KR20100074975A - Apparutus and method for manufacturing black film and coating film with black film - Google Patents

Abstract

PURPOSE: A coating layer having a black film and a method and an apparatus for manufacturing the black film are provided to improve decorative effects by controlling the evaporation rate of a sputtering source and prevent excessive thickness of a black film formed. CONSTITUTION: An apparatus for manufacturing a black film comprises a substrate(4), a sputtering source(2), a metal target(3), and an ion blocking grid(6). The substrate forms a metallic film on the top of the substrate. The metal film is formed from the metal target ionized by the sputtering source. The ion blocking grid is formed between the substrate and the metal target in order to reduce the energy of the ion generated by the sputtering source.

Description

Black coating method and coating layer having a black coating and a black film manufacturing apparatus therefor {APPARUTUS AND METHOD FOR MANUFACTURING BLACK FILM AND COATING FILM WITH BLACK FILM}

The present invention relates to a method for manufacturing a black film using a metal coating, and more particularly, to form a micropore on the surface of the coating layer by forming a film so that only atoms or molecules with low electrical energy are deposited on the substrate by an ion blocking grid. The present invention relates to a method for manufacturing a black film improved to have a black color by scattering of light, and a black film manufacturing apparatus for the same.

Vacuum coating is a deposition method using vacuum as a general method of coating a metal or a compound on a material such as metal, glass and plastic. Vacuum coatings are increasingly being used because they do not affect the environment compared to conventional wet plating.

Vacuum coating is largely classified into physical vapor deposition and chemical vapor deposition, and the physical vapor deposition is divided into evaporation, sputtering and ion plating. In the case of coating metals, vacuum deposition and sputtering methods are mainly used for general application, and sputtering and ion plating methods are mainly used for the purpose of improving corrosion resistance, adhesion of film and density.

Sputtering is a phenomenon in which an ionized inert gas collides with a target to which a negative bias voltage is applied, and particles of an energy-targeted target are ejected out of the material during the momentum transfer of incident ions. The characteristics vary significantly depending on the arrangement of.

On the other hand, the decorative surface treatment method for implementing a variety of colors in the material can be largely divided into anodizing method, using the interference of the oxide or metal film, and coating a film having a unique color, such as gold.

Among these methods, anodization is a method of immersing a substrate in an acidic solution, flowing an electric current to accelerate oxygen ions to the substrate, oxidizing the substrate, and using a color change or interference color according to the thickness of the oxide film. However, in the case of surface treatment by the anodizing method, a separate post-treatment process is required to remove a large amount of pores present in the film after color development, and problems such as causing pollution due to the wet method are used.

The method of producing a color using an oxide or a metal film is a method of forming a variety of colors by the interference of light by depositing a thin oxide or metal. However, this method deposits a very thin film, so when coated on a transparent object such as glass, light is transmitted, making it difficult to produce a clear color film. In particular, it is very difficult to produce black using interference colors.

Finally, a method of realizing color by coating a film having a unique color on a substrate is a method of coating a material having a unique color according to the component ratio of a compound such as a metal or a titanium compound having a unique color such as gold or copper.

As a method of coating these materials, physical vapor deposition and chemical vapor deposition are widely used, and by using these methods, coatings of various colors including black may be formed on substrate surfaces such as metal, glass, ceramics, and plastics. Currently, these coating methods are used to coat gold-like materials such as titanium nitride and are widely used for decoration.

In recent years, as the glossy black surface treatment products are popular in accordance with various demands of the demands and the uptrend of fashion, the technology for making black in various ways has been developed and developed. The main method is to produce a black thin film by reacting carbon, nitrogen, oxygen and the like.

U.S. Patent US2007 / 0154693A1 discloses a method for implementing various colors on a substrate by sputtering. Japanese Patent Laid-Open No. 62-218550 manufactures a black thin film of an oxide main body by ion plating by reacting an appropriate amount of oxygen with a metal. The technique to do that was introduced. However, this method has a disadvantage in that the film itself is easily broken because the film is composed only of oxide, and the adhesion to the substrate is also poor. In addition, Japanese Patent Application Laid-Open No. 61-183458 introduces a technique of using titanium, but using nitrogen and carbon as the main components, and oxygen below 40% of titanium. However, this method has a disadvantage that titanium, which is a metal component in the film, is 40% or less, so that peeling of the film easily occurs, resulting in poor adhesion of the film. On the other hand, Korean Patent No. 0838847 shows that titanium carbide exhibits a blackish gray color to prevent the adhesion and peeling of the film by controlling titanium as a metal to 50% or more, and to control the content of carbon and oxygen to produce a black thin film. Although the technology has been introduced, this method also has the disadvantage that the process is complicated and the economical decrease.

The present invention was created in order to solve all the problems of the prior art as described above, by lowering the electric energy of ions ionized by the ion blocking grid and controlling the evaporation rate at the time of forming a black film, a black film excellent in corrosion resistance and decoration. It is an object of the present invention to provide an improved method for producing a black film and an apparatus for producing a black film for the purpose of economically forming a coating layer.

The black film production apparatus of the present invention for solving the above problems is a substrate for forming a metal thin film, a sputtering source for ionizing to form a metal thin film on the substrate, and ionized by the sputtering source and deposited on the substrate In the film production apparatus comprising a metal target, characterized in that an ion blocking grid for reducing the energy of ions ionized by the sputtering source between the substrate and the metal target.

In this case, the ion blocking grid is characterized in that the mesh (mesh) form.

In addition, the film production apparatus is characterized in that it further comprises a positive voltage applying power supply is connected to one side of the ion blocking grid to apply a positive voltage.

The ion blocking grid is preferably made of the same material as the metal target.

According to another aspect of the present invention, a method for manufacturing a black film according to another aspect of the present invention provides a surface of a coating layer by forming a film so that only atoms or molecules having low electrical energy or no energy are deposited on a substrate by an ion blocking grid. It is characterized in that to form a black hole in the black color by the scattering of light.

More specifically, the method for manufacturing a black film of the present invention comprises forming a metal film by depositing a metal target on a substrate by a sputtering source, and by using an ion blocking grid, atoms having low or no electric energy or And allowing only molecules to be deposited on the metal film to form a black film.

At this time, the evaporation rate by the sputtering source in the step of forming the black film is preferably 70% or less of the evaporation rate by the sputtering source in the step of forming the metal film.

In addition, the voltage applied to the ion blocking grid is preferably 50 ~ 200V.

According to another aspect of the present invention, there is provided a coating layer having a black coating, comprising a substrate, a metal coating formed by depositing on the substrate, and a black coating formed on the metallic coating.

According to the black film production method of the present invention and the black film production apparatus therefor, it is possible to form a black film excellent in corrosion resistance and decorativeness economically by lowering the electrical energy of ions sputtered by the ion blocking grid. In addition, by controlling the evaporation rate of the sputtering source, it is possible to form a black film by a more decorative and economical method.

Hereinafter, with reference to the accompanying drawings will be described in detail a coating film having a black film production apparatus, a black film manufacturing method and a black film of the present invention.

1 is a cross-sectional view of the black film production apparatus according to an embodiment of the present invention, Figure 2 is a schematic view showing an ion blocking grid constituting the film production apparatus according to an embodiment of the present invention.

Hereinafter, the black film production apparatus of the present invention will be described with reference to FIGS. 1 and 2.

The black film production apparatus of the present invention comprises a substrate 4, a sputtering source 2, and a metal target 3, and between the substrate 4 and the metal target 3, an ion blocking grid ( 6) is installed.

Inside the vacuum chamber 1, which is sealed from outside air and maintained in a vacuum state, a substrate 4 supported by the substrate holder 5 and a metal target deposited on the substrate 4 and formed of a metal film. (3) is provided. The substrate 4 and the substrate holder 5 are made to rotate by the substrate rotating apparatus 9. One side of the substrate 4 is provided with a heater 8 for heating the substrate 4.

The substrate 4 and the heater 8 are connected to the bias power source 11 and the heater power supply 12 to receive power.

One side of the vacuum chamber 1 is provided with a sputtering source 2 for ionizing the metal target 3 and being deposited on the substrate 4. The sputtering source 2 is connected to the sputtering power supply device 10 to receive power.

On the side of the metal target 3 between the metal target 3 and the substrate 4, a shutter 7 is provided to control the transfer of the ionized material onto the substrate 4 by the sputtering source 2. do. On the other hand, one side of the vacuum chamber 1 is provided with a gas inlet 13 for injecting the sputtering gas, the other side is provided with a vacuum gauge 14 for measuring the degree of vacuum in the vacuum chamber (1).

The ion blocking grid 6 provided between the metal target 3 and the substrate 4 serves to reduce the energy of ions ionized by the sputtering source 2 and transferred at high speed toward the substrate 4 side. In addition, the ion blocking grid 6 is connected to the positive voltage application power supply device 15 to receive power.

As shown in FIG. 2, the ion blocking grid 6 is formed in a mesh form. The ion blocking grid 6 is applied at a positive voltage by the positive voltage application power supply 15, and is located in front of the substrate 4 to block and neutralize the positive ions emitted from the metal target 3. Play a role of The ion blocking grid 6 is preferably made of the same or similar material as that of the metal target 3 or made of stainless material.

3 is a cross-sectional view showing a coating layer in which a black film is formed by a method of manufacturing a black film according to an embodiment of the present invention.

Hereinafter, a method of manufacturing a black film of the present invention will be described with reference to FIGS. 1 to 3.

First, the metal target 3 is installed in the sputtering source 2, and the board | substrate 4 is fixed to the board | substrate holder 5. When the metal target 3 and the substrate 4 are disposed and completed, a vacuum is formed by evacuating using a vacuum pump (not shown). When the vacuum degree of the vacuum chamber 1 is 10 ⁻⁶ Torr or less, the substrate 4 is cleaned. In this case, a voltage of several hundred volts is applied to the substrate 4 in an argon (Ar) gas atmosphere of about 10 ⁻² Torr. After the substrate 4 has been cleaned, the vacuum degree is restored to its original state, and the heater 4 is heated by applying a current to the heater power supply 10 so that the substrate 4 is maintained at an appropriate temperature. ) Is heated to the desired temperature. When the substrate 4 is heated to an appropriate temperature, argon (Ar) gas is injected to create a vacuum degree (about 10 ^-3 Torr) necessary for sputtering. Next, after the shutter 7 is closed, a voltage is applied to the sputtering power supply 10 to generate a plasma, and then sputtering is performed for several minutes to remove oxides present in the metal target 3. After the preliminary sputtering is completed, the shutter 7 is opened to deposit a metal film 4a having a desired thickness on the substrate 4. At this time, the ion blocking grid 6 is processed in an open state. After the formation of the metal film 4a, the power of the sputtering source 2 is lowered, the sputtering is carried out while the evaporation rate is lowered, and the ion blocking grid 6 is placed in the closed state. Positive voltage is applied to the ion blocking grid 6. The voltage applied to the ion blocking grid 6 is preferably 50 to 200V. If the voltage across the ion blocking grid 6 is less than 50V, a sufficient effect for lowering the electrical energy of the sputtered ions may not be obtained, such that the black film 4b may not be uniformly formed. On the contrary, when the voltage applied to the ion blocking grid 6 is greater than 200V, the sputtered ions are difficult to pass through the ion blocking grid 6 to the substrate 4 side, which may take a long time to form the black film 4b. .

Lowering the evaporation rate by the sputtering source 2 at the time of forming the black film 4b is lower than the evaporation rate by the sputtering source 2 at the time of forming the metal film 4a, which is effective in forming a good black film 4b. In this manner, the black film 4b having the desired thickness is formed, and then the process is completed.

When sputtering is performed by the black film production method of the present invention, a metal film 4a is formed on the substrate 4, and a metal thin film is formed of a coating layer on which a black film 4b is formed on the metal film 4a. do.

Referring to the principle of forming a black film by the black film production method of the present invention in more detail as follows. A thin film of metal formed by vacuum deposition usually contains micropores. When the deposition is carried out by a conventional sputtering method, ions with energy present in the plasma reach the film, which increases the density of the film, and thus a film of a color similar to the target metal is formed. It is formed on the substrate. However, if the surface contains a lot of fine pores or the film is formed of particles consisting of hundreds or more clusters (Cluster), the surface roughness of the film is changed to become a black color due to light scattering. The porous film made of the cluster looks tanned in appearance and has a bad effect on the properties of the film due to the poor adhesion between the cluster particles. However, if a black film is manufactured by artificially making holes only on the surface of the film to control roughness, it is possible to produce a black film without deterioration of characteristics due to the normal film inside.

The principle of forming a porous film using the ion blocking grid 6 is as follows. In the case of sputtering, the plasma generated by the metal target 3 causes the sputtered atoms or molecules to protrude in an ionic state, or ionize while passing through the plasma region to be accelerated to a state of energy and deposited on the substrate 4. In this case, the mobility of atoms or molecules in the film increases due to the energy of ions, and the film becomes dense and the density increases. However, if a positive voltage is applied to the ion blocking grid 6, the ions are either repelled by the positive voltage or attached to the surface in a state of losing energy, causing the surface to be rough or to make numerous fine holes in the coating layer. Scattering will make it appear black.

At this time, the evaporation rate by the sputtering source 2 in the step of forming the black film 4b is preferably 70% or less of the evaporation rate by the sputtering source 2 in the step of forming the metal film 4a. As such, if the evaporation rate at the time of forming the black film 4b is lower than the evaporation rate at the time of forming the metal film 4a, the energy of sputtered atoms or molecules can be lowered primarily, which makes the black film 4b more effective. Can be formed. In addition, by lowering the evaporation rate at the time of forming the black film 4b, the thickness of the black film 4b can be prevented from becoming unnecessarily thicker than the thickness of the metal film 4b.

Hereinafter, the present invention will be described in more detail with reference to the following Examples.

Inventive Example 1 is a case where a black thin film is manufactured by using a stainless film by the method of the present invention to achieve the object of the present invention.

At this time, the substrate 4 used was a cylindrical quartz having a diameter of 15 mm and was sufficiently subjected to pretreatment using acetone and alcohol before being mounted in the vacuum chamber 1. The pretreated specimen was attached to the substrate holder 5 installed inside the vacuum chamber 1, mounted with a metal target 3 made of stainless, and then evacuated using a vacuum pump (not shown). When the vacuum degree is 10 ^-6 Torr or less, 100SCCM is injected into the argon gas to clean the substrate 4, and the vacuum degree is adjusted to 6 × 10 ^-2 Torr. Then, a voltage of 800 V is applied to the substrate bias power supply 11. The substrate 4 was cleaned for 3 minutes. After the cleaning of the substrate 4 was completed, the temperature of the substrate 4 was maintained at 200 ° C. using the heater 8. Next, 400V and 2A power is applied to the sputtering power supply device 10 with the shutter 7 closed to generate plasma, and then sputtering is performed for several minutes to remove oxides present in the metal target 3. . When preliminary sputtering was completed, a metal thin film was manufactured by opening the shutter 7 and depositing a stainless metal film with a thickness of 1 μm on the substrate. When the ion barrier grid 6 is initially coated with a stainless film, the process is carried out in an open state, and when the thickness reaches 0.7 um, sputtering is performed with the evaporation rate lowered by setting the power of the sputtering power supply 10 to 400 V and 1 A. . At the same time, the ion blocking grid 6 is placed in the closed state, and then the positive voltage applying power 15 device is started to apply a positive voltage to the ion blocking grid 6, thereby providing the metal film 4a and the black film ( 4b) was adjusted to the final thickness of the thin film consisting of 1um. Thus, the black film of the desired thickness was formed and the process was completed.

4 is an enlarged photograph of the surface shape of the black film formed by the black film production method according to an embodiment of the present invention using a scanning microscope. As shown in FIG. 4, it can be seen that circular micropores A are visible in various places on the surface of the film. The color of the film varies depending on the size or number of such holes.

When the metal film is manufactured by the method for producing a black film of the present invention, it can be applied to a field using both corrosion resistance and decoration at an economical process. In particular, it is highly applicable to the field of absorbing light using black, such as solar cells.

1 is a cross-sectional view of the film production apparatus according to an embodiment of the present invention.

Figure 2 is a schematic view showing the ion jersey grid constituting the film production apparatus according to an embodiment of the present invention.

3 is a cross-sectional view showing a film formed with a black film by the film manufacturing method according to an embodiment of the present invention.

Figure 4 is an enlarged view showing the surface shape of the black film formed by the film production method according to an embodiment of the present invention.

♧ description of symbols for the main parts of the drawing

1: vacuum chamber 2: sputtering source 3: metal target

4: substrate 4a: metal film 4b: black film

5 substrate holder 6 ion blocking grid 7 shutter

8 heater 9 substrate rotating apparatus 10 power for sputtering

11 bias power supply 12 heater power supply 13 gas inlet

14: vacuum gauge 15: power supply for positive voltage

Claims (9)

A film production apparatus comprising a substrate for forming a metal thin film, a sputtering source for ionizing the metal thin film to be formed on the substrate, and a metal target ionized by the sputtering source and deposited on the substrate. And an ion blocking grid is provided between the substrate and the metal target to reduce energy of ions ionized by the sputtering source. The method of claim 1, wherein the ion blocking grid Black film production apparatus, characterized in that the mesh (mesh) form. The method according to claim 1, wherein the film production apparatus Black film production apparatus characterized in that it further comprises a power supply for applying a positive voltage connected to one side of the ion blocking grid to apply a positive voltage. The method of claim 1, wherein the ion blocking grid Black film production apparatus, characterized in that made of the same material as the metal target. The ion blocking grid forms a film so that only atoms or molecules with low electrical energy or no energy are deposited on the substrate to form black pores on the surface of the coating layer so as to have a black color due to scattering of light. The black film manufacturing method characterized by the above-mentioned. Allowing a metal target to be deposited on the substrate by a sputtering source to form a metal film; And forming a black film by depositing only atoms or molecules having low electrical energy or no energy by the ion blocking grid on the metal film. The method according to claim 6, The evaporation rate by the sputtering source of the step of forming the black film is 70% or less of the evaporation rate by the sputtering source of the step of forming the metal film. The method according to claim 6, The method for producing a black film, characterized in that the voltage applied to the ion blocking grid is 50 ~ 200V. Substrate, A metal film deposited and formed on the substrate; Coating layer having a black coating, characterized in that the black film formed on the metal film.

Images