JPS60197208A - Film forming apparatus - Google Patents

Film forming apparatus

Info

Publication number
JPS60197208A
JPS60197208A JP59052077A JP5207784A JPS60197208A JP S60197208 A JPS60197208 A JP S60197208A JP 59052077 A JP59052077 A JP 59052077A JP 5207784 A JP5207784 A JP 5207784A JP S60197208 A JPS60197208 A JP S60197208A
Authority
JP
Japan
Prior art keywords
film
liquid
liquid surface
film forming
monomolecular
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.)
Pending
Application number
JP59052077A
Other languages
Japanese (ja)
Inventor
Hirohide Munakata
博英 棟方
Hiroshi Matsuda
宏 松田
Yukio Nishimura
征生 西村
Toshihiko Miyazaki
俊彦 宮崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Canon Inc filed Critical Canon Inc
Priority to JP59052077A priority Critical patent/JPS60197208A/en
Publication of JPS60197208A publication Critical patent/JPS60197208A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/122—Separate manufacturing of ultra-thin membranes

Abstract

PURPOSE:To form a uniform monomolecular membrane having uniform molecular arrangement and no flaw, by providing a vibration generating means for vibrating the molecule group developed to the liquid surface in a film forming development liquid tank. CONSTITUTION:Two parallel flat plate electrodes 13, 14 are provided at an interval of 1-10mm. so as to hold a liquid surface 9 therebetween and an AC current is applied between the electrodes 13, 14 from a power supply source to generate an AC electric field between the electrodes and a film forming molecule group is vibrated by utilizing the spontaneous polarization of the film forming molecule group. As other means for vibrating the film forming molecule group, a means for vibrating the film forming molecule group, by such a mechanism wherein an electrode waste with proper frequency is applied to a liquid to raise the temp. of the liquid or the liquid surface and molecular motion is generated with the rising in the temp. thereof, is designated as utilizable.

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とることにより、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, which is its support, thereby forming a monomolecular film or a monomolecular cumulative film on the support. As a method, the so-called
The Langmuir-Prodgett method is known.

ラングミュアＯプロジェット法の原理は、例えば分子内
に親水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 O-Prodgett method is that, for example, in a molecule with a structure that has a hydrophilic group and a hydrophobic group in the molecule, when the balance between the two (balance of amphiphilicity) is maintained appropriately, the molecule will become hydrophilic 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 wood base faces down 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、その上に単分子膜が展開され
る液体、一般には水、メタノール、エチルアルコール等
は、角型水槽１に溜められる。In the apparatus shown in FIG. 1, a liquid on which a monomolecular film is to be developed, generally water, methanol, ethyl alcohol, etc., is stored in a rectangular water tank 1.

角型水槽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製等が水平に吊られてお
り、液面９を所望の広さに仕切っている。A frame 21 made of polypropylene or the like, which functions as a two-dimensional cylinder, is suspended horizontally inside the rectangular water tank 1, and partitions the liquid surface 9 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９
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、例えばボリプ゛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 9.
A float 3 made of, for example, polypropylene is floated to generate a desired surface pressure on the molecules for film formation that are spread out.

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９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（不図示）との反発力によって行われる。The rightward movement of the float 3 is performed 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 9. The leftward movement and stopping of the float 3 is performed by the repulsive force between the magnet 6 provided on the float 3 and a pair of magnets (not shown) 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かした低濃度、一般に
は０．１　ｍｏｌ／ｊ程度の溶液をスポイト等により数
滴液面９に滴下すると、溶媒が揮発したあとに液面９に
単分子膜が展開される。この単分子膜は、液面９上で２
次元系の挙動を示す。For example, film formation is carried out as follows: A few drops of a solution of a desired film-forming molecule group dissolved in an appropriate solvent at a low concentration, generally around 0.1 mol/j, are placed on the liquid surface 9 using a dropper or the like. When the liquid is dropped, a monomolecular film is developed on the liquid surface 9 after the solvent evaporates. This monomolecular film has 2
Demonstrates the behavior of dimensional systems.

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（Ａ）と表面圧ＣＦ）の間に
は。When the areal density of molecules is low, it is called a gas film of a secondary gas, and - between the occupied area per molecule (A) and the surface pressure CF).

Ｆ　Ａ　＝　ｎ　ＲＴ　＋　ｎ　Ｓ　ｐ　Ｆの関係が成
立する。ここで、ｎはモル数、Ｒは気体定数、Ｔ体絶対
温度、Ｓｐは単分子膜構成物質１モル当りの占有面積で
ある。The relationship F A = n RT + n S p F holds true. Here, n is the number of moles, R is the gas constant, T-body absolute temperature, and Sp is the occupied area per mole of the monolayer constituent material.

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１０（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９を横切るように上下すれば、
担体ｌＯ上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. If a desired carrier 10 (generally a glass, ceramic, plastic, or metal substrate is used) is moved up and down across the liquid level 9 while maintaining the solid film state,
A desired monomolecular film or monomolecular cumulative film is deposited on the carrier IO.

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９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水性
部分を有する分子が使用される。As the film-forming molecule group constituting the monomolecular film developed on the liquid surface 9, molecules having a hydrophobic portion and a hydrophilic portion within the molecule are generally used.

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
としては上記アルキル基の他、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、ナフチル、アントラニル等の如き縮合多環フェニル
基、ビフェニル、ターフェニル等の鎖状多ｉｔ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。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 alkyl groups, other groups constituting the hydrophobic moiety include olefinic hydrocarbon groups such as vinylene, vinylidene, and acetylene, fused polycyclic phenyl groups such as phenyl, naphthyl, anthranyl, biphenyl, and terphenyl. Examples include hydrophobic groups such as a chain multi-IT phenyl group. These may be used singly or in combination to form the hydrophobic portion of the molecule.

一方、親水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、４級アミノ基、オキシアミ７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。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構成する。On the other hand, the most typical constituent elements of the hydrophilic moiety are, for example, carboxyl groups and their metal salts and amine salts, sulfonic acid groups and their metal salts and amine salts, sulfonamide groups, amide groups, amino groups, and imino groups. , a hydroxyl group, a quaternary amino group, an oxyamino group, an oximino group, a diazonium group, a guanidine group, a hydrazine group, a phosphoric acid group, a silicate group, an aluminate group, and other wood-loving groups. These also constitute the hydrophilic portion of the above molecule either singly or in combination.

ここで、分子内に親水性部分及び疎水性部分を有するこ
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
の親水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水性で
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 the 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 hydrophilic group and a hydrophobic group, in the overall structure of the molecule, one part is hydrophilic in relation to other parts, while the latter part is hydrophobic in relation to the former part. It means to have.

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下記の如
き分子等が挙げられる。Specific examples of such film-forming molecules include the following molecules that 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
電子系）が同時に強い親水性（又は強い疎水性）として
の性質を併有する分子１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木性
、疎水性を有さす、上記の如き親水基、疎水基等を導入
することで、分子内に親水性部分と疎水性都令を構成し
たもの、例えば、 イ８機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、二０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
Molecules that have strong hydrophilic (or strong hydrophobic) properties at the same time (electronic system) 1 For example, copper phthalocyanine, pyrene, triphenylmethane, etc. ■ The above-mentioned functional moieties are particularly lignophilic and hydrophobic. By introducing a hydrophilic group, a hydrophobic group, etc., a hydrophilic part and a hydrophobic part are formed in the molecule, for example, A8 The functional part is placed on the side of the wood-loving part. For example, a long-chain alkyl compound having photoconductivity, such as a long-chain alkyl carboxylic acid bonded to pyrene, etc., where the functional part is located near the center, that is, between the hydrophobic part and the hydrophilic part. Those with no functional moiety, such as anthracene derivatives and derivatives of diazo dyes, which are made only of hydrophobic and hydrophilic moieties, such as stearic acid substituted with long-chain saturated fatty acids; Specific examples include araxic acid and the like.

このような成膜用分子群を液面上に展開するに際しては
、前述の如く一般にはこれら成膜用分子群を適当な分散
媒、すなわち成膜用分子群が可溶で揮発性の高い溶媒、
例えばベンゼン、クロロホルム等に溶解した後、この溶
液を液面に数滴滴下して液面にこれ等の単分子膜を展開
する。しかしながら、このような分散媒が存在しない場
合には、均一な配向のそろった膜を成膜することができ
なかった。一方、適当な分散媒が存在する場合でも、膜
の構造をミクロに見れば、結晶における格子欠陥にあた
る分子配列の乱れが存在し、そのため膜の諸物性１例え
ば電気伝導度や力学強度等が変化するといった問題があ
った。When developing such film-forming molecular groups on the liquid surface, generally, as mentioned above, these film-forming molecules are mixed with a suitable dispersion medium, that is, a highly volatile solvent in which the film-forming molecules are soluble. ,
For example, after dissolving in benzene, chloroform, etc., several drops of this solution are dropped on the liquid surface to spread a monomolecular film of these on the liquid surface. However, in the absence of such a dispersion medium, a film with uniform orientation could not be formed. On the other hand, even when a suitable dispersion medium is present, if the structure of the film is viewed microscopically, there is a disorder in the molecular arrangement that corresponds to lattice defects in the crystal, and as a result, various physical properties of the film, such as electrical conductivity and mechanical strength, change. There was a problem with doing so.

また上記のような問題の他、例えばメロシアニン色素等
を化学修飾することにより疎水基および親木基を設けた
分子で成膜を行なう場合等に見られる問題、すなわち成
膜用分子群同志が会合を起し、これが海鳥状になってし
まって均一な膜を成膜することができない等の問題があ
った。In addition to the above-mentioned problems, there is also a problem that occurs when film formation is performed using molecules with hydrophobic groups and parent groups provided by chemically modifying merocyanine dyes, etc. This caused problems such as the formation of a seabird-like film, making it impossible to form a uniform film.

（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て、適当な分散媒がな
い場合にも単分子膜または単分子累積膜の成膜を可能と
し、また適当な分散媒がある時でも分子配列が整って欠
陥のない均一な重分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 facts, and an object of the present invention is to solve the above problems and to provide a monomolecular film or a monolayer film even when there is no suitable dispersion medium. It is an object of the present invention to provide a novel film forming apparatus which enables the formation of a molecular cumulative film, and which enables uniform layering with good molecular alignment and no defects even when a suitable dispersion medium is present.

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

成膜用分子群を液面に展開するための成膜用展開液槽を
備え、前記液槽内の液面に展開させた前記分子群を振動
させる振動発生手段を設けたことを特徴とする成膜装置
。It is characterized by comprising a film-forming developing liquid tank for spreading film-forming molecules on the liquid surface, and a vibration generating means for vibrating the molecular groups spread on the liquid surface in the liquid tank. Film deposition equipment.

（０発明を実施するための最良の形態 以下、第２図〜第３図に示す、実施例装置をもとにして
、本発明の方法について詳細に説明する。(BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the method of the present invention will be explained in detail based on the example apparatus shown in FIGS. 2 and 3.

第２図に例示した装置は、第１図に示した装置に成膜用
分子群を振動させる手段としてつ、超音波発生器を設け
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、その断面図である。The apparatus illustrated in Fig. 2 is an example in which an ultrasonic generator is provided as a means for vibrating molecules for film formation in the apparatus shown in Fig. 1, and Fig. 2 (a) shows an outline of the apparatus. FIG. 2(b) is a perspective view illustrating the cross-sectional view.

本例の装置では、第１図におけると同様に単分子膜を展
開させる液体９°は角型水槽ｌに保持される。液面９に
展開された単分子膜には、浮子３により所望の表面圧が
かけられ、成膜に好適な固体膜の状態が維持される。被
成膜体である担体、本例では平板状基板は、不図示のリ
フト機構に・よって図に矢印で示した如くに上下可能な
担体上下腕１１に設けられた担体保持ジグ１５に着脱可
能な状態で固定され、担体上下腕１１の上下により単分
子膜の展開された液面９をほぼ垂直に横切るように移動
する。上記担体１０の上下により、液面９に展開された
単分子膜が担体１０に、移し取られ、担体ｌＯ上に単分
子膜または所望の累積度の単分子累積膜が成膜される。In the apparatus of this example, a liquid 9° for developing a monomolecular film is held in a rectangular water tank l, as in FIG. A desired surface pressure is applied to the monomolecular film spread on the liquid surface 9 by the float 3, and a solid film state suitable for film formation is maintained. The carrier, which is the object to be film-formed, in this example a flat substrate, can be attached to and detached from a carrier holding jig 15 provided on the upper and lower arms 11 of the carrier, which can be moved up and down as shown by arrows in the figure, using a lift mechanism (not shown). The carrier is fixed in this state and moved by the upper and lower carrier arms 11 so as to almost perpendicularly traverse the liquid surface 9 on which the monomolecular film has been developed. The monomolecular film developed on the liquid surface 9 is transferred to the carrier 10 by the upper and lower sides of the carrier 10, and a monomolecular film or a monomolecular cumulative film with a desired degree of accumulation is formed on the carrier IO.

液面９に展開された単分子膜を構成する成膜用分子群の
振動は、水槽ｌ内に設けられた超音波発せることで行な
う、超音波発生器の取り付は位置は、水槽１の底面、側
面あるいは液体９°中等のいずれの部位にも設置可能で
あり、また設置部位を複数個所としてもよい、また、音
波レンズを用いて液面９に超音波を集める等のことも可
能である。The vibration of the film-forming molecules constituting the monomolecular film developed on the liquid surface 9 is carried out by emitting ultrasonic waves installed in the water tank 1. The ultrasonic generator is installed in the water tank 1. It can be installed at any location such as the bottom, side, or 9° of the liquid, or it can be installed at multiple locations.It is also possible to use a sonic lens to collect ultrasonic waves at the liquid surface 9. It is.

第３図の装置は、第２図に示した装置の超音波発生器の
かわりに、成膜用分子群を振動させる手段を交流電場と
した例であり、第３図（ａ）は装置の概要を説明する斜
視図、第３図（ｂ）はその断面図である。The apparatus shown in Fig. 3 is an example in which an alternating current electric field is used as a means for vibrating the film-forming molecule group instead of the ultrasonic generator of the apparatus shown in Fig. 2. A perspective view for explaining the outline, and FIG. 3(b) is a sectional view thereof.

本例の装置では、液面９をはさむ形で２枚の電極、本例
では平行平板電極　１３．１４を設け、該電極間に不図
示の電力供給源から交流電流を印加することにより、該
電極間に交流電場を生じさせ、成膜用分子群の自発分極
を利用して成膜用分子群を振動させる。In the device of this example, two electrodes, parallel plate electrodes 13 and 14 in this example, are provided to sandwich the liquid surface 9, and an alternating current is applied between the electrodes from a power supply source (not shown). An alternating current electric field is generated between the electrodes, and the spontaneous polarization of the film-forming molecules is used to vibrate the film-forming molecules.

電極１３．１４の設定位置は、液面９をはさむ形であれ
ばよいが、好ましくは１３と１４の間隔はｌ−１０１で
ある。電極形状や設置個数等に関しては、所望とし得る
。The electrodes 13 and 14 may be set at positions that sandwich the liquid level 9, but preferably the distance between the electrodes 13 and 14 is 1-101. The shape of the electrodes, the number of electrodes, etc. can be determined as desired.

上記装置によれば、成膜用分子群に振動を加えることが
可能であるが、成膜用分子群を振動させる手段としては
上記例の他、例えば液体あるいは液面の温度を適当な周
波数の電磁波をあてるなどして上げ、これらの温度上昇
に伴う分子運動により成膜用分子群を振動させる等の手
段が利用し得るものとして挙げられる。According to the above-mentioned apparatus, it is possible to apply vibration to the film-forming molecular group, but in addition to the above-mentioned method, for example, the temperature of the liquid or the liquid surface can be adjusted to an appropriate frequency. Possible methods include raising the temperature by applying electromagnetic waves, etc., and vibrating the film-forming molecule group by the molecular motion accompanying the temperature rise.

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
状等の担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
も上下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.
The present invention is not limited to the above examples; for example, when a cylindrical carrier is rotated around a substantially horizontal axis provided near the liquid surface to move the carrier up and down to form a film, Alternatively, it can be applied to the case where a film is formed by bringing into contact with the liquid surface a flat plate-like carrier that is held substantially horizontally with the liquid surface and can be moved up and down.

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種以上の
成膜用分子群を液面に展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、成膜用分子群を液面
に展開する方法としては、タンク等から必要量づつ液面
に滴下する等のことも可能である。また、本発明におけ
る担体としても上記の平板状や円筒状の担体の他、球状
、角柱状、シート状等の所望の形状の担体を使用し得る
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 developing two or more types of film-forming molecule groups on the liquid surface. Further, as a method of spreading the film-forming molecules on the liquid surface, it is also possible to drop the necessary amount onto the liquid surface from a tank or the like. Further, as the carrier in the present invention, in addition to the flat plate-shaped or cylindrical carriers described above, carriers having a desired shape such as spherical, prismatic, sheet-shaped, etc. can be used.

以下に上記装置を用いて成膜を行った場合の具体例を示
し、本発明について更に詳細に説明する。The present invention will be explained in more detail below by showing specific examples of film formation using the above-mentioned apparatus.

〈具体例１） 第２図の装置を用いて、平板状のシリコン基板の上にメ
ロシアニン色素 の単分子累積膜を成膜した。水槽中に少なくとも２回蒸
留した清浄な水を入れ、ＣｄＣｊ！２を４．０×１０′
４ｍｏｌ／Ｉｔ以下の濃度になるように溶かし、さらに
ＨＣＩまたはＫ　ＨＣ０３を添加して、単分子膜を展開
する液体のｐＨをＰ）！−θ〜８．５に調整した。予め
調整したメロシアニンの　０．１　ｍｏｌ／ｊ！クロロ
ホルム溶液を、スポイトで液面上に０．１１滴下し、液
面にメロシアニンの単分子膜を展開した。浮子を動かし
単分子膜の表面圧を上げ、表面圧０．１ｄｙｎｅ／ｃｍ
で保持した後、駆動周波数１００ＫＨｚ、出力０．３Ｗ
／ｃｒｎ’で１０分間超音波発生器を駆動した。その後
さらに表面圧を上げて２０〜３０ｄｙｎｅ／ｃｍとし、
累積操作に好適な固体膜の状態を保持した。この液面に
垂直に、清浄なシリコン基板を上下に数回移動させたと
ころ、基板上に会合することなく、しかもピンホール等
の膜欠陥のない強度にも優れた均一なメロシアニン色素
の単分子累積膜が成膜された。<Specific Example 1> Using the apparatus shown in FIG. 2, a monomolecular cumulative film of a merocyanine dye was formed on a flat silicon substrate. Fill the aquarium with clean water that has been distilled at least twice, and CdCj! 2 to 4.0×10'
Dissolve to a concentration of 4 mol/It or less, and then add HCI or K HC03 to adjust the pH of the liquid in which the monomolecular film will be developed (P)! -θ~8.5. 0.1 mol/j of pre-adjusted merocyanine! A 0.11 drop of the chloroform solution was dropped onto the liquid surface using a dropper to spread a monomolecular film of merocyanine on the liquid surface. Move the float to increase the surface pressure of the monolayer to a surface pressure of 0.1 dyne/cm.
After holding at , drive frequency 100KHz, output 0.3W
The ultrasonic generator was driven at /crn' for 10 minutes. After that, the surface pressure was further increased to 20 to 30 dyne/cm,
A solid membrane condition suitable for accumulation operation was maintained. When a clean silicon substrate was moved up and down several times perpendicular to the liquid surface, it was found that the monomolecules of merocyanine dye were uniform and did not aggregate on the substrate and had excellent strength and no film defects such as pinholes. A cumulative film was deposited.

基板をガラス、セラミック、プラスチック等の各種の材
質のものに変え、上記と同様の成膜を行なったところ、
どの場合にも上記と同様の良好なメロシアニンの単分子
累積膜が成膜された。When the substrate was changed to a variety of materials such as glass, ceramic, and plastic, and the same film formation as above was performed,
In each case, a good monomolecular merocyanine cumulative film similar to that described above was formed.

（具体例２〉 第３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。(Specific Example 2) Using the apparatus shown in FIG. 3, a monomolecular cumulative film of stearic acid was formed on a flat silicon substrate.

具体例１と同様の液体を水槽中に調整した後、予め調整
したステアリン酸の０．１％ベンゼン溶液を液面上に滴
下し、液面にステアリン酸の単分子膜を展開した。具体
例１と同様にして表面圧０．１ｃｌｙｎｅ／ｃｍを保持
した状態で、電極間に電圧８００　Ｖ　、周波数５０Ｋ
Ｈｚの交流を１０分間かけステアリン酸分子を振動させ
た。その後、具体例１と同様に表面圧２０〜３０ｄｙｎ
ｅ／ｃｍとしてｆ＆膜を行なったところ、電気電導率３
　Ｘ　１０’　ｍｏｈ／　ｃｍ″で破壊電圧１０８Ｖ／
ｗ以上の分子会合のない均一なステアリン酸の単分子累
積膜が得られた。After preparing the same liquid as in Example 1 in a water tank, a 0.1% benzene solution of stearic acid prepared in advance was dropped onto the liquid surface to spread a monomolecular film of stearic acid on the liquid surface. Similar to Example 1, a voltage of 800 V and a frequency of 50 K were applied between the electrodes while maintaining a surface pressure of 0.1 cline/cm.
A Hz alternating current was applied for 10 minutes to vibrate the stearic acid molecules. After that, as in Example 1, the surface pressure was set at 20 to 30 dyn.
When f& film was conducted as e/cm, the electrical conductivity was 3
Breakdown voltage 108V/ at X 10'moh/cm''
A uniform monomolecular cumulative film of stearic acid with no molecular association of more than W was obtained.

基板を具体例１に示したと同様の各種の基板に変えた場
合にも、上記と同様の結果が得られた。Even when the substrate was changed to various substrates similar to those shown in Example 1, the same results as above were obtained.

〈具体例３〉 酵素は水溶性の高分子タンパクであるが、これに直線状
もしくは分子状の長鎖アルキル基または芳香環等を導入
したものは水に不溶化してしまう。このため、これ臀が
親木基と疎水基をバランスよく持ち、単分子膜として成
膜可能５であるにもかかわらず、水に対しては不溶であ
り、有機溶媒を用いれば酵素活性が失活してしまう等に
より、これ等を液体上に単分子膜として展開するための
適当な分散媒がなく成膜ができなかった。そこでそのよ
うな成膜分子の例として、酵素としてはグルコースオキ
シターゼを用い、これにステアリル基を導入して水に対
して不溶化した分子を合成し、これを固体状のまま第２
図の装置の液面に滴下した後、超音波をかけ具体例１に
示したと同様の各種の基板の上に成膜を行なったところ
、どの場合にも分子会合やムラのない非常に均一な酵素
活性を持つ単分子累積膜が成膜された。尚、上記分子を
展開する液体の調整や超音波をかける時間等の成膜条件
は具体例１と同様とした。<Specific Example 3> Enzymes are water-soluble polymeric proteins, but when linear or molecular long-chain alkyl groups or aromatic rings are introduced into them, they become insoluble in water. Therefore, although it has a good balance of parent groups and hydrophobic groups and can be formed as a monomolecular film5, it is insoluble in water and loses enzyme activity when organic solvents are used. As a result, film formation was not possible due to lack of a suitable dispersion medium to spread these as a monomolecular film on a liquid. Therefore, as an example of such a film-forming molecule, glucose oxidase was used as an enzyme, and a stearyl group was introduced into it to make it insoluble in water.
After dropping the liquid onto the liquid surface of the device shown in the figure, ultrasonic waves were applied to form a film on various substrates similar to those shown in Example 1. In all cases, a very uniform film was formed with no molecular association or unevenness. A monomolecular cumulative film with enzymatic activity was deposited. The film forming conditions, such as adjusting the liquid for developing the molecules and applying ultrasonic waves, were the same as in Example 1.

尚、上記諸例では、成膜前に振動を加える場合を例示し
であるが、もちろん本発明は上記例に限定されるもので
はなく、例えば成膜時に、一時的に液面上の成膜用分子
群に乱れが生じた場合等に、担体を一時的に停止させ、
振動を加えて分子の乱れをなくす等のことももちろん可
能である。In the above examples, vibrations are applied before film formation, but of course the present invention is not limited to the above examples. If the molecular group for use is disturbed, the carrier can be temporarily stopped,
Of course, it is also possible to eliminate molecular disorder by applying vibrations.

以上に説明した如く、成膜装置に成膜用分子群を振動さ
せる手段を設けたことにより、 （イ）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となり、しかも膜の力学特性、導電
率、破壊電圧等が向上した、（ロ）分子会合のない均一
な単分子膜または単分子累積膜の成膜が容易になった、 （ハ）適当な分散媒のない分子の成膜を可能にした、等
の効果が得られた。As explained above, by providing the film-forming apparatus with a means for vibrating the film-forming molecular group, (a) it becomes possible to form a defect-free uniform monomolecular film or monomolecular cumulative film; Moreover, the mechanical properties, electrical conductivity, breakdown voltage, etc. of the film have been improved, (b) it has become easier to form a uniform monomolecular film or monomolecular cumulative film without molecular association, and (c) the use of an appropriate dispersion medium has improved Effects such as making it possible to form a film with molecules that are

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

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である。 １−−一水槽 ２−　枠 ３−ｍ−浮子 ４−一一重り ５−ｍ−滑車 ６−ｍ−磁石 ７−ｍ−吸引バイブ ８−ｍ−吸引ノズル ９−ｍ−液面 ９°−ｍ−液体 １０−ｍ−担体 １１−ｍ−担体上下腕 １２−ｍ−超音波発生器 １３．１４−−一電極板 １５−ｍ−担体保持ジグ 特許出願人　キャノン株式会社 第　１　図　（ａ） 第　１１１（ｂ） 第　２　１！Ｉ　（ａ） 第　２　１ｍ　（ｂ）FIG. 1 shows an example of a conventional film forming apparatus, and FIGS. 2 and 3 show examples of the film forming apparatus according to the present invention. 1--Aquarium 2-Frame 3-m-Float 4-11 Weight 5-m-Pulley 6-m-Magnet 7-m-Suction vibe 8-m-Suction nozzle 9-m-Liquid level 9°-m -Liquid 10-m-Carrier 11-m-Carrier upper and lower arms 12-m-Ultrasonic generator 13.14--One electrode plate 15-m-Carrier holding jig Patent applicant Canon Co., Ltd. Figure 1 (a) 111(b) 2nd 1! I (a) 2nd 1m (b)

Claims (3)

【特許請求の範囲】[Claims] （１）成膜用分子群を液面に展開するための成膜用展開
液槽を備え、前記液槽内の液面に展開させた前記分子群
を振動させる振動発生手段を設けたことを特徴とする成
膜装置。(1) A film-forming developing solution tank for spreading film-forming molecules on the liquid surface, and a vibration generating means for vibrating the molecules spread on the liquid surface in the liquid tank. Characteristic film forming equipment. （２）前記手段が超音波である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, wherein the means is ultrasonic waves. （３）前記手段が交流電場である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。(3) The film forming apparatus according to claim 1, wherein the means is an alternating current electric field.
JP59052077A 1984-03-21 1984-03-21 Film forming apparatus Pending JPS60197208A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59052077A JPS60197208A (en) 1984-03-21 1984-03-21 Film forming apparatus

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59052077A JPS60197208A (en) 1984-03-21 1984-03-21 Film forming apparatus

Publications (1)

Publication Number Publication Date
JPS60197208A true JPS60197208A (en) 1985-10-05

Family

ID=12904751

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59052077A Pending JPS60197208A (en) 1984-03-21 1984-03-21 Film forming apparatus

Country Status (1)

Country Link
JP (1) JPS60197208A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63146464A (en) * 1986-07-10 1988-06-18 Canon Inc Semiconductor element
WO2010081193A1 (en) * 2009-01-13 2010-07-22 Cavitus Pty Ltd Mass transfer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5273913U (en) * 1975-11-29 1977-06-02
JPS539007B2 (en) * 1972-11-30 1978-04-03
JPS5355216U (en) * 1976-10-14 1978-05-11
JPS54141712U (en) * 1978-03-25 1979-10-02
JPS5535298U (en) * 1978-08-31 1980-03-06

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS539007B2 (en) * 1972-11-30 1978-04-03
JPS5273913U (en) * 1975-11-29 1977-06-02
JPS5355216U (en) * 1976-10-14 1978-05-11
JPS54141712U (en) * 1978-03-25 1979-10-02
JPS5535298U (en) * 1978-08-31 1980-03-06

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63146464A (en) * 1986-07-10 1988-06-18 Canon Inc Semiconductor element
WO2010081193A1 (en) * 2009-01-13 2010-07-22 Cavitus Pty Ltd Mass transfer

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