JPH0274072A - Organic thin film manufacturing device - Google Patents

Abstract

PURPOSE:To enable the manufacture of an organic thin film which is uniform and has no defect in structure by a method wherein at least a detecting probe of a surface pressure gauge is arranged at the position of a movable barrier and a substrate so as to enable the deviation of its detected surface pressure from a set surface pressure to be within 10% after a compressing operation or in an accumulating operation. CONSTITUTION:At least, a detecting probe 14 of a surface pressure gauge is arranged at the position of a movable barrier 12 and a substrate 13 so as to enable the deviation of its surface pressure detected value from a set surface pressure to be within 10% after a compressing operation or in an accumulating operation. And, the surface pressure change due to the barrier 12 at a compressing operation of a molecular film by the barrier 12 can be accurately detected, and the surface pressure decrease of the molecular film near the substrate 13 can be accurately detected at an accumulating operation. Therefore, the surface pressure detected value of the detecting probe 14 of the surface pressure gauge can be used as an index that a moving rate of the movable barrier at the compression of the molecular film and an up-down speed at the accumulation of the molecular film on the substrate are controlled, whereby a molecular film which is uniform and has no defect in structure can be accumulated on a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to an apparatus used for producing organic thin films by the Langmuir-Prodgett method.

(Prior Art) In recent years, research on organic thin films typified by Langmuir-Blodgett films (hereinafter abbreviated as LB films) has been actively conducted with the aim of applying them to various electronic devices with new functions. In such devices, the alignment of functional molecules containing dyes, etc., the layered structure,
It becomes possible to realize a predetermined function only by controlling the intermolecular distance and the like.

In the normal LB film forming method, amphiphilic organic molecules, which have a highly hydrophilic part and a highly hydrophobic part within the molecule, are spread on the water surface so that they exhibit a predetermined surface tension. After forming a monomolecular film on the water surface in which molecules are backed closely together by compressing the area, the monomolecular film is deposited on the substrate by moving a given substrate perpendicularly or horizontally to the monomolecular film. The film is transferred to form a cumulative film.

The film forming apparatus for performing the above-mentioned film forming operation basically consists of a water tank for obtaining a water surface for developing a monomolecular film, and
It is composed of a movable barrier for changing the spread area of molecules, a surface pressure gauge for detecting the surface pressure on the water surface, and an accumulation mechanism for moving the substrate up and down in order to transfer the monomolecular film onto the substrate. ing. However, with conventional film forming equipment, the area of the water tank is simply reduced in order to shorten the compression time of the lli molecular film, and the substrate and surface pressure gauge are simply installed at the edge of the water tank in order to increase the cumulative area of the a effect. The device has not been optimized to form a high-quality cumulative film. For this reason, in our research, we used a commercially available film-forming equipment to produce standard stearic acid (cadmium salt).
It has become clear that the cumulative film obtained by forming molecules has many defects (Synthetic Metals, Vol. 18, pp. 11103-807 and 809-814, 1987
After that, it became common knowledge in the academic world that LB films were defective.

The occurrence of defects in the LB film described above is due to the fact that a predetermined surface pressure is not applied to the monomolecular film on the water surface near the substrate during film formation. This is because the conventional manufacturing apparatus has the following problems.

Firstly, with some exceptions, most molecules behave as a viscoelastic fluid when they form a monomolecular film on the water surface, and when the area is compressed by a barrier, it is not compressed uniformly, and the surface pressure distribution shows. For this reason, surface pressure gauges (especially their detectors)
Depending on where the barrier is installed, the surface pressure at the center of the water surface may not reach a predetermined value, or the surface pressure near the barrier may become abnormally high, leading to problems such as the monomolecular film not being stabilized. Furthermore, there was a problem in that the vertical position of the substrate with respect to the monomolecular film was different from the value set by the detector of the surface pressure meter. Second, when moving the substrate to transfer the monolayer on the water surface, the surface pressure exerted by the monolayer near the substrate decreases, especially for monolayers with high viscoelasticity. The tendency is remarkable, and the surface pressure is almost Odyn/CN
(the same surface tension as the water surface). this is,
It shows that the surface pressure is not controlled at all in the cumulative operation. In such a state, the monomolecular film on the water surface immediately before being transferred to the substrate cannot be said to be a monomolecular film with a close-packed backing, and furthermore, the accumulated film may also have structural disturbances or defects. This is because the surface pressure drop in the vicinity of the substrate is not correctly detected by the detector of the surface pressure meter, which is supposed to be observed, and as a result, the compression control system is not functioning at all. Third, when the monolayer is transferred to the substrate under the conditions already described, the barrier must be compressed by the area reduction of the monolayer above the water surface to maintain the surface pressure. However, the higher the viscoelasticity of the monomolecular film, the worse the responsiveness of recovery of the surface pressure near the substrate due to compression of the barrier.

Therefore, in conventional organic thin film production equipment, the uniformity of the surface pressure distribution of the monomolecular film on the water surface and the surface pressure near the substrate during accumulation are not well controlled, making it difficult to produce excellent organic thin films. There was a word.

(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned conventional problems, and aims to provide an organic thin film manufacturing apparatus capable of manufacturing an organic thin film with a uniform structure and no defects. It is something.

[Structure of the Invention] (Means for Solving the Problems) The present invention provides a water tank for developing a 91-molecular film of amphipathic organic molecules, and changing the developed area of the surface of the tank on which the monomolecular film is developed. at least one surface pressure meter for detecting the surface pressure of the monomolecular film; and an accumulation mechanism for driving the substrate in order to accumulate the monomolecular film on the substrate. In the organic thin film manufacturing apparatus, the detector of the at least one surface pressure meter is positioned at the movable barrier and the substrate so that the deviation from the set surface pressure after compression or during cumulative operation is within 10%. This is a thin film manufacturing apparatus characterized by being arranged in a.

When arranging the at least one surface hand movement detector, the deviation from the set surface pressure after compression or during cumulative operation is 1
The reason why it is set within 0% is that if it exceeds 1096, the molecular backing state in the monomolecular film on the water surface will not be uniform, making it impossible to accumulate a homogeneous film.

In order to arrange the at least one surface hand movement detector at the position of the movable barrier and the substrate such that the deviation from the set surface pressure after compression or during cumulative operation is within 1096, The detector may be placed within 5 cm of a location bordering the water surface of at least one of the movable barrier and the substrate. In this arrangement, especially by placing the substrate within 5α from the movable barrier,
This method is effective in producing an LB film with a more uniform structure and no defects.

(Function) The present inventors have completed the invention based on the following findings. That is, as a result of intensive research by the present inventors on the monomolecular film of molecules with high viscoelastic properties on the water surface, we found that the boundary 1 formed by the barrier, the tank side wall, and the water surface as shown in FIG. 9 during compression and accumulation operations. We have discovered the important finding that a large surface pressure distribution occurs in the area between boundaries 3a and 3b (shaded area), which is 5c11M away from boundary 2, which is formed by the substrate and the water surface. This was generally observed regardless of the tank shape, molecule type, or substrate circumference. Regarding the surface pressure distribution, each case of compression and accumulation will be briefly explained below.

First, in order to investigate the surface pressure distribution on the water tank in which the monomolecular film was developed during the compression operation, compression was performed with a number of surface needle movement detectors installed, and the pressure distribution detected by each detector was observed. The results revealed that molecules with high viscoelasticity do not compress the monolayer uniformly, and that the surface pressure increases significantly near the barrier, and that the area around the aquarium is compressed more strongly. The non-uniformity of surface pressure that appears prominently near the boundary between the barrier and the water surface varies slightly depending on the molecules used, but it can be detected for most molecules within approximately 5 cM from the boundary. It was possible to do so.

Next, we investigated the change in surface pressure near the substrate in the vertical immersion method regarding the accumulation of monolayers on the substrate. the result,
As schematically shown in FIG. 10, it has become clear that a surface pressure distribution occurs as the monomolecular film flows during accumulation on the substrate 4. The surface pressure distribution that appears prominently near the boundary formed by the substrate 4 and the water surface at this time differs slightly depending on the molecules used, but it can be detected for most molecules within approximately bcH from the boundary. was possible.

Based on the above findings, the present invention provides at least one surface hand movement detector arranged at the position of the movable barrier and the substrate so that the deviation from the set surface pressure after compression or during cumulative operation is within 10%. Specifically, the above-mentioned surface pressure distribution can be compensated for by placing at least one surface hand movement detector within 5 cM of the movable barrier and the substrate (both of which form a boundary with the water surface on one side). During the compression operation of the monomolecular film by the barrier, it is possible to accurately detect the change in surface pressure due to the barrier, and during the cumulative operation, it is possible to accurately detect the decrease in the surface pressure of the monomolecular film near the U plate. Therefore, the surface pressure detection value from the surface hand movement detector can be used as an index for controlling the moving speed of the movable barrier when compressing the monomolecular film, the lifting speed when accumulating the monomolecular film on the substrate, etc. By this method, a uniformly structured and defect-free monolayer can be deposited on the substrate.

Furthermore, by installing the substrate within 5 cm from the boundary formed by the movable barrier and the water surface while satisfying the above conditions, it becomes possible to further compensate for the surface pressure distribution. In particular, by setting the boundaries formed by the surface pressure 2 detector, the movable barrier, and the substrate and water surface within 5oI of each other, changes in surface pressure caused by the barrier during compression of the monomolecular film by the barrier can be avoided. Not only is it possible to accurately detect and accurately detect the decrease in surface pressure of the monomolecular film near the substrate during the accumulation operation, but it is also possible to further improve the compression effect of the barrier on the monomolecular film.

In addition, the surface pressure distribution described above can be compensated for more effectively by arranging a plurality of single-surface needle detectors within 501 degrees of a location forming a boundary with the water surface of at least one of the movable barrier and the substrate. can.

(Example) Hereinafter, an example of the present invention will be described in detail with reference to the drawings. Incidentally, in the manufacturing apparatus shown in FIGS. 2 to 8 used in Example 2 and later, the same members as those in the manufacturing apparatus shown in FIG.

Example 1 FIG. 1 is a schematic plan view showing an organic thin film manufacturing apparatus according to Example 1 of the present invention. 11 in the figure is a water tank whose inner surface is coated with a fluororesin film. This water M
Inside the IL, a monomolecular film is developed and filtered water or an aqueous solution is accommodated, and the accommodated water and the like are maintained at a constant temperature by a temperature control mechanism (not shown). A movable barrier 12 made of fluororesin is disposed at one end of the water tank 11 to partition a monomolecular film on the water surface. This barrier 12 is moved by a barrier drive mechanism (not shown) so that it can compress the monomolecular film on the water surface. Further, an accumulation mechanism (not shown) is disposed near the side wall of the water tank 11 to drive the substrate 13 horizontally and vertically in order to accumulate a monomolecular film on the substrate 13. A filter paper 14 serving as a detector for the surface single needle is placed at about 20 ril (shaded area in the figure) from the location formed by the substrate 13 and the water surface. The surface needle is of a Wilhelmy type that measures the surface tension applied to the filter paper 14, and the tension is detected by a right-angle displacement type strain gauge.

In a manufacturing apparatus having such a configuration, after N5N-dioctadecylbaraphenylenediamine is spread on the water surface of water tank II containing pure water, the movable barrier 12 is moved to transfer the spread monomolecular film to the surface single needle. The indicated value is 40 d
It was compressed to exhibit a surface pressure of yn/cM. After such a compression operation, using a silicon wafer subjected to hydrophobization treatment as the substrate 13, accumulation was performed by a vertical dipping method at a rate of 0.5 ii/sin so that the indicated value of the surface needle did not decrease by more than 4 dyn/cx.

When the accumulated film on the substrate after repeating the above operation 10 times was examined by X-ray diffraction and SEM, it was confirmed that a 10-layer accumulated film with a uniform structure and no defects was formed.

Example 2 FIG. 2 is a schematic plan view showing an organic thin film manufacturing apparatus according to Example 2 of the present invention. In this manufacturing apparatus, a filter paper 14' serving as a detector of a single surface needle is moved from a place formed by the movable barrier 12 and the water surface to a position 1c11 (the shaded area in the figure) by following the movement of the barrier 12 and moving the filter paper 14' over the distance described above. It has a movable arrangement structure that allows it to maintain a constant level.

In a manufacturing apparatus having such a configuration, after N,N-dioctadecylparaphenylenediamine is spread on the water surface of the water tank 11 containing pure water, the movable barrier 12 is moved to spread the spread monomolecular film onto the surface. The indicated value for one needle is 40dy.
It was compressed to exhibit a surface pressure of n/C11. After such a compression operation, using a silicon wafer subjected to hydrophobization treatment as the substrate 13, accumulation was performed by a vertical dipping method at a rate of 0.511 Jl/sin so that the indicated value of the surface needle did not decrease by more than 4 dyn/ax.

When the cumulative film of the substrate after repeating the above operation 10 times was examined by SEM, it was confirmed that a 10-layer cumulative film with a uniform structure and no defects was formed.

Example 3 FIG. 3 is a schematic plan view showing an organic thin film manufacturing apparatus according to Example 3 of the present invention. In this manufacturing apparatus, a first filter paper 141 as a detector of a single surface needle is connected to the barrier via a connecting jig 15 from a place formed by the movable barrier 12 and the water surface to a position 2IS11 (shaded area in the figure). The structure is such that the second filter paper 142 is disposed at a position 2 cM from the inner wall of the water cell on the opposite side to the barrier 12 (the shaded area in the figure).

In the manufacturing apparatus having such a configuration, after N,N-dioctadecylparaphenylenediamine is spread on the water surface of water Ill containing pure water, the movable barrier 12 is moved to the first and second
Surface pressure (π1) detected on filter paper 141% 142
, (π2) at a speed that does not exceed 4 dyn/n.
It was compressed to show the surface pressure of the dynlof. After such compression operation, the silicon wafer 1 subjected to hydrophobization treatment was used as the substrate 13, and the indicated value of the surface pressure gauge was 4 dyn/
Accumulation was carried out by a vertical dipping method at a rate of 0.5 mm/1 rl so as not to reduce C11 or more.

However, when the accumulated film on the substrate after repeating the above operation 10 times was examined by X-ray diffraction and SEM, it was found that the structure was uniform and defect-free! It was confirmed that an i-cumulative film was formed.

Example 4 Figure 4 shows the production of an organic thin film according to Example 4 of the present invention!
FIG. 3 is a schematic plan view showing the jt position. In this manufacturing apparatus, two movable barriers 12s s 122 are movably arranged so as to approach and separate from each other, and a first filter paper 141 as a detector of a surface pressure meter is connected to the first movable barrier 12s. The transfer barrier 12. The connecting jig 15 is arranged to be movable following the movement of the second filter paper 142, and is located at a position 2c11 (shaded area in the figure) from the place where the second filter paper 142 is formed by the second movable barrier 122 and the water surface. The barrier 122 is disposed horizontally so as to be movable following the movement of the barrier 122.

In the production apparatus having such a configuration, after N,N-dioctadecylparaphenylenediamine is developed on the water surface of the water Ill containing pure water, the first and second movable barriers IL
122 is the surface pressure detected at 14° of the first filter paper (π
l) and the surface pressure (π2) detected by the second filter paper 142 is 4 dyn/. was compressed so that it exhibited a surface pressure of 40 dyn/c11. After such a compression operation, a silicon wafer subjected to hydrophobic treatment was used as the substrate 13, and the indicated value of the surface pressure gauge was 4.
0.5m/sin so as not to drop more than dyn/α
The accumulation was carried out by the vertical dipping method at a speed of .

When the accumulated film on the substrate after repeating the above operation 10 times was examined by X-ray diffraction and SEM, it was confirmed that a 10-layer accumulated film with a uniform structure and no defects was formed.

Example 5 FIG. 5 is a schematic plan view showing an organic thin film manufacturing apparatus according to Example 5 of the present invention. In this manufacturing device, two movable barriers 121 and 122 are movably arranged so as to approach and separate from each other, and a first filter paper 141 as a detector of a surface pressure meter is formed by the first movable barrier 121 and the water surface. The second filter paper 14□ is movable from the position 2c11 (the shaded area in the figure) via the connecting jig 15 to follow the movement of the barrier 121. 2c from the place formed by barrier 12□ and the water surface
A third filter paper 143 is disposed at a position 1M (hatched area in the figure) via a connecting jig 15 so as to be movable following the movement of the barrier 122, and a third filter paper 143 is arranged from the boundary formed by the substrate 3 and the water surface. It has a structure in which it is arranged parallel to the substrate 13 at a position 2CM (shaded area in the figure).

In the manufacturing apparatus having such a configuration, after N%N-dioctadecylparaphenylenediamine is spread on the water surface of the water tank 11 containing pure water, the first and second movable barriers 12
．． 122 to the first, second, and third filter papers 141 142.
The surface pressure detected at 143 (πl), (π2), (π3
) The monomolecular films were spread so as to move close to each other at a speed that the difference in dyn/c11 did not exceed 4 dyn/c11, and the monomolecular films were compressed so that the reading on the surface pressure meter indicated a surface pressure of 40 dyn/c11. After such a compression operation, a hydrophobically treated silicon wafer is used as the substrate 13, and the first filter paper 1 is
4. The surface pressure (πl) detected on the second and third filter paper 1
Surface pressure detected at 4□, 143 (π2) (π3)
The barriers 121 and 122 are controlled so that the surface pressure (π3) detected on the third filter paper 143 is not different from the set surface pressure by 4 dyn/cm or more.
Accumulation was carried out by a vertical immersion method at a substrate speed of 0.5 mm/i1n so that no more than 2 people were involved.

When the accumulated film on the substrate after repeating the above operation 10 times was examined by X-ray diffraction and SEM, it was confirmed that a 10-layer accumulated film with a uniform structure and no defects was formed.

Example 6 FIG. 6 is a schematic plan view showing an organic thin film manufacturing apparatus according to Example 6 of the present invention. This manufacturing equipment is 1.2! 2a from the interface formed by the plate 13 between the movable barrier 12 and the water surface
A filter paper 14', which is disposed movably following the movement of the barrier 12 via a connecting jig 15 at a position I, and serves as a surface needle movement detector, connects the barrier from the interface formed by the substrate 13 and the water surface. The structure is such that the barrier 12 is movably disposed at a position 2G along the longitudinal direction of the barrier 12 via a connecting jig I5 to follow the movement of the barrier 12.

In the manufacturing apparatus having such a configuration, after N,N-dioctadecylbalaphenylenediamine is spread on the water surface of the water tank IT containing pure water, the movable barrier 12 is moved to spread the spread monomolecular film onto the surface. The indicated value of the hand movement is 40 d
It was compressed to show a surface pressure of yn/c11. After such a compression operation, a hydrophobically treated silicon wafer was used as the substrate 13, and the indicated value of the surface hand movement was 4 dyn/c!
Accumulation was carried out by the vertical dipping method at a rate of 0.51111/win so as not to decrease by more than 1.

When the accumulated film on the substrate after repeating the above operation 10 times was examined by X-ray diffraction and SEM, it was confirmed that an IO layer stack 85@ with a uniform structure and no defects was formed.

Example 7 FIG. 7 is a schematic plan view showing an organic thin film manufacturing apparatus according to Example 7 of the present invention. In this manufacturing apparatus, two movable barriers 12Is 122 are movably arranged so as to approach and separate from each other, and the substrate 13 is connected to the first movable barrier 12Is 122.
．． The barrier 121 is disposed at a position 2 cM from the interface formed by the water surface and the surface pressure via a connecting jig 15 so as to be movable following the movement of the barrier 121, and furthermore, a surface pressure; It is disposed at a position 2C1M along the longitudinal direction of the barrier 12 from the interface formed by the substrate 13 and the water surface via a connecting jig 15 so as to be movable following the movement of the barrier 12, and a second 2c from where the filter paper 142 is formed by the second movable barrier 122 and the water surface.
11 (shaded area in the figure) via a connecting jig 15 so as to be movable following the movement of the barrier 122.

In the manufacturing apparatus having such a configuration, after N,N-dioctadecylvar phenylenediamine is spread on the water surface of the water tank 11 containing pure water, the first and second movable barriers 12
The surface pressures (π1) and (π2) detected on the first and second filter papers 14+ and 142 are 4dyn/c11.
The monomolecular films, which were developed by moving toward each other at speeds that did not differ above, were compressed so that the indicated value of the surface needle movement indicated a surface pressure of 40 dyn/CM. After such a compression operation, a silicon wafer subjected to hydrophobization treatment is used as the substrate I3, and the first and second filter papers 1'h are
The accumulation was carried out by the vertical dipping method at a speed of 0.5 m/a1n so that the surface pressure (π1) (π2) detected at 142 did not differ by more than 4 dyn/α from the set surface pressure.

After repeating the above operation 10 times, the cumulative film on the substrate is determined to be X! When examined by single diffraction and SEM, it was confirmed that a 10-layer cumulative film with a uniform structure and no defects was formed.

Example 8 FIG. 8 is a schematic plan view showing an organic thin film manufacturing apparatus according to Example 8 of the present invention. This manufacturing device consists of two movable barriers 12. , 122 are arranged to be movable toward and away from each other, and with the size of the water tank 11 being compressed to a predetermined surface pressure by the movable barriers 12+ and 122, the entire periphery of the water tank 11 is in the area from 3 to 51 of the substrate. (the shaded area in the figure), so that the filter paper 14, which serves as a detector for surface hand movement, is 2 cI from the boundary formed by the substrate 13 and the water surface.
It has a structure in which it is placed parallel to the substrate I3 at a position 1.

In the manufacturing apparatus having such a configuration, after N5N-dioctadecylbaraphenylenediamine is spread on the water surface of water tfJll containing pure water, the movable barrier 12. 12
．． The monomolecular film, which was developed by moving them close to each other, was compressed so that the indicated value of the surface hand movement indicated a surface pressure of 40 dyn/ff. After such a compression operation, the substrate 1
3, using a silicon wafer subjected to hydrophobization treatment, accumulation was performed by a vertical dipping method at a substrate speed of 0.5 Ill/min so that the indicated value of the surface pressure detected by the filter paper 14 did not decrease by 4 dyn/CM or more. .

When the accumulated film on the substrate after repeating the above operation 10 times was examined by X-ray diffraction and SEM, it was confirmed that a 10-layer accumulated film with a uniform structure and no defects was formed.

Comparative Example 1 FIG. H is a schematic plan view showing a conventionally used Q-type thin film manufacturing apparatus. 21 in the figure is a water tank whose inner surface is coated with a fluororesin film. This water tell
Water or an aqueous solution in which a monomolecular film is developed is housed inside, and the housed water and the like are kept at a constant temperature by a temperature control mechanism (not shown). On one end side of the water tank 11, there is a surface needle movement detection device for surface pressure control in order to maximize the movable distance of the barrier 22 based on the premise that the surface pressure distribution within the surface of the water 1'621 is uniform. Filter paper as a child 24
．． is installed. Further, the substrate 23 is connected to the filter paper 24.
It is placed 15cm from the center. Historically, in order to perform continuous film formation using the vertical dipping method, the initial position of the barrier 22 during monomolecular film compression was 25 to 35 minutes from the end of the water tank 2I.
Set the developed molecular weight to be at the cM position.

In the production apparatus having such a configuration, after N,N-dioctadecylparaphenylenediamine is spread on the water surface of the water Ffj 21 containing pure water, the movable barrier 22 is moved to spread the spread monomolecular film onto the surface. The indicated value of the hand movement is 40
It was compressed to exhibit a surface pressure of dyn/,3. After such a pressure M operation, a hydrophobically treated silicon wafer was used as the substrate 23, and the conventional standard cumulative speed was 5++u.
Accumulation was carried out by the vertical dipping method in y/win. In this arrangement, the indicated value of the filter paper 242 as another surface hand movement detector placed at a position 2 cz from the substrate 23 is Oday/
It had decreased to cIM.

However, when the accumulated film on the substrate after repeating the above operation 10 times was examined by X-ray diffraction and SEM, no xvA diffraction pattern indicating a periodic structure was observed. Disturbances were observed everywhere.

As a result, it was found that the accumulated film was a film with a disordered structure and many defects.

Comparative Example 2 FIG. 12 is a schematic plan view showing another conventionally used organic thin film manufacturing apparatus. In this device, a movable barrier 22. , 222 are placed approximately in the center of the water tank 21, so that a substrate 23 and a filter paper 241 as a surface needle movement detector for surface pressure control are installed in order to compress from both sides.

However, since it is based on the assumption that the surface pressure distribution within the surface of the water tank 21 is uniform, the filter paper 241 and the substrate 2
3 are placed approximately 80 degrees apart.

In the manufacturing apparatus having such a configuration, after N,N-dioctadecylbaraphenylenediamine is spread on the water surface of the water tank 21 containing pure water, the movable barrier 22. ．． The monomolecular film developed by moving 22 □ was compressed so that the indicated value of the surface hand movement indicated a surface pressure of 40 dyn/α. At this time, the distance between barrier ll+ and 222 is approximately 25c
'11, and the distance of the barrier from the substrate 23 is 11cII.
It was about. After such a compression operation, a hydrophobized silicon wafer was used as the substrate 23, and accumulation was performed by a vertical dipping method at a conventional standard accumulation rate of 5R/sin. The indicated value of the filter paper 242 as another surface hand movement detector disposed at a position 2c11 from the substrate 23 in a tilted arrangement had decreased to Oday/cIM.

However, when the accumulated film on the substrate after repeating the above operation 10 times was examined by X-ray diffraction and SEM, it was found that X! ! The j1 diffraction pattern was not observed at all by 71PI,
Furthermore, in the SEM, disturbances in the structures of thank you letters and enemy letters were observed everywhere. As a result, it was found that the accumulated film was a film with a disordered structure and many defects.

〔Effect of the invention〕

As described in detail below, according to the present invention, not only is it possible to uniformly compress and form a monomolecular film on a water surface, but also it is possible to immediately detect a drop in surface pressure near the substrate during accumulation and quickly compress it to form a monomolecular film on a predetermined surface. It is possible to provide an apparatus for producing a 6-layer thin film that can recover the pressure and, in turn, produce a 47-layer thin film with a uniform structure and no defects.

[Brief explanation of the drawing]

1 to 8 are schematic plan views showing an organic thin film manufacturing apparatus according to Examples 1 to 8 of the present invention, respectively, and FIG. 9 is an explanation schematically showing nonuniform surface pressure on a water tank. Figures 10 and 10 are explanatory diagrams showing the surface pressure drop that occurs near the substrate due to the board accumulation operation in the direction perpendicular to the plate surface, Figures 11 and 12.
Each figure is a schematic plan view showing a conventional organic thin film manufacturing apparatus. 11...Aquarium, 12.12+, 122...Movable barrier, 13...Substrate, 14, +4', 141.14
2.143... Surface hand movement detector (filter paper). Applicant's agent Patent attorney Takehiko Suzue Figure 9 Figure 9

Claims (3)

[Claims] (1) A water tank for developing a monomolecular film of amphiphilic organic molecules, a movable barrier that partitions the water tank for changing the development area of the surface of the tank on which the monomolecular film is developed, and An organic thin film manufacturing apparatus comprising at least one surface pressure meter for detecting surface pressure, and an accumulation mechanism for driving the monomolecular film on a predetermined substrate in order to accumulate the monomolecular film on the substrate. An apparatus for manufacturing an organic thin film, characterized in that a detector of a surface pressure meter is arranged at the position of the movable barrier and the substrate so that the deviation from the set surface pressure after compression or during cumulative operation is within 10%. (2) The organic thin film manufacturing apparatus according to claim 1, wherein the detector of at least one surface pressure gauge is arranged within 5 cm from a location forming a boundary with the water surface of at least one of the movable barrier and the substrate. . (3) The organic thin film manufacturing apparatus according to claim 2, wherein the substrate is placed within 5 cm from the movable barrier.