KR20030092888A - Coated structure and method for manufacturing the same - Google Patents

Abstract

PURPOSE: A coated member is provided to improve surface roughness and reduce damage to a member during a process for forming roughness by forming roughness on the member made of an inorganic ceramic material while using silicon carbide whose hardness is higher than that of the inorganic ceramic material. CONSTITUTION: Roughness(110) is formed on the member(100) composed of the first inorganic ceramic material. A coating layer(120) is coated on the member including the roughness, composed of an oxide compound. The second inorganic ceramic powder with hardness higher than that of the first inorganic ceramic material is injected to the surface of the member to form the roughness.

Description

Coated structure and method for manufacturing the same

The present invention relates to a coated substrate. More specifically, the present invention relates to a thermally coated substrate that forms a process chamber of an apparatus for performing an etching process, a sputtering process, a chemical vapor deposition process, and the like, in a manufacturing process of a semiconductor device.

Recently, the manufacturing technology of semiconductor devices has been developed to improve the degree of integration, reliability, response speed, etc. in order to meet various needs of consumers. Generally, a semiconductor device is manufactured by forming a predetermined film on a silicon semiconductor substrate used as a semiconductor substrate and forming the film in a pattern having electrical properties.

The pattern is formed by sequential or repeated performance of unit processes such as chemical vapor deposition, sputtering, photolithography, etching, ion implantation, chemical mechanical polishing (CMP), and the like. The chamber of the apparatus performing the unit process as described above is manufactured using an inorganic ceramic bulk such as aluminum anodizing or aluminum oxide for insulation. Recently, in order to provide corrosion resistance to an etching gas used in an etching process, a process chamber is made of a substrate on which aluminum is spray-coated with an inorganic ceramic material such as aluminum oxide. In addition, a high temperature process such as a heat treatment process, a chemical vapor deposition process, etc. occupy a large number of manufacturing processes of the semiconductor device. Therefore, the process chamber should be made of a material having heat resistance. That is, the process chamber should be made of a material that satisfies insulation, heat resistance, corrosion resistance, and the like, and in particular, minimizes defects caused by polymers.

Examples of the substrate coated with the above are disclosed in Korean Unexamined Patent Publication No. 193-624, Japanese Unexamined Patent Publication No. 12-94574, and Japanese Unexamined Patent Publication No. 6-256926. Japanese Patent Laid-Open No. 6-256926 discloses a buffer layer including a metal layer and an intermediate layer. In addition, Japanese Patent Laid-Open No. 12-94574 discloses a buffer layer including a metal oxide bond coating layer and a high density metal bond coating layer.

The thermal spray coating technology is recently attracting attention as a surface modification technology that provides corrosion resistance, abrasion resistance, heat resistance, flame resistance and conductivity by coating a metal, an inorganic ceramic or the like on the surface of various materials such as metal, inorganic ceramic or plastic. The thermal spray coating technology is a method of forming a coating layer by spraying particles formed in a molten or near state by heating the thermal spray material to form a coating layer, and according to the method of heating and spraying the thermal spray material (combustion spraying) , Detonation-gun spraying, high-velocity oxygen fuel spraying, arc spraying, atmospheric plasma spraying, vacuum plasma spraying, and the like.

The most common application range of the thermal spray coating technology is applied to enhance the corrosion resistance, abrasion resistance, heat resistance, and the like of a process chamber used in a semiconductor device manufacturing process. It is applied to coating an oxidizing compound such as yttrium oxide (Y ₂ O ₃ ). At this time, when the manufacturing shape is not easy, the inorganic ceramic powder, such as aluminum oxide, is spray-coated on the surface of the base material which is easy to manufacture the shape, and is manufactured.

In coating an inorganic ceramic material on the surface of the substrate made of the quartz or inorganic ceramic material, the most problematic problem is the bond strength between the thermal spray material and the thermal spray material. In general, the bond strength is determined by a complex action such as mechanical bonding due to irregularities on the surface of the thermal sprayed material, metallurgical bonding, and physical bonding due to intermolecular attraction such as Van der Waals bonding force. However, since the instantaneously melted particles are laminated to the thermal spraying material to form a coating layer, most of the mechanical bonding to the unevenness of the surface of the thermal spraying material is a main bonding principle. In this case, the surface roughness of the thermal spraying material serves as a factor in determining the bond strength.

For example, when yttrium oxide is coated on the surface of a substrate made of aluminum oxide, a step of spraying aluminum oxide powder is performed to form irregularities on the surface of the substrate as a pretreatment step for imparting bond strength. However, imparting artificial unevenness to aluminum oxide, which is a homogeneous material, has a limit in increasing the unevenness, and the substrate is locally damaged by the injection pressure. Such local damage will be present as a residual stress leading to the destruction of the substrate. In fact, when unevenness is applied to the same type of aluminum oxide to thermally coat the yttrium oxide on the surface of the plate-shaped gas injection head made of aluminum oxide used in the semiconductor substrate etching apparatus, a problem arises in that two parts are broken during use. It was. In particular, the plate-shaped gas injection head is used not only for injecting gas but also for maintaining the vacuum in the chamber, and thus the internal damage and residual stress generated in the pretreatment process of imparting irregularities to the aluminum oxide and aluminum oxide. Interactions were analyzed to be the cause of destruction.

The first object of the present invention for solving the above problems is to provide a coated substrate that improves the bonding force between the substrate and the coating layer, and reduces the damage occurring during the coating process.

A second object of the present invention for solving the above problems is to provide a method for producing a coated substrate that improves the bonding force between the substrate and the coating layer, and reduces the damage occurring during the coating process.

1 is a schematic cross-sectional view for explaining a coated substrate according to an embodiment of the present invention.

FIG. 2 is a flowchart for explaining a method of manufacturing the coated substrate shown in FIG. 1.

FIG. 3 is a schematic diagram illustrating a silicon carbide spraying apparatus for performing the method of manufacturing the coated substrate shown in FIG. 2.

4 is a graph showing the surface roughness when irregularities are formed by using silicon carbide on a substrate made of quartz.

FIG. 5 is a graph showing surface roughness when unevenness is formed by using aluminum oxide on a substrate made of quartz. FIG.

6 is a graph showing bond strength of a coating layer of an aluminum oxide material coated on a surface of a substrate on which irregularities are formed by silicon carbide injection.

Explanation of symbols on the main parts of the drawings

100: base material 110: irregularities

120: coating layer

The present invention for achieving the first object, the uneven surface is formed on the surface, a substrate made of a first inorganic ceramic material, and a coating layer made of an oxidized compound is coated on the surface of the substrate formed with the irregularities The irregularities are provided by coating the second inorganic ceramic powder having a higher hardness than the first inorganic ceramic material on the surface thereof.

The present invention for achieving the second object, the step of spraying the second inorganic ceramic powder having a hardness higher than the first inorganic ceramic material on the surface of the substrate made of the first inorganic ceramic material to form irregularities on the surface; It provides a method for producing a coated substrate, comprising the step of thermal spray coating the coating layer consisting of an oxidized compound on the surface of the substrate on which the irregularities are formed.

Hereinafter, the present invention will be described in detail.

The coated substrate according to the present invention includes a substrate having irregularities formed on a surface thereof, a substrate made of a first inorganic ceramic material, a coating layer formed on the surface of the substrate having the irregularities formed thereon, and an oxide compound. The unevenness is formed by spraying on the surface a second inorganic ceramic powder having a higher hardness than the first inorganic ceramic material.

The first inorganic ceramic material may include quartz, aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₃ ), aluminum nitride (AlN), and silicon nitride; Si ₃ N ₄ ) may be used, and silicon carbide (SiC) may be used as the second inorganic ceramic powder. As the oxidizing compound, yttrium oxide (Y ₂ O ₃ ), aluminum oxide, silicon oxide (SiO ₂ ), zirconium oxide, titanium oxide (TiO ₂ ), and the like may be used.

The hardness of the first inorganic ceramic material is about 10 to 15 GPa, and the hardness of the silicon carbide is about 23 to 24 GPa. When forming a concave-convex surface on the surface of the substrate by injecting a material having a hardness higher than the hardness of the substrate as described above, the surface roughness of the substrate is formed to be larger than when injecting a material having a hardness similar to the substrate. For example, when aluminum oxide is sprayed on the surface of the substrate made of quartz, the surface roughness hardly changes according to the spraying pressure.However, when silicon carbide is sprayed on the surface of the substrate made of quartz, the surface is produced by the spraying pressure. Illuminance changes significantly. In addition, when the aluminum oxide is injected, a phenomenon occurs that the substrate is damaged as the injection pressure increases. Therefore, the material sprayed on the surface of the substrate to form the unevenness on the surface of the substrate is preferably a material having a higher hardness than the material forming the substrate.

In the case where the coated substrate is used in a process chamber of a device that performs a semiconductor device manufacturing process, the coating layer made of the oxidized compound may have corrosion resistance, abrasion resistance, and heat resistance with respect to the process gas used in the semiconductor manufacturing process. Strengthen flame resistance, etc. That is, the substrate is prevented from being etched, deteriorated or damaged by the process gas, thereby extending the life of the substrate.

The method of manufacturing a coated substrate of the present invention comprises the steps of: forming an unevenness on the surface by spraying a second inorganic ceramic powder having a higher hardness than the first inorganic ceramic material on the surface of the first inorganic ceramic material And spray coating a coating layer made of an oxidized compound on the surface of the substrate on which the unevenness is formed.

When the second inorganic ceramic powder having a hardness higher than that of the first inorganic ceramic material forming the substrate is injected onto the surface of the substrate, the surface roughness of the substrate increases as the injection pressure of the second inorganic ceramic powder increases. Here, the injection pressure is preferably about 3 to 4 kgf / cm ² . Was the injection pressure is low is less than 3㎏f / ㎝ ² surface roughness forming effect, when it is higher than 4㎏f / ㎝ ² rather reduce the surface roughness, and it is not preferable because there is a fear that the substrate is damaged. Therefore, the unevenness formed on the surface of the substrate improves the mechanical bonding force between the substrate and the coating layer, and prevents damage to the substrate.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a schematic cross-sectional view illustrating a coated substrate according to an embodiment of the present invention, and FIG. 2 is a flowchart illustrating a method of manufacturing the coated substrate shown in FIG. 1.

1 and 2, the unevenness 110 is formed on the surface of the substrate 100 made of the first inorganic ceramic material by spraying the second ceramic powder. The coating layer 120 made of an oxidizing compound is formed on the surface of the substrate 100 on which the unevenness 110 is formed. Here, the unevenness 110 formed on the surface of the substrate 100 is formed to improve the bonding force of the coating layer 120, and the second inorganic ceramic powder sprayed onto the surface of the substrate 100 to form the unevenness 110. The hardness of is higher than the hardness of the first inorganic ceramic material forming the substrate 100.

Looking at the method of manufacturing the coated substrate 100 as described above, first, by spraying a second inorganic ceramic powder having a higher hardness than the first inorganic ceramic material on the surface of the substrate 100 made of the first inorganic ceramic material The unevenness 110 is formed on the surface of the substrate 100. (S100) Next, the coating layer 120 is formed by thermally coating an oxidized compound on the surface of the substrate 100 on which the unevenness 110 is formed.

Here, the hardness of the various inorganic ceramic materials that can be used is shown in Table 1 below.

TABLE 1

Material Quartz Aluminum Oxide (Al ₂ O ₃ ) Zirconium Oxide (ZrO ₃ ) Silicon Nitride (Si ₃ N ₄ ) Aluminum Nitride (AlN) Silicon Carbide (SiC) Longitude (GPa) 11-13 14-15 11-12 13-14 10-11 23-24

In general, the material to which the unevenness is applied should have a higher hardness than the thermal spray material on which the unevenness is formed. Therefore, when spraying the same kind of material, it is difficult to form effective unevenness, and even if unevenness is formed, damage occurs to the thermal spraying material during the uneven formation process.

In order to confirm the above phenomenon, aluminum oxide and silicon carbide were sprayed onto the substrate made of quartz, respectively, to form irregularities on the surface, and the respective coated substrates prepared by thermally coating the coating layer on the uneven surface were analyzed. . Here, as shown in Table 1, the hardness of silicon carbide is higher than that of aluminum oxide.

FIG. 3 is a schematic diagram illustrating a silicon carbide spraying apparatus for performing the method of manufacturing the coated substrate shown in FIG. 2.

<Example>

First, the substrate 100 having a thickness of 3 mm made of quartz is fixed to the stage 200, and silicon carbide powder is sprayed onto the surface of the substrate 100 using the pneumatic injection device 210 to unevenness 110 (FIG. 1). Reference). The separation distance between the pneumatic injection device 210 and the substrate 100 was about 12 cm, and the silicon carbide powder was injected under the condition that the unevenness 110 was applied at 0.5 cm ² / sec. Here, the separation distance may be adjusted between 10 to 15 cm. And the injection pressure of the silicon carbide formed the uneven | corrugated 110, changing in the range of 1-6 kgf / cm <^2> . Subsequently, the coating layer 120 was formed by thermally spraying aluminum oxide powder on the surface of the substrate 100 on which the unevenness 110 was formed. In this case, the thermal spray for forming the coating layer is formed by inert gas such as argon (Ar), helium (He), nitrogen (N ₂ ) to a high-temperature plasma using an electric arc, and melted and sprayed aluminum oxide powder therein Plasma spraying was used.

Comparative Example

Except for using aluminum oxide powder as a material for forming the concavities and convex (110) on the surface of the substrate 100 was prepared a substrate treated with the same conditions as the above embodiment.

<Test Example>

In the above embodiment, the surface roughness of the substrate was measured according to the injection pressure of silicon carbide, and the measurement results are shown in the graph of FIG. 4. In addition, the surface roughness change of the substrate according to the injection pressure of the aluminum oxide in the comparative example was measured, and the measurement results are shown graphically in FIG. 5. In addition, the bonding strength of the substrate made of quartz and the final coated aluminum oxide of the coated substrate prepared in Example was measured according to the injection pressure of silicon carbide, and the measurement results are shown graphically in FIG. 6.

4 is a graph showing surface roughness when irregularities are formed by using silicon carbide on a substrate made of quartz, and FIG. 5 is a graph showing surface roughness when aluminum irregularities are formed by using aluminum oxide on a substrate made of quartz. to be.

Referring to FIG. 4, when roughness was applied to the surface of the substrate made of quartz using silicon carbide powder, the surface roughness was changed to 3.6 to 6.5 μm in a spray pressure of 1 to 6 kgf / cm ² . In contrast, referring to FIG. 5, when the unevenness was applied to the surface of the substrate made of quartz using aluminum oxide powder, the surface roughness was changed to 2.5 to 2.8 μm in a spray pressure of 1 to 6 kgf / cm ² . .

As shown in FIGS. 4 and 5, when the aluminum oxide powder is sprayed to impart irregularities to the surface of the substrate, the surface roughness does not change significantly even when the injection pressure is increased. In the case of imparting irregularities to the surface of the formed substrate, the surface roughness is changed to about 3 to 6 μm, and it can be seen that it is more effective to impart irregularities using the silicon carbide powder.

In addition, when the aluminum oxide is sprayed to impart unevenness to the surface of the substrate made of quartz, a phenomenon in which the substrate is destroyed without increasing the surface roughness is found as the injection pressure is increased.

As a result, it can be seen that it is effective to form silicon bumps by spraying silicon carbide powder whose hardness of the powder is relatively higher than the hardness of the material in pretreatment for imparting irregularities to the surface of the substrate made of the inorganic ceramic material. there was. In addition, when the hardness of the powder to be sprayed to form surface irregularities using a material similar to the hardness of the substrate and the substrate was found to be damaged by the injection pressure.

6 is a graph showing bond strength of a coating layer of an aluminum oxide material coated on a surface of a substrate on which irregularities are formed by silicon carbide injection.

Referring to FIG. 6, silicon carbide is sprayed onto the surface of the quartz substrate to form irregularities, and the bonding strength of the coating layer formed by thermally spraying aluminum oxide on the surface of the irregular substrate is analyzed with respect to the injection pressure of silicon carbide. One result is shown. It can be seen that the bonding strength of the substrate and the coating layer increases to about 3N / mm ² as the injection pressure of the silicon carbide increases, but at the injection pressure of ⁴ kgf / cm ² or more, a similar or large decrease tends to occur.

From the above results, it can be seen that there is a limit in providing irregularities to the surface of the substrate made of an inorganic ceramic material, and the appropriate range corresponds to that the injection pressure of silicon carbide corresponds to about 3 to 4 kgf / cm ² . Able to know. Here, the same may be applied to other inorganic ceramic materials as well as the case where the material of the substrate is quartz.

According to the present invention as described above, in the manufacture of the coated substrate used in the process chamber of the device for performing the manufacturing process of the semiconductor device, the silicon carbide having a hardness higher than the inorganic ceramic material to the substrate made of an inorganic ceramic material By forming the irregularities on the surface of the substrate, the surface roughness can be improved and the damage of the substrate occurring during the formation of the irregularities can be reduced.

Therefore, it is possible to improve the bonding strength of the coating layer formed on the surface of the uneven substrate is formed, the damage reduction of the substrate can reduce the breakdown due to residual stress during use of the coated substrate.

Furthermore, the lifetime of the device used in the manufacturing process of the semiconductor device using the coated substrate can be extended.

Although described above with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.

Claims (6)

A substrate having irregularities formed on a surface thereof, the substrate made of a first inorganic ceramic material; And It is coated on the surface of the substrate on which the irregularities are formed, and comprises a coating layer made of an oxidizing compound, The uneven surface is formed by spraying a second inorganic ceramic powder having a hardness higher than the first inorganic ceramic material on the surface. The coated substrate of claim 1, wherein the first inorganic ceramic material comprises any one selected from the group consisting of quartz, aluminum oxide, zirconium oxide, aluminum nitride, and silicon nitride. The coated substrate of claim 1, wherein the second inorganic ceramic powder comprises silicon carbide. The coated substrate of claim 1, wherein the oxidizing compound comprises at least one selected from the group consisting of yttrium oxide, aluminum oxide, silicon oxide, zirconium oxide, and titanium oxide. Spraying a second inorganic ceramic powder of higher hardness than the first inorganic ceramic material on the surface of the substrate made of the first inorganic ceramic material to form irregularities on the surface; And A method of manufacturing a coated substrate, comprising the step of thermal spray coating the coating layer consisting of an oxidizing compound on the surface of the substrate is formed. The method of claim 5, wherein the spraying pressure of the second inorganic ceramic powder is 3 to 4 kgf / cm 2.