KR101837402B1 - Method for manufacturing polymer film shaped of nanorod - Google Patents

Abstract

The present invention relates to a method for producing a thin film of a polymer, comprising the steps of: preparing a precursor solution by mixing a polymer resin with a solvent so that electrostatic spraying can be performed by adjusting viscosity; And spraying the precursor solution onto a substrate to be coated using an electrostatic atomizer, wherein spraying the precursor solution onto a substrate comprises spraying the precursor solution from the nozzle onto the substrate, Is formed on the surface of the polymer film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a polymer membrane,

The present invention relates to a method of manufacturing a vertically aligned micro-rod-shaped polymer or carbon thin film using an electrostatic atomization method.

Vertically aligned microstructured thin films are attracting much attention because of their advantages of increased specific surface area and ease of space utilization.

In general, a template method, a chemical vapor deposition (CVD) method, a physical vapor deposition (PVD) method and the like are used to manufacture a vertically aligned microstructure.

The template method is difficult to control the organization, the complexity of producing the pattern, the problem of the template removal process, and it is difficult to apply to the complex object. The chemical vapor deposition method has a relatively high process temperature and requires a high-level vacuum device for high purity, resulting in a high process cost and a relatively long process time. Also, the physical vapor deposition method has a disadvantage in that it requires a high level vacuum device for high purity such as a chemical vapor deposition method, though the process temperature is not high, and thus the process cost is high and the process time is relatively long and it is difficult to apply to a complicated shape.

In addition, the above methods have a disadvantage in that it is difficult to apply a continuous process in common, and it is difficult to apply to a large area object.

The present invention can overcome complexity, high temperature, and high device cost, which are disadvantages of the above-mentioned template method, chemical vapor deposition method, and physical vapor deposition method, The present invention relates to a method for producing a polymer or carbon thin film in the form of a microspheres.

According to an aspect of the present invention, there is provided a method of preparing a precursor solution, the method comprising: preparing a precursor solution by mixing a polymer resin with a solvent so that electrostatic spraying can be performed by controlling viscosity; And spraying the precursor solution onto a substrate to be coated using an electrostatic atomizer, wherein spraying the precursor solution onto a substrate comprises spraying the precursor solution from the nozzle onto the substrate, Wherein the polymer thin film is formed by a method comprising the steps of:

According to an aspect of the present invention, the step of spraying the precursor solution onto the substrate may include preheating the substrate to a temperature higher than the curing temperature of the polymer resin.

According to an aspect of the present invention, the step of spraying the precursor solution onto the substrate may further include heat treating the sprayed substrate in a vacuum or an inert atmosphere.

According to an aspect of the present invention, the heat treatment may be performed at 900 to 1200 ° C.

According to an aspect of the present invention, the step of spraying the precursor solution onto the substrate may include the step of forming the nozzle with multiple nozzles or providing a transfer device on the substrate to coat the substrate with the large area.

According to an aspect of the present invention, the polymer resin may be a phenolic resin.

According to an aspect of the present invention, there is provided a polymer thin film in the form of vertically arranged microspheres produced by any one of the above methods.

According to one embodiment of the present invention, there are the following advantages when using the electrostatic spraying method in the production of vertically aligned micro rod-shaped polymer and carbon thin film.

According to the embodiment of the present invention, since only a precision injection pump, a DC high voltage generator, and a target heating apparatus are required in the apparatus configuration, the apparatus cost is much simpler and cheaper than the above-mentioned process.

According to one embodiment of the present invention, the waste of solution is reduced by direct spraying.

According to an embodiment of the present invention, a high temperature is not required as in a chemical vapor deposition method requiring a process temperature of about 200 ° C or more and a temperature of generally 500 ° C or more, and it is easy to pattern through masking.

According to the embodiment of the present invention, the process is very simple since only the solution is supplied and sprayed after the apparatus is constructed.

According to one embodiment of the present invention, since it is a coating process using an electric field, it is possible to coat even a complicated shape.

According to an embodiment of the present invention, since a nozzle can be uniformly sprayed in a range of about 4 cm in diameter, it is possible to form multiple nozzles and to coat a large area easily by adding a transfer device.

Further scope of applicability of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and specific examples, such as the preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art.

1 is a schematic diagram of an electrostatic atomizing apparatus used in an embodiment of the present invention.
FIG. 2 is an enlarged photograph of a vertically arranged micro rod-shaped polymer thin film formed by an electrostatic spraying method on a silicon target according to an embodiment of the present invention.
FIG. 3 is an enlarged view of a vertically arranged micro rod-shaped polymer thin film produced according to an embodiment of the present invention, which is carbonized in a high-temperature vacuum atmosphere and converted into a vertically arranged micro rod-shaped carbon thin film.
4 is a flowchart of a carbon thin film manufacturing process according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, wherein like reference numerals are used to designate identical or similar elements, and redundant description thereof will be omitted. The suffix "module" and " part "for the components used in the following description are given or mixed in consideration of ease of specification, and do not have their own meaning or role. In the following description of the embodiments of the present invention, a detailed description of related arts will be omitted when it is determined that the gist of the embodiments disclosed herein may be blurred. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. , ≪ / RTI > equivalents, and alternatives.

Terms including ordinals, such as first, second, etc., may be used to describe various elements, but the elements are not limited to these terms. The terms are used only for the purpose of distinguishing one component from another.

It is to be understood that when an element is referred to as being "connected" or "connected" to another element, it may be directly connected or connected to the other element, . On the other hand, when an element is referred to as being "directly connected" or "directly connected" to another element, it should be understood that there are no other elements in between.

The singular expressions include plural expressions unless the context clearly dictates otherwise.

In the present application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

An embodiment of the present invention relates to a method of manufacturing a thin film of a micro-rod type vertically aligned by using an electrostatic spraying method, more specifically, by spraying a phenol resin solution onto a heated object (substrate) by an electrostatic spraying method, To a technique capable of coating a film of a simple vertically aligned rod tissue.

 In one embodiment of the present invention, a thermosetting resin is used, a solvent is mixed to form a spray mode, the substrate is heated to a temperature higher than the curing temperature of the phenol resin, and the process parameters include spray time, solution concentration, spray flow rate, .

Hereinafter, an embodiment according to an embodiment of the present invention will be described in detail for each step.

Step 1 according to one embodiment of the present invention relates to the preparation of a solution to be used in the electrostatic atomization method. The resin used in one embodiment of the present invention is preferably selected from phenol-formaldehyde resin. In particular, phenol resins are characterized by their ability to be used for vertically aligned microporous carbon thin film coatings because of their high carbon conversion when carbonized in a high temperature inert atmosphere. The solvent uses a solvent which can be mixed with the resin. When the viscosity is too high, it is necessary to select an appropriate viscosity since the spray mode 80 of FIG. 1 is changed into a spinning form rather than a sprayed form.

Step 2 according to an embodiment of the present invention is to spray the solution prepared in step 1 onto the substrate using electrostatic atomization. Specifically, in FIG. 1, the substrate 50 is placed on the heating device 60 and heated to a temperature higher than the curing temperature of the resin in advance. Then, the solution is injected into the solution storage container 10, the anode of the direct current high voltage generator 40 is connected to the metal nozzle 20, and the grounded opposite electrode is connected to the substrate 50. Finally, the solution is injected by using the precision injection pump 30, and a high voltage of several kV is applied by using the DC high voltage generator 40.

When the appropriate high voltage is applied, the liquid overcomes the surface tension at a high voltage and forms a cone-jet 70 in the form of a cone at the end of the metal nozzle, and atomization begins. Here, a higher voltage should be applied as the distance between the nozzle 20 and the substrate 50 increases. In addition, if the spray mode appears as spinning rather than spraying, the viscosity of the solution should be lowered.

When spraying is carried out according to the above-described method, a vertically aligned micro rod-shaped polymer thin film of a desired shape can be obtained within a few minutes to several hours by the process of FIG. More specifically, droplets that are charged and dispersed through electrostatic spray form a dense thin film on a target substrate at first, and then are attracted to a protruding portion of the film due to a preferential landing phenomenon. At this time, as soon as the landing, the viscosity is lowered enough to be dispersed instantaneously, and then hardened again, so that the protruding portion is dense and continues to grow up to have a rod shape. By such a process, a polymer thin film which is vertically tilted in a microstructure is formed.

Next, step 3 is required to produce vertically aligned micro rod-shaped carbon thin films.

Step 3 according to an embodiment of the present invention is a step of converting the vertically aligned micro rod-shaped polymer thin film formed in step 2 into a carbon thin film. At this time, a phenol resin can be used as the polymer resin used. This is because, as described above, carbon conversion is relatively high compared to other resins. When the vertically aligned thin film phenol thin film prepared by the electrostatic spraying method is heated in a vacuum or an inert atmosphere at a temperature of 800 ° C or more for 30 minutes or more, the phenol resin is converted to amorphous carbon. At this time, as the heating temperature is increased, carbon having high electrical conductivity and high crystallinity can be obtained. Generally, in the case of phenol resin, the shrinkage of the rod when converted to carbon is about 20%, so this should be taken into consideration when coating a film having a desired shape.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of one embodiment of the present invention.

FIG. 4 is a flowchart of a carbon thin film manufacturing process according to an embodiment of the present invention, which will be described below with reference to FIG.

<Preparation of Vertically Aligned Small Bar Phenol Thin Films Using Electrostatic Spray Method>

The mixture was mixed with commercial phenolic resin (KC-4703, Kangnam Hwaseong, Korea) and anhydrous ethanol at a weight ratio of 1:10 and stirred for about one day to prepare a precursor solution (S110).

The substrate 50 is placed in the heating device 60 and the object is heated to 200 ° C.

The precursor solution prepared in the syringe is inserted, and the metal nozzle 20 is connected to the precision injection pump 30. At this time, the distance between the nozzle and the substrate is fixed to 30 to 40 mm.

Then, the anode of the direct current high voltage generator 40 is connected to the metal nozzle, and the earth electrode is connected to the substrate.

When a solution is supplied at a rate of 1 to 10 μL per minute by using a precision injection pump and a DC voltage of about 4 to 7 kV is applied by using a DC high voltage generator, a cone (70) is formed in the nozzle and a spray (80) (S120) starts.

The spray time can be adjusted to produce a vertically aligned micro rod-shaped phenolic thin film having a desired thickness (see S120). The results are shown in FIG.

<Fabrication of Vertically Aligned Small Bar Carbon Thin Films Using Electrostatic Spray Method>

The mixture was mixed with commercial phenolic resin (KC-4703, Kangnam Hwaseong, Korea) and anhydrous ethanol at a weight ratio of 1:10 and stirred for about one day to prepare a precursor solution (S110).

The substrate 50 is placed in the heating device 60 and the object is heated to 200 ° C.

The precursor solution prepared in the syringe is inserted, and the metal nozzle 20 is connected to the precision injection pump 30. At this time, the distance between the nozzle and the substrate is fixed to 30 to 40 mm.

Then, the anode of the direct current high voltage generator 40 is connected to the metal nozzle, and the earth electrode is connected to the substrate.

When the solution is supplied at 1 to 10 μL per minute using a precision injection pump and approximately 4 to 7 kV is applied using a direct current high voltage generator, the cone (70) is formed in the nozzle and the spray (80) starts.

By adjusting the spraying time, a vertically aligned micro rod-shaped phenol thin film having a desired thickness can be obtained (S120)

The phenol thin film thus formed is placed in a vacuum or argon atmosphere chamber and maintained at 900 to 1200 ° C for about 30 minutes (S130) to carbonize the phenol resin to obtain a vertically aligned microporous carbon thin film. At this time, The thin film is shown in Fig.

The foregoing detailed description should not be construed in all aspects as limiting and should be considered illustrative. The scope of the present invention should be determined by rational interpretation of the appended claims, and all changes within the scope of equivalents of the present invention are included in the scope of the present invention.

10: Solution storage container
20: Metal nozzle
30: Precision injection pump
40: DC high voltage generator
50: substrate
60: Heating device
70: Cone-jet
80: Spray mode

Claims (7)

Preparing a precursor solution by mixing a phenol resin with a solvent so as to be electrostatically sprayed by controlling the viscosity; And
Spraying the precursor solution onto a substrate to be coated using an electrostatic atomizer,
The step of spraying the precursor solution onto the substrate comprises:
And spraying the precursor solution from the nozzle onto the substrate to form a vertically aligned micro rod-shaped polymer thin film. The method according to claim 1,
And heating the substrate to a temperature higher than the curing temperature of the phenolic resin before spraying the precursor solution onto the substrate. The method according to claim 1,
Further comprising the step of spraying the precursor solution onto the substrate, and then heat treating the sprayed substrate in a vacuum or an inert atmosphere. The method of claim 3,
Wherein the heat treatment is performed at a temperature of 900 to 1200 占 폚. The method according to claim 1,
The step of spraying the precursor solution onto the substrate comprises:
Wherein the step of forming the polymer thin film comprises the steps of forming the nozzle with multiple nozzles or providing a transferring device on the substrate to coat the substrate with a large area. delete 6. A vertically aligned microballoon-like polymer thin film produced by the method of any one of claims 1 to 5.

Images