KR100820744B1 - Method of coating metallic material - Google Patents

Abstract

A method of coating tungsten on a metal matrix is provided to increase life of the vacuum chamber and reduce the pollution level by improving plasma resistance, heat crack resistance and corrosion resistance of aluminum subsidiary materials of a vacuum chamber and electrodes used in fabrication processes of semiconductors and TFT-LCD, and semiconductor and TFT-LCD parts fabricated by the coating method are provided. A method of coating tungsten on a metal matrix comprises the steps of: performing an anodizing process of a metal matrix comprising aluminum or aluminum alloy to form an anodizing film; carrying out an electroplating process or an electroless plating process on the anodizing film of the metal matrix to form a tungsten coating film; and a heat treatment step, wherein the tungsten electroplating is performed by adjusting a temperature of the aqueous solution to a temperature of 75 to 85 deg.C and applying electricity to the aqueous solution at a current density of 1 to 10 A/dm^2 after preparing an aqueous solution with a pH of 6 to 7 containing 5 to 50 g/L of Na2OWO3.H2O, 10 to 30 g/Lof Na2CO3, 1 to 15 g/L of NH4OH, 1 to 5 g/L of CH2OHCOONa, and 20 to 50 g/L of Na3C6H5O7, and the tungsten electroless plating is conducted by adjusting a temperature of the aqueous solution to a temperature of 80 to 90 deg.C after preparing an aqueous solution with a pH of 8 to 10 containing 10 to 30 g/L of Na2WO4.H2O, 5 to 15 g/L of NiCl2.6H2O, 10 to 30 g/L of NaH2PO2.H2O, 5 to 15 g/L of CH2OHCOONa, 5 to 10 g/L of Na3C6H5O7, 5 to 10 g/L of CH4N2S, 10 to 25 g/L of Na2CO3, and 5 to 15% of NH4NF2.

Description

Tungsten coating method of metal base material {METHOD OF COATING METALLIC MATERIAL}

The present invention relates to a tungsten coating method of a metal base material, and more particularly, the plasma resistance, cracking resistance and corrosion resistance of an aluminum base material used as a subsidiary material of a vacuum chamber and an electrode used in a semiconductor and TFT-LCD manufacturing process. The present invention relates to a coating method of a metal base material that can improve the life of the vacuum chamber and reduce the degree of contamination.

In semiconductor or TFT-LCD manufacturing, an etching or deposition gas is supplied by using an electrode in a vacuum chamber, and the gas is applied to activate a plasma to etch or perform chemical vapor deposition on a substrate at a high temperature. have.

Due to such a process, an auxiliary material made of aluminum (Al) constituting the vacuum chamber and the electrode is exposed to the corrosive plasma gas at a high temperature. As a result, cracks or corrosion of the aluminum subsidiary materials appear, and in a serious case, particles are generated from the aluminum subsidiary materials, and not only the lifetime of the aluminum subsidiary materials but also flow into the semiconductor or TFT-LCD substrate to be deposited and bring about product defects or stop the process. Happens.

Accordingly, technologies for treating the surface of the aluminum subsidiary materials in various ways have been proposed to have plasma resistance and thermal crack resistance to withstand the harsh atmosphere in the vacuum chamber.

U. S. Patent No. 5,641, 375 discloses a technique in which an aluminum chamber wall is subjected to anodization to reduce plasma corrosion and wall wear to form an anodized film. However, in the case of anodization, it is possible to secure some degree of plasma resistance or thermal crack resistance by controlling the film thickness at high temperature, but another problem occurred because the film damage due to corrosion by plasma gas is serious.

Japanese Patent Application Laid-Open No. 62-103379 proposes a technique for forming a corrosion preventing film such as Al ₂ O ₃ , AlC, TiN, TiC, and AlN on an aluminum material. In the case of the anti-corrosion film, the plasma resistance is improved, but there is a problem that a crack occurs due to the adhesive strength with aluminum.

In addition, a method of coating a chromium oxide (Cr ₂ O ₃ ) film on the surface of an aluminum subsidiary material has been proposed, but the chromium oxide film alone has a limit in improving corrosion resistance.

Korean Patent Publication No. 2000-59295 mentions that tungsten alloy can be coated on a metal surface by electroplating to improve surface hardness and corrosion resistance, and Korean Patent Publication No. 2004-272 describes tungsten and palladium on an aluminum alloy surface. , Nickel and phosphorus are proposed by electroless wet plating method.

As in these patents, the plasma resistance of aluminum subsidiary materials can be secured to some extent by tungsten plating. However, even though tungsten is plated on aluminum subsidiary materials, the process temperature itself is high, and due to such causes such as cracks, peeling and bubbles due to large thermal expansion characteristics between aluminum subsidiary materials and tungsten plating layers, aluminum subsidiary materials in the vacuum chamber by conventional coating techniques are used. In this case, a new problem has occurred that can cause a sudden particle.

Korean Patent Publication No. 2005-22184 says that the life of equipment can be improved by sequentially installing the first nickel plating layer, the second nickel plating layer, the tungsten plating layer, the third nickel plating layer, and the rhodium plating layer on the surface of the metal module which is a semiconductor component. I'm proposing. Due to this technology, the corrosion resistance of the metal module and the peeling between the metal layers can be eliminated. However, since the 5-layer thin film must be formed, the process is complicated and the manufacturing cost increases.

SUMMARY OF THE INVENTION An object of the present invention is to improve the plasma resistance, crack resistance and corrosion resistance of aluminum subsidiary materials of vacuum chambers and electrodes used in semiconductor and TFT-LCD manufacturing processes. It is to provide a tungsten coating method.

Another object of the present invention is to provide a semiconductor and a TFT-LCD component manufactured by the coating method.

The present invention

Forming an anodized film by performing an anodizing process on a metal base material including aluminum or an aluminum alloy;

Forming a tungsten plated film by performing an electrolytic or electroless plating process on the anodized film of the metal base material, and

Heat treatment step

It provides a coating method of a metal base material comprising a.

At this time, after forming the anodized film further, the step of forming a nickel plating film on the anodized film by an electroplating process.

The present invention also provides a vacuum chamber, a chamber accessory or an electrode for manufacturing a semiconductor and a TFT-LCD, in which an aluminum oxide film and a tungsten plating film are sequentially formed on the surface by the above method.

The present invention forms an anodized film and a tungsten plating film on the surface of the metal base material of the aluminum material to improve the plasma resistance, thermal crack resistance and corrosion resistance of the metal.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. It is preferable to understand that the shape and the like of the elements in each drawing are exaggerated in order to emphasize a more clear description. In this case, elements denoted by the same reference numerals in the drawings mean the same elements. In addition, where a layer is described as being "on" another layer, the layer may exist in direct contact with the other layer, or a third layer may be interposed therebetween.

1 is a flow chart showing a coating method of a metal base material according to a first embodiment of the present invention, Figures 2 to 4 is a schematic diagram thereof.

First, a metal base material 11 of aluminum or aluminum alloy is prepared (FIG. 2).

The metal base material 11 is subjected to a pretreatment step consisting of a degreasing step, a water washing step, an etching step, and an electrolytic degreasing step.

In the pretreatment process, the metal base material 11 is put in a degreasing solution at 60 to 80 ° C. to remove grease on the surface so that the film is well formed, followed by a degreasing (degreesing) process, and then the degreasing solution and foreign substances are removed. To carry out the washing process. Then, an etching process is performed to increase the surface area, and electrolytic degreasing is performed. This pretreatment process may be used in addition to or in addition to the known pretreatment processes such as ultrasonic application.

Next, the surface of the metal base material 11 is anodized to form an anodized film 13 having pores on the surface of the metal base material 11 (FIG. 3).

Specifically, the metal base material 11 is a positive electrode, immersed it in an anodizing electrolyte containing an acid, and then applied a voltage to cause anodization. At this time, the metal base material 11 is electrically oxidized from the surface by the applied voltage, and the surface of the metal base material 11 is converted into the aluminum oxide film Al ₂ O ₃ , which is an anodized film 13. Subsequently, when voltage is continuously applied, pores are formed in the anodized film 13 in a direction perpendicular to the metal base material 11.

The anodic oxidation electrolyte used for anodic oxidation includes one acid selected from the group consisting of phosphoric acid, oxalic acid, sulfuric acid, organic acid, and combinations thereof, and is used in a dilute concentration, preferably 15 to 18% by weight of sulfuric acid or oxalic acid. An aqueous solution of 1 to 5% by weight is used.

In this case, anodization is performed at a voltage of 0.1 to 100 V, and is performed at a temperature of 25 to 100 ° C. for 0.5 to 5 hours, and the conditions are in the above range in consideration of various factors such as acid type, nanopore diameter, and alignment. It can be sufficiently modified by those skilled in the art within.

Such anodization is carried out one or more times, if necessary 2 to 4 times to increase the degree of alignment of the pores.

The anodic oxidation film 13 having a plurality of pores thus formed forms an amorphous Al ₂ O ₃ film, not a complete crystalline film. The anodic oxide film 13 grows 50% toward the metal base material 11 and grows 50% to the outside, and thus exhibits ceramic characteristics. However, cracking with the metal base material 11 does not exist. In the case of the complete crystalline coating (that is, Al ₂ O ₃ coating formed on the Al base material by thermal spraying), since it is a perfect ceramic crystal, the thermal expansion property difference is about 4 times that of the Al base material.

After the anodization, a washing process is performed to increase the efficiency of subsequent plating processes. Since this plating process is very sensitive, a thorough washing process should be performed between the processes.

Next, the tungsten plating film 15 is formed by performing an electrolytic or electroless plating process on the anodized film 13 (FIG. 4).

Tungsten has excellent corrosion resistance, plasma resistance, and thermal crack resistance, thereby improving physical properties of the metal base material 11.

In particular, in the present invention, a tungsten plated film 15 is formed on the porous anodized film 11. In this case, as shown in FIG. 3, tungsten is present in the pores of the anodized film 13 and tungsten is formed thereon. It is coated. As a result, the adhesion between the metal base material 11 and the tungsten plated film 15 is improved, thereby maximizing the effect obtained by forming the tungsten plated film 15.

The tungsten plating film 15 is formed through an electrolytic or electroless plating process.

First, the electroplating process is performed by electrolytic tungsten plating solution, Na ₂ OWO ₃ · H ₂ O (5-50 g / l), Na ₂ CO ₃ (10-30 g / l), NH ₄ OH (1-15 g / l), CH ₂ aqueous solution (pH 6-7) consisting of OHCOONa (1-5 g / l) and Na ₃ C ₆ H ₅ O ₇ (20-50 g / l) was prepared, which was then adjusted to a temperature of 75-85 ° C. , By applying electricity at a current density of 1 to 10 A / dm ² .

In addition, the electroless plating process is performed by electroless tungsten plating solution Na ₂ WO ₄ · 2H ₂ O (10 to 30 g / l), NiCl ₂ · 6H ₂ O (5 to 15 g / l), NaH ₂ PO ₂ · H ₂ O (10 30 g / l), CH ₂ OHCOONa (5-15 g / l), Na ₃ C ₆ H ₅ O ₇ (5-10 g / l), CH ₄ N ₂ S (5-10 g / l), Na ₂ CO ₃ (10 to 25 g / l), an aqueous solution (pH 8 to 10) consisting of NH ₄ NF ₂ (5 to 15%) was prepared and then adjusted to a temperature of 80 to 90 ° C.

At this time, the electrolytic and electroless plating process time is performed until the tungsten plating film 15 has a thickness of 5 ~ 50㎛. If the thickness is less than the above range, there is a problem that the plasma characteristics are seriously degraded. If the thickness exceeds the above range, bubbles and interfacial separation problems, which have been a problem even in the existing tungsten coating, occur, so that the thickness is adjusted within the above range.

After the tungsten plating film 15 is formed, a washing process and a drying process are performed.

Next, the metal base material is heat treated to complete the process.

The heat treatment is performed under an oxidizing or reducing atmosphere of 350 to 600 ° C., through the heat treatment, the film density of the tungsten plated film 15 is increased and the adhesion to the anodized film 13 is increased. If the heat treatment temperature is less than the above range, there is a problem that the mechanical properties of the tungsten film is inferior, on the contrary, if the heat treatment temperature exceeds the above range, there is a problem such as damage to the base material and crack of the anodized film, it is performed properly within the above range.

Thus, according to the present invention, the anodic oxide film 13 having a porous structure is formed on the surface of the metal base material 11 by anodization to ensure plasma resistance and thermal crack resistance, and a tungsten plating film 15 is formed thereon. As a result, corrosion resistance is present, and tungsten is present in the pores of the anodic oxide film 13 having a porous structure, thereby eliminating the separation between the anodized film 13 and the tungsten plating film 15.

In the case of coating a metal layer, such as tungsten on the conventional metal base material 11, due to the low adhesion between the metal base material 11 and the metal layer to increase the adhesion, or (Zincate) treatment between the metal base material 11 and the metal layer There is no need to further form an adhesive layer, which simplifies the process, thereby reducing the manufacturing cost.

In another aspect, the present invention after the formation of the anodized film, and performing a step of forming a nickel plating film on the anodized film by an electroplating process.

The nickel plated film is positioned between the anodized film and the tungsten plated film to increase interfacial adhesion therewith and to improve the adhesion between the anodized film and the tungsten plated film.

5 is a flowchart showing a coating method of a metal base material according to a second embodiment of the present invention, and FIGS. 6 and 7 are schematic views.

Specifically, the surface of the metal base material is anodized to form an anodized film.

In this case, the details of the anodic oxidation are as described in the first embodiment.

Next, a nickel plated film 17 is formed by electroplating the metal base material 11 on which the anodized film 13 is formed (see FIG. 7).

The electroplating process is made of NiSO ₄ · 6H ₂ O (100-500 g / l), NiCl ₂ · 6H ₂ O (20-80 g / l), H ₃ BO ₃ (20-50 g / l) as an electrolytic nickel plating solution. After preparing an aqueous solution (pH 8-10), it is carried out by adjusting the temperature to 40-80 ° C and applying electricity at a current density of 1-20 A / dm ² .

In this case, as shown in FIG. 6, nickel plated film 17 has nickel present in the pores of anodized film 13 and nickel is coated thereon. As a result, the adhesion between the metal base material 11 and the nickel plated film 17 is improved, and the tungsten plated film 19 is subsequently formed thereon.

Next, an electrolytic or electroless plating process is performed on the nickel plated film 17 to form a tungsten plated film 19 (see FIG. 7).

The tungsten plating film 19 is performed by an electrolytic or electroless plating process, and the detailed processing process is as described in the first embodiment.

Next, the metal base material is heat treated to complete the process.

At this time, the tungsten plating film 19 is formed before the heat treatment, and then a drying process is performed.

Through the above-described steps, anodization / tungsten plating or anodization / nickel plating / tungsten plating is sequentially formed on the surface of the metal base material.

The surface treatment of the metal base material according to the present invention is applied to the surface treatment of various subsidiary materials such as heaters and shower heads (diffusers) used in vacuum chambers and vacuum chambers of semiconductor and TFT-LCD manufacturing equipment.

The subsidiary material is mainly made of aluminum or aluminum alloy, the surface of the subsidiary material is coated with tungsten has the effect of improving the corrosion resistance, plasma resistance and thermal crack resistance. The method according to the present invention exhibits the greatest improvement in physical properties of tungsten, increases the adhesion between the tungsten plated film and the subsidiary materials, and the process is simple, so that the effect is excellent and the cost is reduced compared to the conventional surface treatment process. have.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the examples.

Example 1

The aluminum substrate was pretreated by degreasing, washing with water, etching and electrolytic degreasing by a known method.

Subsequently, sulfuric acid and oxalic acid were immersed in an acid solution having a concentration of 0.5 M dissolved in a weight ratio of 1: 5, and then a 0.2 A / cm 2 current was supplied at 28 ° C. for 60 minutes to form an anodic oxide film.

After washing the aluminum substrate with DI water, an electroless plating bath (Na ₂ WO ₄ · 2H ₂ O (30 g / l), NiCl ₂ · 6H ₂ O (5 g / l), NaH ₂ PO) was formed to form a tungsten plated film. _{2 · H 2 O (12g /} l), CH 2 OHCOONa (5.5g / l), Na 3 C 6 H 5 O 7 (10g / l), CH 4 N 2 S (5g / l), Na 2 CO 3 (15 g / l), NH ₄ NF ₂ (12%), and then stirred and deposited at pH 10 and 90 ° C. for 30 minutes. By using the electroless plating method, a tungsten plating film having a thickness of 25 μm was formed on the anodized film.

Then washed with water and then dried at room temperature for 1 hour, and then heat treatment was performed at 400 ℃ for 2 hours under oxygen atmosphere.

Example 2

The aluminum substrate was pretreated by degreasing, washing with water, etching and electrolytic degreasing by a known method.

Subsequently, sulfuric acid and oxalic acid were immersed in an acid solution having a concentration of 0.5 M dissolved in a weight ratio of 1: 5, and then a 0.2 A / cm 2 current was supplied at 28 ° C. for 60 minutes to form an anodic oxide film.

After washing the aluminum substrate with DI water cleanly, an electrolytic cell for forming a tungsten plated film (Na ₂ OWO ₃ · H ₂ O (20 g / l), Na ₂ CO ₃ (10 g / l), NH ₄ OH (5 g / l), CH ₂ OHCOONa (1 g / l), and Na ₃ C ₆ H ₅ O ₇ (15 g / l)), and then a current of 5A was supplied for 40 minutes. . By using the electrolytic plating method, a tungsten plated film having a thickness of 25 μm was formed on the anodized film.

Then washed with water and then dried at room temperature for 1 hour, and then heat treatment was performed at 400 ℃ for 2 hours under oxygen atmosphere.

Example 3

The aluminum substrate was pretreated by degreasing, washing with water, etching and electrolytic degreasing by a known method.

Subsequently, sulfuric acid and oxalic acid were immersed in an acid solution having a concentration of 0.5 M dissolved in a weight ratio of 1: 5, and then a 0.2 A / cm 2 current was supplied at 28 ° C. for 60 minutes to form an anodic oxide film.

After washing the aluminum substrate cleanly in an electrolytic cell (NiSO ₄ · 6H ₂ O (400 g / l), NiCl ₂ · 6H ₂ O (20 g / l), H ₃ BO ₃ (30 g / l) to form a nickel plated film After dipping, a current of 20A was supplied for 10 minutes to form a nickel plated film having a thickness of 5 μm on the anodized film.

Subsequently, after washing with DI water, the aluminum substrate was again electrolyzed to form a tungsten plated film (Na ₂ OWO ₃ · H ₂ O (20 g / l), Na ₂ CO ₃ (10 g / l), NH ₄ OH (5 g / l), CH ₂ OHCOONa (1g / l), and Na ₃ C ₆ H ₅ O ₇ (15g / l) and then immersed in a 5A current for 40 minutes to form a tungsten plated film having a thickness of 30 ㎛.

Subsequently, drying was performed at 40 ° C. for 4 hours, and then heat treatment was performed at 400 ° C. for 4 hours under oxygen atmosphere.

Comparative Example 1

The aluminum substrate was pretreated by degreasing, washing with water, etching and electrolytic degreasing by a known method.

After washing the aluminum substrate cleanly in an electrolytic cell (NiSO ₄ · 6H ₂ O (400 g / l), NiCl ₂ · 6H ₂ O (20 g / l), H ₃ BO ₃ (30 g / l) to form a nickel plated film After dipping, a current of 20A was supplied for 10 minutes to form a nickel plated film having a thickness of 5 μm on the anodized film.

Comparative Example 2

The aluminum substrate was pretreated by degreasing, washing with water, etching and electrolytic degreasing by a known method.

Subsequently, sulfuric acid and oxalic acid were immersed in an acid solution having a concentration of 0.5 M dissolved in a weight ratio of 1: 5, and then a 0.2 A / cm 2 current was supplied at 28 ° C. for 60 minutes to form an anodic oxide film.

Experimental Example 1

In order to confirm the formation of a tungsten plated film on the substrate through Example 1, the surface components were analyzed by scanning electron microscopy (SEM) and EDAX, the results obtained are shown in FIG.

FIG. 8A is a spectrum showing the components of the tungsten plated film surface of Example 1, and (b) shows the composition.

Referring to FIGS. 8A and 8B, it can be seen that 30% of tungsten (W) is formed on the anodized film.

FIG. 9 is a front photograph of a tungsten plating film prepared in Example 1, and FIG. 10 is a side photograph showing an anodized / tungsten plating film deposited on a substrate in Example 1. FIG. 9 and 10, it can be seen that an anodizing film is formed on the Al base material, and a tungsten plating film is formed thereon.

Experimental Example 2: Corrosion Resistance Measurement

In order to measure the corrosion resistance of the substrates obtained in Examples 1 to 3 and Comparative Examples 1 and 2, the degree of corrosion over time was measured after immersion in HCl 10% solution (25 ° C.), and the obtained results are shown in FIG. 8. It was.

11 is a graph showing the degree of corrosion with time of the substrate obtained in Examples 1 to 3 and Comparative Examples 1 and 2. Referring to Figure 11, in the case of the substrate of Examples 1 to 3 it can be seen that the degree of corrosion of the coating film is very small.

Experimental Example 3: Measurement of Plasma Resistance

After injection into the PECVD chamber to measure the plasma resistance of the substrates obtained in Examples 1 to 3 and Comparative Examples 1 and 2 and confirmed the surface damage by generating a plasma using NF ₃ gas at 380 ℃ The results are shown in Table 1 below.

division 24 hours 48 hours 96 hours Example 1 Substrate / Anodized / Tungsten Plating No damage No damage No damage Example 2 Substrate / Anodized / Tungsten Plating No damage No damage No damage Example 3 Substrate / Anodized film / Nickel plated film / Tungsten plated film No damage No damage No damage Comparative Example 1 Substrate / Nickel Plating No damage Slight damage Serious damage Comparative Example 2 Substrate / Anodized Slight damage Serious damage Serious damage

Experimental Example 4: Measurement of thermal crack resistance

In order to measure the thermal crack resistance of the substrates obtained in Examples 1 to 3 and Comparative Examples 1 and 2, the surface was measured by a scanning electron microscope after 10 times of cooling to 500 ° C. in water at room temperature.

12 is a scanning electron micrograph of a tungsten plated film obtained in Example 1, FIG. 13 is a scanning electron micrograph of a nickel plated film obtained in Comparative Example 1, and FIG. 14 is a scanning electron micrograph of an anodized film obtained in Comparative Example 2. to be.

12, it can be seen that no crack is generated in the case of the tungsten plated film formed according to the present invention. In comparison, as shown in FIGS. 13 and 14, it was confirmed that cracks occurred when a nickel plated film was simply formed on the substrate or only an anodized film was formed.

The surface treatment of the metal base material according to the present invention is applied to the surface treatment of various subsidiary materials such as heaters and shower heads (diffusers) used in chambers and chambers of semiconductor and TFT-LCD manufacturing equipment.

1 is a flow chart showing a coating method of a metal base material according to a first embodiment of the present invention, Figures 2 to 4 is a schematic diagram thereof.

5 is a flowchart showing a coating method of a metal base material according to a second embodiment of the present invention, and FIGS. 6 to 7 are schematic views thereof.

FIG. 8A is a spectrum showing the components of the tungsten plated film surface of Example 1, and (b) shows the composition.

9 is a front photograph of a tungsten plating film prepared in Example 1.

FIG. 10 is a side photograph showing an anodized / tungsten plated film deposited on a substrate in Example 1. FIG.

11 is a graph showing the degree of corrosion with time of the substrate obtained in Examples 1 to 3 and Comparative Examples 1 and 2.

12 is a scanning electron micrograph of a tungsten plating film obtained in Example 1. FIG.

13 is a scanning electron micrograph of a nickel plated film obtained in Comparative Example 1. FIG.

14 is a scanning electron micrograph of the anodized film obtained in Comparative Example 2. FIG.

Claims (9)

Forming an anodized film by performing an anodizing process on a metal base material including aluminum or an aluminum alloy; Forming a tungsten plated film by performing an electrolytic or electroless plating process on the anodized film of the metal base material, and A heat treatment step, In this case, the tungsten electroplating may be performed using Na ₂ OWO ₃ H ₂ O (5 to 50 g / l), Na ₂ CO ₃ (10 to 30 g / l), NH ₄ OH (1 to 15 g / l), and CH ₂ OHCOONa (1 To 5 g / l), and an aqueous solution (pH _{6 to 7} ) consisting of Na ₃ C ₆ H ₅ O ₇ (20 to ₅₀ g / l), and then adjusted to a temperature of 75 to 85 ° C., 1 to 10 By applying electricity at a current density of A / dm ² , The tungsten electroless plating includes Na ₂ WO ₄ H ₂ O (10 to 30 g / l), NiCl ₂ · 6H ₂ O (5 to 15 g / l), NaH ₂ PO ₂ H ₂ O (10 to 30 g / l). ), CH ₂ OHCOONa (5-15 g / l), Na ₃ C ₆ H ₅ O ₇ (5-10 g / l), CH ₄ N ₂ S (5-10 g / l), Na ₂ CO ₃ (10-25 g / l), after preparing an aqueous solution (pH 8-10) consisting of NH ₄ NF ₂ (5-15%), it is carried out by adjusting to a temperature of 80 ~ 90 ℃. The method of claim 1, In the anodic oxidation process, a voltage of 0.1 to 100 V is applied in an anodic oxidation electrolyte including one acid selected from the group consisting of phosphoric acid, oxalic acid, sulfuric acid, and combinations thereof, and 0.5 to 0.5 at a temperature of 25 to 100 ° C. Method of coating a metal base material to be carried out for 5 hours. delete delete The method of claim 1, The heat treatment is a coating method of a metal base material to be carried out at 350 ~ 600 ℃. The method of claim 1, And after forming the anodized film, forming a nickel plating film on the anodized film by an electroplating process. The method of claim 6, The nickel electroplating is composed of NiSO ₄ · 6H ₂ O (100 to 500 g / l), NiCl ₂ · 6H ₂ O (20 to 80 g / l), and H ₃ BO ₃ (20 to 50 g / l) as an electrolytic nickel plating solution. After preparing an aqueous solution (pH 8-10), it is controlled to a temperature of 40 ~ 80 ℃, it is carried out by applying electricity at a current density of ^{1 to} 10A / dm ² . A vacuum chamber accessory for manufacturing a semiconductor and a TFT-LCD formed by the manufacturing method of claim 1, wherein an aluminum oxide film and a tungsten plating film are sequentially formed on a surface thereof. The vacuum chamber accessory for semiconductor and TFT-LCD manufacturing according to claim 8, wherein a nickel plating film is further formed between the aluminum oxide film and the tungsten plating film.

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