KR100237166B1 - The method for tin coating using ion beam - Google Patents

Abstract

The present invention relates to a method of coating a TiN thin film using an electron beam evaporator and an ion beam on a base material in order to improve the decorative properties of large decorative products and to improve the life of materials such as tools, machinery, and mold products. In a vapor deposition process of forming a titanium metal film on a substrate by evaporation, a conventional method of forming a TiN thin film on a substrate by irradiating the substrate with an inert gas in an ion beam generator, wherein the energy of the inert gas and the arrival rate of the inert gas ions When the energy per atom is called E _c , the E _c is adjusted to be equal to or more than a predetermined value to form a TiN thin film, and the inert gas is neon (Ne), argon (Ar), krypton (Kr), xenon (Xe). ), The value of E _c is 550 V or more, and the initial temperature of the substrate is at room temperature.

Description

Coating method of TiN thin film using ion beam

The present invention relates to a method of coating a TiN thin film using an electron beam evaporator and an ion beam on a base material for improving the decorativeness of a large decorative product and improving the life of materials such as tools, machinery and mold products. In the TiN thin film coating method of forming a TiN thin film on a substrate comprising the step of evaporating the titanium metal film on the substrate by evaporation to irradiate the substrate with inert gas ions generated from the ion beam generator. When the energy per atom multiplied by the arrival rate of the energy and the inert gas ion is called Ec, the present invention relates to a method for producing a TiN thin film using an ion beam which coats the TiN thin film by adjusting the Ec to be equal to or more than a predetermined value.

In general, TiN thin films are not only used for hard coating for various mechanical applications such as high strength, high corrosion resistance, and high melting point, but because they have gold color, they are widely used for surface hardening of tools and improving decoration of various parts.

In addition, the TiN thin film has an electrical conductivity similar to that of metals and has a dense structure, and thus is widely used in the manufacture of semiconductors as diffusion barriers.

Until now, physical vapor deposition (PVD) and chemical vapor deposition (CVD) have been widely used for forming TiN thin films.

The physical vapor deposition methods include sputtering and ion plating, in which sputtering generates a plasma discharge by applying a high voltage to the titanium target in an inert gas atmosphere, and inert gas ions present in the discharge collide with the titanium target to cause titanium discharge. A method of depositing a TiN thin film on a substrate by removing atoms and reacting with nitrogen gas contained in a container.

Ion plating is a method of forming a TiN thin film on a substrate by ionizing an evaporation material in a nitrogen atmosphere and simultaneously applying a negative voltage to the substrate to accelerate the energy.

Therefore, until now, such a physical vapor deposition method is coated with a gold-like material such as TiN and widely used in decorative and wear-resistant thin films (Japanese Patent Publication No. 62-2880 and Japanese Patent Publication No. 63-62865).

However, there are some disadvantages in the physical vapor deposition method, one of which is that the process control is difficult because the control range that can control the ionization rate is small, and the other is that the adhesion and the density of the membrane and the corrosion resistance is not sufficient.

Another point of physical vapor deposition is that the substrate temperature is high. In other words, in order to form a thin film having good adhesion and well-defined stoichiometry, the substrate should be generally heated to 200 ° C. or higher. In this case, a problem occurs in selecting a substrate material.

That is, a substrate sensitive to temperature such as plastic or polymer cannot form TiN thin film by physical vapor deposition.

Recently, Japanese Patent Laid-Open No. 2-294470 discloses that a thin film of high quality is obtained by attaching a separate ion beam generator to an ion plating apparatus and irradiating nitrogen ion beam as a means to solve these disadvantages. Since a separate ion beam generator is used while the ion plating method is basically used, the device is complicated and there is a high possibility of occurrence of a phenomenon such as an abnormal discharge due to the presence of an ion beam in the plasma.

On the other hand, chemical vapor deposition is a method of forming a TiN thin film on a substrate by reacting a gas containing titanium metal and nitrogen gas in a high temperature container. This method also has a disadvantage in that the substrate must be heated to a high temperature, such as tool steel. Even if the material does not deform even if it is not so widely used.

A thin film forming process is performed by irradiating an ion beam to a substrate while evaporating a material by vacuum deposition. The ion beam auxiliary deposition can be used to improve the corrosion resistance, adhesion and uniformity of a thin film. Background Art Recently, it has been widely used as a thin film forming means because there is an advantage that a compound thin film having various compositions that could not be manufactured by the conventional method can be manufactured.

In Japanese Unexamined Patent Publication No. Hei 1-215965 and Japanese Unexamined Patent Publication No. 63-16155, a TiN thin film is formed using an ion beam of nitrogen. However, since the two patents use ion beams of nitrogen, when the current of the ion beams needs to be adjusted, the nitrogen partial pressure of the atmosphere may be changed, and thus the composition of the thin film may be changed.

For this reason, Japanese Patent Laid-Open No. 63-16155 solves the problem by installing a separate variable electrode in front of the ion beam generator in order to change the conditions of the ion beam.

The present invention has been invented to solve all the problems of the prior art in view of the above situation, and keeps the atmosphere gas at all times and manufactures a TiN thin film using an inert gas ion beam generator, using ion beam auxiliary deposition. In the case of forming a compound thin film such as TiN, the composition and the color of the compound are changed according to the number of atoms of the evaporated material and the number of irradiated ion beams, and the ratio of the number is called the arrival rate. define.

In the present invention, the method of coating a TiN thin film using an ion beam for controlling the color of the TiN thin film by adjusting the energy per atomic multiplied by the arrival rate of the ion and the energy of the irradiated ion is closely related to the characteristics and color of the thin film. The purpose is to provide.

1 is a schematic diagram of a coating apparatus for a TiN thin film using an ion beam for explaining 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

TiN thin film coating method using the present invention ion beam for achieving the above object is a vapor deposition process of forming a titanium metal plate on a substrate by evaporating the titanium metal in a nitrogen gas atmosphere, and at the same time irradiating an inert gas to the substrate in the ion beam generator In the method for producing a TiN thin film by forming a TiN thin film on a substrate, any one of neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe) is used as the inert gas. The energy per atom (Ec) multiplied by the arrival rate of the energy and the inert gas ion is 550 eV or more, and the TiN thin film is formed by using the initial temperature of the substrate at room temperature.

In the present invention, the energy per atom multiplied by the energy of the inert gas and the arrival rate of the inert gas ion without heating the substrate by irradiating the substrate with argon ions generated by the ion beam generator using simple vacuum deposition, Ec, In other words, when "Ec (V) = ion arrival rate x ion beam energy", the TiN thin film is formed by setting the energy per atom (Ec) of 500 eV or more.

Hereinafter, a coating method of the TiN thin film using the ion beam of the present invention will be described in detail with reference to the accompanying drawings.

1 is a schematic view of a coating apparatus for a TiN thin film using an ion beam employed in the method of the present invention. The configuration of the apparatus shows that an electron beam evaporator 2 and an evaporation source shutter 3 for evaporating titanium on the bottom of the vacuum chamber 1 are provided. In the upper portion, the substrate 5, the substrate holder 6 for installing the substrate 5, the substrate heater 7 and the substrate shutter 8 for controlling the temperature of the substrate 5 are provided.

In addition, the apparatus is equipped with an ion beam generator 4 for generating an ion beam, a thickness meter 9 for thickness measurement and evaporation rate control, and an ion current meter 10 for measuring current of the ion beam.

Hereinafter, the thin film formation process of the present invention will be described in detail. First, the titanium material used for the thin film material is charged into the electron beam evaporator 2, the substrate 5 is mounted, and the gas in the vacuum chamber 1 is evacuated using a vacuum pump (not shown).

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 process 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 this oxide film is not removed sufficiently, it will affect the adhesion and should be sufficiently cleaned. At this time, the conditions of the ion beam are 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 eV.

After the substrate is cleaned, the next step is to form a thin film in earnest.

In this step, first, nitrogen gas is injected through the gas inlet 11, and the pressure in the vacuum chamber 1 is adjusted to a vacuum atmosphere of 10 ⁻⁴ to 10 ⁻⁵ torr, and then argon gas is injected into the ion beam generator. Induce discharge.

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

In this manner, when the evaporation of titanium is stabilized at a desired evaporation rate, the evaporation source shutter 3 and the substrate shutter 8 are simultaneously opened to form a TiN thin film.

Power of the ion beam is set by adjusting the energy per atom described above, so that the value is more than a constant voltage to form a golden TiN thin film.

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

EXAMPLE

Inventive Example 1 in Table 1 is a case where a golden TiN thin film was formed by the method of the present invention to achieve the object of the present invention. At this time, the substrate 5 used was a stainless steel (SU S 304) steel plate polished like a mirror and subjected to sufficient pretreatment 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).

When the degree of vacuum became 10 ⁻⁶ Torr or less, the substrate 5 was cleaned by using the ion beam generator 4.

At this time, the conditions of the ion beam were clean | cleaned for 2 minutes by 500 eV and 40 kV. 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 6 × 10 ⁻⁵ Torr, and then argon gas was injected into the ion beam generator to induce discharge.

After the discharge of the ion beam generator was stabilized, the power of the ion beam was set to 600 eV and 40 mA, so that the current density of the ion beam reaching the substrate was 120 mA / 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 mA / s so that the arrival rate of argon ions per titanium atom was 1.5. This results in 900eV of energy per atom.

After the evaporation rate became stable, the evaporation source shutter 3 and the substrate shutter 8 were simultaneously opened to form a TiN thin film with a thickness of 2,000 kPa. The formed TiN thin film was visually compared the color and the brightness of the color.

Table 1 shows an example of changing the energy per atom by controlling the voltage, evaporation rate, and ion arrival rate of the ion beam, and comparing the color and the brightness of the formed thin film at this time. On the other hand, in the case of Comparative Example 5 in the example was produced by evaporating only Ti in a nitrogen atmosphere without irradiating an ion beam. It can be seen that in all cases of the present invention, a bright golden TiN thin film can be produced.

As described above, when the TiN thin film is manufactured by the method of the present invention, it is possible to predict the characteristics and color of the thin film, thereby reducing the defect rate of the product, and to obtain the maximum effect by the simple process compared to the conventional method. In addition, it is possible to manufacture a thin film at a low temperature, thereby increasing the selection range of the substrate.

Claims (1)

In the deposition process of evaporating a titanium metal in a nitrogen gas atmosphere to form a titanium metal film on a substrate, and at the same time, a method of manufacturing a TiN thin film in which an inert gas is irradiated onto a substrate to form a TiN thin film on the substrate. Neon (Ne), argon (Ar), krypton (Kr) or xenon (Xe) is used as the inert gas, and the energy per atom (Ec) multiplied by the energy of the inert gas and the arrival rate of the inert gas ion is 5500 eV or more. A method of coating a TiN thin film using an ion beam, characterized in that to form a TiN thin film at an initial temperature of the substrate at room temperature.

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