JPH0671576B2 - Monomolecular adsorption cumulative film formation method - Google Patents
Monomolecular adsorption cumulative film formation methodInfo
- Publication number
- JPH0671576B2 JPH0671576B2 JP63160061A JP16006188A JPH0671576B2 JP H0671576 B2 JPH0671576 B2 JP H0671576B2 JP 63160061 A JP63160061 A JP 63160061A JP 16006188 A JP16006188 A JP 16006188A JP H0671576 B2 JPH0671576 B2 JP H0671576B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- monomolecular adsorption
- monomolecular
- bond
- cumulative film
- 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.)
- Expired - Fee Related
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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、任意の基板上に、膜内にジアセチレン結合を
有する単分子吸着累積膜を、化学吸着法及び酸化反応を
用いて形成することを特徴としたものであり、導電膜及
び絶縁膜等として半導体産業全般に利用できるものであ
る。The present invention relates to the formation of a monomolecular adsorption cumulative film having a diacetylene bond in the film on an arbitrary substrate by using a chemisorption method and an oxidation reaction. It is a feature and can be used in the entire semiconductor industry as a conductive film, an insulating film, and the like.
従来の技術 従来より、ポリジアセチレン化合物は、分子内に非常に
長い共役ポリジアセチレン結合を有することから、非線
形光学効果や導電性など機能性に富む材料として注目さ
れている。そこでこのポリマーをモノマー分子から重合
させて形成する手法として、より機能性の高い結晶を得
るために、ラングシュア・ブロジェット法や真空蒸着法
などが検討されている。2. Description of the Related Art Conventionally, since polydiacetylene compounds have a very long conjugated polydiacetylene bond in the molecule, they have been attracting attention as a material having high functionality such as nonlinear optical effect and conductivity. Then, as a method of polymerizing this polymer from a monomer molecule, a Langure-Blodgett method, a vacuum vapor deposition method, or the like has been studied in order to obtain a crystal with higher functionality.
発明が解決しようとする課題 例えば、ラングシュア・ブロジェット法を用いた場合、
あらかじめモノマーの分子配向性・密度等を自在に制御
できるので、エネルギー線照射などに対する反応性を容
易に制御できる。Problems to be Solved by the Invention For example, in the case of using the Langsuer-Blodgett method,
Since the molecular orientation and density of the monomer can be freely controlled in advance, it is possible to easily control the reactivity to energy beam irradiation and the like.
しかし、この手法で単分子膜を作成する場合、2Bトラフ
内の水面上のジアセチレンモノマーが、外部からの表面
圧にかかわらず結晶化して欠陥をつくり、結果として、
重合後ある一定の長さまでの共役長しか持てないという
問題があった。However, when a monolayer is formed by this method, the diacetylene monomer on the water surface in the 2B trough crystallizes regardless of the surface pressure from the outside to form a defect, and as a result,
There was a problem that after the polymerization, it could only have a conjugate length up to a certain length.
一方、真空蒸着法によるポリジアセチレンの形成も、製
法上、過度に加熱するとモノマーの分解が発生したりす
る問題があった。On the other hand, the formation of polydiacetylene by the vacuum deposition method also has a problem in that the monomer is decomposed when it is excessively heated due to the manufacturing method.
課題を解決するための手段 本発明は上述のような、従来の問題点に鑑みなされたも
のである。すなわち、化学吸着法と種々の酸化反応を併
用して、膜内にジアセチレン結合を有する単分子吸着累
積膜を、任意の基板上に形成することを特徴とするもの
である。Means for Solving the Problems The present invention has been made in view of the conventional problems as described above. That is, the chemical adsorption method is used in combination with various oxidation reactions to form a monomolecular adsorption cumulative film having a diacetylene bond in the film on an arbitrary substrate.
作用 本発明により、液用での吸着反応であるために膜内に欠
陥を持たず、また、膜間が化学結合で結ばれるため非常
に安定なジアセチレン系単分子吸着累積膜を形成するこ
とができる。Effect According to the present invention, since it is an adsorption reaction for liquids, there is no defect in the film, and since the films are connected by a chemical bond, a very stable diacetylene-based monomolecular adsorption cumulative film is formed. You can
実施例 本発明の第１の実施例と第１図に基づいて説明する。第
１図（ａ）において、表面にSiO2の形成されたSi基板１
の上に、分子内にアセチレン結合を有するシラン界面活
性剤（たとえばHC≡Ｃ−（CH2）ｍ−SiCl3,（ｍは整
数））を化学吸着法で、基板１の表面で反応させ、第１
図（ｂ）に示すように単分子吸着膜２を形成する。例え
ば、CH≡Ｃ−（CH2）17−SiCl3を用い、室温で１×10-2
mol/L（２×10-3〜５×10-2mol/Lの範囲でよい）の濃度
で溶かした80％ｎ、ヘキサン、12％四塩化炭素、８％ク
ロロホルム中に浸漬し、SiO2表面上で の結合３を形成する。ここで、第１図（ｃ）に示すよう
に単分子吸着膜２のアセチレン基４は基板表面に並んで
成膜されている。次に、単分子吸着膜２の上に、分子内
にアセチレン結合をもつ長鎖脂肪酸（たとえば、HC≡Ｃ
−（CH2）ｎ−COOH,（ｎは整数））を用いて、酸化カッ
プリング法によって、吸着膜２の表面で反応させ、第１
図（ｄ）に示すように２層目の累積膜５を形成する。例
えば、CH≡Ｃ−（CH2）17−COOHを用い、第一塩化銅、T
MDAを含むアセトン溶液中２×10-2mol/Lの濃度にて酸素
存在下で約50℃にて浸漬すると、第１図（ｅ）に示すよ
うに吸着膜２の表面でジアセチレン結合６を形成する。
このとき、累積膜５のカルボキシル基７は、膜５の表面
に並んで成膜されている。First Embodiment A first embodiment of the present invention and FIG. 1 will be described. In FIG. 1 (a), a Si substrate 1 on the surface of which SiO 2 is formed
A silane surfactant having an acetylene bond in the molecule (for example, HC≡C- (CH 2 ) m-SiCl 3 , (m is an integer)) is reacted on the surface of the substrate 1 by the chemisorption method, First
The monomolecular adsorption film 2 is formed as shown in FIG. For example, CH≡C- (CH 2 ) 17 -SiCl 3 is used and 1 × 10 -2 at room temperature.
Soaked in 80% n, hexane, 12% carbon tetrachloride, 8% chloroform dissolved in a concentration of mol / L (2 × 10 -3 to 5 × 10 -2 mol / L is sufficient), SiO 2 On the surface To form a bond 3 of Here, as shown in FIG. 1C, the acetylene groups 4 of the monomolecular adsorption film 2 are formed side by side on the substrate surface. Next, a long-chain fatty acid having an acetylene bond in the molecule (for example, HC≡C is formed on the monomolecular adsorption film 2).
- (CH 2) n -COOH, (n is an integer) using), by the oxidative coupling method, it is reacted with the surface of the adsorption film 2, the first
As shown in FIG. 3D, the second layer cumulative film 5 is formed. For example, using CH≡C- (CH 2 ) 17 -COOH, cuprous chloride, T
When immersed in an acetone solution containing MDA at a concentration of 2 × 10 -2 mol / L at about 50 ° C. in the presence of oxygen, as shown in FIG. 1 (e), the diacetylene bond 6 is formed on the surface of the adsorption film 2. To form.
At this time, the carboxyl groups 7 of the cumulative film 5 are formed side by side on the surface of the film 5.
次に、再び化学吸着法によって前記シラン界面活性剤を
２層目の累積膜５の表面で反応させ、第１図（ｆ）に示
すように３層目の累積膜８を形成する。このとき、累積
膜８は２層目の累積膜５の表面のカルボキシル基７と の結合９を形成する。また、累積膜８の表面では、アセ
チレン結合10が並んで成膜されている。そこで次に遠紫
外線などのエネルギ線11を、第１図（ｈ）に示すように
累積膜全面に照射すると、第１図（ｉ）に示すように前
記ジアセチレン結合６は隣り同士で重合し、ポリジアセ
チレン結合12を結成する。Next, the silane surfactant is reacted again on the surface of the second layer cumulative film 5 by the chemical adsorption method to form the third layer cumulative film 8 as shown in FIG. 1 (f). At this time, the accumulating film 8 is formed with the carboxyl groups 7 on the surface of the accumulating film 5 of the second layer. To form a bond 9. Further, on the surface of the cumulative film 8, acetylene bonds 10 are formed side by side. Then, when an energy ray 11 such as deep ultraviolet rays is irradiated to the entire surface of the cumulative film as shown in FIG. 1 (h), the diacetylene bonds 6 are polymerized next to each other as shown in FIG. 1 (i). , Forming a polydiacetylene bond 12.
次に、第２の実施例を第２図に基づいて説明する。ま
ず、本発明の第１の実施例の第１図（ａ）〜（ｃ）まで
と同様の工程を行い、単分子吸着膜２を形成する。次
に、膜２の上に分子内にアセチレン結合をもつ長鎖アル
コール（たとえば、HC≡C-（CH2）m-OH,（ｍは整数））
を用いて、ジインジオール酸化法を用いて、吸着膜13の
表面で反応させ、第２図（ａ）に示すように２層目の累
積膜13を形成する。例えば、CH≡C-（CH2）17-OHを用
い、酸化クロム（IV）、硫酸を含むアセトン溶液中１×
10-2mol/Lの濃度にて、約０℃に温度を下げて浸漬する
と、第２図（ｂ）に示すように吸着膜２の表面でジアセ
チレン結合14を形成する。このとき、累計膜13の水酸基
15は膜13の表面に並んで成膜されている。次に、再び化
学吸着法によって前記シラン界面活性剤を２層目の累積
膜13の表面で反応させ、第２図（ｃ）に示すように３層
目の累積膜16を形成する。このとき、累積膜16は第２図
（ｄ）に示すように２層目の累積膜13の表面の水酸基15
と の結合17を形成する。そこで次に遠紫外線などのエネル
ギー線11を、第２図（ｅ）に示すように膜全面に照射す
ると、第２図（ｆ）に示すように前記ジアセチレン結合
14は隣り同士で重合し、ポリジアセチレン結合18を形成
する。Next, a second embodiment will be described with reference to FIG. First, the steps similar to those of FIGS. 1A to 1C of the first embodiment of the present invention are performed to form the monomolecular adsorption film 2. Next, a long-chain alcohol having an acetylene bond in the molecule on the membrane 2 (for example, HC≡C- (CH 2 ) m-OH, (m is an integer))
Is used to react on the surface of the adsorption film 13 using the diynediol oxidation method to form a second-layer cumulative film 13 as shown in FIG. 2 (a). For example, using CH≡C- (CH 2 ) 17 -OH, 1 × in an acetone solution containing chromium (IV) oxide and sulfuric acid.
When the temperature is lowered to about 0 ° C. and immersed at a concentration of 10 −2 mol / L, a diacetylene bond 14 is formed on the surface of the adsorption film 2 as shown in FIG. 2 (b). At this time, the hydroxyl group of the cumulative film 13
The film 15 is formed side by side on the surface of the film 13. Next, the silane surfactant is reacted again on the surface of the second layer cumulative film 13 by the chemisorption method to form the third layer cumulative film 16 as shown in FIG. 2 (c). At this time, as shown in FIG. 2 (d), the accumulating film 16 has hydroxyl groups 15 on the surface of the accumulating film 13 of the second layer.
When To form a bond 17. Then, next, an energy ray 11 such as deep ultraviolet rays is applied to the entire surface of the film as shown in FIG. 2 (e), and the diacetylene bond is formed as shown in FIG. 2 (f).
14 polymerize adjacent to each other to form a polydiacetylene bond 18.
発明の効果 本発明によれば、分子オーダーでピンホールがなく、し
かも有効共役長の非常に長いポリジアセチレンの単分子
吸着累積膜の形成が可能となる。EFFECTS OF THE INVENTION According to the present invention, it is possible to form a monomolecular adsorption cumulative film of polydiacetylene having no pinholes on the molecular order and having a very long effective conjugation length.
第１図は本発明の第１の実施例の単分子吸着累積膜形成
方法の工程断面図で、（ａ），（ｂ），（ｄ），
（ｆ），（ｈ）は基板断面図、（ｃ），（ｅ），
（ｇ），（ｉ）はそれぞれ（ｂ），（ｄ），（ｆ），
（ｈ）の要部拡大図、第２図は本発明の第２の実施例の
単分子吸着累積膜形成方法の工程断面図で、（ａ），
（ｃ），（ｅ）は基板断面図、（ｂ），（ｄ），（ｆ）
はそれぞれ（ａ），（ｃ），（ｅ）の要部拡大図であ
る。 １……基板、２……単分子吸着膜、3,9,17……結合、4,
10……アセチレン結合、5,13……２層目の累積膜、6,14
……ジアセチレン結合、７……カルボキシル基、8,16…
…３層目の累積膜、11……エネルギー線、12,18……ポ
リジアセチレン結合、15……水酸基。FIG. 1 is a process sectional view of the method for forming a monomolecular adsorption cumulative film according to the first embodiment of the present invention, in which (a), (b), (d),
(F) and (h) are cross-sectional views of the substrate, (c), (e),
(G) and (i) are (b), (d), (f), and
FIG. 2 (h) is an enlarged view of a main part, and FIG. 2 is a process sectional view of a method for forming a monomolecular adsorption cumulative film according to a second embodiment of the present invention.
(C) and (e) are cross-sectional views of the substrate, (b), (d), and (f).
3A and 3B are enlarged views of a main part of FIGS. 1 ... Substrate, 2 ... Monomolecular adsorption film, 3,9,17 ... Bonding, 4,
10 …… Acetylene bond, 5,13 …… Second layer cumulative film, 6,14
...... Diacetylene bond, 7 ... Carboxyl group, 8,16 ...
… Cumulative film of the third layer, 11 …… Energy rays, 12,18 …… Polydiacetylene bond, 15 …… Hydroxyl group.
Claims (2)
有するシラン系単分子吸着膜を形成する工程と、 酸化カップリング反応を用いて、分子内にアセチレン結
合を有する脂肪族単分子膜を、前記単分子吸着膜に結合
させる工程とを行うことを特徴とする単分子吸着累積膜
形成方法。1. A step of forming a silane-based monomolecular adsorption film having an acetylene bond in a molecule on an arbitrary substrate, and an oxidative coupling reaction to form an aliphatic monomolecular film having an acetylene bond in the molecule. And a step of binding the monomolecular adsorption film to the monomolecular adsorption film.
有するシラン系単分子吸着膜を形成する工程と、 ジインジオール酸化反応を用いて、分子内にアセチレン
結合を有するアルコール系単分子膜を前記単分子吸着膜
に結合させる工程とを行うことを特徴とする単分子吸着
累積膜形成方法。2. A step of forming a silane-based monomolecular adsorption film having an acetylene bond in the molecule on an arbitrary substrate, and an alcohol-based monomolecular film having an acetylene bond in the molecule by using a diynediol oxidation reaction. A method for forming a monomolecular adsorption cumulative film, comprising the step of binding to a monomolecular adsorption film.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63160061A JPH0671576B2 (en) | 1988-06-28 | 1988-06-28 | Monomolecular adsorption cumulative film formation method |
| DE68915873T DE68915873T2 (en) | 1988-06-28 | 1989-06-27 | Process for the production of monomolecular adsorption films or films built up from monomolecular layers using silanes containing acetylene or diacetylene bonds. |
| EP89306531A EP0351092B1 (en) | 1988-06-28 | 1989-06-27 | Method for the formation of monomolecular adsorption films or built-up films of monomolecular layers using silane compounds having an acetylene or diacetylene bond |
| EP93202997A EP0584891B1 (en) | 1988-06-28 | 1989-06-27 | Method for the formation of built-up films of monomolecular layers using silane compounds having an acetylene bond |
| US07/371,893 US5035782A (en) | 1988-06-28 | 1989-06-27 | Method for the formation of monomolecular adsorption films or built-up films of monomolecular layers using silane compounds having an acetylene or diacetylene bond |
| DE68927865T DE68927865T2 (en) | 1988-06-28 | 1989-06-27 | Process for the production of films made up of monomolecular layers using silanes containing acetylene bonds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63160061A JPH0671576B2 (en) | 1988-06-28 | 1988-06-28 | Monomolecular adsorption cumulative film formation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH029478A JPH029478A (en) | 1990-01-12 |
| JPH0671576B2 true JPH0671576B2 (en) | 1994-09-14 |
Family
ID=15707058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63160061A Expired - Fee Related JPH0671576B2 (en) | 1988-06-28 | 1988-06-28 | Monomolecular adsorption cumulative film formation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0671576B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4331256B2 (en) | 2006-04-12 | 2009-09-16 | パナソニック株式会社 | Method for forming organic molecular film structure |
-
1988
- 1988-06-28 JP JP63160061A patent/JPH0671576B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH029478A (en) | 1990-01-12 |
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