KR100256354B1 - The method for thin coating of composite - Google Patents

Abstract

PURPOSE: A manufacturing method for thin film of metal compound is provided, which can manufacture thin film of metal compound stably and economically by controlling the composition rate of thin film by using reflection degree. The thin film of metal compound is used as a lustered watch case and chain, rim of glasses and rings. CONSTITUTION: The system comprises a vacuum room(1) that has an evaporation source(2), a shutter(3), an ion beam source(4) at the side bottom, a laser(12) at the opposite side of an ion beam source(4), a substrate(5), a substrate heater(7) at the top center, and a light detector(13) set just above the ion beam source(4) for detecting laser. The method is characterized by: (i) irradiate ion beam of the same gas as the atmospheric gas to the substrate(7) for forming thin film of metal compound on the substrate; (ii) evaporate metal by the evaporation source(2) in a gas atmosphere; and (iii) carrying out the control of the composition of thin film of metal by changing the amount of the atmosphere gas, the evaporation amount of metal, and reaching rate of energy and ion of ion gas, thereby changing the composition rate of thin film of metal compound and by computing the co-relation of composition rate and reflection degree.

Description

Manufacturing method of metal compound thin film

The present invention relates to a method for manufacturing a glossy compound thin film, such as a watch case, watch band, eyeglass frame, ring, etc. More specifically, the method for producing a compound thin film that can control the component ratio by measuring the reflectivity during formation of the compound thin film It is about.

Decorative surface treatment methods can be largely divided into anodizing method and a coating method for coating a black film. The anodizing method 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.

This method requires a separate post-treatment process to remove a large amount of pores present in the coating after the color development, there is a problem such as pollution caused by using a wet method.

Physical coating method (PVD) is a method of forming a compound thin film by coating a substrate, and using this PVD method, a metal, a compound, an inorganic material, or an organic polymer may be formed on a substrate surface such as metal, glass, ceramic, or plastic. Thin films can be easily formed. In the PVD method, sputtering and ion plating are performed again. Among them, sputtering generates a plasma discharge by applying a high voltage to the target in an inert gas atmosphere, and then inert gas ions present in the discharge collide with the target to remove the target atom. A method of forming a thin film on a substrate. On the other hand, ion plating is a method of forming a thin film on a substrate with high energy by ionizing the evaporation material and simultaneously applying a negative voltage to the substrate. The use of these methods to make separate gas supply devices makes the film-forming process technology well suited to reacting metals with gases to form compound coatings. Therefore, until now it has been widely used for decoration by coating a gold-like material such as TiN in this way. In recent years, in order to meet such demands as the glossy black surface treatment products are popular in accordance with the various demands of the demands and the high-class trend 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 nitrogen, oxygen, and the like.

Japanese Patent Laid-Open No. 62-218550 proposes a method for producing a black thin film of an oxide main body by ion plating by reacting an appropriate amount of oxygen with a metal.

However, the above method has a disadvantage that since the coating is made of only oxide, the coating itself is easily broken and the adhesion to the substrate is also poor.

In addition, Japanese Patent Application Laid-Open No. 61-183458 proposes a method of using titanium, but using nitrogen and carbon as the main components, in which oxygen is 40% or less than titanium. However, this method has a problem that titanium, which is a metal component in the film, is 40% or less, which causes peeling of the film easily and inferior film adhesion.

The present inventors have conducted research and experiments to solve the problems of the conventional methods described above and proposed the present invention based on the results. The present invention uses a simple vacuum deposition and inerts onto a substrate using a separate ion beam source. Taking into account that gas ions can be used to produce a compound thin film, the compound ratio is controlled by measuring the reflectivity during formation of the compound thin film, thereby manufacturing a compound thin film that can produce a metal compound thin film having a simple, stable and more economical process. The purpose is to provide a method.

1 is a schematic view showing an example of a metal compound thin film manufacturing apparatus for implementing the present invention

2 is a graph showing the change in reflectivity according to the Ti / N component ratio

Explanation of symbols on the main parts of the drawings

1: vacuum chamber 2: electron beam evaporation source

2: evaporation source shutter 4: ion beam source

5: substrate 6: substrate holder

7: Substrate heating device 8: Substrate shutter

9: thickness measuring instrument 10: ion current measuring instrument

11: gas inlet 12: laser

13: light detector

The present invention provides a metal compound thin film manufacturing apparatus including a vacuum chamber having an evaporation source, an ion beam source, and a substrate therein, so that the metal is removed by the evaporation source under a gas atmosphere of the components constituting the compound in the vacuum chamber. In the method of manufacturing a metal compound thin film by evaporating, the ion beam of the active gas for activating the component gas or the ion beam of the same gas as the component gas by the ion beam source to form a metal compound thin film on the substrate,

The metal compound thin film manufacturing apparatus includes a laser irradiator positioned to irradiate a laser toward the substrate and an optical detector for detecting the laser irradiated from the laser irradiator, and then irradiate the laser toward the substrate at a constant angle of incidence. , By changing the amount of atmosphere gas, the amount of evaporation of metals, and the amount of energy and ions of ions, and forming the metal compound thin film while changing the composition ratio of the metal compound thin film. Determining the correlation between the component ratio and the reflectivity of the metal compound thin film; And

Based on the correlation between the component ratio and the reflectivity of the metal compound thin film

The present invention relates to a method for manufacturing a metal compound thin film, comprising controlling a component ratio of a metal compound thin film by varying an amount of an atmosphere gas, an amount of evaporation of a metal, and an energy (a) of an ion gas and a rate of arrival of an ion.

Hereinafter, the present invention will be described in detail with reference to the drawings.

1 shows an example of a metal compound thin film production apparatus for producing a metal compound thin film according to the present invention.

As shown in FIG. 1, an electron beam evaporation source 2 and an evaporation source shutter 3 for evaporating a metal (Ti or the like) to form a thin film on the bottom of the vacuum chamber 1 are provided. In addition, the substrate holder 6 for installing the substrate, the substrate heating device 7 for controlling the temperature of the substrate 5 and the substrate shutter 8 are provided. In addition to this apparatus, an ion beam source 4 for generating an ion beam, a thickness meter 9 for measuring thickness and evaporation rate control, and a current meter 10 for measuring current of the ion beam are attached.

And. A laser irradiator 12 and an optical detector 13 are attached to the reflectance measurement.

Referring to the method for producing a metal compound thin film according to the present invention using the apparatus for producing a metal compound thin film shown in Figure 1 as follows.

Evaporation of the metal by the evaporation source under the gas atmosphere of the components constituting the compound in the vacuum chamber (1), the same as the ion beam or the component gas of the active gas for activating the component gas by the ion beam source (4) In forming the metal compound thin film on the substrate by irradiating the ion beam of the gas to the substrate 5, the amount of the atmosphere gas, the amount of evaporation of the metal, and the ion gas are emitted while irradiating a laser toward the substrate 5 at a constant angle of incidence. The composition ratio of the metal compound thin film is changed by changing the energy and ion arrival rate (quantity), and the change in reflectivity according to the change in the component ratio of the metal compound thin film is measured, and then the correlation between the component ratio and the reflectance of the metal compound thin film is obtained.

The composition ratio of the metal compound thin film is controlled by varying the amount of the atmosphere gas, the amount of evaporation of the metal, the energy and the ion arrival rate (amount) of the ion gas, using the correlation between the component ratio and the reflectivity of the metal compound thin film obtained as described above.

When the compound thin film is manufactured by using ion beam assisted deposition, the composition or color of the compound is changed depending on the ratio of the number of atoms of the evaporated material and the number of irradiated ion beams. The ratio of the number is called the arrival rate and is defined as in the following equation (1).

In the present invention, by using the correlation between the reflectance and the component ratio of the metal compound thin film, the component ratio of the metal compound is controlled by controlling the rate of ion arrival, the energy of the ion beam, the amount of the atmospheric gas, and the amount of evaporation of the metal.

On the other hand, when the compound thin film is manufactured using the ion beam assisted deposition, the phenomenon that the reflectivity is changed as the composition or color of the compound is changed. Reflectivity is defined as in the following formula (2).

(2)

(2)

Reflectivity ≈ C · f (θ) σ (3)

here I _i Is the intensity of the incident laser I _a Is the intensity of the reflected laser, θ Is the angle at which the laser is incident ω Is the frequency of the incident laser. In equation 2, the reflectance is the incident angle θ And the electrical conductivity of the material. For example, in the case of TiN thin film, when the Ti and nitrogen components are changed, the electrical conductivity is changed accordingly. The above formula (3) represents the relationship between the reflectivity and the composition ratio of the compound, and C is a general proportion. Is a constant. In the case of a compound having a good electrical conductivity such as a metal and a material having poor electrical conductivity such as nitrogen or oxygen, the more gaseous components are added, the lower the electrical conductivity and the smaller the reflection. With this in mind, that is, when the composition of the compound changes, the reflectivity changes, and thus the composition of the compound can be controlled according to the reflectance measurement.

Referring to the method for producing a Ti compound thin film according to the present invention using the apparatus for producing a metal compound thin film shown in Figure 1 as follows.

First, the Ti material used for the thin film material is charged into the electron beam evaporation source 2, the substrate 6 is mounted, and then evacuated using a vacuum pump (not shown). When the vacuum degree is 10 ^-6 Torr or less, the ion beam source 4 is used to clean the substrate 5. Cleaning of the substrate 6 is a very important step and includes removing not only impurities such as organic matter present in the substrate 6 but also naturally occurring oxide films. If this oxide film is not removed sufficiently, it will affect the adhesion and should be sufficiently cleaned. At this time, the condition of the ion beam is not particularly determined, and it is sufficient to carry out for several minutes under conditions of a discharge current of 20 to 60 mA at a voltage of 300 to 700 V. After the substrate is cleaned, the next step is to prepare a thin film in earnest. In this step, first, nitrogen gas is injected through the gas inlet 11, and the pressure in the vacuum vessel 1 is adjusted to 10 ^-4 to 10 ^-5 torr of nitrogen gas atmosphere, and then argon gas is injected into the ion beam source. Induce discharge. When the discharge of the ion beam source is stabilized, the power of the beam is adjusted to a desired voltage and current, and then Ti is evaporated by applying power to the electron beam evaporation source 2. When the evaporation of Ti is stabilized to a desired evaporation rate, the evaporation source shutter 3 and the substrate shutter 8 are simultaneously opened to form a compound thin film. At the same time, reflectance is measured when adjusting the composition ratio of the thin film, and this value is fed back to the evaporation source to adjust the evaporation rate to prepare a metal compound thin film.

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

(Example)

A Ti compound thin film was prepared according to the present invention using the apparatus for manufacturing a metal compound thin film of FIG. 1.

That is, when the vacuum degree is 10 ^-6 Torr or less, the ion beam source 4 is used to clean the substrate 5. At this time, the condition of the ion beam was cleaned for 2 minutes at 500V, 40mA. After the substrate was cleaned, nitrogen gas was injected through the gas inlet 11 to adjust the nitrogen pressure in the vacuum chamber 1 to be 6 × 10 ⁻⁵ Torr, and then argon gas was injected into the ion beam source to induce discharge. After the discharge of the ion beam source was stabilized, the power of the ion beam was set at 200 V and 20 mA so that the current density of the ion beam reaching the substrate was 20 μA / cm ² .

Next, electric power was applied to the electron beam evaporation source 2 to evaporate Ti. At this time, the evaporation rate of Ti was adjusted to 1.2 mA / s so that the arrival rate of argon ions per Ti atom was 0.31. Next, while the evaporation source shutter 3 and the substrate shutter 8 were opened at the same time to form a thin film with a thickness of 2,000 mW, the laser was incident on the substrate and the reflectance was measured with a photodetector. The components of the thin film were analyzed by Auger electron microscope and shown in FIG. 2 in comparison with reflectance.

As shown in FIG. 2, it can be seen that the component ratio and the reflectivity of the thin film have a linear relationship.

As described above, the present invention has the effect of providing a method for producing a metal compound thin film which can produce a metal compound thin film more stably and more economically by controlling the component ratio of the metal compound thin film using reflectivity.

Claims (1)

The metal compound is evaporated by the evaporation source under a gas atmosphere of a component constituting the compound in the vacuum chamber by using a metal compound thin film manufacturing apparatus including a vacuum chamber having an evaporation source, an ion beam source, and a substrate therein, In the method of manufacturing a metal compound thin film to form a metal compound thin film on a substrate by irradiating the substrate with an ion beam of an active gas for activating the component gas or an ion beam of the same gas as the component gas by the ion beam source, The metal compound thin film manufacturing apparatus includes a laser irradiator positioned to irradiate a laser toward the substrate and an optical detector for detecting the laser irradiated from the laser irradiator, and then irradiate the laser toward the substrate at a constant angle of incidence. , By changing the amount of atmosphere gas, the amount of evaporation of metal, and the amount of energy of ions and the rate of arrival of ions, to form the metal compound thin film while changing the composition ratio of the metal compound thin film, and the reflectance change according to the change of the component ratio of the metal compound thin film Determining the correlation between the component ratio and the reflectivity of the metal compound thin film; And Based on the correlation between the component ratio and the reflectivity of the metal compound thin film Controlling the component ratio of the metal compound thin film by varying the amount of the atmosphere gas, the amount of evaporation of the metal, the energy of the ion gas and the rate of arrival of the ions (amount).

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