JPS60222173A - Film forming device - Google Patents

Abstract

PURPOSE:To form a uniform monomolecular film without any defects wherein molecules are orderly arranged by charging a liquid for developing a group of film forming molecules in a vessel, providing a carrier, and forming films by remote manipulation. CONSTITUTION:A carrier 11 is held almost vertical to a liquid surface 10 on which a group of molecules for forming films is developed. The holding, attaching and detaching of the carrier 11 and the developing of the group of molecules over the liquid surface 10 are carried out by an automatic carrier holder 32, an automatic carrier attaching and detaching tool 13, and an automatic pipette of a remote manipulation means for preventing the intrusion of foreign matter. The intrusion of foreign matter is prevented in this way, and a uniform monomolecular film or built-up films of monomolecular films without any defects wherein molecules the orderly arranged is formed.

Description

【発明の詳細な説明】 （１）技術分野 本発明は、成膜装置に関する。[Detailed description of the invention] (1) Technical field The present invention relates to a film forming apparatus.

（２）背景技術 従来、液面に展開された単分子膜を、その支持体である
固体担体の表面上に移し取ることにより、該担体上に単
分子膜又は単分子累積膜を成膜する方法として、所謂ラ
ングミュア−プロジェット法が知られている。(2) Background technology Conventionally, a monomolecular film developed on a liquid surface is transferred onto the surface of a solid carrier that is its support, thereby forming a monomolecular film or a monomolecular cumulative film on the support. As a method, the so-called Langmuir-Prodgett method is known.

ラングミュア・プロジェット法の原理は、例えば分子内
に親木基と疎水基を有する構造の分子において、両者の
バランス（両親媒性のバランス）が適度に保たれている
とき、分子は水面上で親木基を下に向けて単分子の層に
なることを利用して単分子膜または単分子層の累積膜を
作成する方法である。The principle of the Langmuir-Prodgett method is that, for example, in a molecule with a structure that has a parent wood group and a hydrophobic group in the molecule, when the balance between the two (balance of amphiphilicity) is maintained appropriately, the molecule will move on the water surface. This is a method of creating a monomolecular film or a cumulative film of monomolecular layers by using the fact that the parent tree faces downward to form a monomolecular layer.

この方法に使用される成膜装置の代表的な例を第１図に
示し、図面も参照しながらこの種の技術について以下に
説明する。A typical example of a film forming apparatus used in this method is shown in FIG. 1, and this type of technology will be described below with reference to the drawings.

第１図の装置において、その上に単分子１模が展開され
る展開液、一般には水、メタノール、エチルアルコール
等は、角型液槽ｌに溜められる。角型液槽ｌの内側には
、２次元シリンダーとして機能する枠２１例えばポリプ
ロピレン酸等が水平に吊られており、液面ｌＯを所望の
広さに仕切っている。In the apparatus shown in FIG. 1, a developing solution, generally water, methanol, ethyl alcohol, etc., on which a single molecule is developed is stored in a rectangular liquid tank l. Inside the rectangular liquid tank l, a frame 21 functioning as a two-dimensional cylinder, such as polypropylene acid, is hung horizontally, and the liquid surface lO is partitioned into a desired width.

枠２の内側には、２次元ピストンとして機能し、液面ｌ
Ｏに展開される成膜用分子群に所望の表面圧を生じさせ
るための浮子３、例えばポリプロピレン製等が浮かべら
れている。Inside the frame 2, it functions as a two-dimensional piston and has a liquid level l.
A float 3 made of, for example, polypropylene is floated to generate a desired surface pressure on the film-forming molecular group developed in O.

浮子３の幅は枠２の内側より僅かに狭く作ってあり、２
次元ピストンとして図の左右方向に滑らかに動けるよう
になっている。The width of the float 3 is made slightly narrower than the inside of the frame 2,
As a dimensional piston, it can move smoothly in the left and right directions in the figure.

浮子３の右方向への動作は、浮子３を右方向に引っばる
とともに液面ｌＯに展開された成膜用分子群に所望の表
面圧を与えるための重り４によって行われる。浮子３の
左方向への動作ならびに停止は、浮子３に設けられた磁
石６と、不図示の保持機構によって左右に動くことが可
能な対磁石７との反発力によって行われる。The rightward movement of the float 3 is carried out by a weight 4 that pulls the float 3 to the right and applies a desired surface pressure to the film-forming molecules spread on the liquid surface lO. The leftward movement and stopping of the float 3 is performed by the repulsive force between a magnet 6 provided on the float 3 and a pair of magnets 7 that can be moved left and right by a holding mechanism (not shown).

成膜は、例えば以下のようにして行なう。すなわち、所
望の成膜用分子群を適当な溶媒に溶した低濃度、一般に
は５ＸｌＧ−３■ｏｌ／４１以下程度の溶液をスポイト
等により液面１０に滴下すると、溶媒が揮発したあとに
液面ｌＯに単分子膜が展開される。この単分子膜は、液
面ｌｏ上で２次元系の挙動を示す０分子の面密度が低い
ときは２次元気体の気体膜と呼ばれ、−分子あたりの占
有面積と表面圧の間には、２次元理想気体の状態方程式
が成立する。Film formation is performed, for example, as follows. That is, when a solution of a desired film-forming molecule group dissolved in an appropriate solvent at a low concentration, generally about 5 A monomolecular film is developed on the plane lO. This monomolecular film exhibits the behavior of a two-dimensional system on the liquid surface lo. When the areal density of molecules is low, it is called a gas film of a second-dimensional gas, and there is a relationship between the occupied area per molecule and the surface pressure. , the equation of state for a two-dimensional ideal gas holds true.

気体膜の状態から、徐々に浮子３を右方に動かし、単分
子膜が展開する液面の広がりを次第に縮めて面密度を増
してゆくと、分子間相互作用が強まり、２次元液体の液
体膜を経て２次元固体の固体膜へと変わる。該固体膜の
状態を維持したまま、所望の担体１１　（一般には、ガ
ラス、セラミックス、プラスチックあるいは金属等の基
板が使用される）を該液面ｉｏを横切るように上下すれ
ば、担体１１にに所望の単分子膜または単分子累積膜が
成膜される。From the gas film state, the float 3 is gradually moved to the right to gradually reduce the spread of the liquid surface on which the monomolecular film develops and increase the surface density, which strengthens the intermolecular interactions and transforms the two-dimensional liquid into a two-dimensional liquid. After passing through the film, it changes into a two-dimensional solid film. While maintaining the state of the solid film, if a desired carrier 11 (generally, a glass, ceramic, plastic, or metal substrate is used) is moved up and down across the liquid surface io, the carrier 11 is exposed to A desired monomolecular film or monomolecular cumulative film is formed.

しか°しながら、従来の成膜装置では以下に述べるよう
な問題があった。However, conventional film forming apparatuses have the following problems.

液面ｌＯに展開される単分子膜を構成する成膜用分子群
としては、一般にはその分子内に疎水性部分および親木
性部分を有する分子が使用される。Molecules having a hydrophobic portion and a phyllophilic portion within the molecule are generally used as the film-forming molecule group constituting the monomolecular film developed on the liquid surface IO.

このような分子の疎水性部分の構成要素として最も代表
的なものはアルキル基であって、直鎖状のものも分枝状
のものも使用しうる。その他の疎水性部分を構成する基
としては上記フルキル基の他、例えばビニレン、ビニリ
デン、アセチレン等のオレフィン系炭化水素基、フェニ
ル、ナンチル、アントラニル等の如き縮合多環フェニル
基、ビフェニル、ターフェニル等のｍ状条ｓフェニル基
等の疎水基等が挙げられる。これらは各々単独又はその
複数が組合されて上記分子の疎水性部分を構成する。一
方、親木性部分の構成要素として最も代表的なものは、
例えばカルボキシル基及びその金属塩並びにアミン塩、
スルホン酸基及びその金属塩並びにアミン塩、スルホン
アミド基、アミド基、アミノ基、イミノ基、ヒドロキシ
ル基。The most typical component of the hydrophobic portion of such a molecule is an alkyl group, and both linear and branched groups can be used. In addition to the above-mentioned furkyl group, other groups constituting the hydrophobic moiety include olefinic hydrocarbon groups such as vinylene, vinylidene, and acetylene, fused polycyclic phenyl groups such as phenyl, nanthyl, anthranyl, etc., biphenyl, and terphenyl. Examples include hydrophobic groups such as m-shaped phenyl groups. These may be used singly or in combination to form the hydrophobic portion of the molecule. On the other hand, the most typical components of the parent tree are:
For example, carboxyl groups and their metal salts and amine salts,
Sulfonic acid groups and their metal salts, amine salts, sulfonamide groups, amide groups, amino groups, imino groups, hydroxyl groups.

４級アミノ基、オキシアミノ基、オキシイミノ基、ジア
ゾニウム基、グアニジン基、ヒドラジン基、リン酸基、
ケイ酸基、アルミン酸基等の親木性基等が挙げられる。Quaternary amino group, oxyamino group, oximino group, diazonium group, guanidine group, hydrazine group, phosphoric acid group,
Examples include wood-philic groups such as silicic acid groups and aluminic acid groups.

これらも各々単独又はその複数が組み合されて上記分子
の親水性部分をａｔする。Each of these may be used alone or in combination to att the hydrophilic portion of the molecule.

ここで、分子内に親水性部分及び疎水性部分を有すると
は、例えば分子が上記のような親木基及び疎水基の両者
を分子内に１つずつ有するか、又は分子内に１つ以上の
親木基及び疎水基を有する場合には、分子全体の構成に
おいである部分が他の部分との関係において親木性であ
り、一方後者の部分は前者の部分との関係において疎水
性の関係を有することをいう。Here, having a hydrophilic part and a hydrophobic part in a molecule means, for example, that a molecule has both one parent group and one hydrophobic group as described above in the molecule, or one or more in the molecule. When it has a woody group and a hydrophobic group, in the overall structure of the molecule, one part is woody in relation to other parts, while the latter part is hydrophobic in relation to the former part. It means having a relationship.

このような成膜用分子群を具体的に示せば、例えば光導
電性等の所望の機能性を有する薄膜を形成するＦ記の如
き分子等が挙げられる。Specific examples of such a group of molecules for film formation include molecules such as those listed in F, which form a thin film having desired functionality such as photoconductivity.

■所望の機能性を荷う部位、即ち機能性部分（例えばπ
°市子系）が同時に強い親木性（又は強い疎水ｅＪ：）
としての性質を併有する分子、例えば銅フタロシアニン
、ピレン、トリフェニルメタン等、（？）機能性部分が
特に親水性、疎水性を有さず、Ｉ−記の如き親木基、疎
水基等を導入することで１分子内に親木性部分と疎水性
部位を構′成したもの、例えば、 イ、４１＆能性部分が親木性部分の側に配設されている
もの、例えば、光導電性を有する長鎖アルキル置換のメ
ロシアニン色素等、 口９機能性部分が疎水性部分の側に配設されているもの
、例えば、ピレンに長鎖アルキルカルボン酸を結合した
もの等、 ハ１機能性部分が中央付近、即ち疎水性部分と親水性部
分の中間に配設されているもの、例えば、アントラセン
誘導体、ジアゾ色素の誘導体等、 二９機能性部分がなく、疎水性部分と親水性部分のみで
できているもの、例えば、長鎖飽和脂肪酸置換のステア
リン酸、アラキシン酸等が具体的なものとして挙げられ
る。■ Parts that carry the desired functionality, i.e., functional parts (for example, π
° Ichigo system) and strong tree parentness (or strong hydrophobic eJ:) at the same time
Molecules that have properties such as copper phthalocyanine, pyrene, triphenylmethane, etc. (?) The functional moiety does not have particular hydrophilicity or hydrophobicity, and has parenteral groups, hydrophobic groups, etc. as described in I-. Those in which a lignophilic part and a hydrophobic part are formed in one molecule by introducing them, for example, those in which the functional part is placed on the side of the lignophilic part, for example, photoconductive long-chain alkyl-substituted merocyanine dyes with a functional property, etc., in which a functional moiety is placed on the side of a hydrophobic moiety, such as those in which a long-chain alkyl carboxylic acid is bonded to pyrene; Those in which the moiety is located near the center, that is, between the hydrophobic and hydrophilic moieties, such as anthracene derivatives, diazo dye derivatives, etc.29 There is no functional moiety, only the hydrophobic moiety and the hydrophilic moiety. Specific examples include stearic acid and alaxic acid substituted with long-chain saturated fatty acids.

このような分子を用いて担体上に単分子膜又は単分子累
積膜を成膜する場合、分子配列の均一な秩序正しい膜を
成膜するためには、装置内をゴミ等のない清浄な状態に
維持することが望まれる。When forming a monomolecular film or a monomolecular cumulative film on a carrier using such molecules, in order to form a film with a uniform and orderly molecular arrangement, it is necessary to keep the inside of the equipment clean and free of dust. It is desirable to maintain the

装置内にゴミ等の異物が混入する−・番大きな原因は、
成膜用分子群の液面への展開や担体を、着脱する際に、
装置内、中でも液面上に手を差し延べる等の操作を行な
うことにある。このため従来の装置では、手に付着して
いたゴミ等により液面や担体が汚染されるという問題が
あった。また、外気中のゴミ等が装置内に入り、液面や
担体を汚染するといった問題もあった。Foreign matter such as dust gets into the device - The biggest cause is
When deploying molecules for film formation on the liquid surface and attaching and detaching the carrier,
It involves performing operations such as reaching inside the device, especially above the liquid surface. For this reason, in the conventional apparatus, there was a problem in that the liquid surface and the carrier were contaminated by dirt and the like adhering to hands. Additionally, there was a problem in that dust and the like in the outside air entered the device and contaminated the liquid surface and the carrier.

（３）発明の開示 本発明は、上記の事実に鑑み成されたものであって、本
発明の目的は、上記の問題点を解消し、更には分子配列
の整った欠陥のない均一な単分子膜または単分子累積膜
を成膜することが可能な新規な成膜装置を提供すること
にある。(3) Disclosure of the Invention The present invention has been made in view of the above-mentioned facts, and an object of the present invention is to solve the above-mentioned problems, and furthermore, to produce uniform molecules with well-arranged molecules and no defects. An object of the present invention is to provide a new film forming apparatus capable of forming a molecular film or a monomolecular cumulative film.

本発明のｔ記目的は、以下の本発明によって達成される
。The objects of the present invention are achieved by the present invention as follows.

成膜用分子群をその液面に展開させる展開液を収容する
液槽と、前記分子群を成膜して受領する１１体とを備え
、成膜操作に係る遠隔操作手段を設けたことを特徴とす
る成膜装置。It is equipped with a liquid tank containing a developing solution for developing a film-forming molecule group on the liquid surface, and 11 bodies for forming and receiving the molecule group into a film, and a remote control means for film-forming operation. Characteristic film forming equipment.

以下、第２図〜第３図に示す実施例装置をもとにして、
本発明について詳細に説明する。Hereinafter, based on the example device shown in FIGS. 2 and 3,
The present invention will be explained in detail.

第２図に例示した装置は、第１図に示したと同様の装置
に異物混入防止のための遠隔操作手段と外気遮断手段を
設けた例であり、第２図（ａ）は装置の概要を説明する
斜視図、第２図（ｂ）は正面図である。尚、第２図では
説明を簡略化するため、外気遮断手段である遮断箱内の
部分も実線で示しである。The device illustrated in FIG. 2 is an example of the same device as shown in FIG. 1, but equipped with remote control means and outside air blocking means to prevent foreign matter from entering. FIG. 2(a) shows an overview of the device. The perspective view to be explained, and FIG. 2(b) is a front view. In addition, in FIG. 2, in order to simplify the explanation, the portion inside the isolation box, which is the outside air isolation means, is also shown by solid lines.

本例の装置では、成膜は第１図におけると同様に、成膜
用分子群が展開された液面ｌＯにほぼ垂直になるよう保
持された抗体１１、本例では平板状基板を液面１０をほ
ぼ垂直に横切るように上下させることで行なうが、該抗
体１１の保持および着脱並びに該液面ｌＯへの前記分子
群の展開を、異物混入防止のために設けた遠隔操作手段
たる自動担体保持具３２および自動担体着脱具１３並び
に自動ピペット１４で行なう。更に、これ等を外気遮断
手段たる遮断箱３３内に設置し、外気からの異物混入を
も防止する。本例の遮断箱３３は、密閉性を保つ目的で
遮断材１８を間にはさんだ２重構造の壁（本例ではアク
リル製）　１？で構成されている。遮断箱３３には作業
用扉１５が設けられているが、内部観察等、不必要に該
扉１５を開閉する必要がないようにするため、該扉１５
には透明なのぞき窓１Ｂが設けらている。In the apparatus of this example, film formation is carried out in the same manner as in FIG. The holding and attachment of the antibody 11 and the deployment of the molecular group to the liquid surface 10 are carried out by moving the antibody 11 up and down almost vertically across the surface of the liquid using an automatic carrier, which is a remote control means provided to prevent contamination with foreign matter. This is carried out using a holder 32, an automatic carrier attachment/detachment device 13, and an automatic pipette 14. Furthermore, these are installed in a cutoff box 33, which is an outside air cutoff means, to prevent foreign matter from entering from the outside air. The isolation box 33 of this example has a double wall structure (made of acrylic in this example) with a barrier material 18 sandwiched between them for the purpose of maintaining airtightness.1? It is made up of. The isolation box 33 is provided with a work door 15, but in order to avoid the need to open and close the door 15 unnecessarily for purposes such as internal observation, the door 15 is
A transparent peephole 1B is provided.

成膜時における担体１１の保持は、第１図におけると同
様に不図示のリフト機構により図に矢印で示す如く上下
可能とされた担体−上下腕１２（本例では中空構造とさ
れている）に設けられた担体保持手段たる自動担体保持
具３２で行なう。該保持具３２は、その細部構成を説明
する第６図に示す如く、軸３４を中心としてバネ３５お
よび不図示の巻き取り共により１１体上下腕１２内を伸
縮することが可能なピアノ線３Ｂによって開閉自由とさ
れ、バネ３５の収腟力を利用してＩＱ体１１を保持する
。該保持具３２の開閉動作は、ピアノ線巻き取り具に設
けられた不図示のモーターを、遮断箱３３外から電気的
に制御することで行なう。The carrier 11 is held during film formation by a carrier-upper and lower arms 12 (having a hollow structure in this example) that can be moved up and down as shown by arrows in the figure by a lift mechanism (not shown), as in FIG. 1. This is carried out using an automatic carrier holder 32, which is a carrier holding means provided in the. As shown in FIG. 6 illustrating the detailed structure of the holder 32, the holder 32 is composed of 11 pieces of piano wire 3B that can be expanded and contracted within the upper and lower arms 12 by a spring 35 and a winding (not shown) around a shaft 34. It can be opened and closed freely, and the IQ body 11 is held using the vaginal contraction force of the spring 35. The opening and closing operations of the holder 32 are performed by electrically controlling a motor (not shown) provided on the piano wire winding tool from outside the cutoff box 33.

上記保持具３２への担体１１の着脱は、抗体着脱手段た
る自動担体着脱具１３で行なう、該着脱具１３は、第５
図に示す如く、その主要部を担体はさみ具２２、支持棒
長調整部２０、モーター２３およびキャ２４で構成され
ており、以下の動作によって担体１１の着脱を行なう、
前記自動担体保持具３２と同様の構成とされた担体はさ
み具２２に保持された担体１１は、支持棒２．１により
液面ＩＯＬを該保持Ｊｔ３２まで運ばれる。該支持棒２
１は、モーター２３およびギヤ２４により液面１０と平
行に正逆に回転することが可能な支柱１９に固定され、
該支柱１８の動作によって前記保持具３２への方向状め
が成される。液面１０−Ｅでの支持棒１８の伸縮は、不
図示のモーターおよびギヤ等により支持棒１９を図に矢
印で示す如くに伸縮させる支持棒長調整部２０で行なう
。−上記動作で担体１１の位置決めをして、担体１１を
前記保持具３２に着脱させる。これら動作も、第６図に
おけると同様に遮断箱３３外から電気的に制御すること
で行なう。The carrier 11 is attached to and detached from the holder 32 using an automatic carrier attachment/detachment tool 13 which is an antibody attachment/detachment means.
As shown in the figure, its main parts are composed of a carrier scissors 22, a support rod length adjustment part 20, a motor 23, and a carrier 24, and the carrier 11 is attached and detached by the following operations.
The carrier 11 held by the carrier scissors 22, which has the same structure as the automatic carrier holder 32, carries the liquid level IOL to the holding Jt32 by the support rod 2.1. The support rod 2
1 is fixed to a support 19 that can be rotated forward and backward parallel to the liquid level 10 by a motor 23 and a gear 24,
The movement of the strut 18 provides orientation toward the holder 32. Expansion and contraction of the support rod 18 at the liquid level 10-E is performed by a support rod length adjustment section 20 that expands and contracts the support rod 19 as shown by arrows in the figure using a motor, gears, etc. (not shown). - Position the carrier 11 by the above operation, and attach and detach the carrier 11 to and from the holder 32. These operations are also performed by electrical control from outside the isolation box 33, as in FIG.

液面ｌＯへの成膜用分子群の展開は、分子縦聞手段たる
自動ピペット１４で行なう、該ピペット１４は、第４図
に示す如く、その主要部を該分子群が溶解された成膜用
分子溶液を保持する保持容器３７に入れられた成膜用分
子溶液をチューブ３８を通してオートポンプ２６で吸引
し、該溶液を液面１０上に固定したピペットチップ２５
に送り込み、該チップ２５から該溶液を病上して、液面
ｌＯに上記分子群を展開させる。ピペットチップ２５の
液面ｌＯ上への保持は、該チップ２５を固定する支持棒
３８を液槽ｌ外に設けた支柱２８に固定することで行な
い、またオートポンプ２５の動作は遮断箱３３外から制
御される。The development of the molecule group for film formation on the liquid surface 10 is carried out by an automatic pipette 14, which is a molecular probe means.As shown in FIG. A molecule solution for film formation placed in a holding container 37 that holds a molecule solution for film formation is sucked through a tube 38 by an auto pump 26, and the solution is fixed on a pipette tip 25 on a liquid surface 10.
The solution is discharged from the chip 25, and the above molecules are spread on the liquid surface. The pipette tip 25 is held above the liquid level 1O by fixing the support rod 38 for fixing the tip 25 to a column 28 provided outside the liquid tank 1, and the auto pump 25 is operated outside the isolation box 33. controlled from.

Ｌ記構成の装置によれば、成膜用分子群の液面への展開
および担体の着脱を、従来の如く手を差し延べる等によ
らず遠隔操作により行なうことがｉ（能であり、従って
液面や担体を汚染することなく成膜を行なうことができ
る。また、液面や相体を外気と遮断するための外気遮断
手段を設けたことで、外気中のゴミ等による液面や担体
の汚染を防市することも可能である。尚、本発明におい
ては外気遮断手段を設けることを必ずしも必要とするも
のではないが、本例の如く遠隔操作手段と外気遮断手段
の両方を設けることで、本発明をさ、らに有効にし得る
ものである。According to the apparatus having the configuration L, it is possible to deploy the molecules for film formation on the liquid surface and to attach and detach the carrier by remote control, without having to reach out by hand as in the past. Therefore, film formation can be performed without contaminating the liquid surface or the carrier.In addition, by providing an outside air shielding means to isolate the liquid surface or the carrier from the outside air, the liquid surface may be contaminated by dirt or other substances in the outside air. It is also possible to prevent contamination of the carrier.In addition, in the present invention, it is not necessarily necessary to provide an outside air blocking means, but it is possible to provide both a remote control means and an outside air blocking means as in this example. This makes the present invention even more effective.

第３図は１本発明の別の実施態様であり、第３図（ａ）
はその概要を説明する斜視図、第３図（ｂ）は正面図で
ある。FIG. 3 shows another embodiment of the present invention, and FIG. 3(a)
is a perspective view illustrating the outline thereof, and FIG. 3(b) is a front view.

本例の装置は、第２図におけると同様の遠隔操作手段を
遮断箱３３外に設けた例であり、遮断箱３３外で担体１
１の着脱を行ない、成膜用分子群の展開も遮断箱３３外
から行なう。このため遮断箱３３には、開閉自由とされ
た担体取り出し窓２８、成膜用分子溶液滴下管３１およ
び該滴下管３Ｋを外気と遮断するための開閉自由な蓋３
０が設けられている。The device of this example is an example in which a remote control means similar to that shown in FIG. 2 is provided outside the isolation box 33, and the carrier is
1 is attached and detached, and the film-forming molecule group is also developed from outside the isolation box 33. For this reason, the isolation box 33 includes a carrier takeout window 28 that can be opened and closed freely, a molecular solution dropping tube 31 for film formation, and a lid 3 that can be opened and closed to isolate the dropping tube 3K from the outside air.
0 is set.

成膜は、担体取り出し窓２８を開放し、第２図における
と同様の担体上下腕１２を該窓２Ｂを通して上下させる
ことで行ない、担体１１の着脱は該窓２８を閉じ、遮断
箱３３外で自動担体保持ｊＬ（不図示）を操作して行な
う。Film formation is performed by opening the carrier take-out window 28 and moving the carrier upper and lower arms 12 up and down through the window 2B, similar to those shown in FIG. This is done by operating automatic carrier holding jL (not shown).

成膜用分群の展開は、蓋３０を開放し、蓋３０の丘部に
設けられた自動ピペット（不図示）から滴下した成膜用
分子溶液を前記滴下管３１を通して液面１０に滴下する
ことで行なう。The film forming subgroup is developed by opening the lid 30 and dropping the film forming molecular solution dropped from an automatic pipette (not shown) provided on the hill of the lid 30 onto the liquid surface 10 through the dropping tube 31. Let's do it.

以上、担体をほぼ垂直に液面を横切るように上下させる
ことで、成膜する場合を例として、本発明を説明したが
、本発明は上記例に限定されるものではなく、例え゛ば
円筒状等の相体を液面付近に設けられたほぼ水平な軸の
回りを回転させることで、担体を上下に移動させ成膜す
る場合、あるいは液面とほぼ水平になるように保持され
しかも七ド可能な平板状等の担体を液面と接触させるこ
とで成膜する等の場合にも適用し得るものである。The present invention has been described above using an example in which a film is formed by moving the carrier up and down almost vertically across the liquid surface, but the present invention is not limited to the above example. When forming a film by moving the carrier up and down by rotating the carrier around a nearly horizontal axis provided near the liquid surface, or when forming a film by moving the carrier up and down, or by holding it almost horizontally to the liquid level and The present invention can also be applied to cases where a film is formed by bringing a flat plate-like support that can be loaded into contact with a liquid surface.

また、本発明における成膜用分子群としては、例えば前
述したようなものが使用し得るものとして挙げられるが
、液面に展開する成膜用分子群は同じものとしてもよい
し、異る種類のものとしてもよい。もちろん２挿具りの
成膜用分子群を液面に１１（開して混合単分子累積膜を
成膜する等のことも可能である。また、本発明における
相体としてもＩ−記の平板状や円筒状の担体の他１球状
、角柱状、シート状等の所望の形状の相体を使用し得る
ものである。Furthermore, as the film-forming molecule group in the present invention, for example, those mentioned above can be used, but the film-forming molecule group developed on the liquid surface may be the same or different types. It can also be used as a. Of course, it is also possible to form a mixed monomolecular cumulative film by opening two sets of molecules for film formation on the liquid surface. In addition to flat or cylindrical carriers, support bodies of desired shapes such as spherical, prismatic, or sheet-shaped carriers may be used.

以下に上記装置を用いて成膜を行なった場合の実施例を
示し、本発明について更に詳細に説明する。The present invention will be described in further detail below by showing examples in which film formation was performed using the above-mentioned apparatus.

〈実施例１〉 第２図の装置を用いて、平板状のシリコン基板の上にス
テアリン酸の単分子累積膜を成膜した。<Example 1> Using the apparatus shown in FIG. 2, a monomolecular cumulative film of stearic acid was formed on a flat silicon substrate.

水槽中に少なくとも２回蒸留した清浄な水を入れ、Ｃｄ
Ｃｌ２を４Ｘ　１０層４ｍｏｌ／文以下の濃度になるよ
うに溶かし、さらにＨＣＩまたはＫＨＣ：０３を添加し
て、単分子膜を展開する展開液のｐｌをｐｌ（−８〜６
．５に調整した。清浄なシリコン基板を液面に、垂直に
浸漬し、液面温度をｌＯ℃゛とした後、予め調整したス
テアリン酸の０．１％ベンゼン溶液を、自動ピぺ、トで
液面上に０．１ｍ１滴下し、液面にステアリン酸の単分
子膜を緘開した。浮子を動かし単分子膜の表面圧を上げ
て２０〜３０ｄｙｎｅ／　ｃｍとし、累積操作に好適な
固体膜の状態を保持した。自動担体着脱具を用いてシリ
コン基板を担体上下腕に取り付け、シリコン基板を液面
に垂直に一ヒ下させて基板上にステアリン酸の単分子膜
を累積させた。基板の上下を繰り返して８１層の累積膜
を成膜したところ、ゴミ等のない清浄で均一な膜が安定
に得られた。Fill the aquarium with clean water that has been distilled at least twice, and
Dissolve Cl2 to a concentration of 4 mol/liter or less in 4X 10 layers, add HCI or KHC:03, and adjust the pl of the developing solution for developing the monolayer to pl (-8 to 6
．． Adjusted to 5. After vertically dipping a clean silicon substrate into the liquid surface and bringing the temperature of the liquid surface to 10°C, a pre-adjusted 0.1% benzene solution of stearic acid was poured onto the liquid surface using an automatic pipette. A monomolecular film of stearic acid was dropped on the liquid surface. The surface pressure of the monomolecular film was increased to 20 to 30 dyne/cm by moving the float to maintain a solid film state suitable for accumulation operation. The silicon substrate was attached to the upper and lower arms of the carrier using an automatic carrier attachment/detachment device, and the silicon substrate was lowered perpendicularly to the liquid surface for a moment to accumulate a monomolecular film of stearic acid on the substrate. When a cumulative film of 81 layers was formed by repeatedly moving the substrate up and down, a clean and uniform film free of dust etc. was stably obtained.

〈実施例２〉 第３図の装置のを用いて、平板状のシリコン基板の上に
ステアリン酸の単分子累積膜を成膜した。成膜条件を実
施例１と同様にして１！を膜を行なったところ、実施例
１と同様のゴミ等のない清浄で均一な膜が安定に得られ
た。<Example 2> Using the apparatus shown in FIG. 3, a monomolecular cumulative film of stearic acid was formed on a flat silicon substrate. The film forming conditions were the same as in Example 1 and 1! When a film was formed, a clean and uniform film free of dust and the like similar to that in Example 1 was stably obtained.

以上に説明した如く、異物混入を防止する遠隔操作手段
を設けたことで、成膜用分子群が展開される液面や担体
上の該分子群等に、ゴミ等の異物が混入するのが防止５
れた。また、外気遮断手段を設けたことで、外気中のゴ
ミ等による液面や担体の汚染が防止され、成膜環境を清
浄な状態に長く保持することが可能となった。その結果
、ゴミ等の異物混入のない清浄で均一な膜を安定に成膜
できるようになった。As explained above, by providing a remote control means to prevent foreign matter from getting mixed in, it is possible to prevent foreign matter such as dust from getting into the liquid surface where the film-forming molecules are developed or the molecules on the carrier. Prevention 5
It was. In addition, by providing the outside air blocking means, contamination of the liquid surface and the carrier by dust in the outside air is prevented, and it becomes possible to maintain the film-forming environment in a clean state for a long time. As a result, it has become possible to stably form a clean and uniform film without contamination by foreign matter such as dust.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は、従来の成膜装置の一例、第２図〜第３図は本
発明に係る成膜装置の実施例、第４図〜第６図はそれぞ
れ自動ピペット、自動担体着脱具、自動指体保持具を説
明する図である。 １−ｍ−液槽　２−−一枠 ３−−−浮子　４−一一重り ５−−一滑車　６一−−磁石 ７−−一対磁石　８−一一吸引パイブ ９−−−吸引ノズル　ｌＯ−ｍ−液面 １１−−−担体　１２−−一担体上下腕１３−−−自動
担体着脱手段 １４−ｍ−自動ピペット １５−一一作業扉　１Ｂ−ｍ−のぞき窓１７−−−壁　
１８−ｍ−断熱材 １９−−−支柱　２０−ｍ−支柱棒長調整部２１　、３
９−−一支持棒　２２−ｍ−担体はさみ具２３−−−モ
ーター　２４−ｍ−ギヤ ２５−−−　ピペットチップ ２６−−−オートポンプ ２７一−−成膜用分子溶液 ２８−ｍ−支柱 ２８−一一拒体取り出し窓 ３〇−蓋 ３１−ｍ−成膜用分子溶液滴下管 ３２−−一自動相体保持具 ３３−一一遮断箱 ３４−一一軸　３５−ｍ−バネ ３Ｇ−−−ピアノ線　３７−−−保持容器３８−−−チ
ューブ 第４図 １４ 第５図Fig. 1 shows an example of a conventional film forming apparatus, Figs. 2 and 3 show examples of a film forming apparatus according to the present invention, and Figs. It is a figure explaining a finger body holder. 1-m-liquid tank 2--one frame 3--float 4--11 weight 5--1 pulley 6--magnet 7--pair of magnets 8-11 suction pipe 9--suction nozzle 1O- m-Liquid level 11--Carrier 12--Carrier upper and lower arms 13--Automatic carrier attachment/detachment means 14-m-Automatic pipette 15-11 Working door 1B-m-Peep window 17--Wall
18-m-Insulating material 19--Strut 20-m-Strut rod length adjustment part 21, 3
9--support rod 22-m-carrier scissors 23--motor 24-m-gear 25--pipette tip 26--auto pump 27--molecular solution for film formation 28-m-support 28 - 11 Rejection window 30 - Lid 31 - m - Molecular solution dropping tube for film formation 32 - 1 Automatic phase holder 33 - 11 Shutoff box 34 - 11 axis 35 - m - Spring 3G - -Piano wire 37---Holding container 38---Tube Fig. 4 14 Fig. 5

Claims (2)

【特許請求の範囲】[Claims] （１）成膜用分子群をその液面に展開させる展開液を収
容する液槽と、前記分子群を成膜して受領する相体とを
備え、成膜操作ｉ係る遠隔操作手段を設けたことを特徴
とする成膜装置。(1) Equipped with a liquid tank containing a developing solution that spreads a group of molecules for film formation on the liquid surface, a phase body that forms a film and receives the group of molecules, and a remote control means for the film forming operation. A film forming apparatus characterized by: （２）前記装置に外気遮断手段をさらに設けたことを特
徴とする特許請求の範囲第１項に記載の成膜装置。(2) The film forming apparatus according to claim 1, characterized in that the apparatus further includes outside air blocking means.