JPS60222169A - Film forming device - Google Patents

Abstract

PURPOSE:To form easily hetero-type built-up films of monomolecular layers continuously in a short time by separating the liquid surface, and passing a substrate successively through plural movable monomolecular layers. CONSTITUTION:Plural different monomolecular layers formed on the liquid surface of a vessel 1 are separated by floats 4a, 4b, and 4c to form the parts 3a, 3b, and 3c. A building substance A is then added dropwise to 3a and B to 3B, respectively and the floats 4a, 4b, and 4c are moved. Then a substrate is moved vertically and passed successively through 3a and 3b, then moved in the liquid in the direction as shown by the arrow A, and successively moved in the directions 15 and 16 to transfer the monomolecular layers to the substrate. The built-up films having heterojunction between hydrophilic groups can be 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 stacking single molecules, which is used for 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 demand for the development of functional organic materials as new functional materials that surpass inorganic materials. The advantages of organic materials include being cheap, easy to manufacture, and highly functional.On the other hand, the disadvantages of organic materials, such as heat resistance and mechanical strength, have recently been overcome. Organic materials are being 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 the conventional inorganic thin film with an organic thin film,
Recently, there have been several proposals to create molecular electronic devices in which a single organic molecule has functions such as a logic element or memory element, as well as logic elements made from biologically related materials (e.g., biochips). Published by research institutes.

Organic thin films, which are the main components of such devices, are fabricated using single-molecule accumulation methods. 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] As shown in FIG. 1, a conventional film forming apparatus is placed inside a shallow and wide rectangular water tank l 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 two-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,
It is dissolved in a volatile solvent such as chloroform and dropped onto the water surface 31. After the solvent evaporates, a monomolecular film exhibiting two-dimensional behavior 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 expanse of the water surface 3 on which single molecules develop and increase the surface density, the interaction between molecules becomes stronger, and a two-dimensional solid forms through the liquid film of the two-ash source liquid. Transforms into a membrane.

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 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 Figure 2 (a), an
There are three types: Y-type, in which the monomolecular film 10 is attached both during immersion and pulling up, as shown in FIG. 2(c), and Z-type, in which the monomolecular film 10 is attached only during pulling up, as shown in FIG. In the molecule shown in FIG. 2, 11 represents a hydrophilic group and 12 represents a hydrophobic group.

Using the apparatus shown in Figure 1, for example, a third layer is formed as a hetero-cumulative film in which the constituent molecules of the monolayer are different in the Y-shaped cumulative direction.
When creating a stacked aS as shown in the figure (see Figure 2 (b)), that is, when creating a Peter junction between the hydrophilic group 11a of liA and the hydrophilic group ttb of membrane B, first raise and lower the substrate. TeM
Attach Al and A2, keep the substrate in water, throw away monomolecular film A on the water surface, purify the water surface, form monomolecular film B on the water surface, and move the substrate up and down to attach film Bl + B2. Furthermore, membrane A3 was attached using the same procedure. 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 the water, and when cleaning the membrane, the water surface may ripple or the water level may change. As a result, the accumulated film near the water level on the substrate is not lined up neatly, and the accumulated film formed near this area cannot be used.

As mentioned above, with conventional equipment that manufactures cumulative films by suspending the substrate from above, it takes time and effort to create a heterogeneous cumulative film, and when replacing the film, there is no need to discard the film that can still be used. There were many drawbacks such as:

[Purpose] The present invention was made in order to eliminate the drawbacks of the conventional device described above, and is to sequentially attach a substrate to each of two or more types of movable monomolecular layers provided isolated on the liquid surface. The purpose is to form a hetero-type monomolecular cumulative film continuously, quickly, and easily by using a simple device that allows the film to pass through.

[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 monomolecular layers while maintaining the monomolecular layers in a separated state. This film forming apparatus is characterized in that it is provided with a driving means for causing the film to move.

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. Floaters 4a, 4b, and 4c are provided as means for separating two or more different monomolecular layers formed on the liquid surface of the rectangular water tank l, which is a developing liquid tank, so as not to mix with each other, and the water surface is set at 3a.
It is divided into three parts: , 3b and 3C. The constituent material A of the monomolecular film is dropped onto 3a and the constituent material B is dropped onto 3b, and the floats 4a, 4b, and 4c are moved by a moving device (not shown), and an arbitrary surface pressure is applied to the MA on the water surface 3a and 3b. , put it on B.

Next, the substrate is moved vertically in the A membrane liquid in the order of arrows 3a and 3b, and while the substrate is submerged in water, floats 4a, 4b +' 4c are moved in the direction of arrow 14 to isolate the monomolecular layer. Then, after moving the substrate vertically in the B film liquid in the order of arrows 15 and 16, each float is moved in the direction of arrow 17 in the same manner as above, and the substrate is moved in the direction of arrow 18. When the monomolecular films A and B are transferred to the substrate, the third
A cumulative film having a heterojunction between hydrophilic groups as shown in the figure 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.

The present invention is an apparatus characterized in that, as described above, it is possible to move two or more monomolecular layers while maintaining them in a separated state so as not to mix them with each other.

Note that, as described above, the substrate may be moved not only in the vertical direction but also in the lateral direction in the water together with the vertical direction.

[Example] An example of the present invention is shown in Fig. 5. Fig. 5 shows an apparatus capable of accumulating many kinds of monomolecular films using a circular water tank as a developing liquid tank. 5(a) is a perspective view, and FIG. 5(b) is a partial plan view of the main parts of the movable means. A frame 2 is placed horizontally on a water surface 3 inside a circular water tank l which is a developing liquid tank.・The water surface inside the frame 2 has floats 4a, 4b,
It is divided into four layers 3a, 3b, 3c, and 3d by 4c and 4d, and the four different monomolecular layers formed on the water surface are isolated so as not to mix with each other.

The floats 4a, 4b, 4c, and 4d each have a rotating shaft 18,
20, 21° and 22, each rotating shaft is fitted coaxially with each other, and each is provided so that it can rotate independently. When rotated by a motor located under the water tank via a coupling device, the monomolecular layer is isolated. The structure is such that the float can be rotated while maintaining the same state.

The vertical movement of the board 7 is carried out by the vertical movement rail 2 by a motor in a movement mechanism 24 attached to the base 23.
A board holder 8 is provided on the lower part of the vertically moving rail 25, which is submerged in water, as shown in step 5, and the board 7 is attached thereto. Each float 4a, 4b.

Surface pressure gauges (not shown) are attached to 4c and 4d,
By moving the float, the water surface 3a, 3b.

The surface pressure of the monomolecular film developed in 3c and 3d can be adjusted to any value. Constituent substances of monolayer A, B, C
, D are dropped onto the water surfaces 3a, 3b, 3c, and 3d, respectively, and surface tension is applied with each float to form a monomolecular film A.

A hetero-cumulative film can be easily formed by forming B, C, and D, moving the substrate in the vertical direction, and rotating the float.

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.

In the example shown in FIG. 5, 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 for attaching the substrate, there may be two or more parts.Furthermore, the insufficient amount can be replenished by using a dropping device for the film constituent material on the water surface.

FIG. 6 shows another embodiment of the present invention using a circular water tank,
The float movable means is different from FIG. 5. Float 4
Divide a, 4b, 4c, 4d into two and float 4 facing each other.
a and 40 on the same rotating shaft 28, and opposing floats 4b and 4
d are fixed to the same rotating shaft 27, and the rotating shafts 26 and 27 are fitted together coaxially, each rotatably provided independently, and rotated by a motor located under the water tank via a coupling device. It is configured so that it can be done. Therefore, for example, when the float is rotated in directions a and b in the figure, a monomolecular layer is formed on the water surfaces 3a and 30, and the float can be moved while being maintained in an isolated state.

Next, still another embodiment of the present invention is shown in FIG. 7, where FIG. 7(a) is a front sectional view and FIG. 7(b) is a side sectional view.

A frame (partition) 2 is placed horizontally inside a square aquarium l. Floaters 4a, 4b, and 4c are provided on the water surface inside the frame 2, and the water surface is divided into three parts, 3a, 3b, and 3c. , 3b are configured so that the surface pressure can be adjusted to an arbitrary constant surface pressure. The board 7 is attached to a board holder 8, and is configured to be able to move vertically on a board vertical movement rail 25 by a motor in a moving mechanism section 24 that can move the board vertically and horizontally.

Further, the board holder 8 to which the board 7 is attached can also be moved in the left and right lateral directions on the right and left movement rails 28 by a motor in the movement mechanism section 21 via the substrate's lower movement rail 25. After submerging the substrate 7 in water, for example, the constituent material A of the monomolecular film is lowered into 3a and the constituent material B is lowered into 3b, and the float 4 is lowered.
A, 4b, and 4c give surface tension to form monomolecular films A and B. Next, the board 7 is moved downward to -L to attach [A], and then the float is moved and the board is moved up and down in the same way as above to attach MB, thereby creating a Peter pile as shown in Fig. 3. 81 film can be easily formed. A conventional device can be used as the drive means for moving the float,
For example, using a device such as that shown in Fig. 1, the frame 2 is used as a two-dimensional cylinder, and the float is used as a two-dimensional piston to move smoothly from side to side. It is configured by being connected to a winding device 6 using 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.

[Effect] As explained above, the present invention provides a means for isolating two or more different monomolecular layers formed on the liquid surface in a developing liquid tank so as not to mix with each other, and a means for separating the monomolecular layers so that they do not mix with each other. Since it is equipped with a driving means that moves the monolayer while maintaining it in an isolated state, there is no need to replace the constituent substances of the monomolecular film in a single developing solution tank as in conventional devices, and the monomolecular layer can be 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 a simple operation of moving it on the liquid surface.

[Brief explanation of the drawing]

Figure 1 is a perspective view showing a conventional film forming apparatus, and Figure 2 is an explanatory diagram showing the structure of the LB film as seen from the molecular orientation. (a) is an explanatory diagram of the X type, and (b) is an illustration of the Y type. , (C) is an explanatory diagram of an X-type, FIG. 3 is a structure 1 peeled off showing an example of a hetero-cumulative film obtained by the apparatus of the present invention, and FIG. 4 is a schematic diagram showing an example of the apparatus of the present invention. , 5th
The figure shows one embodiment of the present invention, FIG. 5(a) is a perspective view,
FIG. 5(b) is a partial plan view of the main part of the driving means, FIG. 6 is a perspective view showing another embodiment of the present invention, and FIG. 7 is a perspective view showing still another embodiment of the present invention. FIG. 7(a) is a front sectional view, and FIG. 7(b) is a side sectional view. l...Aquarium 2...Frame 3a, 3b, 3c, 3d-water surface 4a,
4b, 4c, 4d-Float 5...wire
6... Winding device 7... Substrate 8... Substrate holder 9... Vertical direction lO... Monomolecular film 11...
・Oyaki base 12... Cast water base 19, 20.21, 22.28.27... Rotating shaft 2
3...Base 24...Moving mechanism part 25...L
Upper movement rail 28...Rail for left and right movement Fig. 1 Fig. 2 (G) Fig. 2 (b) Fig. 2 (C) Fig. 3 Fig. 4 Fig. 5 ((1) Fig. 5 (b) ) Figure 6 Figure 7 (G) Figure 7 (b)

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: The present invention is characterized by comprising means for separating two or more different types of monomolecular layers formed in the same manner so that they do not mix with each other, and a driving means for moving the means while maintaining the monomolecular layers in a separated state. Film forming equipment.