JPH03157156A - Method and device for horizontal sticking type monomolecular film accumulation - Google Patents

Abstract

PURPOSE:To stick a 2nd layer to a substrate surface by sticking a monomolecular film as a 1st layer on the substrate surface by a process for sticking the 1st layer to the substrate surface, then horizontally sinking the substrate, and sinking this substrate into water and again pressing the substrate in parallel to the water surface. CONSTITUTION:A 1st screw rod 62 rotates so as to lower a post 56 when a motor 60 is turned on. A carriage 74 and all the parts connected thereto descend and the substrate 26 is immersed into liquid 24 when the post 56 descends. The first monomolecular film is then formed on the surface 27 of the substrate 26. The substrate 26 is lowered by the operation of the motor 60 and the carriage 74 is moved by the operation of a motor 66. The substrate 26 is positioned in the liquid 24 and is faced opposite, by which the monomolecular film on the surface 25 of the liquid 24 is again formed on the surface formed with the 1st monomolecular film of the substrate 26. The formation of the accumulated monomolecular films having the Y structure is possible in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a method and apparatus for forming a monomolecular cumulative film used in fields such as electronics.

(Prior Art) The present invention relates to a method for producing a monomolecular cumulative film and an apparatus therefor, and particularly to a method for forming a monomolecular cumulative film by a horizontal deposition method and an apparatus therefor.

In the past, attempts have been made to apply such thin films to a wide range of fields such as electronics, energy conversion, and material separation, taking advantage of their remarkable thinness and ability to control their structure on the order of the molecular level.

In the field of electronics, attention has been paid to the useful properties exhibited by certain monomolecular cumulative films, such as electrical conductivity, photoconductivity, optical properties, temperature properties, insulation properties, and chemical reactivity, to develop optical memory elements, Many applications have been attempted, including display elements, resists, light-emitting elements, light-receiving elements, MIS field transistors, MISI channel elements, image sensors, gas sensors, and many others.

There are two types of methods for producing monolayers. namely, the vertical dipping method and the horizontal deposition method. The most commonly used of these is the vertical immersion method. An example of this method will be explained below based on FIG. 4.

In the vertical immersion method, film-forming molecules are first dissolved in a suitable solvent and then spread out on the surface of clean water.

Film-forming molecules are typically molecules with both hydrophilic and hydrophobic groups, such as saturated or unsaturated fatty acids. After the molecules are expanded, they are compressed two-dimensionally on the water surface, forming a monomolecular film with an ordered structure with hydrophilic groups facing the water surface and hydrophobic groups facing the opposite side. The monolayer on the water surface is then transferred perpendicularly thereto onto the surface of the substrate, which is immersed in water from above the water surface. With this method, it is possible to form a monomolecular cumulative film by raising or lowering the substrate once.

As shown in Figure 4, the frame 2 acts as a two-dimensional cylinder to divide the water surface 3 in the shallow and wide rectangular aquarium 1, and the rectangular floating plate 4 serves as a two-dimensional cylinder to divide the water surface 3 in the frame. floating on.

The width of the floating plate 4 is slightly narrower than the inner width of the frame 2, and it is moved forward and backward by a two-dimensional piston.

In order to move the floating plate 4 from one end to the other, the floating plate 4 is connected to a wire 5 provided on a winding device 6 driven by a motor.

The membrane material is dissolved in a volatile solvent such as Hensen or chloroform, and a small amount of this is dropped onto the water surface.

After the solvent evaporates and fills, the membrane material spreads two-dimensionally on the water surface 3 and remains on the water surface. When the surface concentration of molecules is low, it is called a two-dimensional gas film. When the floating plate 4 moves slowly, for example, to the right in FIG. 4, it narrows the area of the water surface over which the membrane molecules spread, thereby increasing the surface concentration. In this way, interactions between molecules are strengthened, and the gas film becomes a two-dimensional gas film and then a two-dimensional solid film. When transferring the monomolecular film from the water surface 3 to the surface of the substrate 7, the substrate 7 is held by the holder 8 and moved in the vertical direction indicated by the arrow 9 in the figure, that is, up and down. - A constant surface pressure is applied to the monomolecular film on the force water surface 3.

With the vertical dipping method described above, three types of membrane structures can be obtained as shown in FIGS. 5a to 5b. first fifth
The X type shown in figure a will be explained. In the X type, when submerging the board 7 in water, not when pulling it out of the water,
Transfer of membrane molecules occurs. In this structure, for example, a hydrophilic group of a molecule in one layer forms a boundary with a hydrophobic group 12 of a molecule in an adjacent layer. Next, in the Y type shown in FIG. 5b, the monomolecular film changes when the substrate 7 moves both upward and downward, and in this structure, hydrophilic groups or hydrophobic groups overlap each other. Thirdly, in the X type shown in FIG. 5C, the monomolecular film is transferred only when the substrate 7 is removed from water, and like the X type, hydrophobic groups and hydrophilic groups form a boundary.

Although the vertical dipping method is effective in many applications, it may not be suitable for certain film-forming materials, e.g. .

In this example, the film material is highly crystalline at the water surface and does not have sufficient mobility to transfer the film from the water surface to the substrate. In such cases, horizontal deposition methods are used. In addition, the horizontal deposition method has the possibility of transferring the orientation and packing of molecules on the water surface onto the substrate as they are, without moving the monomolecular film on the water surface.

FIG. 6 shows a typical horizontal deposition device. This device includes a Teflon-coated water tank A, a Teflon partition plate 17,
It consists of a movable partition plate 16 and a substrate 15 to be coated. The operation of this type of apparatus for transferring a monomolecular film onto the substrate 15 will be explained based on FIGS. 3 and 7. The width of the bath is designed to match the width of the substrate to be coated, and the length is long enough to allow many films to be formed in succession. The water bath 14 is typically coated with purified paraffin wax, and the monolayer is spread on the surface of distilled water using conventional solvents. One side of the substrate 15 is held nearly parallel to the ice surface and the Teflon partition, and then contacts the monolayer on the water surface under constant surface pressure. After that, a partition plate is placed adjacent to the substrate, and after sweeping away the monomolecular film remaining around the substrate, the substrate is pulled up, and the monomolecular film is transferred to the surface. By repeating this operation, a cumulative layer of several hundred layers is formed. Furthermore, the film formed by this method inevitably has an X-type head-to-tail structure, as is clear from the above operations.

(Problems to be Solved by the Invention) Although the horizontal deposition method is a method that has the potential to offer many advantages, it has so far been less popular than the vertical immersion method. One of the reasons for this is that the horizontal deposition method is generally difficult to operate and is performed manually, requiring skill and experience. For example, precise control of the angle between the substrate and the surface is necessary to obtain a good quality film. However, with the prior art, it has been impossible to maintain a 100% horizontal angle when the substrate contacts the monomolecular film on the water surface.

Furthermore, conventional horizontal deposition methods yield only X-type cumulative films and cannot form Y-type films.

Therefore, the technical problem of the present invention is to overcome the above-mentioned problems, to make it possible to form a Y-type film by a horizontal deposition method, and to automate the formation of a Y-type monomolecular film.

(Structure of the Invention) (Means for Solving the Problem) The technical solution taken to solve the above problem is that in a horizontal deposition method for accumulating a monomolecular film on a substrate,
(1) A step in which the substrate is lowered horizontally from above the water surface and brought into contact with the monomolecular film of monomolecular film-forming molecules consisting of hydrophilic and hydrophobic groups formed on the water surface, and the first layer is deposited and then submerged horizontally. , (2) the first part of the substrate with the first layer attached that is submerged in water.
(3) positioning the layer deposition surface parallel to and in contact with the portion of the monomolecular film on the water surface that was not removed in the first deposition step; (3) removing the substrate from the water in order to accumulate the second layer on the substrate; By repeating each step of the pulling process, the molecules constituting the monomolecular cumulative film have a monomolecular film cumulative structure consisting of overlapping bimolecular layers with hydrophilic groups or hydrophobic groups facing each other. This is a horizontally deposited monolayer accumulation method. Further, an apparatus for accumulating a monomolecular film in a horizontal deposition type includes a substrate on which a monomolecular film is accumulated, a holding means for holding the substrate reversibly with respect to the water surface, and a holding means for holding the substrate in an aquarium. a first driving means for moving the substrate up and down above and below the water surface so that the surface of the substrate is parallel to the water surface by driving in a direction substantially perpendicular to the water surface; and a first driving means for inverting the substrate with respect to the water surface. The monomolecular film accumulation device has a second driving means and a third driving means for driving the holding means parallel to the water surface.

(Operation) The above technical solution operates as follows. That is,
The substrate is driven by the first driving means so that the surface of the substrate comes into contact with the water surface where the monomolecular film is spread out in parallel with the monomolecular film on the water surface. When the substrate and the monomolecular film come into contact with each other, only the portion of the monomolecular film that comes into contact with the monomolecular film is cut off and transferred onto the substrate as the first layer of the monomolecular film. The substrate is submerged under the water surface by the first driving means while the first layer monomolecular film remains attached to the surface. Then, the substrate is turned over by the second driving means so that the surface of the substrate is again oriented parallel to the water surface, and the third
It is moved horizontally by a driving means and is positioned below the water surface where the uncut monomolecular film is spread as the first layer.

In this manner, the substrate is again driven toward the water surface by the first driving means so that the surface of the substrate is in horizontal contact with the water surface. When the substrate contacts the water surface, a second layer of monolayer is deposited on the substrate. By repeating the above operations, it is possible to form a cumulative monomolecular film in which a desired number of layers of monomolecular films are stacked. Furthermore, the monomolecular cumulative film formed in this manner consists of overlapping bimolecular layers in which hydrophilic groups or hydrophobic groups face each other.

(Example) The present invention relates to a process of accumulating a monomolecular film on a substrate by horizontally immersing the substrate in a water tank in which a monomolecular film is formed on the liquid surface. Typically, the liquid used is water, and the film-forming substance is deployed to form a uniform monolayer on the water surface.

Further, the present invention is effective for all substances that form a monomolecular film at the gas-liquid interface. As a substance, from 11 to -
Monolayer-forming substances such as saturated and unsaturated fatty acids having 16, especially 16 to 26 carbon atoms are suitable. Examples of such fatty acids are shown in Tables 1 and 2 below. Also, US Patent Nos. 4,740,396 and 4,801
Polymeric materials such as those described in No. 420 are also available.

What is even more revolutionary is that the present invention makes it possible to form a monomolecular film with a substance that is difficult or impossible using the vertical dipping method. Such substances include, for example, a series of polymerized diacetylenes, R+-(CH2)m-C=C-C:E
Examples include C-(CHz)n-Rz.

Here, R3 is a hydrophobic group, and R2 has C00H1OH,
There are NH,, etc. Furthermore, the numbers "mouth" and "m" may be the same or different, and are generally from 2 to 16. These substances form a rigid (brittle) monomolecular film at the air-liquid interface.

Before spreading the film-forming substances on the water surface, these substances are dissolved in a solvent, and after spreading on the water surface, the solvent is removed by evaporation. - For boat fishing, the solvent is selected from Hensen, chloroform, etc., which are insoluble in water and volatile. Sometimes it becomes necessary to increase the solubility of a film-forming substance in a solvent. In such cases, the aforementioned solvents may include N,N-dimethylformamide, N5N-dimethylacetamide, N,
N-diethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidine, pyridine, dimethylsulfone, hexamethyl-phosphoric acid amide, tetraethylenesulfone, dimethyltetramethylenesulfone, etc. , mixed with an organic polar solvent. It is believed that when used in combination with organic polar solvents such as benzene and chloroform, the benzene, chloroform, etc. evaporate into the gas phase, and the organic polar solvent dissolves into a large amount of water.

The techniques of this invention include an improved method for forming two-dimensionally oriented thin films at least 1000, or hundreds, or tens of thick. Additionally, at least 1ooo
Membranes with a thickness of 100 mm can also be obtained by the technique of the present invention.

The substrates used in the devices of this invention are limited only by the ultimate use of the deposited film. In this way, a wide variety of substrates are used. Suitable substrates for boat fishing include glass, aluminum, crystal, metal, plastic, and combinations of group II such as Si, group II and group III such as GaAs, and group III and group III such as ZnS. Semiconductors that can be listed in combination, PbTi0ff, BaTi
Examples include strong dielectric substrates such as O3, LiNb○3, and LiTa3. Preferably, the substrate is glass, dinocon, germanium, or aluminum.

In a thin film deposition operation, a post supporting a substrate is placed on top of a liquid having a monolayer on its surface. The substrate supported by the pillars is immersed in the liquid such that the horizontal surface to which the monomolecular film is to be attached first contacts the liquid surface.

It is then turned over by an initial descent into the water so that the side with the monolayer attached faces the liquid surface.

In one embodiment of the invention, before the substrate is lifted out of the liquid, excess film-forming material and liquid not deposited by the first lowering of the substrate is removed, and new liquid is removed.
and membrane-forming substances. After this, the inverted substrate is held parallel to the substrate surface and the liquid and pulled up, and the second layer is deposited.

In another embodiment of the invention, 'V!' is not transferred onto the substrate. A method is used that does not remove the IJ quality. In this method, which does not remove the film material, the part that first contacts the substrate is isolated from the rest of the film. This method is, for example, the method shown in FIG. The immersed substrate is repositioned under the film-forming material that it did not come into contact with during the first descent. The substrate position is repositioned before or after being rotated in the tank so that the horizontal surface of the coated substrate faces the tank surface.

The substrate is then repositioned and lifted from the water bath onto the water bath to form a second film.

What is important in this invention is that a film structure that could not be obtained by conventional horizontal deposition methods can be formed. In this structure, a hydrophilic group or a hydrophobic group is in contact with a group of the same polarity in the first monolayer. As shown in FIG. 8, the hydrophilic groups of the second monomolecular layer are preferably in contact with the hydrophilic groups of the first monomolecular layer.

The present invention includes several embodiments of an apparatus for constructing a monolayer on a substrate according to the method described above. As shown in FIG. 1, an apparatus 20 that is an embodiment of the present invention is comprised of a column 22 for fixing to a water tank, a water tank (not shown) containing a liquid in which a substrate 26 is immersed, and the like. Alternatively, the strut 22 may be connected to some other device,
To ensure that the support column 22 is fixed securely.

Support rod 28 is slidably connected to column 22 at collar 30. Since the collar 30 is loosely attached to the column 22, it is supported by the collar 30! 128 is free to move relative to strut 22.

The holding member 32 is an extension member 29 disposed on the support rod 28.
It is connected to the. The holding member 32 has a mechanism for holding the substrate 26 on which a monomolecular film is formed. The holding member 32 holds the surface 2 of the substrate 26 on which a monomolecular film is formed.
7 is held parallel to the surface 25 of the liquid 24 in which the substrate 26 is immersed.

The holding member 32 is an extension member 29 disposed on the support rod 28.
At the end of the pivot pin and the clamp are connected by a fitting 34. The pivot pin and tightening tool 34 can be tightened at the position shown by the solid line in FIG. 1, or at the position shown by the broken line.
be maintained. Pivot bin and tightening tool 3
The specific structure of 4 is not shown. This is because it is a feature of the invention that it can take any form known in the prior art, such as a threaded clamp surrounding the bottle extending from the retaining member 32.

It will be clear that fasteners other than those shown may be used to enable the retaining member 32 to be secured in the solid line position and then rotationally secured in the dashed line position. Instead of such a fastening tool, a motor-driven fastening tool, such as that used for joining in the second embodiment, can also be used. This will be described in detail in later examples.

Furthermore, the device 20 according to the first embodiment is provided with a frame 36 which is rigidly mounted on a trough (not shown) containing the liquid 24 in which the substrate 26 is immersed. Additionally, the frame 36 can be attached to other suitable structures. A screw 40 passed from the outside is passed through the frame 36, and a motor 38 is disposed at the upper end. The external thread on the threaded rod 40 mates with the thread on the inside of the hole 42 in the post 28. When the motor 38 operates, the threaded rod 40 rotates,
Depending on the direction of rotation of the threaded rod 40, the strut 28 is raised or lowered as shown by arrow A. motor 3
8 is connected to a sensor (not shown), and this sensor detects the amount by which the threaded rod 40 has rotated.

In this way, by moving the support rod 28 up and down, the holding member 32 and the base Fi 26 can be moved up and down, and can be moved up and down as much as desired.

The apparatus 20 shown in FIG. 1 operates in the following manner.

The substrate 26 on which the monomolecular film is formed is attached to the holding member 32
is held by. At this time, the holding member 32 and the substrate 26 are firmly fixed at the positions shown by solid lines in FIG. When the motor 38 is switched on, the threaded rod 40 rotates and lowers the column 28 into the liquid 24. When the post 28 is lowered to the appropriate position, the substrate 26 is immersed in the liquid 24 and a first layer of monolayer is formed on the surface 27 of the substrate 26. When this first layer of monomolecular film is formed, the motor 38 is turned on to rotate the screw rod 40 in the opposite direction, and the screw rod 40 rotates in the opposite direction, causing the column 28 to rotate in the opposite direction.
to rise. The substrate 26 is thus separated from the liquid 24,
Motor 38 is switched off. Thereafter, the pivot bin and clamp 34 are loosened and the retaining member 32 is manually rotated into the configuration shown in phantom in FIG.

It is clear that the holding member 32 is positioned such that it does not come into contact with the extension member 29 when the holding member 32 and the substrate 26 are moved to the position shown by the dashed line.

Once the holding member 32 has been rotated to the position indicated by the dashed line in FIG. 1, the surface 25 of the liquid 24 is cleaned by a suitable device, not shown, to ensure that no molecules forming a monomolecular film remain. Then motor 3 will start working again and prop 28
lower. As the support column 2 moves downward, the substrate 26 moves downward and is submerged in the liquid 24, and the motor 3
8 is switched off. At this time, the surface of the substrate 26 on which the monomolecular ffi is formed faces the surface of the liquid 24. A monolayer-forming substance is then spread over the surface of the liquid 24. After this, the motor 38 is turned on again and the column 28 and base plate 26 are moved upwardly. In this way, the surface 27 of the substrate 26 becomes the surface 25 of the liquid 24.
, and a second monolayer is formed on the surface 27 of the substrate 26.

By continuing to operate the apparatus 20 in the manner described above, a monomolecular film is continuously formed on the substrate 26.

The previously described embodiment of apparatus 20 according to the invention is useful for forming a monolayer on surface 27 of substrate 26 in a continuous operation. The efficiency, eg, cost effectiveness, of the device is demonstrated by using device 50, which is another embodiment of the invention. A second embodiment of the invention will be described based on FIGS. 2 and 3.

As first shown in FIG. 2, the device 50 is rigidly mounted with a column 52 connected to a frame 54. As shown in FIG. Frame 54 can be connected, for example, to a water bath (not shown) containing liquid 24 in which substrate 26 is immersed. Alternatively, frame 54 may be connected to other suitable devices to ensure that frame 54 and struts 52 are tightly and properly fastened.

The strut 56 smoothly climbs up the strut 52 via a collar 58 (shown in the third figure). Collar 58 is rigidly connected to post 56;
Collar 58 and strut 56 are loosely disposed on strut 52.
can move freely with respect to the post 52.

Motor 60 is disposed on frame 54 .

A first screw 62 is connected to the motor 60 so as to transmit power from the motor 60. The first screw 62 passes through the frame 54. The first screw 62 also passes through a hole drilled inside the column 56 (not shown). The thread provided on the outside of the first threaded rod 62 is threadedly engaged with the thread provided on the inside of the threaded hole (not shown) of the support column 56, and when the motor 60 is turned on, The support column 56 rises and falls in the vertical direction indicated by arrow B.

Inside the column 56 arranged in this way, a second screw stud 6 is provided.
4 is provided. The second threaded rod 6 as shown in FIG.
4 is closed at one end with a cap 70 and at the other end with a cap 72. The cap 70.72 is the second screw 64
can freely rotate within the support column 56. A motor 66 is drivably connected to one end of the second threaded rod 64 to which the cap 72 is fitted by a connecting member 68 . When the motor 66 is turned on, the second threaded rod 6
4 rotates inside the column 56. Continuing to explain based on FIG. 3, the carriage 74 is slidably disposed on the support column 56. The reciprocating table 74 is threadedly engaged with an outer thread of the second screw 64 at a portion not shown. In this way, the second threaded rod 64 rotates under the driving force of the motor 66, and the carriage 74 moves from end to end in the direction indicated by arrow C.

A flange 76 extending upward is firmly fixed to the carriage 74, and a bracket 78 is attached to one side of the flange 76, and a gear 80
is placed on the other side.

Bracket 78 and gear 80 are connected at pin 82 via flange 76 . Therefore, the bracket 78 and gear 80 are interlocked and move relative to the flange 76.

A motor 8 that drives a gear 80 is mounted on the carriage 74.
4 is placed. Worm 86 is connected to worm gear drive motor 84 by an unthreaded portion 88 of worm 86 that freely rotates through an outwardly extending member 90 of flange 76 . The other end of the worm 86 operated by the motor 84 is rotatably disposed on another extension 92 projecting outward from the flange.

Due to the above configuration, when the motor 84 is turned on, the worm 86 rotates, thereby causing the gear 80 to rotate. When the gear 80 rotates, the bracket 78 also rotates in conjunction. Additionally, the various parts of the device connected to bracket 78 are also rotated by the mechanism described above. (
The equipment will be described later. ) Gear 80, bracket 7
The date and direction of rotation of each part are as indicated by the arrows.

The holding member 94 holds the base Fj, 26, and the substrate 26
is submerged in the liquid 24 and forms a molecular film on its surface. The first arm 96 has a pivot pin connecting member 98
It is rotatably connected to the holding member 94 via.

The second arm 100 is rotatably coupled to the first arm 96 via a pivot bin coupling member 102 .

The second arm 100 is also firmly connected to the bracket 78, and as the float 80 and the bracket 78 rotate, the second arm 100 also rotates at the same time.

On the 7th bracket, there is a motor 1 that rotates the first arm.
04 is fixed. Third threaded rod 10 with threads on the surface
6 is connected to a motor 104, and when the motor 104 is turned on, the third threaded rod 106 rotates. 3rd screw 10
The tip of 6 is passed through an indicator member 108 having a screw thread inside. Since the support member 108 is adjusted so that the connection between the third threaded rod 106 and the first arm 96 is natural, the first arm 96 can rotate around the pivot pin 102 without being caught on the third threaded rod 106. be able to. Any material other than the support member 108 may be used as long as it prevents the first arm 96 and the third threaded rod 106 from being pinched at the corners.

With the above configuration, when the motor 104 operates, the third
Threaded rod 106 rotates and pivots about pivot pin 102 relative to second arm 100 .

The rotation of the third threaded rod 106 is as shown by the arrow in FIG.

The motor 110 is fixed to the bracket 7 and rotates in conjunction with the bracket 78. One end of a shaft 112 is disposed in the motor 110, and when the motor 110 is turned on, the shaft 112 rotates. The other end of the shaft 112 is connected to a connecting member 114. Also, the connecting member 11
A flexible member 116 is disposed on the other side of 4. The flexible member 116 is bent so that the first arm 96 and the second arm 100 can operate while transmitting rotational motion of the connecting member 114, the shirt 112, and the motor 110. The other end of the flexible member 116 is
It is connected to another connecting member 118. Connecting member 118
A fourth screw rod 120 is attached to the fourth screw rod 1.
At least a portion of 20 is provided with threads on the outside. A thread is attached to the inside of the shaft 122 located near the end of the extension portion 124 of the holding member 94, and the threaded portion of the fourth threaded rod 120 is arranged to be screwed into this thread. has been done. The shaft 122 has an extension 1
24 and the fourth threaded rod 120, the first arm 9
The extension part 124 supports the holding member 94 so as not to interfere with the rotation of the holding member 94 about the pivot pin 98 in accordance with the rotation of the holding member 94. shaft 1
22, the extension part 124 and the fourth threaded rod 120
It can be substituted as long as it does not interfere with rotation by meshing with each other.

With the configuration having the above-described characteristics, when the motor 110 is turned on, the fourth threaded rod 120 rotates, and this rotation is transmitted one after another, causing the holding member 94 to rotate relative to the first arm 96. The rotation of the holding member 94 with respect to the first arm 96 is in the direction indicated by the arrow F in FIGS. 2 and 3.

The operation of the entire device 50 showing the second embodiment of the present invention is as follows.
This will be explained with reference to FIG. Referring first to FIG. 2, the apparatus 50 of FIG.
Shows the state before being immersed in water.

Before the substrate 26 is immersed in the liquid 24, a monomolecular film is spread on the surface of the liquid 24. Then, when the motor 60 is turned on, the first threaded rod rotates to lower the support column 56. When the column 56 is lowered, the carriage 74 and all parts connected thereto are lowered. The substrate 26 is in a substantially horizontal state, and the surface 27 of the substrate 26 and the surface 25 of the liquid 24 are set in a substantially parallel state, such that the substrate 26 is in a substantially horizontal state.
4, the first monolayer is immersed in the surface 27 of the group Fi26.
is formed.

After the group Fi 26 is immersed in the liquid 24, cracks G (FIG. 3) are formed on the surface of the liquid 240 where no monomolecular film is formed. The fissure G corresponds to the part where the substrate 26 enters the liquid 24 and as a result the monolayer is transferred from the surface of the liquid 24 to the substrate 26. Therefore, in order to form a second monolayer by raising the substrate 26, the position of the substrate 26 must be shifted to a point where a monolayer is present thereon. The device 50 according to the invention is specially devised to allow such operation.

Additionally, motor 60 continues to operate to lower substrate 26 even after substrate 26 is immersed in liquid 24 and an initial film is formed. At the same time, motor 66 and gear 8
The motor 84 that rotates the 0, the motor 104 that rotates the first arm 96, and the motor 110 are all turned on. As a result, the operation of the motor 60 causes the substrate 26 to
is lowered, the carriage 74 moves toward the left in FIGS. 2 and 3 due to the operation of the motor 66, and the second arm 100 rotates counterclockwise in FIGS. 2 and 3 due to the operation of the motor 84. The first arm 96 is moved to the second arm by the operation of the motor 104.
2 and 3 about the pivot pin 102, and the holding member 94 rotates about the pivot pin 98 in the counterclockwise direction in FIGS. 2 and 3 due to the operation of the motor 110.

Operation of these motors 60,66,84,104,110 continues until the substrate 26 is reversed. The state of the device 50 at this time is shown in FIG.

As shown in FIGS. 2 and 3, when the apparatus 50 is operated, the retaining member 94 and the substrate 26 are lowered and shifted to the right in the opposite direction. To change the position of substrate 26 in this manner, second arm 100 is rotated approximately 90 degrees. 1st
Arm 96 rotates about pivot pin 102 until it is approximately perpendicular to second arm 100. The various parts of apparatus 50 continue to move until the position of substrate 26 reaches its destination in the manner described above.

As shown in FIG. 3, the substrate 26 is placed in the liquid 24, and the monomolecular film on the surface 25 of the liquid 24 is formed again on the surface of the substrate 26 on which the first monomolecular film has already been formed. Ru.

Once retaining member 94 and substrate 26 are in the position shown in FIG. 3, all motors 60, 84, 104, 110 are turned off. Then, the motor 60 is turned on again and the first threaded rod 62 rotates, thus raising the column 56.
Similarly, the holding member 94 and the substrate 26 also rise. When the substrate 26 is lifted out of the water tank, a second monolayer is deposited on the substrate 2.
6 is formed on the first monolayer.

Once the substrate 26 is lifted from the liquid 24, each motor 60, 66, 84, 104, 110 is turned on and operated in the reverse direction in the manner described above to return to the position shown in FIG. In this manner, apparatus 50 repeats the same operations described above to form further new films on substrate 26 or to form monolayers on new substrates.

As an alternative operation of the device 50 to that described above, the following method is conceivable. First, motor 60 lowers substrate 26. Even after the initial monolayer is formed on the substrate 26, the group F
This continues until the depth is such that i26 can move to the right in the liquid 24 and even be turned upside down. Board 2
6 reaches this depth, the motor 60 is turned off and the motor 66.84 is turned off until the board 26 is in the position of FIG.
．． 104.110 is turned on. The difference between the above-mentioned operation and the first-mentioned operation is that in the first-mentioned operation, after the substrate 26 is immersed in the liquid 24, the motor 6 is
0 operates together with the other motors 66.84.104.110, but in the operation described above, motor 60 is turned off before the other motors 66.84.104.110 are turned on.

Each motor 60, 66, 84, 104, 110 is connected to a sensor to indicate the amount of time the motor is to be operated to the extent necessary for the aforementioned operations. For example, motor 60 is connected to a sensor that detects when strut 50 has been lowered a sufficient distance. The motor 66 is also connected, as indicated by arrow C, to a sensor that detects when the carriage has moved to the right or left to the point where the above operations can be performed.

The aforementioned operating characteristics are the same for all motors 60.66.84
．． 104.110 is connected to the control center. This control center controls operations such as turning on and turning off each motor 60, 66, 84, 104, and 110. This ensures that each motor is turned on and off at the appropriate times.

〔Effect of the invention〕

According to the present invention, a monomolecular film is attached to the substrate surface as a first layer by bringing the substrate into contact with the water surface in parallel, and then submerging this substrate in water and bringing the substrate into contact with the water surface in parallel again. The second N can be deposited on the substrate surface by
It becomes possible to form a monomolecular film using a horizontal deposition method.

Furthermore, since the monomolecular film accumulated by the device of the present invention consists of overlapping bimolecular layers in which hydrophilic groups or hydrophobic groups face each other, monomolecular films with a Y structure, which has been impossible to produce until now, Allows the formation of a cumulative film.

[Brief explanation of the drawing]

FIG. 1 is an overall view of a monolayer accumulating device according to a first embodiment of the present invention, and FIGS. 2 and 3 are overall views of a monolayer accumulating device according to a second embodiment of the present invention. FIG. 2 shows an overall view of the apparatus when the substrate is located above the water surface, and FIG. 3 shows an overall view of the apparatus when the substrate is located below the water surface. Fig. 4 is an overall view of a monomolecular film accumulation device using the conventional vertical dipping method, and Figs. 5a to 5c schematically show how a monomolecular film is formed on the surface of a substrate by the vertical dipping method. Figure 6 shows a monomolecular film accumulation device using the conventional horizontal deposition method, and Figures 7a to 7d schematically show how a monomolecular film is formed using the device shown in Figure 6. Figure 8 shows a cumulative film with a Y structure in which the hydrophilic groups of the monomolecular layer face each other. Explanation of symbols 26... Board, 2... Extension member, 32.94...
・Holding member, 34.98... Pivot bin, 40.6
2.64... Threaded rod, 56. Support, 96... 1st arm, 100... 2nd arm, 38.60.66
．． 84.104.110...Motor,

Claims (1)

[Claims] 1. In the horizontal deposition method for accumulating a monolayer on a substrate, (1) the substrate is deposited horizontally on the water surface from above the water surface onto a monolayer of monolayer-forming molecules consisting of hydrophilic and hydrophobic groups formed on the water surface; (2) The first layer adhering surface of the substrate submerged in water to which the first layer was attached was not removed in the first adhesion process. (3) lifting the substrate out of the water in order to accumulate the second layer on the substrate; by repeating the following steps, the single molecule accumulation A method for horizontally depositing a monolayer film, characterized in that the molecules constituting the film have a monolayer structure consisting of overlapping bilayers with hydrophilic groups or hydrophobic groups facing each other. 2. A substrate on which a monomolecular film is accumulated; a holding means for holding the substrate reversibly relative to the water surface; a first driving means for moving the substrate above and below the water surface so that the surface is parallel to the water surface; a second driving means for inverting the substrate with respect to the water surface; and a driving means for driving the holding means parallel to the water surface. and a third driving means for causing the monolayer to accumulate.