KR100347763B1 - The manufacturing method of multilayer thin film using spin coating - Google Patents

Abstract

The present invention relates to a method of manufacturing a multilayer ultra thin film, and to provide a method of manufacturing a multilayer ultra thin film using a rotation coating that can produce a high quality multilayer thin film for a short time, the present invention is to introduce a positive charge or negative charge Or a substrate into which a hydrogen bondable material is introduced is placed on a rotor capable of rotating at high speed, and then a material (A) capable of bonding by a mutual force with the material introduced to the substrate is introduced at the top of the substrate, and then 500 rpm to 15000 rpm The first coating by rotating for 4 to 60 seconds at a speed, and after the first coating is completed, the cleaning solvent is dropped to the center of the upper end of the substrate to wash for 4 to 60 seconds at a speed ranging from 500rpm to 15000rpm Repeated 1 to 3 times to remove the material (A) that is weakly bonded to the substrate surface to produce a thin film (A), the material coated on the substrate ( A) and a material (B) having different properties that can be bonded by mutual force are introduced to the top of the substrate and subjected to secondary coating under the same conditions as the primary coating, and then the cleaning process is performed after the secondary coating is completed. By repeating one to three times under the same conditions to remove the material (B) weakly bonded to the substrate surface to produce a thin film (B), and by repeating the above-described manufacturing process of the thin film (A, B) several times under the same conditions The above object can be achieved by providing a method of manufacturing a multilayer ultra-thin film using a rotation coating.

Description

The manufacturing method of multilayer thin film using spin coating}

The present invention relates to a method of manufacturing a multilayer ultra thin film, and more particularly, to manufacture a multilayer ultra thin film by a method of rotating coating, thereby shortening the manufacturing time and manufacturing a high quality multilayer ultra thin film to maximize productivity. It relates to a method for producing a multilayer ultra thin film using a rotation coating.

Recently, widespread use of ultra thin films in various high-tech materials such as optical information recording media, sensors, surface alignment films, lubricating coating films, etc. has increased interest in ultra thin films, especially in the electric, electronic, telecommunication and computer industries. With the rapid launch, ultra-thin materials in the range of 5 to 10 nanometers are expected to make an important contribution to the development of advanced devices.

In general, the ultra-thin film is coated with an organic monolayer on the surface of the substrate to change its physical, chemical or electrical properties to the desired purpose to improve the adhesion through the surface modification of the substrate or to prevent wear or corrosion, or to inherent electrical It can be used in various surface modification directions, such as improving optical properties.

In particular, in general, the desired properties are introduced into the substrate, and in order to fully express the properties, the film thickness of the thin film is assumed to be uniform, and it is based on an ordered structure having high orientation. In addition, it is necessary to coat the substrate with a multilayer ultra-thin film when the coating of the monomolecular layer is insufficient to make the desired change in the surface of the substrate.

In order for ultra thin films to be used as such advanced materials, not only the development of materials having unique orientation and various functions, but also the thickness of the thin films must be freely controlled in the range of several angstroms, and the formation of multilayer thin films between materials having heterogeneous properties should be possible. do.

Conventionally, a rotation coating method is known as a method for manufacturing a single layer ultra thin film, and this rotation coating method is capable of forming a uniform thin film in a short time by spraying a coating agent on a substrate and then rotating the substrate at a high speed. It is used as a method for producing chips.

However, the rotation coating method is easy to manufacture a thin film of a relatively thick single layer of 10 nanometers or more, but the manufacture of ultra-thin films of less than that is not appropriate, in particular in the production of a film having a multi-layer structure is not only difficult to control the thickness of the film layer In addition, since there is no special attraction between the multi-layered thin films, it is difficult to manufacture an ultra-thin film having a multi-layered structure due to limitations such as solvent selection having insolubility in each heterogeneous film layer.

The oldest classical method for producing multilayer ultra-thin films is the Elby (LB) method (Langmuir-Blodgett).

The LB method forms both ultra-molecular monolayers at the interface between air and water and transfers them to the surface of the solid substrate to form an ultra-thin film. The above-described process is repeated to produce a multilayer ultra-thin film.

However, the LB method has a problem in that it is difficult to be introduced into an automated process or an enlargement process because the stability of the produced film is inferior and special structural conditions or manufacturing conditions of molecules are very difficult.

As a method for solving the above problems, US Patent No. 5,208, 111 discloses a technique for preparing ultra-thin or multilayer thin films by introducing a kind of molecular self-assembly method based on electrostatic attraction. .

The method involves immersing a substrate substituted with an ion or an ionizable compound in an aqueous polyelectrolyte solution having a counter ion opposite to the substrate, whereby polyions are adsorbed onto the surface of the substrate by electrostatic attraction to form a monomolecular film, thereby reducing the surface charge of the substrate. Ultra-thin films are formed by the conversion of cations to anions or from anions to cations.

In this case, in order to create a multilayer ultra thin film, the ultra thin substrate is immersed again in an aqueous polyelectrolyte solution having a charge opposite to that formed on the surface thereof, and repeated adsorption of poly ions by electrostatic attraction results in formation of a multilayer ultra thin film. It will be possible.

Figure 1 shows the manufacturing process of the multilayer thin film by the conventional molecular magnetic assembly method, as shown in Figure 1 by introducing a material having a positive charge on the silicon or glass substrate to replace the substrate surface with a positive charge (1), A negatively charged material is introduced again (2) to form an ultra thin film.

In particular, by introducing a material having a positive charge after the introduction of a material having a negative charge as described above, it is possible to manufacture a multi-layer ultra-thin film by repeating the process of introducing a material having a negative charge again several times.

The layer thickness and structure of each layer deposited above are determined by the physical and chemical properties of the stacking solution, for example, by increasing the diffusion rate using a polyelectrolyte solution having a relatively high concentration of polyelectrolyte or an ion salt added thereto. Due to the structural deformation of the polymer chain, the thickness of the polyelectrolyte layer to be adsorbed becomes thick, whereas when the solution is very thin, the thickness of the adsorbed layer becomes thin.

Based on the above method, it can be widely applied to various kinds of polyions including polyions having a conjugated structure, and the introduction of multi-layered thin films and proteins with nano-sized gold particles and mercapto compounds In addition, the range of application is increasing, such as the application of various inorganic materials, such as CdS, CdSe, and ZnS, which are known as quantum particles, to a hybrid structure thin film combined with organic materials.

The above method mainly forms an ultra-thin film using the electrostatic attraction of ions or ionizable compounds, but US Pat. No. 5,518,767 does not apply ionization to the attraction of partially positively conductive conductive polymers and negatively charged polyions. The technique for forming an ultra-thin film is disclosed.

In addition, US Pat. No. 5,536,573 improves the US Pat. No. 5,518,767, unlike a conventional polyelectrolyte having a fixed ionization group, a conductive polymer such as polyaniline and various other polyanions can be controlled according to the degree of doping. By manufacturing a multi-layered thin film through electrostatic attraction or hydrogen bonding using the technology to disclose applications such as small electrical devices, chemical or biological sensors, anti-corrosion coating and anti-static coating.

However, all of the above methods absorb adsorption by spontaneous diffusion through mutual attraction, that is, electrostatic attraction, hydrogen bonding, or chemical bonding, while the substrates are immersed in various coating solutions including polyelectrolytes. Forming a thin film by induction requires a relatively long adsorption time of about 5 to 30 minutes to form a stable thin film layer having a constant orientation.

This results in a fatal drawback in that the production time becomes very long when manufacturing the multilayer thin film, and the productivity is deteriorated. In particular, in order to make the thickness and surface roughness of the multilayer thin film uniform, strict washing conditions and a large amount of solvent are required for washing. Doing.

Accordingly, the present inventors have completed the present invention as a result of earnest research efforts to supplement various problems as described above and to develop high quality ultra thin films or multilayer ultra thin films by precisely and automating the ultra thin film manufacturing process.

The present invention is to solve the above-mentioned problems, the conventional multilayer thin film manufacturing method is divided into adsorption, washing, drying process, etc. and has a disadvantage that it takes a relatively long time to form a uniform thin film is short It is an object of the present invention to provide a method for producing a multilayer ultra thin film using a rotational coating, which enables the production of a high quality multilayer thin film for a time.

1 is a process chart showing a manufacturing process of a multilayer thin film by a conventional molecular magnetic assembly method.

Figure 2 is a process diagram showing the manufacturing process of a multi-layer ultra-thin film using a rotary coating in one embodiment of the present invention.

Figure 3 is a graph showing the change in absorbance with increasing the number of laminated polyarylamine hydrochloride and polystyrenesulfonate composite layer.

Figure 4 is a graph showing the absorbance according to the number of stacked layers of the multi-layer ultra-thin film according to the conventional molecular self-assembly method and the present invention in the production of ultra-thin film using polyarylamine hydrochloride and polystyrenesulfonate.

5 is a graph showing the absorbance for each stacking number according to the concentration change of the polyarylamine hydrochloride and the polystyrenesulfonate solution.

Figure 6 is a graph showing the absorbance by stacking number according to the rotational speed change in the production of multi-layer ultra-thin film using polyarylamine hydrochloride and polystyrenesulfonate.

Figure 7 is a graph showing the absorbance according to the concentration change of sodium chloride added to the polystyrene sulfonate in the production of a multi-layer ultra-thin film using polyarylamine hydrochloride and polystyrene sulfonate.

8 is a graph showing the absorbance according to the acidity change of the polyelectrolyte when preparing a multi-layer ultra-thin film using polyarylamine hydrochloride and polystyrenesulfonate.

Figure 9 is a graph showing the change in absorbance per unit time while storing a multi-layer ultrathin film prepared using polyarylamine hydrochloride and polystyrenesulfonate in distilled water.

10 is a graph showing the absorbance for each stacking number according to the change in molarity of polyarylamine hydrochloride in preparing a multi-layer ultra-thin film using polyarylamine hydrochloride and cadmium sulfide.

FIG. 11 is a graph showing absorbance spectra and absorbances according to the number of stacked layers in the production of multilayer ultra-thin films using hydrogen bonding between polyaniline and polyvinylpyridone. FIG.

In order to achieve the above object, the present invention provides a method of manufacturing a multilayer ultra thin film for producing an ultra thin film or a multilayer thin film on a substrate,

After placing a substrate on which a positive or negative charge is introduced or a substance capable of hydrogen bonding is placed on a rotor capable of high-speed rotation, a material (A) capable of bonding by interpulsion with a material introduced to the substrate is introduced on the substrate. Next, the primary coating by rotating for 4 to 60 seconds at a speed of 500rpm to 15000rpm,

After the first coating is completed, the cleaning solvent is dropped to the center of the upper end of the substrate, and the washing process is repeated 1 to 3 times at a speed ranging from 500 rpm to 15000 rpm for 1 to 3 times to weakly bind the material to the substrate ( Remove A) to prepare a thin film (A),

After the material (A) coated on the substrate and the material (B) having different properties that can be bonded by mutual force is introduced to the top of the substrate and subjected to secondary coating under the same conditions as the primary coating,

After the secondary coating is completed, the cleaning solvent is dropped to the center of the upper end of the substrate and rotates for 4 seconds to 60 seconds at a speed of 500 rpm to 15000 rpm. It is possible to achieve by manufacturing a thin film (B) by removing the), and to provide a method for producing a multilayer ultra thin film using a rotation coating by repeating the above-described thin film (A, B) manufacturing process several times under the same conditions.

In the present invention, in order to manufacture an ultra-thin film having a multi-layer structure using a rotation coating, a substrate in which positive or negative charges are introduced or a substance capable of hydrogen bonding is first placed on a rotor capable of high speed rotation.

At this time, the substrate may be used both organic and inorganic materials, and examples of the inorganic materials may be metals such as gold, palladium, platinum, glass, ceramic materials, germanium, silicon, conductive materials, semiconductor materials, and insulating materials. The process of introducing a positive charge or a negative charge into and a process of enabling hydrogen bonding can be used according to a conventional method.

For example, the process of introducing a negative charge to the substrate is to immerse the substrate in a blend solution consisting of water, ammonia water, hydrogen peroxide for a certain time to introduce a negative charge on the surface of the substrate.

As described above, in order to form an ultra-thin film on a substrate into which charge is introduced, a substrate in which positive or negative charge is introduced is placed on a rotator capable of rotating at a high speed, and then by mutual attraction with a material introduced into the substrate on the substrate. Introducing the bondable material (A) and then the first coating by rotating for 4 to 60 seconds at a speed of 500rpm to 15000rpm.

In this case, the bond is possible by the mutual attraction means the attraction force that can be bonded by the interaction between molecules such as electrostatic ionic bonds, hydrogen bonds, chemical bonds, etc. Considering the concentration of the polyelectrolyte, it is not necessarily limited to the number of revolutions and the coating time presented above.

For example, polyelectrolyte among the materials capable of electrostatic attraction include polyarylamine hydrochloride represented by the following Chemical Formula 1 or polystyrenesulfonate represented by Chemical Formula 2, and the inorganic nanoparticles include cadmium sulfide nanoparticles represented by Chemical Formula 3. It is possible.

In addition, polyaniline represented by the formula (4) or polypyrrolidone represented by the formula (5) can be used as a polymer capable of hydrogen bonding with each other.

At this time, the process of introducing the material (A) which can be combined by the mutual force with the material introduced into the substrate can be introduced in various ways, but the simplest method is to drop or spray the material (A) on the substrate In addition, it can be introduced through a method of immersing and removing the substrate in the material (A) solution to be introduced.

As described above, the bondable material (A) is introduced into the substrate and then rotated to form a thin film. When the rotational speed is less than 500 rpm, the amount of polyion that is weakly adsorbed increases and the solvent is completely removed. The longer the problem occurs, and the rotational speed does not have to exceed 15000rpm, but rather the centrifugal force becomes larger than the adsorption force, so that the amount of removal to the outside becomes larger than the amount adsorbed on the thin film. Considering the concentration and the coating time, the rotation speed is preferably set to 500rpm to 150000rpm.

In addition, the coating is completed on the surface of the substrate in about 4 to 60 seconds at high speed at the rotational speed as described above. In the conventional molecular self-assembly method, the substrates are alternately immersed in each polyelectrolyte solution having opposite charges. After the adsorption process based on spontaneous diffusion of polyions, the rotary coating self-assembly method according to the present invention is not only spontaneous diffusion due to electrostatic attraction but also due to the centrifugal force applied in the horizontal direction and the shear stress applied to the substrate by the polyelectrolyte. By accelerating the diffusion rate of polyions artificially and greatly increasing the likelihood of adsorption, coating is possible in a short time.

After the first coating is completed by rotating at a high speed as described above, the washing solvent is dropped on the upper center of the substrate, and the washing process is repeated one to three times at a speed ranging from 500 rpm to 15000 rpm for 1 to 3 times to weaken the surface of the substrate. By removing the combined material (A) to prepare a thin film (A).

After forming a single layer of thin film (A) through the above process, by introducing a material (B) having a different property that can be bonded to the first coated material (A) on the surface of the thin film by mutual gravitation to the top of the substrate After the second coating under the same conditions as the primary coating, the washing process is repeated once or three times to remove the material (B) weakly bonded to the thin film surface to prepare a thin film (B).

When the above-described thin film introduction process is carried out, the multilayer ultra thin film according to the present invention can be manufactured. In this case, the above-described coating method is not only a multi-layer ultra thin film (ABAB ......) but also mutual bonding. It is possible to produce multilayer ultrathin films composed of as many different materials as possible.

For example, if A and C have the same charge and B and D have the same charge, complex multilayer ultra-thin films between several materials such as ABCABCABC ...., ABCDABCD ....., CBADCBAD .... can be produced. Do.

The conventional molecular self-assembly method used in the manufacture of multilayer thin films induces spontaneous adsorption by immersing the substrate in a solution of different materials with mutual attraction for a period of time to form a thin film. The spontaneous adsorption requires a relatively long time of about 5 to 30 minutes to produce a single monolayer, and also requires a lot of adsorption time and a strict cleaning process in the manufacture of the multilayer thin film. .

However, in the present invention, it is possible to form an ultra-thin film in a fast time of 4 seconds to 60 seconds by using the rotational coating, and thus it is possible to manufacture a multilayer thin film by repeating this process, and thus there is an advantage in that productivity can be greatly improved.

In addition, molecular self-assembly should have sufficient adsorption time for defect-free and uniform thin film formation by spontaneous adsorption process. However, spin coating self-assembly can control surface roughness quickly because the adsorption process takes place under centrifugal force by high speed rotation. A uniform thin film is formed.

In addition, the conventional molecular self-assembly method should remove the weakly adsorbed layer by immediately washing it with a solvent, etc. without drying the adsorbed substrate in the solution in order to have a uniform thin film surface when manufacturing the multilayer thin film. The weakly adsorbed polymer electrolyte is substantially removed by centrifugal force and at the same time the solvent is removed, there is an advantage that the adsorption and drying process proceeds simultaneously.

In particular, in the process of manufacturing a multilayer ultra thin film using the rotation coating of the present invention, the thickness of the thin film can be freely controlled within the range of 4 angstroms to 100 angstroms, in order to control the thickness as described above. This can be achieved by appropriately adjusting the concentration of ions, the addition of ionic salts, the acidity (pH) and the rotational speed.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings, but the accompanying drawings are presented to aid the understanding of the present invention, but are not limited to the descriptions raised by the present invention.

Figure 2 is a view showing a manufacturing process of a multi-layer ultra-thin film using a rotary coating as an embodiment of the present invention, as shown in FIG. (1) while introducing a material having a positive charge to the coating by rotating for 4 seconds to 60 seconds at a speed in the range of 500rpm to 15000rpm (2), the negatively charged material by dropping the negatively charged material in the center of the coated surface again (3) while coating is rotated for 4 seconds to 60 seconds at a speed in the range of 500rpm to 15000rpm (4), and coating while repeating the introduction of the negative charge and positive charge (5) will be able to manufacture a multilayer thin film .

At this time, immediately after the coating as described above (3, 5) drop the washing solvent in the center of the upper substrate and rotates for 8 seconds to 60 seconds at a speed of 500rpm to 15000rpm and repeats the cleaning process 1 to 3 times relatively weakly coupled Substances are removed so that the thickness of the thin film is constant and the surface roughness is able to produce a very thin film.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following description.

<Example 1>

A negatively charged quartz glass substrate (1.3 cm x 4.5 cm) was placed on a high speed rotor, followed by dropping 2 ml of 0.01 M polyarylamine hydrochloride (hereinafter referred to as 'PAH') on the substrate at a speed of 3000 rpm. The coating was rotated for 15 seconds, and after the coating was completed, 2 ml of distilled water was dropped and again rotated for 15 seconds at a speed of 3000 rpm, followed by washing twice, and 0.01M polystyrenesulfonate ( 2 ml of 'PSS') is then dropped and coated by rotating at a speed of 3000 rpm for 15 seconds, and after the coating is completed, 2 ml of distilled water is dropped and then rotated at a speed of 3000 rpm for 15 seconds to wash. Repeat twice, and repeat the process of coating the PAH and PSS several times to produce a multilayer thin film having a stack number of 6, 10, 14, 20, 26, 30, 34, 40, and then absorb the absorbance of the prepared thin film Photometer (Perkin-Elmer Lamb da 4B UV / visible spectrophotometer) measured in the range from 190nm to 400nm is shown in Figure 3, and taken only the absorbance of 225nm is shown in the graph. 225 nm is the light absorption area of PSS.

As shown in FIG. 3, it can be seen that the absorbance increases linearly as the number of stacked layers increases, which shows that the adsorption amount of PSS deposited by the rotating coating is very uniform.

<Example 2>

In the same manner as in Example 1 except that the number of revolutions to 4000rpm to produce a multilayer thin film of 4, 8, 12, 16, 20, and then measured the absorbance of the prepared thin film at 225 nm with an absorbance meter, The results are shown in FIG.

Comparative Example 1

A negatively charged quartz glass substrate (1.3 cm x 4.5 cm) was immersed in a 0.01 M PAH solution for 20 minutes, coated, and then washed twice with distilled water for 2 minutes, and the coated substrate was 0.01 M PSS. After soaking in solution for 20 minutes, and after the coating is completed, repeat washing twice with distilled water for 2 minutes, and repeating the process of coating the PAH and PSS several times to stack 4, 8, 12, 16, and 20 multilayer films. Next, the absorbance of the prepared thin film was measured at 225 nm with an absorbance spectrometer, and the results are shown in FIG. 4.

As shown in FIG. 4, it can be seen that the absorbance of the thin film prepared by the rotation coating is high, so that the adsorption amount is much higher. This is because the concentration of the polyions continues to increase during the rotation time due to the faster removal of the solvent than the solute due to the high speed rotation. In addition, the shear stress and centrifugal force applied in the horizontal direction are considered to form a dense thin film of polyions.

<Example 3>

The multilayer film was prepared in the same manner as in Example 1 while changing the concentration of the PSS solution to 1mM, 2.5mM, 5mM, 10mM, 12.5mM, 16mM, 20mM, 24mM, and 50mM, but the rotation speed was 4000rpm. 4, 8, 12, 16, and 20 were prepared, and then the absorbance of the thin film was measured at 225 nm with an absorbance spectrophotometer, and is shown in FIG. 5, where the ultra-thin thickness of the monolayer according to the concentration of the PSS solution was 1 is shown.

As shown in Figure 5 it can be seen that the absorbance is increased from 0.001M to 0.016M concentration of the solution, but at a subsequent concentration the absorbance was kept constant. This result is that the adsorption amount is increased by increasing the diffusion rate of poly ions with increasing concentration, but if adsorption is sufficiently made by a certain amount, the adsorption is disturbed due to the repulsive force between the same charges.

Molarity (mM) One 2.5 5 10 12.5 16 20 24 50 Thickness per layer (nm) 0.4 0.84 1.63 2.50 3.37 3.72 3.76 3.93 3.97

Therefore, as shown in Table 1, it is possible to control the amount of adsorption by appropriately adjusting the concentration of the solution, so it can be confirmed through Table 1 that the thickness per layer of (PAH / PSS) can be varied within a predetermined range. have.

<Example 4>

In the same manner as in Example 1 while varying the rotational speed to 2000rpm, 3000rpm, 4000rpm, 5000rpm, 6000rpm to produce a multilayer thin film, the number of laminated 4, 8, 12, 16, 20 to produce a multilayer thin film, then The absorbance of the 35 thin films thus prepared was measured at 225 nm with an absorbance spectrometer and is shown in FIG. 6.

As shown in Figure 6, as the rotational speed increases, the amount of adsorption initially decreases relatively much, but the decrease decreases from 4000 rpm or more, which means that the weakly adsorbed layer is removed more by the strong centrifugal force due to the increase of the rotational speed. Because it becomes.

Example 5

The concentration of sodium chloride in 0.01M PSS was 0M, 0.1M, 0.5M, and 1.0M, respectively, followed by the same method as in Example 1 to prepare a multilayer thin film, with the number of laminations 2, 4, 8, 12, 16, After preparing a multilayer thin film of 20 people, the absorbance of the 24 thin films prepared above was measured at 225 nm with an absorbance spectrometer and is shown in FIG. 7.

As shown in FIG. 7, it can be seen that as the amount of sodium chloride is increased, the amount of adsorption increases because the degree of ionization of the solution is increased by adding sodium chloride.

<Example 6>

PAH and PSS acidity (pH) was changed to 5.8, 4.5, 3.2, 2.5 in the same manner as in Example 1 to prepare a multi-film thin film, the number of revolutions to 4000rpm laminated number of 2, 4, 8, 12, After preparing the multilayer thin films of 16 and 20, the absorbance of the 24 thin films prepared above was measured at 225 nm with an absorbance spectrometer and is shown in FIG. 8.

As shown in Figure 8 it can be seen that the amount of adsorption increases as the pH decreases.

<Example 7>

The multilayer film was prepared in the same manner as in Example 1 while changing the concentration of the PSS solution to 1mM, 2.5mM, 5mM, 10mM, 12.5mM, 16mM, 20mM, 24mM, and 50mM, but the rotation speed was 4000rpm. After preparing a multilayer thin film of 20, the nine thin films prepared above were immersed in distilled water, and the absorbance with time was measured at 225 nm with an absorbance spectrometer, and is shown in FIG. 9.

As shown in FIG. 9, even though each of the layers forming the multilayer thin film having the number of stacked layers of 20 is water soluble, there is no change in absorbance even after immersing in distilled water for a long time. Because it is achieved.

<Example 8>

A negatively charged quartz glass substrate (1.3 cm x 4.5 cm) was placed on a high speed rotor, followed by dropping about 2 ml of 0.01 M PAH on the substrate, rotating at a speed of 3000 rpm for 15 seconds to coat, and completing the coating. Then, 2 ml of distilled water is dropped again and rotated for 15 seconds at a speed of 3000 rpm, and the washing process is repeated twice, and 2 ml of a solution of cadmium sulfide (CdS) nanoparticles is dropped on the coated substrate surface, and 15 seconds at a speed of 3000 rpm. Rotate for a while, and after the coating is completed, 2 ml of distilled water is dropped and rotated again for 15 seconds at a speed of 3000 rpm, and the washing process is repeated twice, and the coating process of PAH and CdS is repeated several times. , 2, 4, 6, 8, 10, 12, 14, 16, 18, 20 to prepare a multilayer thin film. At this time, the concentration of CdS was changed to 0.25mM, 0.5mM, 1.0mM, 3.0mM, 5.0mM, 10mM, 12mM, and 20mM, respectively, to prepare a multilayer foil, and then absorbance of the 88 thin films. 10 was measured at 360 nm with an absorbance spectrometer. In the above, 360 nm is an absorption region of cadmium sulfide.

The cadmium sulfide nanoparticles used in the above solution was prepared by adding 40 mg of cadmium perchlorate (Cd (ClO ₄ ) ₂ ) and 2 ml of thoramatic acid (CH ₃ CH (SH) CO ₂ H) into distilled water to make 250 ml. 1M sodium hydroxide was added to adjust pH to pH10, and then 10 mg of sodium sulfide was added to prepare cadmium sulfide nanoparticles having a negative charge.

As shown in FIG. 10, it can be seen that the absorbance increases linearly as the number of stacked layers increases, which shows that the adsorption amount of cadmium sulfide deposited by the rotating coating is very uniform.

In addition, as the concentration of the solution increases, it was confirmed that the absorbance was increased to a certain degree, but the concentration was kept constant at the concentration after that. This result is because the adsorption amount is increased by increasing the diffusion rate significantly with increasing concentration, but if the adsorption is sufficiently made by a certain amount, the adsorption is disturbed due to the repulsive force between the same charges.

Example 9

A negatively charged quartz glass substrate (1.3 cm x 4.5 cm) was placed on a high speed rotor, and then the polycation PAH and poly anion PSS were alternately stacked and coated in the same manner as in Example 1 on the substrate, 2 ml of polyaniline aqueous solution was dropped on the surface of the coated substrate, rotated for 15 seconds at a speed of 4000 rpm, and then 2 ml of distilled water adjusted to pH2.5 was dropped for 2 seconds at a speed of 4000 rpm, and then washed twice. The solution was repeated, and 2 ml of 0.01 M aqueous polyvinylpyrrolidone solution was rotated for 15 seconds at a speed of 4000 rpm, and then rotated twice for 15 seconds at a speed of 4000 rpm with distilled water of pH 5.5. The polyaniline and polyvinyl The coating process of the pyrrolidone was repeated several times to prepare a multilayer thin film having 2, 4, 6, 8, and 10 stacked layers. The absorbance spectra of the five thin films thus prepared were measured with an absorbance spectrometer, and the relationship between the absorbance absorbed at 630 nm and the number of stacked layers is shown in FIG. 11. The broad absorption spectrum region shown above at 500 nm and 800 nm is a typical absorption region of polyaniline.

The polyaniline aqueous solution used above was dissolved in an emerald-based polyaniline in a dimethylacetamide solution at a concentration of 20 mg / ml for 8 hours to 10 hours, and then purified with a 0.45 μm filter. Then, 10 ml of the polyaniline filtered by the filter was taken It was added to 90 ml of distilled water adjusted to pH3.0 to pH3.5 with methanesulphonic acid, and then adjusted to pH2.5 to pH2.6 with methinesulphonic acid. At this time, the polyvinylpyrrolidone aqueous solution used in the above was used by adjusting the polyvinylpyrrolidone purchased from Aldrich company in distilled water at a concentration of 0.01M.

As shown in FIG. 11, it can be seen that the absorbance increases linearly as the number of stacked layers increases. This shows that the adsorption amount of the polyaniline deposited by the rotary coating is very uniform. It also shows that multilayer ultra-thin film production is possible.

As described above, the present invention provides a method of manufacturing a multilayer ultra thin film using a rotating coating that maximizes productivity by manufacturing a high quality multilayer ultra thin film by shortening the manufacturing time by manufacturing a multilayer ultra thin film by a method of rotating coating. It is a useful invention to.

Claims (6)

In the manufacturing method of the multilayer ultra thin film which manufactures an ultra thin film or a multilayer thin film on a board | substrate, After placing a substrate on which a positive or negative charge is introduced or a substance capable of hydrogen bonding is placed on a rotor capable of high-speed rotation, a material (A) capable of bonding by interpulsion with a material introduced to the substrate is introduced on the substrate. Next, the primary coating by rotating for 4 to 60 seconds at a speed of 500rpm to 15000rpm, After the first coating is completed, the cleaning solvent is dropped to the center of the upper end of the substrate, and the washing process is repeated one to three times at a speed ranging from 500 rpm to 15000 rpm for one to three times to weakly bind the material to the substrate ( Remove A) to prepare a thin film (A), After the material (A) coated on the substrate and the material (B) having different properties that can be bonded by mutual force is introduced to the top of the substrate and subjected to secondary coating under the same conditions as the primary coating, After the secondary coating is completed, the cleaning solvent is dropped to the center of the upper end of the substrate and rotates for 4 seconds to 60 seconds at a speed of 500 rpm to 15000 rpm. ) To prepare a thin film (B), and to repeat the above-described manufacturing process of the thin film (A, B) several times under the same conditions, the method of manufacturing a multilayer ultra thin film using a rotation coating. According to claim 1, wherein the introduction of the material (A) which can be combined by the mutual attraction with the material introduced into the substrate is introduced by dropping or spraying the introduction material (A) in the process of rotating on the substrate Method for producing a multilayer ultra thin film using a rotation coating. The method of claim 1, wherein the step of introducing the material (A) which can be bonded by mutual attraction with the material introduced to the substrate is a rotary coating, characterized in that the substrate is instantaneously immersed in the solution (A) solution and introduced to it. Method for producing a multilayer ultra thin film used. The rotating coating according to any one of claims 1 to 3, wherein a material having a different property capable of bonding by the mutual attraction is used as a material capable of bonding by electrostatic ionic bonds, hydrogen bonds, or chemical bonds. Method for producing a multilayer ultra thin film using. The method according to any one of claims 1 to 3, wherein the thickness of each thin film is controlled by adjusting the concentration of the solvent, the addition of the ionic salt, the pH control, and the rotational speed. 5. The method of claim 4, wherein each of the thin films is adjusted by the thickness of the solvent, the addition of the ionic salt, the pH adjustment, and the rotational speed.