JPH02191573A - Production of lb membrane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Summary] The present invention relates to a method of accumulating multiple types of LB films in any one order, and aims to enable independent control of the aqueous phase for producing multiple LB films. Then, the aquarium is divided into multiple parts except for the bottom, and the bottom is filled with an inert liquid to form multiple completely separated aqueous phases in the aquarium. After forming an LB film in each aqueous phase, Accordingly, the method is configured to include a step of moving the substrate through the inert liquid.

[Industrial application field]

The present invention relates to a method for manufacturing an LB film, and more specifically, to a method for manufacturing an LB film in which a plurality of different LB films can be cumulatively manufactured in any order.

[Conventional technology]

LB film is an organic ultra-thin film that is created by depositing (accumulating) a monomolecular film formed by expanding and compressing amphiphilic molecules (long-chain saturated fatty acids, etc.) on a water surface layer by layer onto a substrate. It is. In terms of the manufacturing method, the LB film has the following characteristics. ■Since the film thickness can be controlled on the order of molecular length, it is possible to produce uniform, large-area, ultra-thin films that are difficult to produce using other methods. ■The molecules are aligned in the same layer, facing the same direction, so the film has a highly ordered structure. ■Can be manufactured at room temperature and pressure.

From the above feature (■), it is possible to form a highly ordered organic superlattice by alternately accumulating different types of molecules (heteroaccumulation), which may bring out new properties based on intermolecular interactions, etc. Research is being conducted. A currently commercially available hetero LB film manufacturing apparatus has a structure as shown in FIG. 4 ((a) is a side sectional view, and (b) is a plan view). That is, the surface of the aqueous phase 1 is partitioned by a barrier 2 to prevent different monomolecular films A and B from intersecting with each other. Then, the substrate 3 is suspended by a support rod 4, for example, as shown in FIG. 4(a).
While the substrate 3 moves in the aqueous phase 1 after passing through the monomolecular film A and being immersed in the aqueous phase, the support rod 4 moves as shown by the arrow in the partition 2 (elastic body). Pass 5. Then, after passing through the monomolecular film B, the substrate 3 passes through the air,
It passes through the monolayer A again. At this time, the structure of the LB film formed by hetero-accumulation is as shown in FIG. In the figure, A and B indicate molecules of monomolecular films A and B, respectively.

[Problem to be solved by the invention]

The composition of the aqueous phase has an important influence on LB film production. For example, long-chain saturated carboxylic acids are unstable when the aqueous phase is pure water, but when Cd'' ions are included in the aqueous phase, they form salts and become stable. Similarly, temperature, pH, etc. affect the stability of monomolecular films. The stability conditions differ depending on the film-forming molecule.Therefore,
When accumulating multiple molecules, it is desirable to be able to control the aqueous phase separately. However, in the apparatus shown in FIG. 4, the aqueous phases must be the same, and it is not possible to control each molecule with a separate aqueous phase. Furthermore, when the substrate is moved between a plurality of accumulators, it is necessary to take the substrate out into the air each time it is moved, and there is also the problem that the structure shown in FIG. 3 cannot be constructed.

Therefore, an object of the present invention is to provide a method for producing an LB film that allows movement of a substrate under the water surface and also enables control of the water phase for each accumulated molecule.

[Means to solve the problem]

In order to achieve the above object, the present invention separates the water tank into a plurality of aqueous phases by filling the bottom of a water tank divided into a plurality of parts except for the bottom with an inert liquid, and applying the separated water phase onto a substrate. A method for producing an LB film, comprising the steps of forming monomolecular films of different compositions, transferring the substrate through an inert liquid at the bottom of a water tank to another aqueous phase, and accumulating a plurality of types of monomolecular films. I will provide a.

To divide an aquarium, it is appropriate to divide a single aquarium into a plurality of aquariums using partition plates, but it is not excluded to configure the bottoms of a plurality of aquariums by specifically joining them together.

The inert liquid that fills the bottom of the aquarium is a liquid that is incompatible with the aqueous phase and has a higher specific gravity than the aqueous phase.

[Function] Since multiple aqueous phases are completely separated via an inert liquid,
It is possible to independently control the temperature, pH, etc. of each aqueous phase, and different monomolecular films can be stably formed.

〔Example〕

FIG. 1 shows a diagram of the principle of the present invention. In the figure, 11 is a water tank, and 12 is a partition plate. Reference numeral 12 is a single plate having heat insulating properties, and its edge must be in close contact with the water tank so that the solution does not pass through. 11 and 12 may be formed integrally. 13 is an inert liquid having a higher specific gravity and larger heat capacity than the solution. 14 is a moving device for moving the substrate through the partition plate. 15 is a support rod.

In the present invention, as shown in FIG.
3 is injected beyond the lower end of the partition plate 12.

If two types of aqueous solutions that will become the aqueous phase of the monomolecular film are gently poured into parts A and B separated by the partition plate 12 and the liquid 13,
Due to the relationship between the specific gravity of the aqueous solution and the liquid 13, the two types of aqueous solutions do not mix. Not only can the composition and pl+ be changed between the two types of aqueous solutions, but it is also possible to independently control the temperature within the range allowed by the insulation properties of the partition plate 12 and the liquid 13. In this method, it is not possible to move the support rod through the partition as shown in FIG. After moving it to the bottom of the section B, the support rod 15 picks up the substrate 10 again and pulls it up through the section B. By repeating this operation, a structure as shown in FIG. 3 can be constructed.

As shown in FIG. 2, according to this method, in principle, the aquarium can be divided into two or more arbitrary parts. That is,
A water tank 21 is divided by a number of partition plates 22, the bottom is filled with an inert liquid 23, and the water tank 21 is divided into a plurality of water phases A, B...x, Y. At this time, the method of compressing the membrane becomes an issue, but the second
This is possible if the compression direction F is taken as shown in the plan view of Figure (b).

A heterostructure LB film was actually fabricated using the above-mentioned apparatus. As the liquid 13, a fluorocarbon-based inert liquid was used. This liquid has desirable properties such as a specific gravity of 1.95 and a surface tension of 18, but its specific heat is as small as 0.25, making it unsuitable for independent temperature control. Further, as the moving device 14, a magnet fixed on a trolley was used.

A metal piece is attached to the bottom of the board in advance, and the support rod 15
After the substrate descended from the A side is adhered to the magnet, the support rod 15 is removed. Then, the board and the cart are moved to the B side by another magnet from the outside, and the board 1 is placed on the support rod 15 again.
Moved 0. A heterostructure was constructed by repeating this operation.

Araxic acid was used for the A part and heminanine dye was used for the B part as film forming molecules. Their molecular structures are as follows.

CL (CH2) + gcOOH (araxic acid) NCCHj)z (heminanine dye) In addition, the aqueous phase contains pure water + cdc1t (4xxO-J/1
) +KHC(h (5X10-'M/1) solution (HC
(adjusted to pH ~ 6 with I), pure water (adjusted to pH ~ 9 with NH:+) was used in part B, and the cumulative pressure was 3 Qdyne/cm on the A side, 35 dyne/am on the B side, and The B side was accumulated when descending, and the B side was accumulated when ascending.The heterostructure LB film thus obtained exhibits spontaneous polarization and exhibits piezoelectric, pyroelectric, and nonlinear optical effects.Actually, the four-layer accumulation of araxic acid-hemin anine dye Generation of second harmonics was confirmed from the membrane.

〔Effect of the invention〕

As explained above, according to the method of the present invention, when different types of molecules are accumulated by the LB method, the composition, pH, and temperature of the aqueous phase can be controlled for each molecular type, and a heterostructure can be constructed. It makes a large contribution to the production of LB films.

[Brief explanation of the drawing]

Fig. 1 is a diagram explaining the principle of the present invention, Fig. 2 is a schematic diagram showing another embodiment of the invention, Fig. 3 is a schematic diagram showing the film structure of a hetero-cumulative LB film, and Fig. 4 is a commercially available It is a principle diagram of a hetero cumulative LB film production apparatus. 10... Substrate, 11... Water tank, 12...
Partition plate, ]3... Inert liquid, 14... Moving device, 15... Support body.

Claims (1)

[Claims] 1. Separate the tank into multiple aqueous phases by filling the bottom of the aquarium, which is divided into multiple parts except for the bottom, with an inert liquid, and form a monomolecular film with a different composition on the substrate with the separated aqueous phases, A method for producing an LB film, comprising the steps of: transferring the substrate to another aqueous phase through an inert liquid at the bottom of a water tank and accumulating a plurality of types of monomolecular films.