JPS60261569A - Film forming device - Google Patents

Abstract

PURPOSE:To form surely a highly orderly monomolecular film which is excellently arranged and oriented by regulating the developing area of the monomolecular film with a film-forming frame, and expanding and reducing the developing region two-dimensionally with the whole periphery of the frame. CONSTITUTION:A film-forming frame 3, which can be moved up and down relatively to water surfaces 2 and 2' and having a conical inner surface, is provided. Namely, the developing region of a monomolecular film can be expanded or reduced with the whole periphery of the frame by moving the film-forming frame 3 up and down relatively to the water surface, and the developing area of the monomolecular film can be two-dimensionally regulated. Accordingly, the surface pressure of the monomolecular film which is regulated by said process can be made uniform all over, and a highly orderly monomolecular film without any disorder in arrangement and orientation can be surely obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a film forming apparatus suitable for forming a monomolecular film or a monomolecular cumulative film in which monomolecular films are laminated, and in particular, in this apparatus, The present invention relates to an improvement in a film forming frame that adjusts the surface pressure of the monomolecular film on the water surface by adjusting the spread area of the monomolecular film on the water surface.

INDUSTRIAL APPLICATION This invention is utilized, for example to implement the single molecule accumulation method (LB method; Langmuir-Prodgett method).

[Prior Art] Generally, when molecules having at least a hydrophobic part and a hydrophilic part in the same chemical structure aggregate on the water surface with their hydrophobicity and hydrophilicity appropriately balanced, the molecules become watery. It is known that a monomolecular film is formed at the air-water interface by directing the hydrophilic portion toward the water phase without floating or sinking. Then, a monomolecular film or a monomolecular cumulative film is obtained by transferring this monomolecular film to a substrate, and further transferring the monomolecular film multiple times by stacking it on the same substrate. Here, a film with a uniform thickness in which -molecules are connected in a planar manner is called a monomolecular film, and a multilayer stack of these is called a monomolecular cumulative film. Typical hydrophobic parts of the above molecules include, for example, long-chain alkyl groups with 5 to 30 carbon atoms, and common hydrophilic parts include polar groups such as carboxyl groups and amino groups. It is.

Conventionally, various types of film forming apparatuses have been used to obtain monomolecular films or monomolecular cumulative films, such as a vertical immersion type, a horizontal deposition type, and a cylindrical rotation type. However, in either type, the film forming frame is simply rod-shaped or rectangular parallelepiped, and narrows or widens the development area of the monomolecular film spread on the water surface from one specific direction. It is nothing more than a thing. This will be further explained using a vertical immersion type film forming apparatus as an example, together with the principle of forming a monomolecular film or a monomolecular cumulative film.

As shown in FIGS. 6 and 7, an inner frame 32 made of, for example, polypropylene is hung horizontally inside a shallow and wide rectangular water tank 31 containing pure water, and the water surface 40.4
It separates 0'. Inside the inner frame 32, a film forming frame 33 made of, for example, polypropylene is floated. The film forming frame 33 is a rectangular parallelepiped whose width is slightly shorter than the inner width of the inner frame 32, and is capable of two-dimensional piston movement in the left-right direction in the figure.

A weight for pulling the film forming frame 33 to the right in the figure is tied to the film forming frame 33 via a pulley 35. Further, a magnet 36 fixed on the film forming frame 33 and a pair of counter magnets 37 which are movable from side to side in the figure above the film forming frame 33 and repel each other when approaching the magnet 36 are provided.) . From glo, □# 33 If, Q '4' /! E ;e~
. □1°3 stops are possible. Instead of such a weight 34 or a set of magnets 3f3, 37, there is also a system in which a rotary motor or a pulley is used to directly move the film forming frame 33.

Suction nozzles 39 are connected to a suction pump (not shown) via a suction pipe 38 on both sides of the inner frame 32.
are lined up. This suction nozzle 38 quickly removes unnecessary monomolecular films from the previous process on the water surface 40 and 40' in order to prevent impurities from entering the monomolecular film or monomolecular cumulative film. It is used to remove. In addition, 4! is a board attached to a board holder 42 and vertically moved up and down.

First, the film forming frame 33 is moved to sweep up unnecessary monomolecular films and the like on the water surface 40 while sucking them out from the suction nozzle 38 to purify the water surfaces 40 and 40'. A film forming frame 33 is placed at the left end of the water surfaces 40 and 40' that have been cleaned in this way.
For example, a few drops of a solution of a membrane constituent material dissolved in a volatile solvent such as benzene or chloroform at a concentration of 5 x 10" 3 mO/ml are applied to the water surface 40" using a dropper or the like. When this solution spreads over the water surface 40' and the solvent evaporates, a monomolecular film will be left on the water surface 40'.

The monomolecular film described above exhibits the behavior of a two-dimensional system on the water surface 40'. When the areal density of molecules is low, it is called a gas film of a secondary gas, and a two-dimensional ideal gas equation of state is established between the occupied area per molecule and the surface pressure.

Next, from this gas film state, the film forming frame 33 is gradually moved to the right to gradually reduce the region of the water surface 40' where the monomolecular film is developed and increase the areal density, thereby increasing the intermolecular interaction. It becomes stronger and changes from a liquid film of a two-dimensional liquid to a solid film of a two-dimensional solid. In this solid film, the molecules are arranged and oriented neatly, resulting in a high degree of order and uniform ultra-thin film properties.

At this time, the monomolecular film that has become a solid film can be attached to the surface of the substrate 41 and transferred. Furthermore, a monomolecular cumulative film can also be obtained by stacking and transferring monomolecular films multiple times onto the same substrate. Note that the substrate 41 may be made of, for example, glass, synthetic resin, ceramic,
Metal etc. are used.

In order to carry out the transfer operation under conditions of the monomolecular film suitable for transfer to the substrate 41, the surface pressure of the monomolecular film is measured. Generally, the surface pressure of a monomolecular film suitable for transfer is 15 to 3Qdyn/c+n
It is said that Outside this range, the arrangement and orientation of molecules may be disturbed and the film may easily peel off. However, in special cases, for example, depending on the chemical structure of the membrane constituents, temperature conditions, etc., the suitable surface pressure value may exceed the above range, so the above range is only a rough guide.

The surface pressure of the above monolayer was measured using a measuring device (not shown).
It is automatically and continuously measured by Surface pressure measuring instruments include those that apply an indirect method of measuring the surface tension from the difference in surface tension between the water surface 40 that is not covered with a monomolecular film and the water surface 40' that is covered with a monomolecular film; Water surface 40 not covered with a molecular film and water surface 4 covered with a monomolecular film
There are methods that directly measure the two-dimensional pressure applied to the film-forming frame 33, which floats while separating from 0', and each method has its own characteristics. In addition to the surface pressure, the occupied area per molecule of the monomolecular film and the amount of change thereof are also usually measured. The occupied area and the amount of change thereof are determined from the left and right movement of the film forming frame 33.

The movement of the film forming frame 33 described above is controlled based on the surface pressure of the monomolecular film measured by the measuring device. That is, a driving device (not shown) that moves the counter magnet 37 from side to side is measured by a measuring device so that the monomolecular film always maintains a constant surface pressure selected within a range suitable for the transfer operation. controlled based on the surface pressure of the monolayer. This movement control of the film forming frame 33 is performed not only after dropping the solution of the film constituent material until the start of the monomolecular film transfer operation, but also continuously during the transfer operation.

For example, in a transfer operation, as the monolayer is transferred to the substrate, the areal density of monolayer molecules on the water surface 40' will decrease, and the surface pressure will also decrease. Therefore, it is necessary to move the film forming frame 33 to reduce the area in which the monomolecular film is developed, and to correct the decrease in surface pressure to maintain a constant surface pressure.

As described above, film formation frames play an extremely important role in obtaining monomolecular films and monomolecular cumulative films, but conventional film formation frames have the following problems. be.

[Problems to be Solved by the Invention] Conventional film-forming frames are simply rod-shaped or rectangular parallelepipeds that can be moved left and right within the inner frame. It is only a one-dimensional method that shrinks or expands the area from the direction. By the way, in order to form a highly ordered monolayer with uniform alignment,
It is necessary that the surface pressure of the monomolecular film being developed is uniform at any position. However, with conventional film forming frames, when adjusting the spread area of the monomolecular film to adjust its surface pressure, pressure differences tend to occur in parallel and perpendicular directions to the direction of movement of the film forming frame. This is the cause of disordered alignment and order.

The present invention enables adjustment of the developed area of a monomolecular film using a film forming frame.
The purpose of this is to make the developed region two-dimensional by shrinking or expanding it from the entire circumference, thereby making it possible to reliably form a highly ordered monomolecular film with uniform arrangement and orientation.

[Means for Solving the Problems] In the present invention, the means taken to solve the above-mentioned problems include a film forming frame having a frustum-shaped inner surface that is raised and lowered relative to the water surface. The goal is to create a film-forming apparatus with a

Here, being relatively moved up and down means that either the film forming frame may be moved up or down with respect to the water surface, or the water surface side may be moved up or down with respect to the film forming frame.

[Function] Since the film forming frame according to the present invention has a frustum-shaped inner surface, it can be raised and lowered relative to the water surface, and the water surface can be partitioned by the large diameter part or the small diameter part. Depending on the situation, the water surface area surrounded by the film forming frame can be adjusted by reducing or expanding it from its entire circumference. Therefore, if a monomolecular film is spread on the water surface surrounded by the film forming frame, the spread area can be adjusted two-dimensionally.

[Embodiment] Fig. 1 shows an embodiment of the film forming apparatus according to the present invention. In the figure, 1 is a water tank, which has a double structure of an outer frame 1a and an inner frame 1b. Pure water is contained within the inner frame lb, and a film forming frame 3 is provided which can be moved up and down relative to the water surface 2. This film forming frame 3 has a cylindrical shape with a truncated cone shape, and is provided with its large diameter side facing downward.
A substrate 5 is mounted above the substrate holder 4 and is moved up and down. Furthermore, the inner surface of the film forming frame 3 is subjected to hydrophobic treatment to prevent the monomolecular film from adhering to it. As this hydrophobic treatment, for example, Teflon coating or the like can be used.

The procedure for adjusting the spread area of the monomolecular film using the film forming frame 3, adjusting the surface pressure of the monomolecular film on the water surface 2, and transferring the monomolecular film to the substrate 5 will be explained.

Note that it is sufficient that the film forming frame 3 can be moved up and down relative to the water surface 2, but for convenience of explanation, it is assumed that the water surface 2 is at a fixed position and the film forming frame 3 is moved up and down. explain.

First, the position of the film-forming frame 3 is set to 0 so that the water surface 2 is partitioned off at the lower part of the film-forming frame 3 with the largest possible diameter.

Next, using a dropper or the like, a solution of the film constituent material is dropped onto the water surface 2' surrounded by the film forming frame 3 in a circle and spread. and,
After this development, when the film forming frame 3 is lowered and the water surface 2' surrounded by a circle is partitioned by the short diameter part, the area of the partitioned water surface 2' is reduced as the diameter is reduced. This results in an increase in the surface pressure of the monomolecular film developed there.

At this time, since the inner surface of the film-forming frame 3 has been subjected to hydrophobic treatment, the film-forming frame 3 can be lowered without causing the monomolecular film to adhere to the film-forming frame 3. Further, the area of the water surface 2' is reduced uniformly from its entire circumference, resulting in a two-dimensional reduction. The same holds true when expanding the area of the water surface 2'.

When the surface pressure of the monomolecular film developed on the water surface 2' surrounded by the film forming frame 3 is adjusted as described above, the monomolecular film becomes a solid film suitable for transfer, and the monomolecular film becomes a solid film suitable for transfer. It is transferred onto the substrate 5 by raising and lowering the substrate 5 at step 4. When transferring the monomolecular film to the substrate 15, it is possible to initially collapse the substrate 5 below the water surface 2' and then raise it after the monomolecular film has been developed and adjusted. After development and adjustment, board 5
may be lowered to below the water surface 2'.

The film forming frame 3 shown in FIG. 1 has a cylindrical shape with a truncated cone shape, but the outer shape does not need to be shaped like a truncated cone. Enough. Further, the shape is not limited to a truncated cone, but may be a truncated polygonal pyramid. However, if the shape is a truncated polygonal pyramid, there will be a corner on the line dividing the water surface 2', and the surface pressure of the monomolecular film at this corner tends to be uneven, so it is best to use a truncated cone shape. .

FIG. 2 shows an embodiment of another film forming frame 3.
The tube itself has a truncated conical cylinder shape similar to that shown in FIG. 1, but is provided with its small diameter side facing downward. In this case, contrary to what is shown in Fig. 1, by raising the film forming frame 3 relative to the water surface 2, the area in which the monomolecular film is developed is reduced and its surface pressure is increased. .

2. FIGS. 3 to 5 each show means for moving the film forming frame 3 up and down relative to the water surface 2.

In FIG. 3, the lower end of a rack 6 is fixed to the upper edge of the film forming frame 3. As shown in FIG. This rack 6 has a pinion gear 9 that meshes with a drive gear 8 that is rotated forward and backward by a drive shaft 7.
are engaged. Therefore, the film forming frame 3 is moved up and down together with the rack 6 by the pinion gear 9 as the drive gear 8 rotates.

In FIG. 4, the water tank 1 is placed on a lifting device 10 and can be raised and lowered by the lifting device 10, while the film forming frame 3 is suspended at a fixed position by a hanging device 11. ing. In this case, by moving the water tank 1 using the lifting device 10, the water surface 2 is moved up and down with respect to the film forming frame 3, thereby reducing or expanding the monomolecular film development area. As the elevating device 10, for example, a manual jack, a jack expanded and contracted by hydraulic pressure, a motor, etc. can be used.

3 In FIG. 5, the film forming frame 3 is suspended at a fixed position within the water tank l by a hanging tool 11. On the other hand, a water supply and drainage pipe 13 is provided near the bottom of the water tank l via a water supply and drainage pump 12.
are connected. The other end of this water supply and drainage pipe 13 is connected to a reserve tank (not shown) containing pure water.

In this case, the water in the water tank 1 is drained by operation of the water supply and drainage pump 12, or water is supplied from a reserve tank, thereby raising and lowering the water surface 2 with respect to the film forming frame 3.

[Effect 1 According to the present invention, by moving the film forming frame up and down relative to the water surface, the area can be reduced or expanded from its entire circumference, and the monomolecular film can be expanded. The area can be adjusted two-dimensionally. Therefore, the adjustment of the surface pressure of the monomolecular film performed by this method can easily be made uniform over the entire surface, and a highly ordered monomolecular film without disordered alignment can be reliably obtained.

[Brief explanation of drawings]

4. FIG. 1 is a partially cutaway perspective view showing an embodiment of a film forming apparatus according to the present invention, FIG. 2 is a partially cutaway perspective view showing another embodiment of a film forming frame, and FIGS. 3 to 5 Each figure is an explanatory diagram showing means for lowering the film forming frame relative to the water surface.
The figure is a perspective view showing an example of a conventional film forming apparatus, and FIG. 7 is a longitudinal sectional view thereof. l: Water tank, 1a: Outer frame, 1b = Inner frame, 2.2': Water surface, 3: Film forming frame, 4: Substrate holder, 5: Substrate, 6: Rack, 7: Drive shaft, 8: Drive gear, 9: Pinion gear, 10: Lifting device, 11: Hanging tool, 12
:+1i! i Drainage pump, 13: Water supply and drainage pipe. Applicant Canon Co., Ltd. Agent Yutaka 1) Yoshio:: 5 Figure 3 Figure 4 Procedures Amendment August 7, 1980 Manabu Shiga, Commissioner of the Patent Office ■, Patent Application for Indication of Case 1982- 118189 No. 2, Name of the invention Film forming apparatus 3, Person making the amendment Relationship to the case Patent applicant 3-30-2 Shimomaruko, Ota-ku, Tokyo No. (lOO) Canon Co., Ltd. Representative Ryu Kaku Part 4 , Agent Room 204, Sanshin Building, 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Telephone: 501-21385 Column 6 of "Detailed Description of the Invention" of the specification to be amended, Page 10 of the statement of contents of the amendment - Correct line 11 [e.g. Teflon coating, etc.] to "hydrophobic synthetic resin, e.g. coating with polytetrafluoroethylene, etc." J.

Claims (1)

[Claims] 1) A film forming apparatus characterized by comprising a film forming frame whose inner surface is shaped like a truncated cone and which is raised and lowered relative to the water surface.