JPS60222168A - Film forming device - Google Patents

Abstract

PURPOSE:To form hetero-type built-up films of monomolecular layers continuously and easily in a short time by moving and passing a substrate successively through plural monomolecular layers which are formed separately on the liquid surface. CONSTITUTION:A partition 2 is provided at the center of a vessel 1 to separate the water surface to monomolecular layers 3a and 3b, and floats 4a and 4b are moved. Then the substrate is moved horizontally in the liquid in the directions as shown by the arrows 13, 14, 15, 16, 17, and 18 to transfer the monomolecular layers A and B on the water surface 3a and 3b to the substrate. The built-up films having heterojunction between hydrophilic groups are easily formed in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a film forming apparatus. More specifically, the present invention relates to an apparatus for forming an organic thin film on a substrate, such as a single molecule or a monomolecular cumulative film formed by laminating single molecules, which is used in divas and the like.

[Background of the Invention] Conventionally, the use of materials in the semiconductor technology field and the optical technology field has mainly focused on inorganic materials that are relatively easy to handle. One reason for this is that technological progress in the field of organic chemistry has lagged significantly behind that in the field of inorganic materials.

However, recent technological advances in the field of organic chemistry have been remarkable, and it is said that the development of materials for inorganic substances has almost reached its limit. Therefore, there is a need for the development of functional organic materials as new functional materials that surpass inorganic materials. Advantages of organic materials include being inexpensive, easy to manufacture, and highly functional. On the other hand, organic materials that overcome heat resistance and mechanical strength, which have been considered drawbacks up to now, have been produced one after another recently. Based on this technical background, we have developed a system for the functional parts (mainly the ftjM part) of integrated circuit devices such as logic elements, memory elements, and photoelectric conversion elements, and optical devices such as microlens arrays and optical waveguides. The proposal to replace part or all of the conventional inorganic thin film with organic [1] has led to the creation of molecular electronic devices and bio-related materials in which a single organic molecule has functions such as logic elements and memory elements. Several research institutes have recently announced proposals to create logic devices (e.g., biochips) consisting of

Organic S films, which are the main components of such devices, are fabricated using a single molecule accumulation method. The single-molecule accumulation method (also known as the Langmuir-Prodgett method, also known as the LB method for short) is a method that uses the hydrophilicity and hydrophobicity of molecules with parent wood groups and hydrophobic groups to deploy them on water in an orderly manner. A monomolecular film or a monomolecular cumulative film (hereinafter referred to as rLB film), which is a stack of monomolecular molecules, can be formed on a substrate by forming a monomolecular film and then transferring it to the substrate surface. It is.

[Prior Art 1] As shown in FIG. 1, a conventional film forming apparatus is placed inside a shallow and wide rectangular water tank 1 with a frame 2 horizontally partitioning a water surface 3. The frame 2 functions as a two-dimensional cylinder, and a rectangular float 4 is floated inside the frame 2. The width of the float 4 is slightly narrower than the inner dimension of the frame 2, so that it can move smoothly from side to side as a knee-dimensional piston. is formed. The float 4 is connected to a winding device using a motor or the like via a wire 5 in order to move it left and right. When forming a monomolecular film, the constituent substances of the film are benzene,
Dissolve it in a volatile solvent such as chloroform and drop it onto the water surface 3. After the solvent evaporates, a monomolecular film exhibiting the behavior of a two-dimensional system remains on the water surface 3. When the areal density of molecules is low, it is called a gas film of secondary gas. When the float 4 is moved to the right to reduce the extent of the water surface 3 on which single molecules develop and increase the surface density, the interaction between molecules becomes stronger.
After passing through a two-dimensional liquid film, it changes to a two-dimensional solid film. When this solid film is formed, the molecules are arranged and oriented in a neat manner.
This results in the high degree of order and uniform ultra-thin film properties required for materials that make up semiconductors.

As a method of transferring the monomolecular film from the water surface 3 onto the surface of the substrate 7, the substrate 7 is attached to the substrate holder 8 while applying a constant surface pressure suitable for cumulative operation to the monomolecular film on the water surface 3.
There is a vertical dipping method in which a monomolecular film is transferred by moving the monolayer up and down in the vertical direction 9. In this method, as shown in Fig. 2(a), the
There are three types: Y-type, in which the monolayer 1θ is attached both during dipping and pulling up, as shown in ), and Z-type, in which the monomolecular film IO is attached only during pulling up, as shown in FIG. 2(C). In addition, in the molecule shown in FIG. 2, 11 indicates a hydrophilic group 1, and 12 indicates a hydrophobic group.

Using the apparatus shown in Figure 1, for example, a third hetero-cumulative film in which the constituent molecules of the monolayer are different in the Y-shaped cumulative direction is formed.
When making a cumulative a film as shown in the figure (see Fig. 2(b)), that is, the hydrophilic groups 11'a' of the film A, ! - Parent base 11b of membrane B
When creating a heterojunction between the two, first move the substrate up and down to attach the film A 1 * A 2, keep the substrate in water, discard the monomolecular film A on the water surface, and after purifying the water surface, Make a single molecule of 1 MB on the water surface and move the substrate up and down to # Bt
+B2 was attached, and then membrane A3 was attached in the same manner. However, with this kind of equipment, it takes time to purify the water surface when replacing the membrane, especially if there are multiple layers, it takes time to knead, and the water surface may ripple when cleaning the membrane.
Due to changes in the water level, etc., the accumulated film near the water level on the substrate is not lined up neatly, and the accumulated film formed in this vicinity cannot be used.

As mentioned above, with the conventional apparatus for producing a conjunctival membrane by suspending a substrate from above, it takes time and effort to make a heterogeneous membrane, and it is not necessary to throw away membranes that can still be used when replacing the membrane. There were many drawbacks such as:

[Purpose] The present invention has been made to eliminate the drawbacks of the conventional device described in 2. The purpose is to easily form a hetero-type monomolecular cumulative film continuously, in a short period of time, by using a simple device that moves and passes sequentially.

[Structure and operation] That is, the present invention is an apparatus that spreads a group of molecules for film formation on a liquid surface and causes the group of molecules to pass through a substrate to form a monomolecular film or a cumulative film thereof on the substrate. , a means for separating two or more different types of monomolecular layers formed on the liquid surface in the same developing liquid tank so as not to mix with each other, and a means for moving the substrate laterally in the liquid are provided. This is a film forming apparatus characterized by:

Hereinafter, the present invention will be explained based on the drawings.

FIG. 4 shows a schematic diagram of an example of the film forming apparatus of the present invention. A partition 2 is provided in the center of a rectangular water tank 1, which is a developing liquid tank, to separate two or more different types of monomolecular layers formed on the liquid surface so that they do not mix with each other. 2
It is divided into two parts. 3 constituent substances A of the monolayer
A, component B is dropped onto 3b, floats 4a and 4b are moved by a moving device (Ii!J not shown), and arbitrary surface pressure is applied to membranes A and B on water surfaces 3a and 3b.

Next, the substrate is moved laterally in the liquid in the order of arrows 13a-18, and when the monomolecular films A and B formed on the water surfaces 3a and 3b are transferred to the substrate, hydrophilic groups and the like shown in FIG. 3 are formed. A cumulative film with heterojunctions between hydrophilic groups can be easily formed. Such a cumulative film has the advantage that when molecules whose hydrophilic group portions have functions are accumulated, the functional portions of different molecules become very close to each other. As described above, the present invention is an apparatus characterized by being able to move a substrate underwater.

[Embodiment 1] Fig. 5 shows one embodiment of the present invention, in which Fig. 5(a) is a front sectional view and Fig. 5(b) is a side sectional view. square aquarium 1
A frame (partition) 2 is placed inside to horizontally partition water surfaces 3a and 3b. A float 4a is floated on the water surface 3a inside the frame 2, and a float 4b is floated on the water surface 3b, and the areas 3a and 3b on the water surface are set to an arbitrary constant surface pressure using a moving device (not shown) and a surface tension meter. It is configured to be adjustable. The substrate 7 is attached to a substrate holder 8 and is configured to be able to move vertically on a substrate vertical movement rail 20 by a motor in a moving mechanism section 21 that can move the substrate vertically and horizontally. Further, the substrate holder 8 to which the substrate 7 is attached is configured to be able to be moved in the left and right lateral directions on the left and right movement rails 22 via the substrate vertical movement rails 20 by a motor in the movement mechanism section 21. After submerging the substrate 7 in water, for example, drop the constituent material A of the monomolecular film onto 3a and the constituent material B onto 3b, and float the float 4a.
, 4b to apply surface tension to form monomolecular films A and B. Next, move the substrate 7 up and down and left and right in water to form films A and B.
By attaching this, a hetero-cumulative film as shown in FIG. 3 can be easily formed. Furthermore, by replacing the substrate holder 8 and the substrate vertical movement rail 20, this device can of course be applied to an attachment method in which the substrate is suspended from above like the conventional device shown in FIG.

Next, another embodiment of the present invention is shown in FIG. 6. FIG. 6 shows an apparatus that uses a circular water tank as a developing liquid tank and can accumulate many types of monomolecular films. Circular water tank which is a developing liquid tank
Inside the frame 2, the water surface is horizontally 3a, 3b, 3c,
It is placed so that it is partitioned into four parts (3d). Floats 4a, 4b, 4c, and 4d are floated on the water surface inside the frame 2, and each water surface 3a is measured using a moving device (not shown) and a surface tension meter.
, 3b, 3c, and 3d are adjusted to have an arbitrary constant surface pressure. Movement of the board in the vertical and horizontal directions is carried out by a motor in a movement mechanism 21 attached to the base 18 using a vertical movement rail 20 and a left and right movement rail 22. A board holder 8 is provided in the part where the board 7 is held.
is installed. Constituent substances of monolayer A, B, C,
Drop D onto the water surfaces 3at, 3b, 3c, and 3d, and use each float to adjust the surface tension to form monomolecular films A, B, C,
A hetero-cumulative film can be easily formed by making D and rotating the substrate horizontally in an arc in left and right directions under water.

In the example of FIG. 6, the water surface is divided into four partitions, but this number can of course be increased or decreased. Further, although the drawing shows only one part to which the board is attached, there may be two or more parts. Furthermore, the insufficient amount can be replenished by using a dropping device for the membrane constituent material on the water surface.

FIG. 7 is a partial plan view showing an example of the main parts of the float movable means in an apparatus using a circular water tank similar to that in FIG. 6. When the movable means is used, the floats 4a, 4b, 4c
, '4d are rotation axes 23, 24, 25, 28, respectively.
The rotating shafts are fitted coaxially with each other, and are rotatable independently, so that when rotated by a motor located under the water tank via a coupling device, each water surface 3a, 3
Regions b, 3c, and 3d can be adjusted to have any constant surface pressure.

In the present invention, it is also possible to form a monomolecular film on the water surface of each of the four partitions as described above, but the condition of the monomolecular film must be taken into account, i.e., if too much surface pressure is applied due to the movement of the float. It is desirable that one of the partitioned water surfaces does not form a monomolecular film or is in the state of a gas film.

[Effects] As explained above, the present invention provides a means for separating two or more different monomolecular layers formed on the liquid surface in a developing liquid tank so that they do not mix with each other, and a means for separating a substrate horizontally in the liquid. Since the device is equipped with a means for moving the substrate in the same direction, there is no need to replace the constituent materials of the monomolecular film in one developing solution tank as in conventional devices, and it is possible to simply place the substrate in the solution and move it. It has the effect that a hetero-cumulative film consisting of two or more types of monomolecular films can be easily and continuously formed by the operation.

[Brief explanation of drawings]

Fig. 1 is a perspective view showing a conventional film forming apparatus, Fig. 2 is an explanatory drawing showing the structure of the LB film as seen from the molecular orientation, Fig. 2(a) is an explanatory drawing of the X-type, Fig. 2(b) ) is an explanatory diagram of the Y type, Fig. 2 (
c) is an explanatory diagram of the Z type, FIG. 3 is a structural diagram showing an example of a hetero-cumulative film obtained by the apparatus of the present invention, FIG. 4 is a schematic diagram showing an example of the apparatus of the present invention, and FIG. is one of the devices of the present invention
5(a) is a front sectional view, and FIG. 5(b) shows an example.
6 is a side sectional view, FIG. 6 is a perspective view showing another embodiment of the present invention, and FIG. 7 is a partial plan view showing an example of a main part of a float movable means. l...Aquarium 2...Frame 3a, 3b, 3c, 3d...Water surface 4a
, 4b, 4c, 4d-Float 5...T wire 6... Winding device 7... Substrate 8... Substrate holder 9... Vertical direction 10... Monomolecular film 11... Hydrophilic group 12...Hydrophobic group 19...Base 20...Vertical movement rail 21...
・Movement mechanism part 22...Left and right movement rails 23, 2
4.25.28... Rotating shaft applicant Yutaka, agent of Canon Co., Ltd. 1) Yoshio Figure 1 Figure 2 ((1) Figure 2 (b) Figure 2 (C) Figure 5 ((1) ) Figure 5 (b) Figure 6 Figure 7

Claims (1)

[Claims] An apparatus that spreads a group of molecules for film formation on a liquid surface and causes a substrate to pass through the group of molecules to form a monomolecular film or a cumulative film thereof on the substrate, the device comprising: 1. A film forming apparatus comprising means for separating two or more different types of monomolecular layers formed in a liquid so as not to mix with each other, and means for moving a substrate laterally in a liquid.