JPH02152573A - Organic thin film forming device and method - 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 [Object of the Invention 1 (Industrial Application Field) The present invention relates to an organic thin film forming apparatus and method for forming a thin film on a substrate surface.

(Prior Art) In recent years, material technology using organic molecules has made remarkable progress. Along with this, there is a growing momentum to create new functional devices using organic molecules. In particular, the development of devices using ultra-thin films made of organic molecules is being actively studied.

. Conventional methods for forming organic thin films include the spin code method, vacuum evaporation method, and Langmuir Pro2 jet (Lang+
The Suir-Brodgett method and the like are known. Among these, in particular, the Langmuir-Prodgett method has attracted much attention in recent years as the only thin film forming method that allows organic molecules to be oriented and stacked in A units. In the following description, the Langmuir-Prodgett method will be abbreviated as the LB method, and the film formed by this LB method will be referred to as an LB film. Devices to which LB films are considered include MIS type light emitting devices (is) transistors using LB films as insulating films, photoelectric conversion devices using dye molecules, optical recording media, various sensors, and devices using polar film structures. There are piezoelectric elements etc.

Further, the use of the LB film as a resist for ultra-fine processing is also being considered.

By the way, in the usual LB method, a single amphiphilic molecule is spread on the water surface, compressed to a predetermined surface pressure to form a condensed film, and then the sample substrate is coated with this monomolecular film. A method is adopted in which a thin film of organic molecules is accumulated on the substrate by moving it up and down across the substrate. This method is called the vertical immersion method. On the other hand, a method of depositing an organic molecule thin film onto a substrate by bringing the sample substrate into contact with the developed monomolecular film in parallel is called a horizontal deposition method. The structures of cumulative monolayers obtained by these methods include Y-type structures in which hydrophilic groups and hydrophobic groups are accumulated adjacent to each other, X-type structures in which hydrophobic groups are accumulated adjacent to hydrophilic groups, and Z-type structures. There is a type. However, when a hydrophilic group and a hydrophobic group are adjacent to each other, their interfacial energy always increases, and the structure of the X, Z type film is unstable in terms of energy and easily changes over time. Therefore, in order to obtain a high-quality laminated structure, a Y-type film is useful in any accumulation method. Furthermore, a hetero-cumulative film in which each layer of the LB laminated film is composed of different molecules is considered to be useful for realizing the organic thin film element. For example, in order to accumulate an alternating heterogeneous Y-type cumulative film consisting of two types of molecules A and B, an LB manufacturing apparatus having two troughs is useful.

Recently, the following proposals have been made as a forming apparatus for forming an LB film having a high-quality heterostructure. (Japanese Patent Application No. 63-3237) This is shown in FIGS. 17 to 19.

FIG. 17 shows an embodiment of a heterostructure film forming apparatus using three completely independent water tanks 101, 102 and 103 in which three types of amphipathic organic molecules are developed. Each tank 101,
102 and 103 are fixed to an anti-vibration pedestal 105 with legs 104. Water tanks 101, 102, and 103 are each
It has a deep groove portion 106 into which the substrate is immersed. These water tanks 101, 102, and 103 are equipped with surface pressure detectors 107 for condensing molecules developed on the water surface into a film at a desired surface pressure.
and a compression drive system 108 independently.

In addition, the substrate for film formation may be immersed in a water tank,
A substrate driving device 118 is provided for vertical movement such as pulling up.

The transportation mechanism between the respective water tanks of the substrate driving device 118 is a pillar 136a fixed on the vibration-proof pedestal 105.

136b. The configuration of this transport mechanism is
It looks like this: The power of the motor 139 serving as the drive source is transmitted to the screw 138 via the gear 140, and the substrate driving device 118 can freely move between the water tanks in the air by being guided by the guide rail 137.

FIGS. 18 and 19 are enlarged views of one water tank, for example, water tank 101, in the organic thin film forming apparatus shown in FIG. 17.

The water tank 101 is separated into two regions by a partition 120, a region A in which molecules 121 are expanded, and a region A in which molecules 121 are expanded.
21 is divided into an undeveloped region B and an undeveloped region B.

Next, the substrate driving device 118 will be explained.

The substrate drive device 118 includes a vertical drive device 122 for vertically driving the substrate 119, and a transport mechanism 123 for transporting the substrate 119 between an area A where molecules 121 are expanded and an area B where molecules 121 are not expanded. has been done.

The board 119 is mounted on a board holder 126 attached to the tip of an L-shaped board mounting rod 125. The board mounting rod 125 is attached to a vertical moving body 127 and can be moved up and down by a feed screw 128.

Further, the vertical moving body 127 and the feed screw 128 are connected to the conveying body 1.
29, this carrier 129 is attached to the feed screw 130.
The substrate 119 is moved between area A and area B by the following steps.

The carrier 129 also includes a substrate holding section 131 for receiving and taking the substrate 119 mounted on the substrate holder 126.
is provided. A claw portion 132 is provided at the tip of this holding portion 131 so that the substrate 119 can be attached or removed.

Therefore, the substrate 119 can be transferred between the holding portion 131 and the substrate holder 126.

A feature of the device configured in this way is that the contact point between the support member for supporting the substrate 119 and driving it up and down and the aqueous phase in the water tank is an area where the monomolecular film is not developed (area). B), even if the support member is moved up and down to move the substrate up and down, there will be no adverse effect on the area where the monomolecular film with increased surface pressure is developed (area A), resulting in high quality. The reason is that it is possible to form a thin film.

However, even with the useful LB film forming apparatus configured as described above, there are the following demands.

That is, this device requires a mechanism for receiving and passing the substrate between underwater and air, which complicates the device structure, so it is desirable to simplify it.

Furthermore, since the substrate mounting rod 125 for supporting the substrate must be located in the region B where molecules are not developed, there is a risk that restrictions will be placed on the process of forming a heterostructured LB film, and the formation process I want to simplify.

Recently, a method has been attempted in which the substrate is inserted obliquely to the water surface when molecules are accumulated on the substrate.

This is because if the substrate is inserted perpendicularly to the water surface, a uniform thin film cannot be formed due to the effect of surface tension (the effect of the phenomenon that the surface pressure of a monomolecular film decreases near the substrate during accumulation). Inserting the substrate at an angle to the water surface in this way is useful for forming a uniform thin film without being affected by surface tension, but in the above-mentioned device, the substrate can be inserted at any angle to the water surface. Inserting the device obliquely would complicate the device and make it difficult.

(Problems to be Solved by the Invention) As described above, in the above-mentioned organic thin film forming apparatus, a transfer mechanism is required to receive the substrate, which complicates the apparatus and the forming process, and There were requests for improvement in that it was difficult to insert the device diagonally to the water surface and it was difficult to form a uniform thin film without being affected by surface tension.

The present invention has been made in view of the above circumstances, and its objectives are to shorten the apparatus and formation process, and to provide an organic thin film forming apparatus and method in which the insertion angle of the substrate can be freely set with respect to the water surface. Our goal is to provide the following.

[Structure of the Invention] (Means for Solving the Problems) The organic thin film forming apparatus of the present invention includes a water tank for spreading a monomolecular film of organic molecules, and a water tank in which the monomolecular film is spread. to separate the first region and the second region in which a monomolecular film is not developed or a monomolecular film different from the monomolecular film is developed in the aquarium, and the first region and the second region; partitioning means, and a substrate for dipping or pulling the substrate into the first or second region along a predetermined direction in order to attach the monomolecular film developed in the water tank onto the substrate. a vertical drive means; a substrate rotation drive means for rotating the substrate in order to vary the holding angle of the substrate with respect to the monolayer surface; and a substrate rotation drive means for rotating the substrate between the first region and the second region. The present invention is characterized by comprising a substrate moving means for moving the substrate.

Further, the method for forming an organic thin film of the present invention includes the steps of preparing a plurality of organic molecule spreading regions that are separated from each other and each containing a liquid, and spreading different organic molecule films on the liquid surface of the spreading regions. and a step of attaching the monomolecular film onto the surface of the substrate by dipping or pulling the substrate along a predetermined direction relative to the monomolecular film in a region where the monomolecular film is developed. and a step of rotating the substrate so that the holding member that always holds the substrate crosses the monomolecular film after substantially dipping or pulling up the substrate when depositing the monomolecular film on the surface of the substrate. It is characterized by consisting of.

(Function) According to the organic thin film forming apparatus and forming method configured as in the present invention, the support member for supporting the substrate crosses the developed molecular film at a time when the substrate has almost finished crossing it. The substrate can be rotated before being immersed and pulled up. Therefore, the monomolecular film can be attached to the substrate without any adverse effects of the support member.

In addition, since the substrate can be rotated, it is possible to immerse and pull up the substrate at any angle when dipping or pulling up the substrate.When attaching molecules to the substrate, the optimal immersion or pulling up can be performed depending on the type of molecule. You can set the angle,
It is possible to minimize the influence of surface tension.

In addition, as described in claim 2, the subordinate rotation mechanism holding the substrate is provided inside the water tank, and it is indirectly driven by the main rotation mechanism provided outside the water tank, so that the substrate can be moved above and below the water surface. There is no need for a bridge structure to pass the substrate, and it is possible to eliminate other members that would interfere with the movement of the substrate across the molecular film with increased surface pressure, making it possible to form a high-quality organic thin film.

In addition, in order to drive the substrate with a drive source provided outside the water tank, in other words, to separate the substrate side and the drive side, we have created a sluice gate (an opening through which the driving means passes) that was conventionally provided in the partition wall separating the water tanks. ) was necessary and the contamination of molecules could not be avoided, but in the present invention, it is unnecessary and no contamination of molecules occurs.

(Example) The present invention will be explained in detail below.

FIG. 1 shows a first embodiment of the present invention, in which one water tank 1 is used to develop five types of amphiphilic organic molecules, and this water tank 1 is divided into four partition plates 5a, 5b, 5c, 5d. 5 separate aquariums 1a.

This is a heterostructure film forming apparatus according to an embodiment, which is divided into lb, lc, ld, and le. The water 11 is placed on the vibration-proof pedestal 6 and the legs 7
Fixed by Each separated water tank 1a, lb,
lc, ld, and le each have a deep groove portion 8 into which the substrate is immersed. These 5 separated waters for $1! la, l
b, lc, ld, and le each independently have a surface pressure detector and a compression drive system for condensing the molecules spread on the water surface into a film at a desired surface pressure. In the figure, the aquarium l
Although a surface pressure detector 9 is shown on water tank c, similar surface pressure detectors are actually located on water tanks 1b, lc, ld, and lc. This surface pressure detector 9 is, for example, of a so-called Wilhelay type using an electronic balance, which determines the surface tension a1 of a molecular film developed by hanging a filter paper. The basic components of the compression drive system are water 1; @la, lb, lc.

To explain each of ld and le, they are movable Teflon barriers for expanding and compressing organic molecules on the water surface.
10a, 10b, 10c, 1
0d and 10e are provided respectively. The movable barriers 10a to 10e are respectively attached to compression movable nuts 12a to 12e by connecting rods 11a to lie, and the compression movable nuts 12a to 12e are attached to the mounting base 1.
They are slidably held by guides 14a to 14e fixed to guides 3a to 13e and connected to screws 15a to 15e, respectively. Both ends of the screws 15a to 15e are held by support stands 16a to 16e and 17a to 17e, and are configured to transmit power from motors 18a to 18e. That is, by driving the motors 18a to 18e, the movable barriers 10a to 10e can be independently moved along the screws 15a to 15e, thereby forming a condensed film with a predetermined surface pressure. In FIG. 1, only the water Vj1 and its corresponding one (subscript e) are shown by reference numerals, but the configuration of the compression drive system is the same for the other water tanks 1a, lb, lc, and ld. be.

Further, there is a substrate vertical drive device 19 for vertically driving the substrate for film formation by immersing it in a water tank and pulling it up.

There is also a substrate left-right drive device 20 for driving the substrate left and right in the figure at low speed. Further, there is a substrate rotation drive device 21 for rotating the substrate 360'. The substrate drive device 22 includes the substrate vertical drive device 19 and the substrate left and right drive device 2.
0, and a substrate rotation drive device 21.

8 water t of the substrate transfer device 22! The transport mechanism between 1a and 10 is provided by pillars 36a and 3 fixed on the vibration-proof pedestal 6.
6b. The configuration of this transport mechanism is as follows. That is, the power of the motor 39 serving as the drive source is transmitted to the screw 38 via the gear 40, and the substrate transport device 22 is guided by the guide rail 37. fj
You can move freely in the air between 1a and 1e.

2 and 3 are enlarged views of one of the five separated water tanks in the organic thin film forming apparatus of the present invention in FIG. 1, for example, water tank 1e. The present invention is effective even when only one water tank is used as described above.

The water tank 1e is separated on the water surface by a partition plate 5d, and is further divided into two areas by a movable barrier 10e, that is, molecules 2 and 2.
The area is divided into an area Ae where the molecule 23 is expanded and an area Be where the molecule 23 is not expanded.

Next, details of the substrate vertical drive device 19 will be explained. The substrate vertical drive device 19 is configured as follows. The driving force of the motor 24 is transmitted to the screw 27 whose both ends are supported by support stands 25 and 26, and then to the left and right mounting bases 28 of the board left and right drive device 20. At this time, the left and right mounting bases 28 are driven up and down while being guided by a vertical guide 30 fixed to the upper and lower mounting bases 29.

Similarly, the substrate left and right drive device 20 is configured as follows. The driving force of the motor 31 is transmitted to a screw 34 whose both ends are supported by support stands 32 and 33,
is transmitted to the rotational mounting base 35 of. At this time, the rotary mounting base 35 is driven left and right by being guided by the left and right guides 43 fixed to the left and right mounting bases 28.

The substrate rotation drive device 21, which is a feature of the present invention, is constructed as shown in FIG.

The driving force of the motor 44 is transmitted to the rotating shaft 47 via gears 45 and 46. A magnet holder 49 containing a magnet 48 is attached to the rotating shaft 47. And is the magnet holder 49 water? ! It is movable along the outer wall of 1.

The rotating shaft 47 is guided by a bearing 50 and is attached to the bearing 50 with a nut 51. Further, the bearing 50 is attached to the rotation mounting base 35.

A magnetic material holder 53 is movably installed on the inner wall of the aquarium 1 and houses a magnetic material 52 (any material that can be attached to a magnet, such as S341) that is attracted by the attraction force of the magnet 48. As the magnetic material 52, a magnet (electromagnet or permanent magnet) may be used to increase the attractive force.

A connecting rod 56 is connected to the magnetic holder 53 for attaching a substrate holder 54 to which a substrate 55 is attached.

Board vertical drive device 19 installed outside the water tank 1.
Board left and right drive unit ri120. When at least one of the substrate rotation drive device 21 and the substrate transfer device 22 is driven, the magnet 48 housed in the magnet holder 49 moves, and the magnetic material holder 53 houses the magnetic material 52 that is attracted to the inner wall of the water tank 1. is moved by the attraction force of the magnet 48, and thereby the substrate 55 is moved.

The basic film forming process in the organic thin film forming apparatus configured as described above will be briefly explained.

First, when accumulating different molecules, Figure 2 is followed by Figure 3.
Although the process is driven as shown in the figure, schematic process diagrams are shown in FIGS. 5(a) to 5(f) for ease of understanding.

As shown in FIG. 5(a), the substrate holder 54 holding the substrate 55 is held at a predetermined angle, and as shown in FIG. 5(b), a predetermined angle ( Although the vertical one is illustrated in Fig. 5, the horizontal one, 45
” (any other angle is possible). This movement is
This is done by driving the drive device 19 up and down the substrate.

The substrate 55 and the magnetic holder 53 are immersed in the water tank 1 as shown in FIG. 5(C), or the substrate 55 is rotated as shown in FIGS. 5(d) to (C) during the immersion process. . Then, as shown in FIG. 5(e), the substrate 55 is lifted after being transported by the substrate lateral drive device 20 to the area Ad where other molecules 23b are developed. Here, the operation of transporting the substrate 55 from the area Ae to Ad and the operation of rotating the substrate 55 may be performed first, or may be performed simultaneously.

Even when the substrate 55 is raised, the angle can be set to a predetermined value. Then, when the substrate 55 has been raised as shown in FIG. 5(r), molecules 23a and molecules 23b different from the molecules 23a can be accumulated on the substrate 55.

As described above, a feature of the present invention is that the substrate 55 always crosses the region A where the molecules 23 are developed before the magnetic holder 53, whether the substrate 55 is immersed or raised. .

In addition, when only one layer of molecules 23 is to be accumulated on the substrate 55, the substrate 55 is immersed from the area A where the molecules are expanded, as shown in FIGS. It may be pulled up in any state as long as it is transported to area B where it is not covered.

Note that the substrate 55 may be immersed from the region B where the molecules 23 are not developed (any state is possible), transported to the region A, and then raised so as to cross the region A first.

As described above, only one layer of molecules 23 is provided on the substrate 55, or
When a plurality of molecules 23 are accumulated, the substrate 55 always crosses the region A in which the molecules 23 are developed, so that a high-quality organic thin film can be formed.

FIG. 6 shows a modified example of the substrate rotation drive device 21 according to the present invention, which uses the repulsive force of a magnet, and is a side sectional view of the water tank 1. FIG. An in-tank movable mechanism 60 is installed in the aquarium 1 and is movable within the aquarium 1 while holding a substrate 55 therein. That is, magnet holders 49a and 49b that house magnets 48a and 48b provided on the outside of the aquarium 1,
A magnet 5 is placed opposite to the magnet 5 so as to generate a repulsive force.
Magnet holders 53a and 5 that housed magnets 2a and 52b
3b is provided. This magnet holder 53a
, 53b are fixed to the connecting rod 56. A board holder 54 to which a board 55 is attached is fixed to the connecting rod 56. On the outside of the water tank 1, substrate rotation drive devices 21a and 21b are arranged front and back (left and right in the figure), and a connecting fitting 61
Fixed by The connecting fitting 61 is a substrate vertical drive device 19 similar to the one described above. Board left and right drive device 20.
It is connected to the substrate transport device 22.

The magnets 52a and 52b of the aquarium movable mechanism 60 are magnets 48a provided outside the aquarium 1.

48b's repulsive force, it is suspended in the air, and the water t! 1
By providing a gap between the substrate 55 and the magnet holders 53a and 53b, the substrate 55 can freely move within the water tank without being affected by frictional force.

FIGS. 7 to 10 are explanatory diagrams showing modifications of the embodiment in which the substrate is moved using the attraction force of a magnet.

FIG. 7 shows a part of the aquarium 1, for example, an aquarium side wall plate in a movable range of the magnet holder 49 (the part marked T in FIG. 7), in order to make it easier for the magnetic force of the magnet 48 to pass through and to strengthen the attraction force. The thickness is reduced. Alternatively, the entire surface of the water tank 1 may be made thinner. However, the plate thickness must be within a range where deformation of the water tank 1 due to the water pressure of the solution in the water tank 1 does not affect the formation of the hetero membrane.

FIG. 8 shows a part of the water tank 1 (the movable range of the magnet holder 49) made of non-magnetic material 6 to facilitate the passage of magnetic force.
This is an example of changing to 3. Furthermore, depending on the ability of the magnet 48 and the method of arrangement, the entire aquarium 1 may be made of non-magnetic material 63.
You may change it to By the way, the non-magnetic material 63 needs to be selected from a material that does not dissolve, for example, depending on the solution or the type of developing molecules.

Figure 9 shows the magnet holder 49 and magnetic material holder 5.
FIG. 3 is an explanatory diagram showing a modification example for realizing smooth movement of No. 3; In FIG. 9(a), in order to reduce the frictional force generated when the magnetic holder 53 or the magnet holder 49 moves, a resin 64 or the like with low sliding friction resistance is pasted on at least a part of the surface of the water tank 1. This is an example of fixing with screws, etc.

Similarly to FIG. 9(a), FIG. 9(b) is also an example in which at least a portion of the surface of the water tank 1 is treated with Teflon coating 65 or the like in order to reduce the sliding friction force. By the way, as a modification to reduce frictional resistance, the magnetic holder 5
3. Alternatively, a material with low frictional resistance (for example, Teflon, etc.) may be selected as the material of the magnet holder 49.

FIG. 10 shows an example in which a bearing 65 is incorporated in at least one of the magnetic holder 53 or the magnet holder 49 in order to reduce the frictional force generated when the magnetic holder 53 or the magnet holder 49 moves. .

FIG. 10(a) is a sectional view of the magnet holder 49 and the magnetic material holder 53, and FIG. 10(b) is a front view thereof.

By incorporating the bearing 65 into the magnet holder 49 and the magnetic holder 53, sliding friction can be changed to rolling friction, and the frictional force can be further reduced.

FIG. 11 shows a modification of the connecting rod 56 of the substrate holder of the present invention, in which the connecting rod 56 is bent two or more times in different directions so that the substrate 55 can be inserted at any angle of 360 inches with respect to the water surface. It is.

In other words, the solid line in Fig. 11(a) is the front view, and the solid line in Fig. 11(b) is the front view.
), two curved portions 56a bend in different directions.
, 56b are provided, it is possible to create a structure in which the substrate 55 always crosses the water surface first even if the substrate 55 crosses the water surface at any angle of 360°, as shown by the broken line in FIG. 11(a).

In this way, by making it possible to insert the substrate 55 into the water surface at any angle of 360'', it is possible to reduce the effects of surface tension due to differences in viscosity of molecules and differences in the type of solution. It is possible to accumulate a hetero film by changing the angle of the substrate 55 by 3 degrees.Furthermore, by driving the substrate vertical drive device 19, substrate left and right drive device 20, and substrate rotation drive device 21 at the same time or separately, high quality film can be accumulated. A hetero-membrane can be formed.

Next, a process for forming a heterostructure film by partitioning and separating the inside of one water tank 1 with a partition plate 5 to provide a plurality of water tanks as shown in FIG. 1 will be described. Note that the board 55 is held by holding the upper end or lower end of the board 55 with the board holder 54.
A film is formed on both sides of 5.

As shown in the process from FIG. 12(a) to FIG. 12(b), the substrate 5
5 is immersed from the region Aa where the molecules 23a are developed, moved and pulled up from the region Ba where the molecules are not developed, and then moved again and immersed from the region Aa.
As shown in Figure (d), the same molecules 23a can be accumulated in the order of substrate, hydrophobic group, hydrophilic group, hydrophobic group, and hydrophilic group.

In the steps shown in FIGS. 12(a) to 12(e), the substrate 55 is immersed in the region Aa of the water tank 1a where the molecules 23a have been developed, moved and pulled up from the region Ba, and then placed in a different water tank 1a.
After being conveyed to point b, when the different molecules 23b are immersed in the region Ab where they are developed, a structure as shown in FIG. 12(e) is obtained.

In addition, in FIGS. 12 to 15, solid line arrows indicate the substrate 5.
This is the direction of movement of 5.

In the steps shown in FIGS. 13(a) and 13(b), the substrate 55 is immersed from the area Aa where the molecules 23a are developed and pulled up as it is, and as shown in FIG.
They are accumulated in the order of hydrophilic groups, hydrophilic groups, and hydrophobic groups.

The steps in FIG. 13(a) to FIG. 13(c) are performed by the molecule 23a
The substrate 55 is immersed in the area Aa of the water tank 1a where the water tank 1a is developed, moved and pulled up from the area Ba, and then transferred to the other water tank 1b.
By transporting the substrate 55 to the area Bb, moving the substrate 55, and pulling it up from the area Ab where other molecules 23b have been developed, a heterostructure film as shown in FIG. 13(e) is obtained. .

In the steps shown in FIGS. 14(a) and 14(b), the substrate 55 is
14(d), the substrate, hydrophilic groups,
Molecules are accumulated in the order of hydrophobic group, hydrophobic group, and hydrophilic group.

In the steps shown in FIGS. 14(a) to 14(e), the substrate 55 is placed in the water tank 1a.
After moving the substrate 55, it was pulled up from the area Aa where molecules 23a were developed, and then transported to the water tank 1b and immersed in it from the area Ab where other molecules 23b were developed. A structure as shown in FIG. 14(e) is obtained.

In the process of FIG. 15(a)→(b), the substrate 55 is
The molecule 23a is moved in and moved from the area Aa, where the molecule 23a is developed, and then moved again, and the molecule 23a is moved in from the area Ba, and the molecule 23a is moved a third time and then pulled up from the area Aa.
As shown in figure (d), a substrate, a hydrophilic group, a hydrophobic group, a hydrophilic group,
Can be accumulated in the order of hydrophobic groups.

In the steps shown in FIGS. 15(a) to 15(C), the substrate 55 is placed in the water tank 1a.
After moving the substrate 55 from area Ba and pulling it up from area Aa where molecules 23a are developed, the substrate 55 is transported to another water tank 1b, and is moved from area Bb to another area where molecules 23b are expanded. It is pulled up from Ab and has a structure as shown in FIG. 15(e).

As shown in FIGS. 12 to 15, monomolecular films can be selectively accumulated, and a plurality of types of monomolecular films can be cumulatively formed in various combinations.

In the above embodiment, one water tel is divided into a plurality of water tanks using a partition plate 5, for example, 5 water tanks as shown in FIG.
Although the water tanks are divided into two water tanks 1a to 1e, a plurality of independent water tanks can be provided.

By making the water tank independent, it is possible to prevent contamination caused by the spread molecules.

In addition, in order to develop different molecules, it is important to create a water phase that is suitable for each molecule in each tank.
Since the ion concentration can be set, the selection range of molecules to be developed is expanded. In addition, by combining each process,
type, Y-type, and Z-type membrane structures can be obtained very easily.

When the aquarium is made independent, as shown in FIG. 16, an aquarium partition wall 4 separating aquarium 1 and aquarium 2, and water tf! The height of the water tank partition wall 4° that separates water I63 from water ml is 2.3.
The height is lower than the common peripheral wall of the water tanks 1, 2.3, and the magnet holder 49 and the magnetic material holder 53 are installed between the independent water tanks 1, 2, 3, etc. along the common peripheral wall of the water tanks 1, 2.3. If each is made movable, the substrate 55 can be moved or rotated as in the previous embodiment.

Note that the present invention is not limited to the above embodiments,
The specific configuration of the drive device that transports the substrate vertically and horizontally twice can be modified in various ways, and the substrate lateral drive device 20 and the substrate transfer device 22 may move the substrate 55 in the same direction. It is also possible to use one for both purposes.

[Effects of the Invention] As described in detail above, according to the present invention, the substrate always crosses the region where molecules are developed first, so the vertical movement of the substrate can be performed without any adverse effect on the region where molecules are developed. This makes it possible to form a high-quality thin film.

Further, when moving the substrate over and across the water surface, a mechanism for transferring the substrate can be omitted, so that the substrate moving mechanism can be simplified. Furthermore, by freely rotating the substrate to change the angle between the substrate and the water surface, a high-quality thin film that is less affected by surface tension can be formed.

[Brief explanation of the drawing]

FIG. 1 is an overall perspective view showing an embodiment of an organic thin film forming apparatus of the present invention, FIGS. 2 and 3 are side views showing an embodiment of essential parts of an organic thin film forming apparatus of the present invention, FIG. 4 is a side view showing an embodiment of the substrate rotation means of the organic thin film forming apparatus of the present invention, and FIG. 5 is a process diagram showing an embodiment of the organic thin film forming method of the present invention. 6 and 7 are side views showing modified examples of the substrate rotating means according to the present invention, and FIGS. 8 to 10 are side views showing means for reducing friction in the substrate rotating means according to the present invention. An explanatory diagram, FIG. 11 is an explanatory diagram for explaining the action of the substrate rotation means according to the present invention, and FIGS. 12 to 15 are schematic diagrams showing the state of heterostructure film formation according to the present invention. FIG. 16 is an overall schematic side view showing a modification according to the present invention, and FIGS. 17 to 19 are a schematic perspective view and a side view of essential parts of an organic thin film forming apparatus according to a prior invention to the present invention. 1.2.3...Water tank 5......Partition plate (partition means) 10...・・・・・・Movable barrier (partition means) 19・・・・・・・・・・・・・・・
...Board vertical drive device 20...
......Substrate left and right drive device (substrate transport means) 21...Substrate rotation drive device 22... ......Substrate transfer device (substrate transfer means) 23...
・・・・・・Molecular 48・・・・・・・・・・・・
・・・・・・Magnet (magnet) 49・・・・・・・・・
・・・・・・・・・Magnetic holder (outer holder)

Claims (11)

[Claims] (1) A water tank for developing a monomolecular film of organic molecules, a first region where the monomolecular film is developed in this tank, and a region where the monomolecular film is not developed in the tank or the monomolecular film a second region in which a monomolecular film different from the first region is developed; a partitioning means for separating the first region and the second region; and adhering the monomolecular film developed in the water tank onto a substrate. a substrate vertical drive means for dipping or pulling the substrate into or out of the first or second region along a predetermined direction; and for varying the holding angle of the substrate with respect to the monomolecular film surface. An apparatus for forming an organic thin film, comprising: a substrate rotation driving means for rotating the substrate; and a substrate moving means for moving the substrate between the first region and the second region. (2) The substrate rotation driving means includes a main rotation mechanism that is arranged outside the aquarium wall and can rotate along the aquarium wall, and a main rotation mechanism that is arranged inside the aquarium wall and follows the rotation of the main rotation mechanism. 2. Formation of an organic thin film according to claim 1, further comprising: a dependent rotation mechanism that is rotatable along the wall of the aquarium, and an angle of the substrate with respect to the surface of the aquarium changes by rotation of the dependent rotation mechanism. Device. (3) The organic thin film forming apparatus according to claim 1, wherein the substrate is attached to an arm for supporting the substrate to the substrate rotation driving means. (4) The organic thin film forming apparatus according to claim 2, wherein the subordinate rotation mechanism follows the rotation of the main rotation mechanism by magnetic force. (5) The main rotation mechanism has an outer magnet or an outer magnetic body that can rotate along the outer wall of the aquarium, and the subordinate rotation mechanism has a magnetic attraction force with the outer magnet or the outer magnetic body on the inner wall of the aquarium. 5. The organic thin film forming apparatus according to claim 4, further comprising an inner magnetic body or an inner magnet that is held by generating a repulsive force. (6) The main rotation mechanism includes an outer holder that can rotate along the outer wall of the aquarium, and an outer magnet or an outer magnetic body provided within the outer holder, and the subordinate rotation mechanism includes an outer holder that is rotatable along the outer wall of the aquarium. an inner holder that is rotatable to follow the outer holder along the inner holder, and an inner magnet or an inner magnetic body that is provided within the inner holder and generates a magnetic attractive force or a repulsive force with the outer magnet or the outer magnetic body. 5. The organic thin film forming apparatus according to claim 4, wherein: (7) In order to strengthen the magnetic force, the thickness of at least a part of the wall of the aquarium is reduced, or at least a part of the wall of the aquarium is made of a non-magnetic material or resin. 4. The organic thin film forming apparatus according to 4. (8) pasting or coating at least a portion of the surface of the aquarium wall with a material having a small coefficient of friction so that at least one of the main rotation mechanism or the subordinate rotation mechanism can easily move by contacting the aquarium wall; 3. The organic thin film forming apparatus according to claim 2, wherein at least one of the main rotation mechanism and the subordinate rotation mechanism is provided with a bearing. (9) The organic thin film forming apparatus according to claim 1, further comprising a plurality of independent water tanks and a substrate transport means for transporting the substrate between the plurality of independent water tanks. (10) The organic thin film according to claim 1, wherein the partition means is movable within the water tank and is capable of setting the surface pressure of the monomolecular film developed on the surface of the water tank to a predetermined value. forming device. (11) a step of preparing a plurality of organic molecule deployment regions that are partitioned from each other and each containing a liquid; a step of deploying a different organic molecule film on the liquid surface of the development region; and a step in which the monomolecular film is attaching the monomolecular film onto the substrate surface by dipping or pulling up the substrate along a predetermined direction with respect to the monomolecular film in a developed area; The method is characterized by comprising the step of rotating the substrate so that the holding member that always holds the substrate when attaching the monomolecular film traverses the monomolecular film after substantially dipping or pulling up the substrate. Method for forming organic thin films.