことができる親撥パターン形成方法を提供することを追加的な課題とする。
さらに、前記親撥パターン形成方法を利用する、導電性パターン膜形成方法、親撥パターン形成用基材、乃至、導電性パターン膜形成用基材を提供することを追加的な課題とする。
The present invention is based on the background of the prior art having such problems, and is a repellent pattern useful for forming a conductive pattern film with fewer steps than by a photolithography method using a photoresist. It is an object to provide a forming method.
Another object of the present invention is to provide a method for forming an oleophobic pattern capable of correcting distortion even if the substrate is easily distorted, such as a flexible substrate.
Furthermore, another object is to provide a conductive pattern film forming method, a repellent pattern forming base material, or a conductive pattern film forming base material using the repellent pattern forming method.
本発明者は、前記課題下における試験研究過程で、次の（ア）〜（ウ）のような知見を得た。
（ア）複数の親水性基と光架橋性とを有する光架橋剤膜をパターニング露光する等の工程により、導電性パターン膜の形成に利用できる親撥パターンを簡易に形成することができる。
（イ）前記光架橋剤膜のパターニング露光には、波長300〜400nmの直描レーザを使用することができるため、基材の歪みに応じた直描パターニングにより歪み補正を行うことができる。
（ウ）前記光架橋剤としては、複数の親水性基を有する化合物にジアジリン、アジド基、ベンゾフェノン基を導入したものが考えられるが、特に、ジアジリンを導入したアミン末端樹状高分子が有用である。
The present inventor has obtained the following findings (a) to (c) in the course of the test and research under the above problems.
(A) By using a process such as patterning exposure of a photocrosslinking agent film having a plurality of hydrophilic groups and photocrosslinkability, an affinity pattern that can be used for forming a conductive pattern film can be easily formed.
(A) Since a direct drawing laser having a wavelength of 300 to 400 nm can be used for patterning exposure of the photocrosslinker film, distortion correction can be performed by direct drawing patterning according to the distortion of the substrate.
(C) As the photocrosslinking agent, a compound having a plurality of hydrophilic groups introduced with a diazirine, an azide group, or a benzophenone group is conceivable. In particular, an amine-terminated dendritic polymer into which diazirine is introduced is useful. is there.
本発明は、このような知見に基づくものであり、本件では、次のような発明が提供される。
（１）複数の親水性基と光架橋性とを有する光架橋剤の膜を疎水性表面に形成し、該光架橋剤膜に対し波長300〜400nmの光を所定パターンで照射し、照射後表面を洗浄することにより表面に親水性部と疎水性部を有する親撥パターンを形成することを特徴とする親撥パターン形成方法。
（２）照射する光が直描レーザであることを特徴とする、（１）に記載の親撥パターン形成方法。
（３）前記光架橋剤は、複数の親水基を有する化合物にジアジリン、アジド基、又は、ベンゾフェノン基を導入したものであることを特徴とする、（１）又は（２）に記載の親撥パターン形成方法。
（４）前記光架橋剤は、ジアジリンを導入したアミン末端樹状高分子であることを特徴とする、（１）〜（３）のいずれか１項に記載の親撥パターン形成方法。
（５）前記疎水性表面は、基層表面に自己組織化単分子膜が形成されたものであることを特徴とする、（１）〜（４）のいずれか１項に記載の親撥パターン形成方法。
（６）前記基層が金属であり、前記自己組織化単分子膜の単分子がチオール基、リン酸基、又は、ホスホン基を有するものであることを特徴とする、（５）に記載の親撥パターン形成方法。
（７）（１）〜（６）のいずれか１項に記載の方法で親撥パターンを形成し、該方法で形成された親撥パターンにおける親水性部に導電性膜を形成することを特徴とする導電性パターン膜形成方法。
（８）疎水性表面を有する基層と、該疎水性表面に形成され、複数の親水性基と光架橋性とを有する光架橋剤の膜からなることを特徴とする親撥パターン形成用基材。
（９）疎水性表面を有する基層と、該疎水性表面に形成され、所定パターンの親水性膜とを有する導電性パターン膜形成用基材であって、該親水性膜は、複数の親水性基と光架橋性とを有する光架橋剤が光照射により架橋することにより形成されたものであることを特徴とする導電性パターン膜形成用基材。
The present invention is based on such knowledge, and the following invention is provided in this case.
(1) A photocrosslinker film having a plurality of hydrophilic groups and photocrosslinkability is formed on a hydrophobic surface, and the photocrosslinker film is irradiated with light having a wavelength of 300 to 400 nm in a predetermined pattern. A method for forming a hydrophilic / repellent pattern comprising forming a hydrophilic / hydrophobic pattern having a hydrophilic part and a hydrophobic part on the surface by washing the surface.
(2) The method for forming a repellent pattern according to (1), wherein the irradiated light is a direct drawing laser.
(3) The photo-crosslinking agent according to (1) or (2), wherein a diazirine, an azido group, or a benzophenone group is introduced into a compound having a plurality of hydrophilic groups. Pattern forming method.
(4) The method according to any one of (1) to (3), wherein the photocrosslinking agent is an amine-terminated dendritic polymer into which diazirine is introduced.
(5) The hydrophobic / hydrophobic pattern formation according to any one of (1) to (4), wherein the hydrophobic surface is a base layer surface having a self-assembled monolayer formed thereon. Method.
(6) The parent according to (5), wherein the base layer is a metal, and the monomolecule of the self-assembled monolayer has a thiol group, a phosphate group, or a phosphone group. Method for forming a repellent pattern.
(7) A repellent pattern is formed by the method according to any one of (1) to (6), and a conductive film is formed on a hydrophilic portion of the repellent pattern formed by the method. A method for forming a conductive pattern film.
(8) A substrate for forming a hydrophobic / repellent pattern, comprising: a base layer having a hydrophobic surface; and a film of a photocrosslinking agent formed on the hydrophobic surface and having a plurality of hydrophilic groups and photocrosslinkability. .
(9) A substrate for forming a conductive pattern film having a base layer having a hydrophobic surface and a hydrophilic film having a predetermined pattern formed on the hydrophobic surface, wherein the hydrophilic film has a plurality of hydrophilic properties. A substrate for forming a conductive pattern film, wherein the photocrosslinking agent having a group and photocrosslinkability is formed by crosslinking by light irradiation.
また、本発明は、次のような態様を含むことができる。
（１０）前記親水性基が、アミノ基、ヒドロキシル基、アルデヒド基、カルボキシル基、アミド基、スルフォン酸基、リン酸基、アンモニウム基、カルボン酸塩基、スルフォン酸塩基、リン酸塩基から選択されるものであることを特徴とする、（１）〜（７）のいずれか１項に記載の親撥パターン形成方法。
（１１）前記金属が金であり、前記チオール基を有するものがアルカンチオール又は環状チオールであることを特徴とする、（６）に記載の親撥パターン形成方法。
（１２）上記（１０）又は（１１）に記載の方法で親撥パターンを形成し、該方法で形成された親撥パターンにおける親水性部に導電性膜を形成することを特徴とする導電性パターン膜形成方法。
（１３）光架橋剤は、複数の親水基を有する化合物にジアジリン、アジド基、又は、ベンゾフェノン基を導入したものであることを特徴とする、（８）に記載の親撥パターン形成用基材、又は、（９）に記載の導電性パターン膜形成用基材。
（１４）前記光架橋剤は、ジアジリンを導入したアミン末端樹状高分子であることを特徴とする、（８）に記載の親撥パターン形成用基材、又は、（９）に記載の導電性パターン膜形成用基材。
In addition, the present invention can include the following aspects.
(10) The hydrophilic group is selected from an amino group, a hydroxyl group, an aldehyde group, a carboxyl group, an amide group, a sulfonic acid group, a phosphoric acid group, an ammonium group, a carboxylate group, a sulfonate group, and a phosphate group. The repellent pattern forming method according to any one of (1) to (7), wherein
(11) The method according to (6), wherein the metal is gold and the one having the thiol group is alkanethiol or cyclic thiol.
(12) Conductivity characterized in that a repellent pattern is formed by the method described in (10) or (11) above, and a conductive film is formed on the hydrophilic portion of the repellent pattern formed by the method. Pattern film forming method.
(13) The substrate for forming a hydrophobic / repellent pattern according to (8), wherein the photocrosslinking agent is obtained by introducing a diazirine, an azide group, or a benzophenone group into a compound having a plurality of hydrophilic groups. Or the base material for conductive pattern film formation as described in (9).
(14) The photo-crosslinking agent is an amine-terminated dendritic polymer into which diazirine is introduced, or the conductive / repellent pattern-forming substrate according to (8) or the conductive material according to (9) Substrate for forming a conductive pattern film.
本発明の方法によれば、種々の親撥パターンを各種表面上に精度良く簡易に形成することができる。形成した親撥パターンを導電性パターン膜の形成に利用する場合、フォトレジストを用いたフォトリソグラフィー法による場合に比べ導電性パターン膜を少ない工程で形成することができる。
本発明では、市販等により容易に入手可能な波長300〜400nmのレーザ直描装置を用いることもできる。そして、フォトマスクを使用せず、レーザ直描を行う場合には、フレキシブル基材のように歪みやすい基材であっても、基材の歪みに応じた直描パターニングにより歪み補正を行うことができる。
また、本発明の親撥パターン形成用基材や導電性パターン膜形成用基材を用いれば、親撥パターンや導電性パターン膜を簡易に形成することができる。
According to the method of the present invention, various repellent patterns can be easily and accurately formed on various surfaces. When the formed hydrophobic / repellent pattern is used for forming a conductive pattern film, the conductive pattern film can be formed with fewer steps than in the case of using a photolithography method using a photoresist.
In the present invention, a laser direct drawing apparatus having a wavelength of 300 to 400 nm, which can be easily obtained commercially, etc. can also be used. When laser direct drawing is performed without using a photomask, even if the substrate is easily distorted such as a flexible substrate, distortion correction can be performed by direct drawing patterning according to the distortion of the substrate. it can.
Moreover, if the base material for forming an electrophobic pattern or the base material for forming an electroconductive pattern film of the present invention is used, an electrophilic pattern or an electroconductive pattern film can be easily formed.
本発明の親撥パターンの形成方法は、疎水性（撥水性）表面に形成した光架橋剤膜に対し波長300〜400nmの光を所定パターンで照射し〔図１（ａ）参照〕、照射後表面を洗浄することにより表面に親水性部と疎水性部を有する親撥パターンを形成する〔図１（ｂ）参照〕。さらに、親水性インクを塗布（さらに、適宜、焼成）することにより親水性部表面に親水性インクパターン膜や導電性パターン膜を形成することができる〔図１（ｃ）参照〕。
このように、本発明では、フォトレジストを用いたフォトリソグラフィー法による場合に比べ、はるかに少ない工程で種々の親撥パターンや導電性パターン膜を各種表面上に高精度に形成することができる。
以下、本発明の発明特定事項ごとに具体的に説明する。
In the method for forming a hydrophilic / repellent pattern according to the present invention, a photocrosslinker film formed on a hydrophobic (water-repellent) surface is irradiated with light having a wavelength of 300 to 400 nm in a predetermined pattern [see FIG. By cleaning the surface, a hydrophilic / hydrophobic pattern having a hydrophilic portion and a hydrophobic portion is formed on the surface [see FIG. 1 (b)]. Furthermore, a hydrophilic ink pattern film or a conductive pattern film can be formed on the surface of the hydrophilic portion by applying hydrophilic ink (and baking as appropriate) (see FIG. 1C).
As described above, according to the present invention, various repellency patterns and conductive pattern films can be formed with high accuracy on various surfaces with much fewer steps than in the case of photolithography using a photoresist.
Hereinafter, each invention specific matter of the present invention will be specifically described.
（疎水性表面）
本発明において、疎水性（撥水性）表面とは、水に対する接触角が90°以上、好ましくは100°以上の表面をいう。
本発明で用いる疎水性表面は、疎水性材料からなる基層の疎水性表面であってもよいし、各種の基層の表面を塗布、被覆等の各種処理によって基層表面上に形成されたものであってもよい。
基層を構成する疎水性材料や、基層表面上の疎水性表面となる塗布乃至被覆材料の疎水性材料としては、限定するものではないが、各種樹脂、自己組織化膜を形成する単分子等が挙げられる。
各種樹脂としては、限定するものではないが、ポリエステル系樹脂、ポリビニルアセタール系樹脂、ウレタン系樹脂、アミド系樹脂、セルロース系樹脂、オレフィン系樹脂、塩化ビニル系樹脂、アクリル系樹脂、スチレン系樹脂、ポリカーボネート、ポリサルフォン、ポリカプロラクトン樹脂、ポリアクリロニトリル樹脂、尿素樹脂、エポキシ樹脂、フェノキシ樹脂、フッ素系樹脂等が挙げられ、これらの樹脂は、１種単独でもよいし、２種以上併用することもできる。
自己組織化膜を形成する単分子としては、限定するものではないが、チオール基を有するもの、リン酸基を有するもの、ホスホン基を有するもの等、一端が基層に結合し他端部が疎水性を示すものをいずれも用いることができる。チオール基を有するものとしては、限定するものではないが、アルカンチオール、環状チオール等を挙げることができる。アルカンチオールとしては、炭素数が7〜30、より好ましくは10〜20、さらに好ましくは12〜18のものが挙げられる。アルカンチオールは、自己組織化能や疎水性表面形成能を大きく阻害しない範囲で各種の置換基を有するものとすることができる。
塗布、被覆等の各種処理によって基層表面上に疎水性表面を形成する場合の基層としては、限定するものではないが、金、銀、銅、アルミニウム等の金属や合金、ハンダ用合金、上述のような樹脂やそれらの樹脂表面が親水化処理されたもの、各種セラミックス等を挙げることができる。
(Hydrophobic surface)
In the present invention, the hydrophobic (water repellent) surface means a surface having a contact angle with water of 90 ° or more, preferably 100 ° or more.
The hydrophobic surface used in the present invention may be a hydrophobic surface of a base layer made of a hydrophobic material, or may be formed on the surface of the base layer by various treatments such as coating and coating the surface of various base layers. May be.
The hydrophobic material constituting the base layer and the hydrophobic material of the coating or coating material that becomes the hydrophobic surface on the surface of the base layer are not limited, but various resins, single molecules forming a self-assembled film, etc. Can be mentioned.
Various resins include, but are not limited to, polyester resins, polyvinyl acetal resins, urethane resins, amide resins, cellulose resins, olefin resins, vinyl chloride resins, acrylic resins, styrene resins, Examples of the resin include polycarbonate, polysulfone, polycaprolactone resin, polyacrylonitrile resin, urea resin, epoxy resin, phenoxy resin, and fluorine resin. These resins may be used alone or in combination of two or more.
The monomolecule forming the self-assembled film is not limited, but one having a thiol group, one having a phosphate group, one having a phosphone group, and the other end is hydrophobic. Any of those exhibiting sex can be used. Examples of those having a thiol group include, but are not limited to, alkane thiols and cyclic thiols. Examples of the alkanethiol include those having 7 to 30 carbon atoms, more preferably 10 to 20 carbon atoms, and still more preferably 12 to 18 carbon atoms. The alkanethiol can have various substituents as long as the self-organization ability and the hydrophobic surface formation ability are not significantly inhibited.
The base layer in the case where a hydrophobic surface is formed on the surface of the base layer by various treatments such as coating and coating is not limited, but includes metals and alloys such as gold, silver, copper, and aluminum, alloys for solder, Such resins, those whose resin surfaces are hydrophilized, various ceramics, and the like.
（光架橋剤）
本発明における光架橋剤は、複数の親水性基と光架橋性とを有する化合物である。親水性基としては、アミノ基、ヒドロキシル基、アルデヒド基、カルボキシル基、アミド基、スルフォン酸基、リン酸基、アンモニウム基、カルボン酸塩基、スルフォン酸塩基、リン酸塩基を挙げることができる。親水性基の数は、限定するものではないが、好ましくは3〜100個、より好ましくは6〜70個である。
光架橋性を有する化合物としては、ジアジリン、アジド基、ベンゾフェノン基等を有するものが挙げられる。
本発明における光架橋剤は、複数乃至多数の親水性基を有する化合物にジアジリン、アジド基、ベンゾフェノン基等を導入することにより得ることができる。複数乃至多数の親水性基を有する化合物としては、限定するものではないが、親水基を末端に有する樹状高分子（デンドリマー）、ハイパーブランチ高分子を挙げることができる。
好適な光架橋剤としては、ジアジリンが導入されたアミン末端樹状高分子を挙げることができる。該アミン末端樹状高分子としては、ポリアミドアミン（ＰＡＭＡＭ）デンドリマー、ポリ（プロピレンイミン）（ＰＰＩ）デンドリマーを挙げることができる。ＰＡＭＡＭデンドリマーやＰＰＩデンドリマーの世代数は、通常２〜７程度であるが、好ましくは３〜５である。ＰＡＭＡＭデンドリマーやＰＰＩデンドリマーは、末端に親水性のアミンを多く有するため、親撥パターンの親水性部の形成に効果的である。
本発明における光架橋剤においては、波長が300〜400nmの紫外光が照射されジアジリンやアジド基、ベンゾフェノン基が該波長の光を吸収すると反応性の高い炭素ラジカルや窒素ラジカルを生じ、近傍にある分子と共有結合して相互に架橋するとともに、疎水性表面の分子とも結合する。
光架橋剤膜や架橋後の光架橋剤膜の親水性としては、水に対する接触角が90°以下、より好ましくは60°以下、さらに好ましくは20°以下である。
(Photocrosslinking agent)
The photocrosslinking agent in the present invention is a compound having a plurality of hydrophilic groups and photocrosslinkability. Examples of the hydrophilic group include an amino group, a hydroxyl group, an aldehyde group, a carboxyl group, an amide group, a sulfonic acid group, a phosphoric acid group, an ammonium group, a carboxylate group, a sulfonate group, and a phosphate group. The number of hydrophilic groups is not limited, but is preferably 3 to 100, more preferably 6 to 70.
Examples of the photocrosslinkable compound include those having a diazirine, an azide group, a benzophenone group, and the like.
The photocrosslinking agent in the present invention can be obtained by introducing a diazirine, an azide group, a benzophenone group or the like into a compound having a plurality of hydrophilic groups. Examples of the compound having a plurality of hydrophilic groups include, but are not limited to, a dendritic polymer (dendrimer) having a hydrophilic group at the terminal and a hyperbranched polymer.
Suitable photocrosslinking agents include amine-terminated dendritic polymers into which diazirine has been introduced. Examples of the amine-terminated dendritic polymer include polyamidoamine (PAMAM) dendrimers and poly (propyleneimine) (PPI) dendrimers. The number of generations of PAMAM dendrimers and PPI dendrimers is usually about 2 to 7, but preferably 3 to 5. PAMAM dendrimers and PPI dendrimers have many hydrophilic amines at the ends, and thus are effective in forming the hydrophilic portion of the repellent pattern.
In the photocrosslinking agent in the present invention, when a light having a wavelength of 300 to 400 nm is irradiated and a diazirine, azide group, or benzophenone group absorbs light of this wavelength, a highly reactive carbon radical or nitrogen radical is generated and is in the vicinity. It is covalently bonded to the molecule to crosslink with each other and to the hydrophobic surface molecule.
The hydrophilicity of the photocrosslinking agent film or the crosslinked photocrosslinking agent film is such that the contact angle with water is 90 ° or less, more preferably 60 ° or less, and even more preferably 20 ° or less.
（光照射）
光照射源としては、前記光架橋剤に光架橋性をもたらす波長300〜400nmの紫外光を照射できるものであればどのようなものでも良いが、例えば、高圧水銀ランプ、メタルハライドランプ、XeFレーザー（発振波長351nm）、XeClレーザー（発振波長308nm）等を用いることができる。
所定パターン領域に対する光照射は、所定パターンを有するフォトマスクを介して行っても良いし、光照射範囲が狭い範囲である光照射源を光架橋剤膜に対し相対的に走査して行うこともできる。フォトマスクを用いることなく、波長が300〜400nmの紫外光照射装置として市販の紫外レーザ直描装置等の直描用の光照射源を用いる場合には、フレキシブル基材のように歪みやすい基材であっても、基材の歪みに応じた直描パターニングにより歪み補正を行うことができる。
(Light irradiation)
Any light irradiation source may be used as long as it can irradiate the photocrosslinking agent with ultraviolet light having a wavelength of 300 to 400 nm which brings photocrosslinking property. For example, a high pressure mercury lamp, a metal halide lamp, a XeF laser ( An oscillation wavelength of 351 nm), a XeCl laser (oscillation wavelength of 308 nm), or the like can be used.
The light irradiation to the predetermined pattern region may be performed through a photomask having a predetermined pattern, or may be performed by scanning a light irradiation source having a narrow light irradiation range relative to the photocrosslinking agent film. it can. When using a light source for direct drawing such as a commercially available ultraviolet laser direct drawing device as an ultraviolet light irradiation device with a wavelength of 300 to 400 nm without using a photomask, a substrate that is easily distorted, such as a flexible substrate Even so, distortion correction can be performed by direct drawing patterning according to the distortion of the substrate.
（導電性パターン膜の形成）
本発明により形成された親撥パターンを利用して導電性パターン膜を形成する方法としては、例えば、親水性で導電膜化可能なインクによる塗布と、該インクの焼成による導電膜化等、プリンタブルエレクトロニクスで採用され得る公知の手法が使用できる。
(Formation of conductive pattern film)
Examples of a method for forming a conductive pattern film using the repellent pattern formed according to the present invention include printing with a hydrophilic conductive film that can be formed into a conductive film, and forming a conductive film by firing the ink. Any known technique that can be employed in electronics can be used.
以下に実施例を示し、本発明の特徴とするところをより一層明確にするが、本発明は、このような実施例に限定されるものではない。 The following examples illustrate the features of the present invention more clearly, but the present invention is not limited to such examples.
（光架橋剤の調製）
市販のアミン末端樹状高分子PAMAMG4（シグマアルドリッチ社PAMAMデンドリマー、エチレンジアミンコア、4.0世代 溶液）を含む10％メタノール溶液にNHS-Diazirine〔スクシンイミジル4,4-アジペンタノエート(Succinimidyl 4,4-Azipentanoate)〕（サーモフィッシャーサイエンティフィック社）を64個のアミン基を有するPAMAMデンドリマーのアミン基、NHS-Diazirine、トリエチルアミンを45：1：2の比で混合し、室温で2時間半放置することにより反応を行った。その後、エタノールで1/10に希釈し、次の式（１）で表されるようなジアジリンを有する光架橋剤を調製した（なお、64個のアミン基のうち、ジアジリンが結合するアミン基の位置は問わないし、ジアジリンが結合するアミン基は、単数であっても良いし、複数であっても良い）。
NHS-Diazirine (Succinimidyl 4,4-Azipentanoate) was added to a 10% methanol solution containing the commercially available amine-terminated dendritic polymer PAMAMG4 (Sigma Aldrich PAMAM dendrimer, ethylenediamine core, 4.0 generation solution). )] (Thermo Fisher Scientific) by mixing PAMAM dendrimer with 64 amine groups, NHS-Diazirine, triethylamine in a ratio of 45: 1: 2 and let stand at room temperature for 2.5 hours Reaction was performed. Thereafter, it was diluted to 1/10 with ethanol to prepare a photocrosslinking agent having diazirine as represented by the following formula (1) (among the 64 amine groups, the amine group to which diazirine binds). The position is not limited, and the amine group to which diazirine is bonded may be singular or plural.
（基板表面の調整）
金コートガラス基板（東亜理化研究所製）をオゾン洗浄した後、金コート面を1mMのアルカンチオール（本実施例ではC16SH）（東京化成、n-ヘキサデシルメルカプタン）エタノール溶液に1晩さらし、金コート表面にアルカンチオールの自己組織化単分子（SAM）膜を形成した。このSAM膜表面は、炭素数16のアルカンに由来して疎水性を示す（水に対する接触角が約105°程度）。
(Adjustment of substrate surface)
After the gold-coated glass substrate (manufactured by Toa Rika Institute) was cleaned with ozone, the gold-coated surface was exposed to a 1 mM alkanethiol (C16SH in this example) ethanol solution (Tokyo Kasei, n-hexadecyl mercaptan) overnight. A self-assembled monomolecular (SAM) film of alkanethiol was formed on the coat surface. The surface of this SAM film is hydrophobic due to the alkane having 16 carbon atoms (the contact angle with water is about 105 °).
（親撥パターンの形成）
上記の調製された光架橋剤のメタノール溶液を前記SAM膜上に塗布し、乾燥させることによりSAM膜上に光架橋剤膜を形成した。その上にフォトマスクを通じて310nmカットフィルターを通して高圧水銀ランプ（モリテックス社、紫外線照射装置MORITEX MUV-250U-L、主波長365nm、波長範囲225nm〜500nm）を10分間照射した。エタノール、水洗浄により、未露光部の光架橋剤を除去した。その後の顕微鏡写真を観察するとフォトマスク通りのパターンコントラストを得た〔図２（ａ）参照〕。架橋後の光架橋剤パターン膜は親水性を示す（水に対する接触角が約75°程度）。
(Formation of repellent pattern)
The methanol solution of the photocrosslinking agent prepared above was applied onto the SAM film and dried to form a photocrosslinking agent film on the SAM film. A high-pressure mercury lamp (Mortex, MORITEX MUV-250U-L, main wavelength 365 nm, wavelength range 225 nm to 500 nm) was irradiated for 10 minutes through a photomask through a 310 nm cut filter. The photo-crosslinking agent in the unexposed area was removed by washing with ethanol and water. When the subsequent micrograph was observed, a pattern contrast equivalent to a photomask was obtained [see FIG. 2 (a)]. The cross-linked photocrosslinker pattern film is hydrophilic (contact angle with water is about 75 °).
さらに、比較的表面自由エネルギーの高い高沸点溶剤ジメチルスルホキシド（DMSO）（キシダ化学）にさらした。DMSOがほぼフォトマスクパターンコントラストに近い状態で残ることが分かった〔図２（ｂ）参照〕。DMSOにさらす替わりに別途、親水性のナノ銀インク水溶液（バンドー化学開発品）を塗り広げたところ、フォトマスクパターン通りに塗り広がることが分かった〔図２（ｃ）参照〕。 Furthermore, it was exposed to a high boiling point solvent dimethyl sulfoxide (DMSO) (Kishida Chemical) with relatively high surface free energy. It was found that DMSO remained in a state almost similar to the photomask pattern contrast [see FIG. 2 (b)]. Instead of exposing to DMSO, when a hydrophilic nano silver ink aqueous solution (bando chemical development product) was spread separately, it was found that the coating spreads according to the photomask pattern [see FIG. 2 (c)].
本発明の方法によれば、フォトレジストを用いたフォトリソグラフィー法による場合に比べ、はるかに少ない工程で種々の親撥パターンを各種表面上に高精度に形成することができる。また、該親撥パターンは、配線や電極等の導電性パターンの形成に用いることができるので、本発明の方法は、各種のデバイス等の製造に幅広く応用することができる。
また、露光をレーザ直描により行う場合には、フレキシブル基材やフレキシブル層のように歪みやすい基材であっても、それらの歪みに応じた直描パターニングにより歪み補正を行うことができるので、レーザ直描により行う態様の本発明は、特に、フレキシブル基材やフレキシブル層を含む積層デバイスの製造に好適である。
According to the method of the present invention, various repellency patterns can be formed with high accuracy on various surfaces with much fewer steps than in the case of photolithography using a photoresist. Further, since the repellent pattern can be used for forming conductive patterns such as wirings and electrodes, the method of the present invention can be widely applied to the production of various devices.
In addition, when performing exposure by laser direct drawing, even if it is a substrate that is easily distorted such as a flexible substrate or a flexible layer, distortion correction can be performed by direct drawing patterning according to those distortions, The aspect of the present invention performed by laser direct drawing is particularly suitable for manufacturing a laminated device including a flexible base material and a flexible layer.
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| WO2018139473A1 (en) * | 2017-01-27 | 2018-08-02 | 国立大学法人信州大学 | Carbon film manufacturing method and film manufacturing method |
| WO2019017386A1 (en) * | 2017-07-19 | 2019-01-24 | 株式会社ニコン | Compound, pattern forming substrate, coupling agent, and pattern forming method |
| JP2022513010A (en) * | 2018-11-13 | 2022-02-07 | 東京エレクトロン株式会社 | Systems and methods to control defects on wafers, metal particle contamination and film growth |
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| JP2003292477A (en) * | 2002-03-29 | 2003-10-15 | Toyo Gosei Kogyo Kk | New photosensitive compound and photosensitive resin and photosensitive composition |
| JP2007310025A (en) * | 2006-05-16 | 2007-11-29 | Fujifilm Corp | Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board |
| JP2008071864A (en) * | 2006-09-13 | 2008-03-27 | Renesas Technology Corp | Method and device for manufacturing semiconductor device |
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| JP2003287885A (en) * | 2002-03-28 | 2003-10-10 | Fuji Photo Film Co Ltd | Image forming method |
| JP2003292477A (en) * | 2002-03-29 | 2003-10-15 | Toyo Gosei Kogyo Kk | New photosensitive compound and photosensitive resin and photosensitive composition |
| JP2007310025A (en) * | 2006-05-16 | 2007-11-29 | Fujifilm Corp | Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board |
| JP2008071864A (en) * | 2006-09-13 | 2008-03-27 | Renesas Technology Corp | Method and device for manufacturing semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018139473A1 (en) * | 2017-01-27 | 2018-08-02 | 国立大学法人信州大学 | Carbon film manufacturing method and film manufacturing method |
| JPWO2018139473A1 (en) * | 2017-01-27 | 2019-11-21 | 国立大学法人信州大学 | Carbon film manufacturing method and film manufacturing method |
| JP7281119B2 (en) | 2017-01-27 | 2023-05-25 | 国立大学法人信州大学 | Method for producing carbon coating and method for producing coating |
| WO2019017386A1 (en) * | 2017-07-19 | 2019-01-24 | 株式会社ニコン | Compound, pattern forming substrate, coupling agent, and pattern forming method |
| JP2022513010A (en) * | 2018-11-13 | 2022-02-07 | 東京エレクトロン株式会社 | Systems and methods to control defects on wafers, metal particle contamination and film growth |
| JP7164777B2 (en) | 2018-11-13 | 2022-11-02 | 東京エレクトロン株式会社 | Systems and methods for suppressing defects, metal particle contamination and film growth on wafers |
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