JPS60206441A - Film forming apparatus - Google Patents

Abstract

PURPOSE:To enlarge the degree of freedom in the planning of a monomolecular built-up film, in a film forming apparatus by Langmuir Blodgett's technique, by providing a detection means for detecting the temp. difference of the liquid and the carrier in a film forming development liquid tank. CONSTITUTION:After a liquid 10' (a liquid for forming a monomolecular film) is poured in a water tank 1, the surface temp. of the liquid is held to a predetermined temp. Subsequently, a desired film forming molecule group is dripped on the liquid surface 10 to develop the monomolecular film on the liquid surface 10. Then, desired surface pressure is applied to the monomolecular film by a float 3 and the liquid surface 10 is quietly moved up and down to form a monomolecular built-up film on the carrier 11. In this case, the temps. of the liquid 10' and the carrier 11 are controlled to a desired temps. by temp. detection means 13, 14, heating means 15, 16 and cooling means 15', 16' electrically connected to a temp. controller 17 and a film is formed while the temp. difference of the liquid 10' and the carrier 11 is controlled.

Description

[Detailed description of the invention] (1) Technical field The present invention relates to a film forming apparatus.

(2) Background technology Conventionally, a monomolecular film developed on a liquid surface is transferred onto the surface of a solid carrier that is its support, thereby forming a monomolecular film or a monomolecular cumulative film on the support. As a method, the so-called Langmuir-Prodgett method is known.

The principle of the Langmuir-Prodgett method is that, for example, in a molecule with a structure that has a parent wood group and a hydrophobic group in the molecule, when the balance between the two (balance of amphiphilicity) is maintained appropriately, the molecule will move on the water surface. This is a method of creating a monomolecular film or a cumulative film of monomolecular layers by using the fact that the parent tree faces downward to form a monomolecular layer.

A typical example of a film forming apparatus used in this method is shown in FIG. 1, and this type of technology will be described below with reference to the drawings.

In the apparatus shown in FIG. 1, a liquid on which a monomolecular film is to be developed, generally water, methanol, ethyl alcohol, etc., is stored in a rectangular water tank 1. Inside the square aquarium l, there are 2
A frame 2 that functions as a dimensional cylinder, for example made of polypropylene, is suspended horizontally and partitions the liquid surface lO into a desired width.

Inside the frame 2, it functions as a two-dimensional piston and has a liquid level 1.
A float 3 made of, for example, polypropylene is floated to generate a desired surface pressure on the film-forming molecules group developed on the surface.

The width of the float 3 is made slightly narrower than the inside of the frame 2,
As a dimensional piston, it moves horizontally in the figure, and as a two-dimensional piston, it can move smoothly in the left-right direction in the figure.

The rightward movement of the float 3 is performed by a weight 4 that pulls the float 3 to the right and applies a desired surface pressure to the film-forming molecules spread on the liquid surface 10. The leftward movement and stopping of the float 3 is performed by the repulsive force between a magnet 6 provided on the float 3 and a pair of magnets 7 that can be moved left and right by a holding mechanism (not shown).

Film formation is carried out in step 1. For example, a desired monomolecular film is spread on the liquid surface 10, a desired surface pressure is applied to the monomolecular film by the float 3, the weight 4, and the magnets 6, 7, and then the carrier 11 is moved across the liquid surface. This is done by moving up and down.

However, conventional devices have the following problems.

A monomolecular film developed on the liquid surface 10 is called a gas film of a secondary gas when the areal density of molecules exhibiting two-dimensional system behavior on the liquid surface 10 is low, and the occupied area per molecule ( The relationship FA=nRT holds between A) and surface pressure CF). Here, n is the number of moles, R is the gas constant, and T is the absolute temperature.

From the state of a gas film, the float 3 is gradually moved to the right to gradually reduce the spread of the liquid surface where the monomolecular film develops and increase the surface density, which strengthens the interaction between molecules and causes the liquid to become a two-dimensional liquid. After passing through the film, it changes into a two-dimensional solid film. A typical F-1 curve showing such a state is shown in Figure 2, where HA is a gas film, EH is a solid film, DE and BC are liquid films, and CD is called an intermediate phase. It is something that exists.

A monomolecular film developed on the liquid surface exhibits the above behavior in the relationship between the occupied surface layer (A) and the surface pressure (F).
In order to transfer the monomolecular film developed on the liquid surface to a carrier, it is necessary to maintain the state of a solid film. However, F-
For example, the shape of a curve changes depending on factors such as the structure of the molecules that make up a monomolecular film, the type of liquid in which the monomolecular film is developed (solvent or solute in the case of a solution), concentration, humidity level, PH, etc. However, depending on these conditions, when the surface pressure is increased from the gas film state, the film structure may be destroyed without passing through the solid film state. In such cases, it is not possible to transfer the monolayer onto the carrier.

Among the factors that govern the F-1 curve, liquid (especially liquid level)
The temperature of the solid film and the temperature of the carrier are particularly important factors, and under these conditions, the phase of the solid film disappears, causing problems such as the inability to form a film.For example, in the case of the pentadecyl acid monomolecular film illustrated in Figure 3, This is an example in which the solid film phase disappears due to an increase in the liquid surface temperature.

Also, the ratio of the area of the monomolecular film developed on the liquid surface to the monomolecular film accumulated on the carrier by transferring this is called the cumulative ratio, but this may not necessarily be 1 depending on the film forming conditions. Rather, it is greatly influenced by temperature conditions, especially the temperature difference between the carrier and the liquid.

However, conventionally, there has been no film forming apparatus equipped with a means for detecting the temperature difference between the carrier and the liquid or a means for controlling the temperature difference.

(3) Disclosure of the Invention The present invention has been made in view of the above-mentioned facts. 1. The purpose of the present invention is to solve the above-mentioned problems and further expand the degree of freedom in designing monomolecular cumulative films. The object of the present invention is to provide a new film forming apparatus that can obtain the desired results.

That is, the present invention includes a film-forming developing solution tank for developing a film-forming molecule group on the liquid surface and transferring a film made of the molecule group to a carrier, and detecting a temperature difference between the liquid in the tank and the carrier. This film forming apparatus is characterized in that it is provided with a detection means for detecting.

Hereinafter, the present invention will be explained in detail based on the embodiment shown in FIG.

The device illustrated in FIG. 4 is an example in which the same device as shown in FIG. 1 is provided with a temperature difference between the liquid and the carrier and a control means for the temperature difference. A perspective view for explaining the outline, and FIG. 4(b) is a sectional view thereof.

In the apparatus shown in FIG. 4, the carrier 11, in this example a flat substrate, can move up and down the liquid level 10, as indicated by arrows in the figure. The carrier 11 is raised and lowered by the companion upper and lower arms 12, which can be raised and lowered by a lift mechanism (not shown), and the carrier 11 is removably fixed to the carrier upper and lower arms 12 by carrier holding jigs 21.

Detection of the temperature difference between the liquid 10' and the carrier 11
This is done by detecting the respective temperatures of 0' and carrier 11.

Detection of the liquid temperature is performed by the liquid temperature sensor 13 electrically connected to the temperature controller 17-.The liquid temperature sensor 13 of this example has a temperature detection section 20 of the thermistor 18 as shown in an enlarged view in FIG. Styrofoam 18 with a donut-shaped cross-section is used to keep the liquid above the liquid level and to avoid being affected by ambient temperature.
A thermistor 19, which is a temperature sensing means, is held at the top. Although the object of the present invention can be sufficiently achieved by detecting the internal temperature of the liquid 10', in order to form a suitable film, as in this example, it is necessary to In other words, in this example, the temperature of the liquid surface 10 is directly detected.The detection of the carrier temperature is performed by the phase temperature sensor 14 which is electrically connected to the temperature controller 17 and is detachably fixed to the carrier 11. The carrier temperature sensor 14 is composed of a thermistor, and its temperature detection part is connected to the carrier 1.
This is a type that directly detects the temperature of 1.

The temperature difference between the liquid 10' and the carrier 11 can be controlled by controlling the temperature difference between the liquid 10' and the carrier 11.
and by controlling the respective temperatures of the carrier 11.

The temperature of the liquid 10' is controlled by heating the liquid lO' with the heater 15 or cooling it with the Bertier element 15'.
' are provided in the aquarium 1 as shown in the perspective view of FIG. 6 when viewed from the same direction as in FIG. 4(a). Further, the heater 15 and the Vertier element 15' are connected to a power supply source (not shown) via a temperature controller 17, and power is supplied to these as necessary to heat or cool the liquid 10'. That is, the liquid 1G' measured by the liquid temperature sensor 13
The temperature of the liquid 10 is transmitted to the temperature controller 17, and the signal output from this automatically supplies power to the heater 15 or the Bertier element 15'.
'Temperature control is performed.

The temperature control of the carrier 11 is carried out by heating the carrier 11 with the heater 1B or cooling it with the Bertier element 1B' in the same manner as in the case of the liquid 10'.
One Pemeche element 1B' is removably fixed to the carrier holding jig 21 on both sides of the carrier 11. The heater 1B and the Vertier element 16' are also connected to a power supply source (not shown) via the temperature controller 17, and power is supplied to these as necessary in the same way as in the case of liquid lO'. The temperature of the carrier 11 is controlled. The liquid 10' or the heater 15.18 which is a heating means for the carrier 11 and the liquid 1 of the Peltier elements 15' and 111' which are cooling means.
The above arrangement of the Peltier elements 15' and the carrier 11 is an example, and the number or arrangement method thereof is not limited to the above example.
' is used only as a cooling means, but the Bertier element 1
5', 18' can also be used as a heating means, and the Vertier element 15' can be used without providing the heater 15.18.
, '1B' may be provided to perform heating and cooling.

According to the device having the above-mentioned configuration, which is provided with a temperature detection means, a heating means, and a cooling means electrically connected to the temperature controller 17, the temperature of the liquid 10' and the carrier 11 is detected, and the temperature of the liquid 10' and the carrier 11 is detected. It is possible to control the temperature of the liquid 10' to a desired temperature, and film formation can be performed while controlling the temperature difference between the liquid 10' and the carrier 11. That is, if the detected temperature is lower than each set value, it is heated by the heaters 15 and 18, and if it is higher, it is cooled by the Vertier elements 15' and 1B', thereby controlling the temperature of the liquid 10' and the carrier 11, respectively. It is possible to maintain the temperature at a desired set temperature, and therefore film formation can be performed while maintaining a desired temperature difference suitable for film formation.

Film formation is carried out, for example, as follows. First, the liquid 10', such as the aforementioned water, ethanol, metal aqueous solution, etc., which are generally known as liquids for forming a monomolecular film, is poured into the water tank L, and then the liquid level is lowered. Maintain the temperature at a predetermined temperature. Next, a well-known method 1, for example, zero-order, in which a desired film-forming molecule group is dropped onto the liquid surface 10 using a dropper or the like, and a monomolecular film is developed on the liquid surface 10.

If a desired surface pressure is applied to the monomolecular film on the liquid surface 10 by the float 3, and the carrier 11 maintained at a predetermined temperature is gently moved up and down the liquid surface 10 on which the monomolecular film is spread, the monomolecular film is formed. Alternatively, a monomolecular cumulative film with a desired cumulative degree is formed on the carrier 11.

As the film-forming molecule group to be developed on the liquid surface, molecules that can form a monomolecular film on the liquid surface, for example, molecules that have a parent group and a hydrophobic group within the molecule, can be used. However, the molecules deployed on the liquid surface may be the same or different types. Of course, two or more types of molecules may be deployed on the liquid surface to form a mixed monomolecular cumulative film. etc. are also possible. Further, as a method of spreading the film-forming molecules on the liquid surface, it is also possible to drop them onto the liquid surface as needed from a tank or the like.

The means for detecting the temperature of the liquid or carrier is not particularly limited, but in addition to the above-mentioned thermistor, for example, thermocouples, capacitance thermometers,
Preferred examples include elements that electrically detect temperature, such as platinum resistance heat susceptors and carbon resistance heat susceptors.

As the means for heating the liquid or carrier, it is possible to use any means that is generally widely known as a means for heating solids or liquids, etc. In addition to the above-mentioned heaters and Peltier elements, for example, infrared lamps, micro Electrically controllable means such as wave heating are preferred.

As a cooling means for a liquid or a carrier, it is possible to appropriately use any means that is generally widely known as a means for cooling solids, liquids, etc. In addition to the above-mentioned Peltier device,
For example, electrically controllable means such as a cooling compressor are preferred.

Furthermore, in order to keep the temperature of the liquid constant, it is also possible to stir the liquid using a fan, a Gnech-Kusterer, or the like.

The present invention has been described above using an example in which a film is formed by moving the carrier up and down almost vertically across the liquid surface.
The present invention is not limited to the above examples; for example, when a cylindrical carrier is rotated around a substantially horizontal axis provided near the liquid surface to move the carrier up and down to form a film, Alternatively, it can be applied to cases where a film is formed by bringing into contact with the liquid surface a flat carrier that is held substantially horizontally with the liquid surface and can be moved up and down.

Further, as the carrier in the present invention, in addition to the above-mentioned flat plate-shaped or cylindrical carriers, carriers having a desired shape such as spherical, prismatic, sheet-shaped, etc. can be used.

The present invention will be described in further detail below by showing specific examples in which film formation was performed using the above-mentioned apparatus.

<Specific Example> Using the apparatus shown in FIG. 4, a monomolecular cumulative film of stearic acid was formed on a flat silicon substrate.

Pour clean distilled water into the aquarium and add Cdα2 to 4×10°4
Proverb: 1/Dissolve to a concentration below, and then add Hα
Alternatively, KHCO3 was added as a shield to adjust the pH of the liquid P) for developing a monomolecular film to 8 to 8.5. Set the liquid surface temperature to 12
℃, and after setting the substrate temperature to 8℃, the stearic acid concentration was 0.5℃.
A 1% benzene solution was dropped at 0.1 mQ onto the liquid surface using a dropper, and a monomolecular film of stearic acid was spread on the liquid surface. When the surface pressure of the monomolecular film was increased by moving the float, the pressure was 20 to 30.
A solid membrane condition suitable for accumulation operation was obtained at a surface pressure of dynes/am. When a clean silicon substrate was moved up and down several times perpendicular to the liquid level, an extremely stable monomolecular cumulative film with no film defects was formed on the silicon substrate.

When films were formed in the same manner as above using silicon substrates such as glass, quartz, and planar substrates on which aluminum was vapor-deposited, stable monomolecular cumulative films with no film defects were formed in all cases. .

Furthermore, the cumulative percentage of these films was 85 to 100%, which was a good value.

As explained above, the feature of the present invention is that the film forming apparatus is equipped with a means for detecting the temperature difference between the carrier and the liquid, and by providing the detecting means, it is possible to control the temperature difference during film formation. Became.

[Brief explanation of drawings]

Figure 1 shows an example of a conventional film forming apparatus, and Figure 2 shows a typical F-
A diagram for explaining the A curve, FIG. 3 is a diagram for explaining the temperature change of the F-A curve, and FIG. 4 is an embodiment of the film forming apparatus according to the present invention.
Fig. 5 is an enlarged view of the liquid surface temperature sensor in Fig. 4, and Fig. 6 is a perspective view for explaining the arrangement of the heater and Pelue element in Fig. 4! be. 1-m-water tank 2-11 frame 3--float 4-11 weight 5-m-pulley 6-1-magnet 7--pair of magnets 8-11 suction pipe 9--suction nozzle 10-m -Liquid level 10'--Liquid 11-'-Carrier 12--Carrier upper and lower arms 13-m-Liquid temperature sensor 14--Carrier temperature sensor 15. 16--heater 15', 1B'-m-Peltier element 17--temperature controller 18-m-styrofoam 18-m-mister 20-m-temperature detection part of the m-mister 21-m-carrier holding Jig No. 11!1 (a) Fig. 2 A (input Fig. 3

Claims (1)

[Claims] A film-forming developing solution tank for developing a film-forming molecule group on a liquid surface and transferring a film made of the molecule group to a carrier, and a detection means for detecting a temperature difference between the liquid in the tank and the carrier. A film forming apparatus characterized in that: