KR100228224B1 - The coating method for hard black color layer by using ion beam - Google Patents

Abstract

The present invention relates to a method of coating a hard black thin film by an ion beam to improve decorative properties by coating a glossy black film on a watch case, watch strap, eyeglass frame, ring, etc., and by evaporating a titanium metal in a nitrogen gas atmosphere, A method of forming a titanium compound thin film in which a compound thin film is formed on a substrate by irradiating an inert gas to a substrate at the same time as the deposition process of forming a titanium metal film on the substrate, the method of controlling the energy of the inert gas and the arrival rate of the inert gas ion To coat a hard black thin film, wherein the inert gas is neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), the energy of the inert gas ions is 150 ~ 250V, The arrival rate is 0.22 to 0.35, the oxygen content in the thin film is 10 to 30 at%, and the initial temperature of the substrate is room temperature to form a hard black thin film. It was made.

Description

Coating method of hard black thin film by ion beam

The present invention relates to a method of coating a hard black thin film by an ion beam to improve decorative properties by coating a glossy black thin film on a watch case, watch band, eyeglass frame, ring, etc., in particular, a separate ion beam using simple vacuum deposition. When the inert gas ions are irradiated onto the substrate using a generator, the thin plate coating of various colors of the compound is possible, and the hard black coating is coated by using the ion beam auxiliary deposition.

In general, the decorative surface treatment method of black can be largely divided into anodizing method and coating method for coating a black film. The anodization method is a method of immersing a substrate in an acidic solution, flowing an electric current to accelerate oxygen ions to the substrate to oxidize the substrate, and then using a color change, that is, an interference color, depending on the thickness of the oxide film.

The 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.

As a method of coating a substrate to produce a black color, a physical vapor deposition method (PVD) is used. When the physical vapor deposition method is used, a thin film of a metal, a compound, an inorganic material, or an organic polymer on the surface of a substrate such as metal, glass, ceramic, or plastic is used. Can be easily formed.

Physical vapor deposition includes sputtering and ion plating, in which sputtering generates a plasma discharge by applying a high voltage to the target in an inert gas atmosphere, and inert gas ions present in the discharge collide with the target to remove target atoms. After that, a thin film is formed on the substrate.

On the other hand, ion plating is a method of forming a thin film by ionizing an evaporation material and simultaneously applying a negative voltage to the substrate to accelerate the evaporation material ionized onto the substrate with high energy.

Using these methods to make a separate gas supply device makes a film forming process technology well suited to reacting metal and gas to form a compound film. 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 fashion trends, technologies for making black in various ways have been developed and developed. A method of coating a black thin film by reacting nitrogen, oxygen, etc. is mainly used.

In Japanese Patent Laid-Open No. 62-218550, a black thin film of an oxide main body was coated by ion plating by reacting an appropriate amount of oxygen with a metal. This method, however, has the disadvantage that the film itself is easily broken because the film is made of only oxide, and the adhesion to the substrate is also poor.

In addition, in Japanese Patent Laid-Open No. 61-183458, titanium is used, and nitrogen and carbon are used as the main components, and oxygen is coated with 40% or less of titanium.

However, this method has a drawback that the metal component in the film is less than 40% of titanium, so that the film is easily peeled off and the adhesion of the film is poor.

Therefore, conventionally, as a means to solve these problems, titanium carbide shows a blackish gray color, and the titanium of metal is 50% or more to prevent adhesion and peeling of the film, and to control the content of carbon and oxygen Although a black thin film was formed (Korean Patent No. 088587), this method also had a disadvantage in that the process was complicated and the economical efficiency thereof decreased.

A thin film formation process is performed by irradiating an ion beam onto a substrate while evaporating a material by vacuum deposition, called ion beam assisted deposition. The use of such ion beam auxiliary deposition can improve the corrosion resistance, adhesion and uniformity of the thin film, and at the same time, it has the advantage of forming a compound thin film of various compositions that could not be formed by the conventional method. It is widely used as a means.

In Japanese Patent Application Laid-Open No. JP-1215965, a TiN thin film having directivity is formed by adjusting the energy of the ion beam to 10 to 120V (111) to form a thin film having excellent adhesion and corrosion resistance.

Meanwhile, in JP-63161155, a nitrogen ion beam is used, but a separate variable electrode is provided to control the energy of the ion beam, and an atmosphere gas is separately injected to form a TiN thin film having excellent adhesion of black purple or blue purple.

However, since the two methods use nitrogen ion beams, when the current of the ion beams needs to be controlled, the nitrogen partial pressure of the atmosphere may change, and thus the composition of the thin film may be changed. .

The present invention has been invented to solve the above problems in consideration of the above problems, and by irradiating inert gas ions to a substrate using a separate ion beam generator while using simple vacuum deposition, it is possible to form a compound thin film of various colors. The purpose is to coat a hard black film using ion beam assisted deposition.

A feature of the present invention having such a purpose is to form a compound thin film on a substrate by irradiating the substrate with an inert gas in an ion beam generator at the same time as the deposition process of evaporating the titanium metal in a nitrogen gas atmosphere to form a titanium metal film on the substrate. In the coating method of the compound thin film, the inert gas energy and the inert gas ion arrival rate (the ratio of the number of inert gas ions per atom of the evaporation material: the number of Ar ⁺ ions / the number of Ti atoms) by controlling the coating.

1 is a schematic diagram of an apparatus for hard black film coating of the present invention.

* Explanation of symbols for main parts of the drawings

1: vacuum chamber 2: electron beam evaporator

3: evaporation source shutter 4: ion beam generator

5 substrate 6 substrate holder

7 Substrate Heater 8 Substrate Shutter

9 thickness measuring instrument 10 ion current measuring instrument

11: gas inlet

In the present invention, the use of ion beams allows the formation of a hard black thin film using only nitrogen gas. As a result of repeated studies and experiments, the fact that oxygen is mixed in addition to titanium and nitrogen when the ion beam is used in a certain condition is used. With attention, it succeeded in forming a hard black thin film.

When the compound thin film is formed 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. This number ratio is called the arrival rate, which is defined as follows.

In the present invention, by coating the hard black thin film using a titanium compound by controlling the rate of arrival of the ion and the energy of the ion beam, the present invention is a vapor deposition to form a titanium metal film on the substrate by evaporating the titanium metal in a nitrogen gas atmosphere In the process and irradiating the substrate with an inert gas in the ion beam generator to form a titanium compound thin film on the substrate, the hard black film is coated by controlling the energy of the inert gas and the arrival rate of the inert gas ions.

Hereinafter, the present invention will be described in more detail. The present invention is made in a conventional vacuum deposition apparatus with an ion beam generator.

1 is a schematic diagram of an apparatus for coating a hard black film of the present invention.

In the construction of the thin film coating apparatus, an electron beam evaporator (2) for evaporating titanium is installed at the bottom center of the vacuum chamber (1), and an evaporation source shutter (3) is provided on the upper part thereof, and the substrate (5) is provided on the upper part thereof. A substrate holder 6 for installing the substrate 5, a substrate heater 7 for controlling the temperature of the substrate 5, and a substrate shutter 8 are provided.

The apparatus further includes an ion beam generator 4 for generating an ion beam on one side of the vacuum chamber 1, a thickness meter 9 for measuring thickness and evaporation rate on the inside of the vacuum chamber 1, and measuring the current of the ion beam. A current measuring instrument 10 is provided.

Referring to the thin film coating sequence of the present invention in detail. The present invention firstly charges the titanium material used for the thin film material in the electron beam evaporator (2), mounts the substrate (5), and then exhausts the gas in the vacuum chamber (1) using a vacuum pump (not shown). To maintain the degree of vacuum.

In this manner, when the vacuum degree in the vacuum chamber 1 is 10 ^-6 Torr or less, the ion beam generator 4 is used to clean the substrate 5.

The cleaning of the substrate 5 is a very important step and includes removing not only impurities such as organic matter present in the substrate 5, but also naturally occurring oxide films.

If the oxide film is not sufficiently removed, the adhesion will be affected, so it should be sufficiently cleaned.

At this time, the conditions of the ion beam are not specifically determined, and it is sufficient to carry out for several minutes under the conditions of the emission current of 20-60 mA at the voltage of 300-700V generally.

After the substrate cleaning process, the next step is to coat the thin film in earnest.

In this step, first, inert nitrogen gas is injected through the gas inlet 11 to adjust the pressure in the vacuum chamber 1 to a nitrogen gas atmosphere of 10 ^-4 to 10 ^-5 torr, and then argon gas to the ion beam source. Injection to induce discharge.

When the discharge of the ion beam generator 4 is stabilized, the power of the beam is adjusted to a desired voltage and current, and electric power is applied to the electron beam evaporator 2 to evaporate titanium.

When the evaporation of titanium is stabilized to the desired evaporation rate, the evaporation source shutter 3 and the substrate shutter 8 are simultaneously opened to form a hard black thin film.

The power of the ion beam may be formed by adjusting the energy of the ion beam and the arrival rate of ions as described above to form a hard black thin film.

Hereinafter, the present invention will be described in more detail through Examples and Table 1 below.

Example 1

Inventive Example 1 of Table 1 is a case where the hard black film is coated by the method of the present invention to achieve the object of the present invention. At this time, the substrate 5 used is a stainless steel (SUS 304) steel plate polished like a mirror, and sufficient pretreatment is performed using acetone and alcohol before being charged into the vacuum chamber 1.

The pretreated specimen was attached to the substrate holder 6 provided inside the vacuum chamber 1, and the gas in the vacuum chamber 1 was evacuated using a vacuum pump (not shown).

At this time, when the vacuum degree of the vacuum chamber 1 is 10 ⁻⁶ Torr or less, the ion beam generator 4 is cleaned to clean the substrate 5.

On the other hand, the conditions of the ion beam were clean | cleaned for 2 minutes at 500 V and 40 kV. After the substrate is cleaned, nitrogen gas is injected through the gas inlet 11 to adjust the nitrogen pressure in the vacuum chamber 1 to 6 × 10 ^-5 Torr, and then argon gas is injected into the ion beam generator 4 to discharge the discharge. Induced.

After the discharge of the ion beam generator 4 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 5 was 20 µA / cm 2.

Next, electric power was applied to the electron beam evaporator 2 to evaporate titanium. At this time, the evaporation rate of titanium was adjusted to 1.2 kV / s so that the arrival rate of argon ion per titanium atom was 0.31.

Next, the evaporation source shutter 3 and the substrate shutter 8 simultaneously formed a thin film with a thickness of 2,000 kPa.

The thin films thus formed were visually compared in color, and the components of the thin films and the adhesion of the thin films were compared. The components of the thin film were analyzed by Auger Electron Microscope, and the adhesion of the thin film was compared with a scratch tester.

In the present embodiment, it can be seen that the components of the thin film contain about 20% of oxygen in addition to titanium and nitrogen, and it can be seen that the content of oxygen becomes an important factor in determining black color.

Table 1 shows an embodiment performed by adjusting the ion beam's voltage, evaporation rate, and the ion's arrival rate, in which case the color of the coated thin film and the case of the present invention are excellent in adhesion and can form a bright hard black thin film. It can be seen.

In the case of Comparative Example 4 in the Example is a case of coating by evaporating only titanium in a nitrogen atmosphere without irradiating an ion beam.

When the hard black thin film is coated by the method of the present invention as described above, the coating is possible only with nitrogen gas and titanium, so that the process is simple and the thin film can be coated with excellent economical efficiency. It has the effect of widening the choices.

Claims (1)

A method of forming a titanium compound thin film in which a compound thin film is formed on a substrate by irradiating an inert gas to the substrate at the same time as the deposition process of evaporating the titanium metal in a nitrogen gas atmosphere to form a titanium metal film on the substrate. The hard black thin film is coated by controlling the energy and the rate of inert gas ions, wherein the inert gas is neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and The energy is 150 ~ 250V, the ion arrival rate is 0.22 ~ 0.35, the oxygen content in the thin film is 10 ~ 30at%, the initial temperature of the substrate is room temperature, and the hard black thin film is formed. Coating method of hard black thin film by.

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