JP2001284289A - Manufacturing method of fine structure - Google Patents
Manufacturing method of fine structureInfo
- Publication number
- JP2001284289A JP2001284289A JP2000098158A JP2000098158A JP2001284289A JP 2001284289 A JP2001284289 A JP 2001284289A JP 2000098158 A JP2000098158 A JP 2000098158A JP 2000098158 A JP2000098158 A JP 2000098158A JP 2001284289 A JP2001284289 A JP 2001284289A
- Authority
- JP
- Japan
- Prior art keywords
- film
- substrate
- thin film
- self
- functional thin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Electrodes Of Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、パターンニングさ
れた機能性薄膜を備えた微細構造体の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a fine structure having a patterned functional thin film.
【０００２】[0002]
【従来の技術】現在、機能性薄膜として、非常に多くの
種類のものが実用化されている。例えば、半導体素子、
ディスプレー、発光素子などへ適用されている。その中
で、機能性薄膜は、配線、電極、絶縁層、発光層、光学
薄膜などの用途に広く用いられている。通常、機能性薄
膜は、スパッタリング法、蒸着法、ＣＶＤ法、スピンコ
ート法、めっき法など、様々な手法により形成されてい
る。しかしながら、いずれの方法でも基板あるいは下地
膜上に選択的に薄膜形成するには何らかの工夫が必要で
ある。したがって、所望の形状を得るためには、機能性
薄膜のパターンニングが必要であり、フォトリソグラフ
ィーを用いてパターンニングを行う場合と、マスクを用
いた物理的蒸着などによりパターンニングされた薄膜を
形成する場合とに大別される。2. Description of the Related Art At present, a very large number of types of functional thin films are in practical use. For example, semiconductor devices,
It is applied to displays, light emitting devices, and the like. Among them, functional thin films are widely used for wiring, electrodes, insulating layers, light emitting layers, optical thin films and the like. Usually, a functional thin film is formed by various methods such as a sputtering method, an evaporation method, a CVD method, a spin coating method, and a plating method. However, any method is required to selectively form a thin film on a substrate or a base film by any method. Therefore, in order to obtain a desired shape, patterning of a functional thin film is necessary. When performing patterning using photolithography, and forming a patterned thin film by physical vapor deposition using a mask, etc. The case is roughly divided.
【０００３】[0003]
【発明が解決しようとする課題】しかし、これらの機能
性薄膜のパターンニング方法には、以下のような問題が
あった。マスクを用いた物理的蒸着法においては、比較
的簡単な工程で形成できるメリットがある反面、５０ミ
クロン程度の寸法精度しか得られないため、微小なサイ
ズのパターンニングには不向きである。パターンサイズ
が５０ミクロン以下においては、基板とマスクのすき間
からの蒸着粒子の回り込みによる、パターン精度の低下
や、薄膜の膜厚分布、マスクの耐久性などの問題が顕著
になり、実用に適さない。However, these methods of patterning a functional thin film have the following problems. The physical vapor deposition method using a mask has an advantage that it can be formed by a relatively simple process, but it is only suitable for patterning of a minute size because it can obtain only a dimensional accuracy of about 50 microns. When the pattern size is 50 μm or less, problems such as a decrease in pattern accuracy, a thin film thickness distribution, and mask durability due to the wraparound of the vapor deposition particles from the gap between the substrate and the mask become unsuitable for practical use. .
【０００４】これに対して、フォトリソグラフィーは高
精細のパターンニングを可能とする。しかしながら、フ
ォトリソグラフィーにおいては、パターンニングの工程
数が多くなるという欠点がある。一般的、フォトリソグ
ラフィーは次のような工程を経てパターンニングが行わ
れる。まず、パターンニングを行う薄膜を基板全面に形
成する。さらに、レジストコート、露光、現像、リンス
などを経てレジストパターンを形成する。その後に、レ
ジストパターンをマスクとしてエッチングを行い不要な
部分を除去して所望のパターン形状を得る。以上で述べ
たように、非常に多くの工程を必要とするのに加えて、
エッチングの工程で問題が発生しやすい。いろいろな材
料の薄膜に対してオールマイティーなエッチング条件と
いうもうのは存在しないため、各薄膜に対して、エッチ
ングガスなど各種のエッチング条件を調整する必要があ
る。さらに、エッチング時の機能性薄膜へのダメージ、
レジストに対する選択比などの問題も、所望のパターン
の機能性薄膜を得る上で大きな課題となる。On the other hand, photolithography enables high-definition patterning. However, photolithography has a disadvantage that the number of patterning steps is increased. Generally, in photolithography, patterning is performed through the following steps. First, a thin film to be patterned is formed on the entire surface of the substrate. Further, a resist pattern is formed through resist coating, exposure, development, rinsing and the like. Thereafter, etching is performed using the resist pattern as a mask to remove unnecessary portions to obtain a desired pattern shape. As mentioned above, in addition to requiring a large number of steps,
Problems are likely to occur in the etching process. Since there is no other almighty etching condition for thin films of various materials, it is necessary to adjust various etching conditions such as an etching gas for each thin film. Furthermore, damage to the functional thin film during etching,
Problems such as the selectivity with respect to the resist also become a major problem in obtaining a functional thin film having a desired pattern.
【０００５】以上で述べたように、ミクロンオーダーの
精度を有し、尚且つ、簡便な工程で良質な機能性薄膜を
得るパターンニング手段がなかった。As described above, there has been no patterning means having a precision of the order of microns and obtaining a high-quality functional thin film by a simple process.
【０００６】本発明は、上記問題点に鑑みてなされたも
ので、その課題とするところは、ミクロンオーダーの精
度を有し、且つ簡便な工程で良好な性能を持つ機能性薄
膜パターンを備えた微細構造体の製造方法を提供するも
のである。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide a functional thin film pattern having a micron-order accuracy and good performance in a simple process. An object of the present invention is to provide a method for manufacturing a microstructure.
【０００７】[0007]
【課題を解決するための手段】本発明者は、特願平11-2
62663号において、基材と、該基材上にアミノ基あるい
はチオール基を有する有機化合物からなる極薄膜パター
ンと、該極薄膜パターンに基づいた層パターンを有する
微細構造体を提案した。本発明は、この有機化合物を含
む分子膜を基板に結合させて基板の表面性を改良し、こ
の基板とスピンコート技術を組み合わせて、既述の課題
を解決したものである。Means for Solving the Problems The present inventor has disclosed Japanese Patent Application No. Hei 11-2
No. 62663 proposed a microstructure having a substrate, an ultrathin film pattern composed of an organic compound having an amino group or a thiol group on the substrate, and a layer pattern based on the ultrathin film pattern. In the present invention, the molecular film containing the organic compound is bonded to a substrate to improve the surface properties of the substrate, and the above-mentioned problem is solved by combining this substrate with a spin coating technique.
【０００８】本発明は、機能性薄膜（パターン）を備え
た微細構造体の製造方法であって、基板表面に有機分子
膜を用いて、親液部と撥液部とを所定のパターンに形成
する工程と、スピンコート法により前記基板上の親液部
に選択的に機能性薄膜を形成する工程とを有する微細構
造体の製造方法である。The present invention relates to a method for manufacturing a fine structure having a functional thin film (pattern), wherein a lyophilic portion and a lyophobic portion are formed in a predetermined pattern using an organic molecular film on the substrate surface. And a step of selectively forming a functional thin film on the lyophilic portion on the substrate by a spin coating method.
【０００９】すなわち本発明によれば、基板上に有機分
子膜によって基板の撥液性や親液性などの基板の表面性
が制御できることにより、この基板とスピンコート法を
組み合わせることによって、機能性薄膜を容易にパター
ンニングできる。前記有機分子膜としては特に好ましく
は自己組織化膜を用いることができる。That is, according to the present invention, the surface properties of the substrate such as the liquid repellency and the lyophilicity of the substrate can be controlled by the organic molecular film on the substrate. The thin film can be easily patterned. Particularly preferably, a self-assembled film can be used as the organic molecular film.
【００１０】[0010]
【発明の実施の形態】本発明に用いられる基板として
は、Ｓｉウエハー、石英ガラス、ガラス、プラスチック
フィルム、金属基板など各種のものを用いることがで
き、また、基板表面に金属膜、誘電体膜、有機膜などが
下地層として形成されていても問題はない。DESCRIPTION OF THE PREFERRED EMBODIMENTS As a substrate used in the present invention, various substrates such as Si wafer, quartz glass, glass, plastic film and metal substrate can be used, and a metal film and a dielectric film are formed on the substrate surface. There is no problem even if an organic film or the like is formed as a base layer.
【００１１】有機分子膜とは、基板上でフォトリソグラ
フィー等のパターンニング技術によって、所定の有機分
子膜のパターンを形成できるものである。有機分子膜は
基板に結合可能な官能基と、その反対側に親液基あるい
は撥液基といった基板の表面性を改質する（表面エネル
ギーを制御する）官能基と、これらの官能基を結ぶ炭素
の直鎖あるいは一部分岐した炭素鎖を備えており、基板
に結合して自己組織化して分子膜、例えば単分子膜を形
成する。The organic molecular film is a film that can form a predetermined organic molecular film pattern on a substrate by a patterning technique such as photolithography. The organic molecular film connects these functional groups with a functional group capable of binding to the substrate and a functional group that modifies the surface properties of the substrate (controls the surface energy) such as a lyophilic group or a lyophobic group on the opposite side. It has a straight or partially branched carbon chain of carbon, and is bonded to a substrate and self-organized to form a molecular film, for example, a monomolecular film.
【００１２】本発明において基板表面に形成される自己
組織化膜とは、基板など下地層等構成原子と反応可能な
結合性官能基とそれ以外の直鎖分子とからなり、該直鎖
分子の相互作用により極めて高い配向性を有する化合物
を、配向させて形成された膜である。前記自己組織化膜
はフォトレジスト材等の樹脂膜とは異なり、単分子を配
向させて形成されているので、極めて膜厚を薄くするこ
とができ、しかも、分子レベルで均一な膜となる。即
ち、膜の表面に同じ分子が位置するため、膜の表面に均
一でしかも優れた撥液性や親液性を付与することがで
き、微細なパターンニングをする際に特に有用である。In the present invention, the self-assembled film formed on the surface of the substrate is composed of a bonding functional group capable of reacting with constituent atoms such as a base layer of the substrate and other linear molecules. It is a film formed by orienting a compound having extremely high orientation by interaction. Unlike the resin film such as a photoresist material, the self-assembled film is formed by orienting single molecules, so that the film thickness can be extremely thin, and the film is uniform at a molecular level. That is, since the same molecules are located on the surface of the film, the film surface can be imparted with uniform and excellent lyophobicity or lyophilicity, which is particularly useful for fine patterning.
【００１３】例えば、前記化合物として、後述するフル
オロアルキルシランを用いた場合には、膜の表面にフル
オロアルキル基が位置するように各化合物が配向されて
自己組織化膜が形成されるので、膜の表面に均一な撥液
性が付与される。For example, when a fluoroalkylsilane described later is used as the compound, each compound is oriented so that the fluoroalkyl group is located on the surface of the film to form a self-assembled film. Liquid repellency is imparted to the surface of the substrate.
【００１４】自己組織化膜を形成する化合物としては、
ヘプタデカフルオロテトラヒドロデシルトリエトキシシ
ラン、ヘプタデカフルオロテトラヒドロデシルトリクロ
ロシラン、トリデカフルオロテトラヒドロオクチルトリ
クロロシラン、トリフルオロプロピルトリメトキシシラ
ン等のフルオロアルキルシラン（以下、「ＦＡＳ」とい
う）を挙げることができる。使用に際しては、一つの化
合物を単独で用いるのも好ましいが、２種以上の化合物
を組み合わせて使用しても、本発明の所期の目的を損な
わなければ制限されない。また、本発明においては、前
記化合物として、前記ＦＡＳを用いるのが、基板との密
着性及び良好な撥液性を付与する上で好ましい。ＦＡＳ
をパターンニングすることによって親液部と撥液部のパ
ターンを作ることができる。ＦＡＳが存在する部分が撥
液部となる。Compounds that form a self-assembled film include:
Examples thereof include fluoroalkylsilanes (hereinafter, referred to as “FAS”) such as heptadecafluorotetrahydrodecyltriethoxysilane, heptadecafluorotetrahydrodecyltrichlorosilane, tridecafluorotetrahydrooctyltrichlorosilane, and trifluoropropyltrimethoxysilane. In use, it is preferable to use one compound alone, but it is not limited even if two or more compounds are used in combination as long as the intended purpose of the present invention is not impaired. In the present invention, it is preferable to use the FAS as the compound in order to impart adhesion to a substrate and good liquid repellency. FAS
By patterning, a pattern of the lyophilic part and the lyophobic part can be formed. The portion where FAS exists is the liquid repellent portion.
【００１５】前記化合物は、ＲnＳｉＸ(4-n)（Ｘは加水
分解基）の構造式を持ち、加水分解によりシラノールを
形成して、基板（ガラス、シリコン）等の下地のヒドロ
キシル基と反応してシロキサン結合で基板と結合する。
一方、Ｒは（ＣＦ3）（ＣＦ2）等のフルオロアルキル基
を有するため、基板等の下地表面を濡れない（表面エネ
ルギーが低い）表面に改質する。The compound has a structural formula of R n SiX (4-n) (X is a hydrolyzable group), forms silanol by hydrolysis, and reacts with a hydroxyl group on a substrate (glass, silicon) or the like. It reacts and bonds with the substrate through a siloxane bond.
On the other hand, since R has a fluoroalkyl group such as (CF 3 ) (CF 2 ), it modifies the surface of a base such as a substrate into a non-wetting (low surface energy) surface.
【００１６】次いで、親液部について述べる。後述する
紫外線などにより自己組織化膜が除去された領域は、ヒ
ドロキシル基が表面に存在する。このため、ＦＡＳの領
域に比べて非常に濡れ易い性質を示す。従って、基板全
面にＦＡＳを形成した後に、一部の領域のＦＡＳを除去
すると、その領域は親液性を示し、親液性と撥液性のパ
ターンが形成されることになる。Next, the lyophilic part will be described. In a region where the self-assembled film is removed by ultraviolet rays or the like described later, a hydroxyl group exists on the surface. For this reason, it shows a property that it is very easy to wet as compared with the FAS region. Therefore, when the FAS is removed from a part of the area after the FAS is formed on the entire surface of the substrate, the area shows lyophilicity and a lyophilic and lyophobic pattern is formed.
【００１７】さらに、ＦＡＳが除去された領域に第２の
自己組織化膜を形成することも可能である。第２の化合
物の結合性官能基が、ヒドロキシル基と結合して第２の
自己組織化膜を形成する。第２の化合物の表面を改質す
る官能基として、より親液性を示すもの、あるいは、機
能性液体原料と親和性の高いものを選ぶことにより、よ
り安定なパターンニングが可能となる。Further, it is possible to form a second self-assembled film in a region where the FAS has been removed. The binding functional group of the second compound binds to the hydroxyl group to form a second self-assembled film. More stable patterning can be achieved by selecting a functional group having a higher lyophilic property or a higher affinity with the functional liquid material as the functional group for modifying the surface of the second compound.
【００１８】なお、自己組織化膜は、例えば、‘An Int
roduction to ULTRATHIN ORGANIC FILMS: Ulman, ACADE
MIC PRESS’に詳しく開示されている。Incidentally, the self-assembled film can be formed, for example, by using “An Int
roduction to ULTRATHIN ORGANIC FILMS: Ulman, ACADE
MIC PRESS '.
【００１９】本発明において、スピンコート法で塗布さ
れる液体材料は、水系、溶剤系の各種液体が使用可能で
ある。撥液性を示すフルオロ基のパターンは、水系、溶
剤系を問わず液体材料に対して濡れないため、パターン
ニングが可能である。In the present invention, as the liquid material applied by the spin coating method, various water-based and solvent-based liquids can be used. The pattern of the fluoro group exhibiting liquid repellency does not get wet with a liquid material regardless of an aqueous system or a solvent system, so that patterning is possible.
【００２０】また、前記機能性薄膜は、用いる液体材料
により決定されるもので、例えば、導電性ポリマーを用
いた場合や、液体金属材料を用いた場合には導電性薄膜
が形成されることになり、非導電性ポリマーを用いた場
合には絶縁性薄膜が形成される。他に、高分子系発光材
料などを用いた場合には薄膜発光層が形成される。さら
に、液体材料として所望の組成のゾルを用いることによ
り、ペロブスカイト酸化膜などが得られることが知られ
ている。これら以外にも様々な機能性薄膜が液体材料か
ら形成することができる。The functional thin film is determined by a liquid material used. For example, when a conductive polymer is used or when a liquid metal material is used, a conductive thin film is formed. When an electrically non-conductive polymer is used, an insulating thin film is formed. In addition, when a polymer light emitting material or the like is used, a thin film light emitting layer is formed. Further, it is known that a perovskite oxide film or the like can be obtained by using a sol having a desired composition as a liquid material. In addition to these, various functional thin films can be formed from a liquid material.
【００２１】本発明によって得られる機能性薄膜は、均
一な厚さを持っており、厚さの変化は±５％以内に抑え
ることができる。この膜厚均一性は、スピンコート法が
有する特徴であり、スピンコートの条件と、液体材料の
物性値を適宜選ぶことにより、容易に実現可能である。The functional thin film obtained by the present invention has a uniform thickness, and a change in thickness can be suppressed within ± 5%. This film thickness uniformity is a feature of the spin coating method, and can be easily realized by appropriately selecting the spin coating conditions and the physical properties of the liquid material.
【００２２】以下、本発明の微細構造体の製造方法を図
面を参照して説明する。微細構造体を得るために、図１
〜５に示すように、基板１１表面に自己組織化膜１４を
形成し、自己組織化膜１４を利用して親液部１１ａと撥
液部１１ｂとを所定のパターンで形成するパターン形成
工程、及びスピンコート法により、親液部１１ａに選択
的に機能性薄膜を形成する機能性薄膜形成工程が行われ
る。Hereinafter, a method for manufacturing a microstructure according to the present invention will be described with reference to the drawings. Fig. 1
5, a self-assembled film 14 is formed on the surface of the substrate 11, and a lyophilic portion 11a and a lyophobic portion 11b are formed in a predetermined pattern using the self-assembled film 14. Then, a functional thin film forming step of selectively forming a functional thin film on the lyophilic portion 11a is performed by spin coating.
【００２３】１）前記パターン形成工程において まず、図１に示すように、基板１１表面に前記化合物か
らなる自己組織化膜１４を形成する。自己組織化膜１４
は、既述の原料化合物と基板とを同一の密閉容器中に入
れておき、室温の場合は２〜３日程度の間放置すると基
板上に形成される。また、密閉容器全体を１００℃程度
に保持することにより、３時間程度で基板上に形成され
る。以上に述べたのは、気相からの自己組織化膜の形成
法であるが、液相からも自己組織化膜は形成可能であ
る。例えば、原料化合物を含む溶媒中に基板を浸積し、
洗浄、乾燥することで基板上に自己組織化膜が得られ
る。1) In the pattern forming step, first, as shown in FIG. 1, a self-assembled film 14 made of the compound is formed on the surface of the substrate 11. Self-assembled film 14
Is formed on a substrate when the raw material compound and the substrate described above are placed in the same closed container and left at room temperature for about 2 to 3 days. In addition, by maintaining the whole closed container at about 100 ° C., it is formed on the substrate in about 3 hours. Although the method of forming a self-assembled film from a gas phase has been described above, a self-assembled film can be formed from a liquid phase. For example, immersing the substrate in a solvent containing the starting compound,
By washing and drying, a self-assembled film is obtained on the substrate.
【００２４】次いで、図２に示すように、最終的に得よ
うとする機能性薄膜のパターンに合わせて自己組織化膜
１４をパターンニングする。基板表面が露出した露出部
分が液体材料に対して濡れ性を持った親液部１１ａとな
り、自己組織化膜１４が残存している部分は液体材料に
対して濡れ性を持っていない撥液部１１ｂとなる。尚、
基板における撥液部の面積比率は、０．２〜０．９の範
囲とすることが好ましい。Next, as shown in FIG. 2, the self-assembled film 14 is patterned in accordance with the pattern of the functional thin film to be finally obtained. The exposed portion where the substrate surface is exposed becomes the lyophilic portion 11a having wettability to the liquid material, and the portion where the self-assembled film 14 remains is the lyophobic portion having no wettability to the liquid material. 11b. still,
The area ratio of the liquid-repellent portion on the substrate is preferably in the range of 0.2 to 0.9.
【００２５】自己組織化膜のパターンニング方法として
は、紫外線照射法、電子ビーム照射法、Ｘ線照射法、Sc
anning Probe microscope（ＳＰＭ）法等が適用可能で
ある。本発明においては、紫外線照射法が好ましく用い
られる。紫外線照射法は、図３に示すように、機能性薄
膜のパターンを形成するための開口が形成されているフ
ォトマスク２０を介して所定の波長の紫外光を自己組織
化膜１４に対して照射することにより行われる。このよ
うに紫外光を照射することにより、自己組織化膜１４を
形成している分子が分解して、除去されてパターンニン
グが行われる。従って、紫外線照射法では、親液部及び
撥液部のパターンは、それぞれのフォトマスクに形成さ
れたパターンに合わせて形成できる。As a method of patterning the self-assembled film, an ultraviolet irradiation method, an electron beam irradiation method, an X-ray irradiation method, Sc
Anning Probe microscope (SPM) method or the like can be applied. In the present invention, an ultraviolet irradiation method is preferably used. In the ultraviolet irradiation method, as shown in FIG. 3, the self-assembled film 14 is irradiated with ultraviolet light of a predetermined wavelength through a photomask 20 in which an opening for forming a pattern of a functional thin film is formed. It is done by doing. By irradiating the ultraviolet light in this manner, molecules forming the self-assembled film 14 are decomposed and removed, and patterning is performed. Therefore, in the ultraviolet irradiation method, the patterns of the lyophilic portion and the lyophobic portion can be formed in accordance with the patterns formed on the respective photomasks.
【００２６】この際採用される紫外光の波長及び照射時
間は、自己組織化膜の原料化合物に応じて適宜決定され
るが、ＦＡＳの場合は２００ｎｍ以下の波長の紫外光が
好ましく用いられる。The wavelength and irradiation time of the ultraviolet light employed at this time are appropriately determined according to the raw material compound of the self-assembled film. In the case of FAS, ultraviolet light having a wavelength of 200 nm or less is preferably used.
【００２７】最初に基板表面に紫外光を照射したり、溶
剤により洗浄したりして、前処理を施すことが望まし
い。First, it is desirable to irradiate the substrate surface with ultraviolet light or wash it with a solvent to perform pretreatment.
【００２８】２）機能性薄膜形成工程について スピンコート法は、液体材料を基板上にコートするプロ
セスであり、この実施形態において説明する工程におい
ては、通常の公知のスピンコート法を適用することがで
きる。2) Regarding the step of forming a functional thin film The spin coating method is a process of coating a liquid material on a substrate, and in the step described in this embodiment, a commonly known spin coating method may be applied. it can.
【００２９】機能性薄膜形成工程は、単に、スピンコー
ト法により液体原料を基板上に塗布するのみである。具
体的には、図４に示すように、スピンコート法におい
て、薄膜の原料溶液（液体材料）を供給し、親液部１１
ａに選択的に液体材料（層）１２を配置する。本発明者
は、自己組織化膜を用いてパターン形成を行った基板に
スピンコートを行うだけで、親液部に選択的に液体材料
を塗布されることを見出した。原料溶液の供給（基板に
対する吐出）は、スピンコート法における基板の回転中
に行うことが好ましい。また、スピンコートは、基板に
前記の原料溶液に対する親液部及び撥液部の形成直後に
行うことが好ましい。In the step of forming a functional thin film, a liquid material is simply applied onto a substrate by spin coating. Specifically, as shown in FIG. 4, in a spin coating method, a raw material solution (liquid material) for a thin film is supplied, and a lyophilic portion 11 is formed.
a, a liquid material (layer) 12 is selectively disposed. The present inventor has found that a liquid material can be selectively applied to a lyophilic portion only by performing spin coating on a substrate on which a pattern has been formed using a self-assembled film. The supply of the raw material solution (discharge to the substrate) is preferably performed during rotation of the substrate in the spin coating method. The spin coating is preferably performed immediately after the formation of the lyophilic part and the lyophobic part for the raw material solution on the substrate.
【００３０】さらに、所望の機能性薄膜のパターンを得
るために、図５に示すように、塗布された液滴から揮発
分が揮発するように加熱等により乾燥させて固形化し、
機能性薄膜（パターン）１３を形成し、微細構造体１を
得る。乾燥条件は、特に制限されず、通常の条件であ
る。Further, in order to obtain a desired functional thin film pattern, as shown in FIG. 5, the applied droplets are dried and solidified by heating or the like so that volatile components are volatilized.
The functional thin film (pattern) 13 is formed, and the fine structure 1 is obtained. The drying conditions are not particularly limited, and are ordinary conditions.
【００３１】機能性薄膜の膜厚は、微細構造体を如何な
る用途のものとするかにより任意であるが、０．０２〜
４μｍとするのが好ましい。The thickness of the functional thin film is optional depending on the intended use of the fine structure,
It is preferably 4 μm.
【００３２】そして、本発明の製造方法においては、所
望の機能性薄膜を形成した後に、残存している自己組織
化膜を上述のパターン形成工程と同様に除去し、更に必
要に応じて通常の手法を特に制限なく用いて、用途に応
じた他の薄膜を形成する等して所望の微細構造体を得る
ことができる。Then, in the manufacturing method of the present invention, after forming the desired functional thin film, the remaining self-assembled film is removed in the same manner as in the above-described pattern forming step, and if necessary, a conventional self-assembled film is formed. Using a technique without any particular limitation, a desired fine structure can be obtained by forming another thin film according to the intended use.
【００３３】このような本発明の製造方法により製造さ
れる微細構造体は、基板の表面側に機能性薄膜が形成さ
れており、該機能性薄膜の厚みがほぼ均一なものであ
る。In the fine structure manufactured by the manufacturing method of the present invention, a functional thin film is formed on the surface side of the substrate, and the thickness of the functional thin film is substantially uniform.
【００３４】ここで、「厚みがほぼ均一」とは、機能性
薄膜が、その断面形状において凹面形状等となることな
く、部位によって厚みにばらつきが生じることがない状
態を意味し、具体的には、最も厚みの厚い部位と最も厚
みの薄い部位の差が、トータル膜厚の±５％の範囲内に
あることを意味する。Here, "substantially uniform thickness" means a state in which the functional thin film does not have a concave shape or the like in its cross-sectional shape and does not vary in thickness depending on the portion. Means that the difference between the thickest part and the thinnest part is within ± 5% of the total film thickness.
【００３５】本発明では、他の態様として、図６に示す
ように、上記の方法において、図２に示す１１ａの領域
（自己組織化膜１４が形成されていない領域）に更に１
１ｂの領域を構成する自己組織化膜１４とは異なる材料
からなり(異なる官能基を有し）、最終的に得る機能性
薄膜の原料溶液に対して親液性を有する第２の自己組織
化膜１５を選択的に形成し、続いて、当該機能性薄膜の
原料溶液をスピンコート法において供給し、必要に応じ
て乾燥固化させ、図７に示すように、当該第２の自己組
織化膜上に機能性薄膜を選択的に形成し微細構造体を得
ることもできる。なお、本発明は、上述の実施形態に制
限されるものではなく、本発明の趣旨を逸脱しない範囲
で種々変更可能である。In the present invention, as another embodiment, as shown in FIG. 6, in the above method, one more region is added to the region 11a (the region where the self-assembled film 14 is not formed) shown in FIG.
The second self-assembly, which is made of a different material (having a different functional group) from the self-assembled film 14 constituting the region 1b and has lyophilicity for the raw material solution of the functional thin film finally obtained The film 15 is selectively formed, and subsequently, a raw material solution for the functional thin film is supplied by a spin coating method, and is dried and solidified as necessary. As shown in FIG. 7, the second self-assembled film is formed. A fine structure can also be obtained by selectively forming a functional thin film thereon. Note that the present invention is not limited to the above-described embodiment, and can be variously modified without departing from the gist of the present invention.
【００３６】[0036]
【実施例】以下、実施例を参照して本発明を具体的に説
明する。The present invention will be described below in detail with reference to examples.
【００３７】[実施例１]石英ガラス基板上に１７２ｎｍ
の波長の紫外光を１０分間照射して、前処理としてクリ
ーンニングを行った。Example 1 172 nm on a quartz glass substrate
Irradiation of ultraviolet light having a wavelength of 10 minutes was performed to perform cleaning as pretreatment.
【００３８】次いで、機能性薄膜のパターン形成工程を
以下のように行った。Next, the step of forming a pattern of the functional thin film was performed as follows.
【００３９】即ち、前記石英ガラス基板とＦＡＳ原料の
一つであるヘプタデカフルオロテトラヒドロオクチルト
リエトキシシランとを、同一の密閉容器に入れて４８時
間室温で放置することにより、該石英ガラス基板表面に
フルオロアルキル基を有する自己組織化膜を形成した。
そして、更に、所定のパターンを有するフォトマスクを
介して、１７２ｎｍの波長の紫外光を照射して、マスク
していない部位の自己組織化膜のみを選択的に除去し
て、親液部と撥液部とを形成した。That is, the quartz glass substrate and heptadecafluorotetrahydrooctyltriethoxysilane, which is one of the FAS raw materials, are placed in the same closed container and left at room temperature for 48 hours, so that the surface of the quartz glass substrate is A self-assembled film having a fluoroalkyl group was formed.
Further, ultraviolet light having a wavelength of 172 nm is irradiated through a photomask having a predetermined pattern to selectively remove only the self-assembled film at the unmasked portion, thereby repelling the lyophilic portion. A liquid part was formed.
【００４０】ここで、用いたフォトマスクの詳細は次の
通りである。基板は、石英を用い、１７２ｎｍの波長の
紫外光を約６０％を透過する。ラインアンドスペースと
呼ばれる線状のパターンで、ラインのピッチは２０μｍ
とした。ラインの幅を変化させた領域を設け、その幅
は、２μｍから１８μｍまで２μｍ刻みで変化させた。
パターンはクロム膜で作成されており、紫外光はクロム
膜で遮られる。ライン状のパターンの幅を変えることに
より、紫外光が照射される領域の面積の比率は、０．１
から０．９の範囲を変化する。Here, the details of the photomask used are as follows. The substrate is made of quartz and transmits about 60% of ultraviolet light having a wavelength of 172 nm. A linear pattern called line and space with a line pitch of 20 μm
And A region having a changed line width was provided, and the width was changed from 2 μm to 18 μm in steps of 2 μm.
The pattern is made of a chrome film, and ultraviolet light is blocked by the chrome film. By changing the width of the line pattern, the ratio of the area of the region irradiated with the ultraviolet light is 0.1%.
From 0.9 to 0.9.
【００４１】次いで、機能性薄膜形成工程を次のように
行った。Next, a functional thin film forming step was performed as follows.
【００４２】即ち、スピンコート法により液体ＩＴＯ原
料を基板上に塗布した。ここで用いた液体ＩＴＯ原料
は、有機酸インジウムと有機錫の混合物を揮発性溶剤に
溶かしたものである。有機酸インジウムと有機錫の重量
比は９７：３とし、溶剤としてキシレンを用いた。固形
分８％で、粘度は約２１ｃｐであった。この液体材料を
塗布した後に１２０℃で３０分間で乾燥し、さらに４０
０℃で６０分間の熱処理を加えることにより、透明で導
電性の比較的高いＩＴＯ膜が得られることを確認されて
いる。That is, the liquid ITO raw material was applied on the substrate by spin coating. The liquid ITO raw material used here is obtained by dissolving a mixture of indium organic acid and organic tin in a volatile solvent. The weight ratio of indium organic acid to organic tin was 97: 3, and xylene was used as a solvent. At 8% solids, the viscosity was about 21 cp. After applying this liquid material, it is dried at 120 ° C. for 30 minutes,
It has been confirmed that a transparent and relatively conductive ITO film can be obtained by applying a heat treatment at 0 ° C. for 60 minutes.
【００４３】スピンコート条件は次の通りである。ま
ず、基板を１０００ｒｐｍで回転させながら液体ＩＴＯ
原料を基板上に滴下して１０秒間保持し、更にその後２
０００ｒｐｍに回転数を上げて１５秒間保持し、その後
に回転を停止した。The spin coating conditions are as follows. First, while rotating the substrate at 1000 rpm, the liquid ITO
The raw material is dropped on the substrate and held for 10 seconds.
The rotation speed was increased to 000 rpm and held for 15 seconds, after which the rotation was stopped.
【００４４】以上の工程を経ることで、幾つかのパター
ン形状においては、親液部にのみ選択的に液体ＩＴＯ原
料が形成されることがわかった。撥液部のパターン幅が
４〜１８μｍの場合には、良好に液体ＩＴＯ原料がパタ
ーン形状に合わせて形成されるのに対して、撥液部のパ
ターン幅が２μｍの場合には、撥液部上にも液体ＩＴＯ
原料が形成されている箇所があり、良好なパターンニン
グができていないことが認められた、良好なパターンニ
ングができた基板について、基板を乾燥して揮発分を蒸
発させて固化し、その後熱処理を行った結果、初期のパ
ターンニングの形状が忠実に再現されることが確認され
た。機能性薄膜として厚さ０．１μｍのＩＴＯ薄膜を有
する微細構造体が得られた。乾燥条件は、１２０℃で３
０分間とし、熱処理条件は４００℃で６０分間とした。
パターンニングされたＩＴＯ薄膜の導電率を測定したと
ころ、パターンニングしないで液体ＩＴＯ原料から作製
した膜と同程度の導電率が得られた。Through the above steps, it was found that in some patterns, the liquid ITO raw material was selectively formed only in the lyophilic portion. When the pattern width of the liquid-repellent portion is 4 to 18 μm, the liquid ITO raw material is satisfactorily formed according to the pattern shape. On the other hand, when the pattern width of the liquid-repellent portion is 2 μm, Liquid ITO on top
It was found that there was a place where the raw material was formed, and that good patterning was not performed.For the substrate with good patterning, the substrate was dried, the volatiles were evaporated and solidified, and then heat treatment was performed. As a result, it was confirmed that the initial patterning shape was faithfully reproduced. A fine structure having an ITO thin film having a thickness of 0.1 μm as a functional thin film was obtained. Drying conditions are 120 ° C and 3
The heat treatment was performed at 400 ° C. for 60 minutes.
When the conductivity of the patterned ITO thin film was measured, the same conductivity as that of a film made from a liquid ITO raw material without patterning was obtained.
【００４５】本実施例では、液体原料の溶剤として揮発
性のキシレンを用いた。このように揮発性成分を含む液
体原料では、基板上に滴下してしばらく放置すると、液
体の粘度が上昇するためか、液滴のパターンニングが良
好にいかない場合があった。２００ｒｐｍ以上の回転数
で基板を回転しながら、液体原料を滴下することによ
り、自己組織化膜のパターンに合わせてＩＴＯ膜のパタ
ーンニングが可能であった。In this example, volatile xylene was used as the solvent for the liquid raw material. In the case of a liquid raw material containing a volatile component as described above, if it is dropped on a substrate and left for a while, the patterning of the droplet may not be performed well, possibly because the viscosity of the liquid increases. By dripping the liquid raw material while rotating the substrate at a rotation speed of 200 rpm or more, it was possible to pattern the ITO film in accordance with the pattern of the self-assembled film.
【００４６】さらに、パターンニング形成工程終了後に
そのまま大気中で放置し、２４時間後に機能性薄膜形成
工程を行った場合、液滴のパターンニングが良好にいか
ない場合があった。ＦＡＳが除去された直後は、親液性
が高く、液滴の安定したパターンニングが可能である
が、機能性薄膜形成工程までの時間が長いと親液部の表
面が汚染、あるいは変化して、パターンニング形成工程
終了直後の良好な親液性が得られないと考えられる。従
って、パターンニング形成工程終了後すみやかに機能性
薄膜形成工程を行うことが望ましい。Furthermore, when the functional thin film forming step is performed 24 hours after standing in the air after completion of the patterning forming step, the patterning of the droplets may not be satisfactory. Immediately after FAS is removed, the lyophilicity is high and stable patterning of droplets is possible. However, if the time until the functional thin film forming step is long, the surface of the lyophilic portion is contaminated or changed. It is considered that good lyophilicity immediately after the completion of the patterning forming step cannot be obtained. Therefore, it is desirable to perform the functional thin film forming step immediately after the patterning forming step is completed.
【００４７】[実施例２]実施例１と同様にして、基板上
にフルオロアルキル基を有する自己組織化膜のパターン
ニングを行った。フォトマスクは実施例１と同じものを
用いた。紫外光によりＦＡＳを除去した領域に、異なる
官能基を有する第２の自己組織化膜の形成を行った。即
ち、前述の図６に示すような２種の自己組織化膜パター
ンを形成した。Example 2 In the same manner as in Example 1, a self-assembled film having a fluoroalkyl group was patterned on a substrate. The same photomask as in Example 1 was used. A second self-assembled film having a different functional group was formed in a region where FAS was removed by ultraviolet light. That is, two types of self-assembled film patterns as shown in FIG. 6 were formed.
【００４８】即ち、ＦＡＳがパターンニングされた基板
を、純水、エタノールの順で洗浄した後に、エタノール
に、１ｖｏｌ％のアミノプロピルトリエトキシシランを
加えた混合液中に５分間浸した。さらに、エタノール、
純水の順で基板の洗浄を行った。このプロセスにより、
図６に示すような、ＦＡＳが除去された領域（１１ｂ）
にのみ、アミノ基を有する自己組織化膜（１５）が形成
された構造が得られた。この場合、アミノ基は、有機化
合物薄膜の分子鎖の末端に形成される。以上の工程を経
て、フルオロアルキル基とアミノ基とを有する自己組織
化膜が基板表面にパターンニングされた。That is, the substrate on which the FAS was patterned was washed with pure water and ethanol in that order, and then immersed in ethanol for 5 minutes in a mixed solution obtained by adding 1 vol% aminopropyltriethoxysilane. In addition, ethanol,
The substrate was cleaned in the order of pure water. With this process,
As shown in FIG. 6, the area where FAS has been removed (11b)
Only in this case, a structure in which a self-assembled film (15) having an amino group was formed was obtained. In this case, the amino group is formed at the terminal of the molecular chain of the organic compound thin film. Through the above steps, a self-assembled film having a fluoroalkyl group and an amino group was patterned on the substrate surface.
【００４９】次いで、機能性薄膜形成工程を実施例１と
同様に行った。液体材料として液体ＩＴＯ原料を用い
た。スピンコートの結果、図７に示すように、アミノ基
を有する自己組織化膜が形成されている領域にのみ選択
的に液体ＩＴＯ原料の層（１３の部分）が形成されるこ
とがわかった。アミノ基を有する自己組織化膜を形成し
た領域（１５に対応する領域）が、親液部として機能す
ることが確認された。さらに、基板を乾燥して揮発分を
蒸発させて固化し、その後熱処理を行った結果、初期の
パターンニングの形状が忠実に再現されることが確認さ
れた。機能性薄膜として厚さ０．１μｍのＩＴＯ薄膜
（１３）を有する微細構造体が得られた。乾燥条件は、
１２０℃で３０分間とし、熱処理条件は４００℃で６０
分間とした。Next, a functional thin film forming step was performed in the same manner as in Example 1. A liquid ITO raw material was used as a liquid material. As a result of the spin coating, as shown in FIG. 7, it was found that a layer (13) of the liquid ITO raw material was selectively formed only in the region where the self-assembled film having an amino group was formed. It was confirmed that the region where the self-assembled film having an amino group was formed (the region corresponding to 15) functions as a lyophilic portion. Further, the substrate was dried, the volatile components were evaporated and solidified, and then heat treatment was performed. As a result, it was confirmed that the initial patterning shape was faithfully reproduced. A fine structure having an ITO thin film (13) having a thickness of 0.1 μm as a functional thin film was obtained. Drying conditions are
30 minutes at 120 ° C., and heat treatment conditions are 60 ° C. at 400 ° C.
Minutes.
【００５０】[0050]
【発明の効果】以上説明したように本発明によれば、現
像、リンス等といったフォトリソグラフィーとエッチン
グの工程が必要なく、簡便なプロセスでミクロンオーダ
ーの精度を有する新規な機能性薄膜のパターンニング技
術を提供することができる。As described above, according to the present invention, there is no need for photolithography and etching steps such as development and rinsing, etc., and a novel functional thin film patterning technique having a micron-order accuracy by a simple process. Can be provided.
【００５１】本発明によれば、形成する薄膜の厚さの均
一化が可能で、パターンの微細化が容易であり、簡便な
工程で微細構造体を製造できる。According to the present invention, the thickness of the thin film to be formed can be made uniform, the pattern can be easily miniaturized, and a fine structure can be manufactured by a simple process.
【図１】基板上に自己組織化膜が形成されている状態を
示す断面図である。FIG. 1 is a cross-sectional view showing a state where a self-assembled film is formed on a substrate.
【図２】自己組織化膜がパターンニングされた状態を示
す断面図である。FIG. 2 is a cross-sectional view showing a state where a self-assembled film is patterned.
【図３】自己組織化膜のパターンニングの工程を示す断
面図である。FIG. 3 is a sectional view showing a step of patterning the self-assembled film.
【図４】基板の自己組織化膜が形成されていない領域に
液体材料がスピンコート法により形成されている状態を
示す断面図である。FIG. 4 is a cross-sectional view showing a state in which a liquid material is formed by spin coating in a region of the substrate where a self-assembled film is not formed.
【図５】基板上の自己組織化膜が形成されていない領域
に機能性薄膜がえれた状態を示す断面図である。FIG. 5 is a cross-sectional view showing a state where a functional thin film is obtained in a region where a self-assembled film is not formed on a substrate.
【図６】自己組織化膜が除去された領域に他の第２の自
己組織化膜が形成されている状態を示す断面図である。FIG. 6 is a cross-sectional view showing a state in which another second self-assembled film is formed in a region where the self-assembled film has been removed.
【図７】第２の自己組織化膜が設けられた領域に機能性
薄膜が形成されている状態を示す断面図である。FIG. 7 is a cross-sectional view showing a state where a functional thin film is formed in a region where a second self-assembled film is provided.
１ 微細構造体 １１ 基板 １１ａ 親液部 １１ｂ 撥液部 １２ 液体材料 １３ 機能性薄膜 １４ 自己組織化膜 １５ 第２の自己組織化膜 ２０ フォトマスク Reference Signs List 1 microstructure 11 substrate 11a lyophilic portion 11b lyophobic portion 12 liquid material 13 functional thin film 14 self-assembled film 15 second self-assembled film 20 photomask
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｌ 21/316 Ｈ０１Ｌ 21/316 Ｇ 21/3205 29/06 29/06 21/88 Ｂ Ｆターム(参考） 2H096 AA25 AA27 AA30 BA20 CA14 FA01 GA60 4D075 AC64 AC94 AD16 AE03 BB23Z CA36 CA37 DA06 DB01 DB13 DB14 DB31 DC21 4M104 AA10 BB36 DD22 DD51 DD62 HH14 5F033 GG04 HH38 PP26 QQ01 QQ91 WW00 5F058 AA03 AA06 AC03 AF04 AG01 BA06 BC05 BF46 BH01 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H01L 21/316 H01L 21/316 G 21/3205 29/06 29/06 21/88 B F-term (Reference) 2H096 AA25 AA27 AA30 BA20 CA14 FA01 GA60 4D075 AC64 AC94 AD16 AE03 BB23Z CA36 CA37 DA06 DB01 DB13 DB14 DB31 DC21 4M104 AA10 BB36 DD22 DD51 DD62 HH14 5F033 GG04 HH38 PP26 QQ01 QQ91 BA0003A01B03A
Claims (11)
法であって、基板表面に有機分子膜を用いて、親液部と
撥液部とを所定のパターンに形成する工程と、スピンコ
ート法により前記基板上の親液部に選択的に機能性薄膜
を形成する工程とを有する微細構造体の製造方法。1. A method for manufacturing a microstructure provided with a functional thin film, comprising: forming an lyophilic part and a lyophobic part in a predetermined pattern using an organic molecular film on a substrate surface; Selectively forming a functional thin film on the lyophilic portion on the substrate by a coating method.
ことを特徴とする請求項１に記載の微細構造体の製造方
法。2. The method according to claim 1, wherein the organic molecular film is a self-assembled film.
ルキル基を有する自己組織化膜であることを特徴とする
請求項２に記載の微細構造体の製造方法。3. The method according to claim 2, wherein the liquid repellent portion of the organic molecular film is a self-assembled film having a fluoroalkyl group.
基を有する有機分子膜により親液部を形成することを特
徴とする請求項２に記載の微細構造体の製造方法。4. The method for producing a microstructure according to claim 2, wherein the lyophilic part is formed by an organic molecular film having a functional group different from that of the organic molecular film of the liquid repellent part.
膜であることを特徴とする請求項４に記載の微細構造体
の製造方法。5. The method according to claim 4, wherein the organic molecular film in the lyophilic portion is a self-assembled film.
含む液体材料であることを特徴とする請求項１に記載の
微細構造体の製造方法。6. The method according to claim 1, wherein a material of the functional thin film is a liquid material containing a volatile solvent.
の回転中に、前記機能性薄膜の原料を前記基板上に供給
してスピンコートを行うことを特徴とする請求項１に記
載の微細構造体の製造方法。7. The microstructure according to claim 1, wherein in the spin coating method, a spin coating is performed by supplying a material of the functional thin film onto the substrate while the substrate is rotating. Manufacturing method.
であることを特徴とする請求項７に記載の微細構造体の
製造方法。8. The method according to claim 7, wherein the rotation speed of the substrate is 200 rpm or more.
を加熱することを特徴とする請求項１に記載の微細構造
体の製造方法。9. The method according to claim 1, wherein the substrate is heated after supplying the raw material for the functional thin film.
ターンに形成した直後に、スピンコート法を行うことを
特徴とする請求項１に記載の微細構造体の製造方法。10. The method according to claim 1, wherein a spin coating method is performed immediately after forming the lyophilic part and the lyophobic part in a predetermined pattern.
が、０．２から０．９の範囲であることを特徴とする請
求項１に記載の微細構造体の製造方法。11. The method according to claim 1, wherein the ratio of the area of the liquid-repellent portion to the substrate is in the range of 0.2 to 0.9.
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