JPS60222171A - Film forming device - Google Patents

Abstract

PURPOSE:To obtain surely an LB film wherein molecular layers are orderly arranged by separating the liquid surface of a liquid vessel into a molecular group developing zone and a nondeveloping zone, and providing a substrate supporting member which is allowed to pass only through the molecular group nondeveloping liquid surface. CONSTITUTION:A frame 2 is placed horizontally to separate water surfaces 3a and 3b at the inside of a water vessel 1, and floats 4a and 4b are floated. A substrate 7 is fixed to a holder 8, and a vertical rail part 14 is raised upward by a motor in a moving part 16 and moved horizontally on a rail 17. After the substrate 7 is submerged into the water, the seeds of monomolecular film building substances are added dropwise to 3a and 3b, and surface tension is given to form molecular films A and B. 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 suitable for forming a monomolecular film or a monomolecular accumulation M (these are referred to as LB films) in which monolayers are stacked. The present invention relates to a film forming apparatus that can reliably obtain a film in which molecular layers are arranged in an orderly manner.

[Prior Art] 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 demand 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, in terms of heat resistance and mechanical strength, which have been considered inferior until now,
Recently, organic materials that overcome this problem have been created one after another. Against this technical background, some of the functional parts (mainly thin film parts) of integrated circuit devices such as logic elements, memory elements, and photoelectric conversion elements, and optical devices such as microlens arrays and optical waveguides have been developed. From the proposal to replace part or all of conventional inorganic thin films with organic thin films, to molecular electronic devices and bio-related materials in which a single organic molecule has functions such as logic elements and memory elements. Recently, several research institutes have announced proposals to create logic devices (eg, biochips).

Organic thin films, which are the main components of such devices, are fabricated using single-molecule accumulation methods. Single-molecule accumulation method (also known as Langmuir-Prodgett method).

LB method) refers to the hydrophilicity of molecules with parent wood groups and hydrophobic groups.
A monomolecular film or a monomolecular cumulative film of monolayers stacked on a substrate is produced by using hydrophobicity to form a monomolecular film on water in an orderly manner and then transferring it to the substrate surface. Formation is possible.

Conventionally, in this type of device, as shown in FIG. 1, a frame 2 is placed inside a shallow and wide rectangular body of water 411i so as to horizontally partition a water surface 3. The frame 2 functions as a two-dimensional cylinder, and a rectangular float 4 is floated inside the frame 2, and the width of the float 4 is made slightly narrower than the inner dimension of the frame 2, so that it can move smoothly from side to side as a two-dimensional piston. It is possible to move. In order to move the float 4 from side to side, the float 4 is connected to a winding device 6 using a motor or the like via a wire 5.

When forming a monomolecular film, the constituent substances of the film are dissolved in a volatile solvent such as benzene or chloroform, and the solution is dropped onto the water surface 3. After the solvent evaporates, a monomolecular film exhibiting two-dimensional behavior is deposited on the water surface 3. When the areal density of molecules is low,
It is called a gas film of secondary gas. By moving the float 4 to the right, the spread of the water surface 3 on which the tp molecules expand is reduced and the surface density is increased, which strengthens the interaction between the molecules.
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 neatly, resulting in the high degree of order and uniform ultra-thin film properties required of materials that make up semiconductors.

As a method of transferring the monomolecular film from the water surface 3 to the substrate 7 surface, the substrate 7 attached to the substrate boulder 8 is vertically moved 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 the monomolecular film is transferred by moving up and down in direction 9. This method uses an
There are three types: Y-type, in which the monomolecular film 1O is attached both during immersion and pulling up, as shown in FIG. In the molecule shown in FIG. 2, 11 is a hydrophilic portion and ]2 is a hydrophobic portion.

When using the apparatus shown in Fig. 1 to make a cumulative film as shown in Fig. 3 as 1, for example, a Y-shaped heterolayer a (the constituent molecules of the monomolecular film differ in the cumulative direction) lI* (second (see figure (b)), that is, the hydrophilic group 11a of membrane A and the hydrophilic group 11b of membrane B.
When creating a heterojunction between the substrates, first move the substrate up and down to attach the membranes A 1 + A 2 , then leave the substrate in water and remove the monomolecules [A] on the water surface, after discarding A and purifying the water surface. Create a single molecule MB on the water surface and move the substrate up and down to form a film B I +
B 2 was attached, and II A 3 was attached using the same procedure.

However, in the above-mentioned apparatus, it takes time to purify the water surface when replacing the membrane, and the more layers there are, the longer it takes to knead. Furthermore, the accumulated film near the water level on the substrate is not lined up neatly because the water surface becomes rippled or the water level changes during cleaning for membrane replacement, and the accumulated film near this area cannot be used.

As mentioned above, in the conventional device, a hetero-cumulative M film is used.

In other words, there were many disadvantages such as the time and effort required to create a film in which layers of different types of molecules were accumulated, and usable films had to be discarded.

[Object of the Invention] An object of the present invention is to provide a film forming apparatus that can reliably obtain an LB film in which molecular layers are arranged in an orderly manner.

According to the present invention, there is provided an apparatus for forming a monomolecular film or a cumulative film thereof on a substrate by spreading a film-forming molecule group on a liquid surface and allowing the molecule group to pass through the substrate. , a liquid tank, a frame that divides the liquid surface of the liquid tank into a region where the molecule group is developed and a region where the membrane is not developed, and a substrate support member provided to penetrate only the liquid surface where the molecule group is not developed. Provided is a film forming apparatus characterized by comprising:

[Example] Next, the present invention will be described in detail with reference to examples shown in the drawings.

FIG. 4 shows an embodiment of the device of the present invention, and the front sectional view is (
a), and a side sectional view is (b).

1 is a water tank, 2 is a frame that divides the liquid surface of the water tank into a region where the membrane is developed and a region where the membrane is not developed, and 13 is a substrate support member provided to penetrate only the liquid surface where the membrane is not developed.

The substrate support member 13 includes an upper and lower rail section 14, an arm section 15 extending perpendicularly from the -E lower rail section 14, and a substrate holder 8 attached to the tip of the arm section 15.

The moving section 1B moves in the left-right direction along the rail 17 and also moves the upper and lower rail sections 14 up and down, and includes a motor (not shown) and a motor (not shown) for moving the upper and lower rail sections 14 up and down. It has a built-in stopper (not shown) for moving it.

A frame (partition) 2a is placed inside the rectangular aquarium 1 so as 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 a moving device and a surface tension meter (not shown) are used to adjust the water surface areas 3a and 3b to an arbitrary constant surface pressure. It has become. The board 7 is attached to the board holder 8,
In this case, the vertical rail section 14 is raised upward by the motor within the moving section IB.

Further, the board holder 8 with the board 7 attached thereto is moved to the rail 17 by the motor in the moving part 16 via the upper and lower rail parts 14.
The top can be moved left and right. After submerging the substrate 7 in water, for example, the constituent material A of the monomolecular film is added to 3a,
Drop B onto 3b and float 4a.

Apply surface tension with 4b to form monomolecular films A and B.

Then, the substrate 7 is moved up and down and left and right in the water to attach the films A and B (the trajectory of the substrate in the above cumulative operation is shown in FIG. 5, and the substrate is moved in the order of arrows 28 to 33), as shown in FIG. A hetero-cumulative film like this can be easily formed. In a cumulative film with a heterojunction between the parent wood groups as shown in Figure 83, when molecules that have a function in the hydrophilic group are accumulated, the functional parts of the different molecules are extremely There is an advantage of being close. Furthermore, the apparatus shown in FIG. 4 can of course also be used in an attachment method in which the substrate is suspended from above, as in the conventional apparatus, by replacing the substrate holder 8 and the upper and lower rail sections 14. Furthermore, since there are two water surfaces on which molecules can develop, it is possible to eliminate the need for membrane replacement, which is required in conventional devices. Note that it is also possible to increase the number of combinations of the frame 2a and floats to make the number of deployed water surfaces three or more.

In the above embodiment, the substrate was moved under the monomolecular film in water, but the substrate may be moved only up and down, and the film may be moved using a float. In addition, although we have listed six examples of two types of monomolecular membranes on the water surface, using a circular tank allows the accumulation of many types of membranes.

The embodiment described above is shown in FIG. Frame 2 inside the circular aquarium l
is placed horizontally on the water surface 3 and is divided into an area where the membrane is deployed and an area where the membrane is not deployed.

The substrate support member 13 is provided so as to penetrate only through the liquid surface where the membrane is not developed.

A frame 2 is placed horizontally on the water surface 3 inside a circular aquarium l. Inside the frame 3, the water surface is divided into four sections 3a, 3b, 3c, and 3d by floats 4a, 4b, 4c, and 4d.

The float 4a is fixed to the inner round rod-shaped rotation shaft 8, the float 4b is fixed to the cylindrical rotation shaft 18, the float 4c is fixed to the cylindrical rotation shaft 20, and the float 4d is fixed to the cylindrical rotation shaft 20. It is fixed at 21. The fixed state of the rotating shaft and the float is shown in the seventh figure.
As shown in the figure. Rotating shaft 13. The rotation centers of +4, 15, and 16 coincide, but each can rotate independently. and rotating shaft 18. ill, 20.21 can be rotated independently by motors (not shown) located under the water tank.

These floats 4a, 4b, 4c, 4d are connected to the rotating shaft 1
The monomolecular film is moved and attached to the substrate 7 by rotating with a motor located under the water tank around 8.19°20.21. The vertical movement mechanism 2 attached to the base 22 moves the board 7 up and down.
This is done using the upper and lower rail sections 14 that pass through the inside of 3. Upper and lower rail part 1
There is a board holder 8 on the lower part of the board 4 that is submerged in water, and the board 7 is attached thereto. Since the upper and lower rail parts 14 are located between the outer wall 24 of the aquarium l and the frame 2, the water surface within the frame 2 will not be disturbed by movement.

Although not shown, surface pressure gauges are attached to the floats 4a, 4b, 4c, and 4d, and by moving the floats with a motor under the water tank, the water surface 3a, 3b, 3c, and 3d is adjusted.
The surface pressure of the monomolecular film developed can be set to any value. It is possible to form a monomolecular film on each of the four partitioned water surfaces, but considering the condition of the monomolecular film (the movement of the float may apply too much surface pressure),
It is preferable not to form a film or to leave it in a gas film state.

FIG. 6 is a schematic perspective view showing another embodiment.

The floats 4e and 4f are fixed to an inner round rod-shaped rotating shaft 21, and the floats 4g and 4h are fixed to an outer cylindrical rotating shaft 22. 25 is the inner wall of the water tank.

The rotating shafts 26 and 27 are connected to motors (not shown) under the water tank.
As the floats rotate in opposite directions, areas with decreasing area and areas with increasing area appear as areas separated by the water surface frame and the float. For example, when floats 4e and 4g in Fig. 6 are rotated in the direction indicated by arrow a, and floats 4f and 4h are rotated in the direction indicated by arrows, the area of regions 3e and 3g decreases, and the area of regions 3f and 3h decreases. expands.

As in the case of the apparatus shown in FIG. 5, a surface pressure gauge is attached to the float so that the surface pressure of the monomolecular film can be set to an arbitrary value.

In the examples of FIGS. 5 and 6, there are four partitions, but this number can of course be increased, and there may also be two or three partitions.

Further, although FIGS. 4 and 6 show examples in which a circular frame is provided in a circular aquarium, a circular frame may also be provided in a rectangular aquarium.

Further, although the figure shows only one part to which the board is attached, there may be two or more parts. Furthermore, it is also possible to replenish the insufficient amount by using a dropping device for the film constituent material on a water surface other than the water surface on which the substrate moves up and down.

[Effect of the invention 1] As described above, in the apparatus of the present invention, a frame and a membrane are deployed to divide the liquid tank and the liquid surface of the liquid tank into an area where the membrane is expanded and an area where the membrane is not expanded. Since it is equipped with a substrate support member that penetrates only the liquid surface that does not spread, even if the substrate support member is moved to transfer the film to the substrate, the movement of the liquid is dammed up by the frame and the area where the film is to be expanded is blocked. The oscillation is not transmitted, and the accumulated film near the water level on the substrate is neatly lined up.
A monomolecular film in which the desired molecular layers are arranged in an orderly manner or a medium-molecular cumulative film in which monolayers are laminated can be reliably obtained.

[Brief explanation of drawings]

FIG. 1 is a schematic perspective view of a conventional device, and FIG. 2 is a structural classification diagram of a monomolecular film or a cumulative film viewed from the molecular orientation. FIG. 3 is a structural diagram of a hetero-cumulative film easily obtained using the apparatus of the present invention, FIG. 4 (1) is a front sectional view of an embodiment of the present invention, and FIG.
Figure (b) is a side sectional view thereof, Figure 5 is a schematic explanatory diagram showing the movement locus of the substrate, Figures 6 and 8 are schematic perspective views showing other embodiments of the present invention, and Figure 7 is a schematic diagram showing the movement locus of the substrate. FIG. 7 is a top view of essential parts of the device shown in FIG. 6; l...Aquarium 2.2a...Frame 3, 3a, 3b, 3c, 3d, 3e, 3f
, 3g, 3h・" Water surface 4... Float 5... Wire 6... Winding device 7... Substrate 8... Substrate holder 9... Vertical direction 10... Tl is molecule 11 11...Hydrophilic portion 11a, Ilb...-Parent wood base 12...Hydrophobic portion 13...Substrate support member 14...Upper and lower rail portion 15...Arm portion 16...Movement portion 17 ...Rail 18, Ill, 20.21... Rotating shaft 22...
Base 23... Vertical movement mechanism 24... Outer wall 25... Inner wall 2B, 2? ...Rotating axis Fig. 1 Fig. 2 ((1) Fig. 2 (b) Fig. 2 (C) Fig. 4 (G) (b) Fig. 5 Fig. 6 Fig. 7 Fig. 8

Claims (1)

[Claims] The molecule group for film formation is developed on the liquid surface, and the molecule group is
A device for forming a monomolecular film or a cumulative film thereof on the substrate by passing a plate through the substrate, the device comprising: a liquid tank and a frame that divides the liquid surface of the liquid tank into a region in which the molecule group is developed and a region in which the molecule group is not developed; and a substrate support member provided to penetrate only the liquid surface that does not allow the molecular group film to develop.