KR20130044813A - Plasma resistant member and method of manufacturing the same - Google Patents

Abstract

PURPOSE: A plasma-resistant member capable of being easily applied to a manufacturing device of integrated circuit devices and a manufacturing method thereof are provided to enhance electric properties and plasma-resistance by including yttrium oxide and nanocarbon with a grain size of 1-200 nanometers. CONSTITUTION: A plasma-resistant member includes yttrium oxide and nanocarbon with a grain size of 1-200 nanometers and is comprised of pellets. The yttrium oxide is 90.0-99.9 wt% and the nanocarbon is 0.1-10.0 wt%. The pellets have 10-1000 Ωcm of resistivity and a relative density of 85-100%. The pellet is obtained by sintering a mixture of the yttrium and nanocarbon at 1,350-1,750 deg. Celsius. A manufacturing method of the plasma-resistant member comprises the following steps: forming a liquid mixture by mixing the yttrium powder and nanocarbon powder with a grain size of 1-200 nanometers with a solvent; forming the liquid mixture into a spherical powder mixture by using a spray dryer; and forming the spherical powder mixture into pellets by using a hot-press. [Reference numerals] (AA) Start; (BB) End; (S11) Form yttrium oxide powder and nanocarbon powder into a liquid mixture; (S13) Form the liquid mixture into a spherical powder mixture; (S15) Form the spherical powder mixture into a sintering agent

Description

Plasma resistant member and method for manufacturing the same

The present invention relates to a plasma member and a method for producing the same, and more particularly, to a plasma member and a method for producing the same containing yttrium oxide.

In the manufacture of integrated circuit devices such as semiconductor devices and display devices, etching processes are performed in a high density plasma environment. Thus, the etching process of the high density plasma environment is performed using an etching apparatus having a plasma member.

Examples of the above-mentioned plasma resistant member include Korean Patent Publication No. 2008-25012 (hereinafter referred to as 'quotation document 1'), Japanese Patent No. 4467453 (hereinafter referred to as 'quotation document 2'), and Japanese Patent Registration 2567491 (Hereinafter referred to as "quotation document 3"), and the like. In particular, Cited Document 1 and Cited Document 2 disclose a plasma resistant member using alumina containing carbon as a base material, and Cited Reference 3 discloses a plasma resistant member using aluminum nitride containing carbon as a base material. Doing. Here, in the cited references 1 to 3, a ceramic material having excellent mechanical strength such as alumina, aluminum nitride, or the like is applied as the plasma member.

However, in recent years, in the manufacture of integrated circuit devices having a line width of about 20 nm, since the etching process is performed in a higher density plasma environment, the development of a plasma member superior to the aforementioned alumina, aluminum nitride, and the like is required.

SUMMARY OF THE INVENTION An object of the present invention is to provide a plasma member and a method of manufacturing the same, which have electrical properties similar to silicon, silicon carbide, and the like, and which have better plasma resistance than alumina, aluminum nitride, and the like.

Plasma resistant member according to an embodiment of the present invention comprises yttrium oxide and nano-carbon consisting of a particle size of 1 to 200nm, made of a sintered body.

In the plasma member according to an embodiment of the present invention mentioned, the yttrium oxide may occupy 90.0 to 99.9 weight percent, and the nano carbon may occupy 0.1 to 10.0 weight percent.

In the plasma member according to an embodiment of the present invention mentioned above, the sintered body may have a specific resistance of 10 to 1,000Ωcm.

In the plasma member according to an embodiment of the present invention mentioned above, the sintered body may have a relative density of 85 to 100%.

In the plasma member according to one embodiment of the present invention mentioned above, the sintered body may be obtained by sintering a mixture of the yttrium oxide and the nano carbon at a temperature of 1,350 to 1,750 ° C.

Method for producing a plasma member according to an embodiment of the present invention comprises the steps of mixing the yttrium oxide powder and the nano-carbon powder consisting of a particle size of 1 to 200nm with a solvent to form a liquid mixture, using a spray dryer Forming a liquid mixture into a spherical powder mixture, and forming the spherical powder mixture into a sintered body using a hot-press.

In the method for manufacturing a plasma member according to an embodiment of the present invention mentioned above, the yttrium oxide powder may be 90.0 to 99.9 weight%, and the nano carbon powder may be mixed to account for 0.1 to 10.0 weight%.

In the method of manufacturing a plasma member according to an embodiment of the present invention mentioned above, the forming of the liquid mixture may be performed by a ball-mill process using ethanol as the solvent.

In the method of manufacturing a plasma member according to an embodiment of the present invention mentioned above, the step of forming the sintered body may use a hot-press at a temperature of 1,350 to 1,750 ℃.

According to the above-mentioned plasma member of the present invention and a method for producing the same, it includes yttrium oxide and nano carbon having a particle size of 1 to 200 nm. Here, yttrium oxide is known to have the best plasma resistance, and nano carbon may impart conductivity to yttrium oxide. In other words, nano carbon is mixed to give yttrium oxide, the material having the highest plasma resistance, to give electrical properties similar to silicon and silicon carbide. Thus, as mentioned above, the plasma member of the present invention may not only have electrical properties similar to silicon, silicon carbide, etc., but also excellent plasma resistance.

Therefore, the plasma member of the present invention can be more easily applied to an apparatus for manufacturing an integrated circuit device which performs an etching process or the like on a silicon substrate in a high density plasma environment. That is, the plasma member of the present invention can be expected to improve the yield according to the manufacture of the integrated circuit device by enabling a stable process even if the process conditions are changed to a more narrow line width of the integrated circuit device, the harsher high-density plasma environment.

In addition, since the plasma member of the present invention has not only excellent plasma resistance but also electrical properties similar to silicon, silicon carbide, etc. as mentioned above, it is also used as a substitute for silicon, silicon carbide, etc., which is widely applied in the manufacturing apparatus of integrated circuit devices. Can be used.

1 is a process chart for explaining a method for manufacturing a plasma member according to an embodiment of the present invention.
FIG. 2 is a photograph observing the plasma member obtained by performing the method of manufacturing the plasma resistant device of FIG. 1 with an electron microscope. FIG.
3 is a graph showing a change in relative density according to the content of nano carbon in the plasma member of the present invention.
4 is a graph showing a change in specific resistance according to the content of nano carbon in the plasma member of the present invention.
5 is a graph showing a change in specific resistance according to the content of carbon having a particle size of the micro unit.
6 is a graph for explaining the corrosion characteristics evaluation of the plasma member of the present invention.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. In describing the drawings, similar reference numerals are used for similar components. In the accompanying drawings, the dimensions of the structures are enlarged to illustrate the invention, and are actually shown in a smaller scale than the actual dimensions in order to explain the schematic configuration. The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a part or a combination thereof is described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

On the other hand, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

Plasma resistance  absence

Plasma resistant member according to an embodiment of the present invention comprises yttrium oxide and nano carbon, it is made of a sintered body. Here, the above-mentioned plasma member of the present invention is a sintered body which uses a base material such as alumina, aluminum nitride, etc. as conventionally, and does not coat yttrium oxide and nano carbon on its surface, but includes yttrium oxide and nano carbon itself. Is done. In addition, the plasma member made of the sintered body of yttrium oxide and nano carbon can be applied to an apparatus for manufacturing an integrated circuit device exposed to a high density plasma environment, for example, a focus ring and an insert ring. ring, collar ring, shield ring, hot edge ring, protection ring, silicon electrode and the like.

In addition, when the particle size of the nano-carbon is less than about 1 nm, it is not preferable because the material development itself is not easy and the handling thereof is not easy, and when it exceeds 200 nm, electrical properties similar to silicon, silicon carbide, etc. will be described. It is not preferable because it does not exhibit properties. That is, when it exceeds about 200nm it is not preferable because it shows the electrical properties of the micro-carbon rather than the electrical properties of the nano-carbon as described later. Therefore, the particle size of the nano-carbons mentioned is preferably about 1 to 200nm.

Here, it is obvious that it is not easy to measure the particle size in the case of nanoparticles. Accordingly, in the present invention, the shape of the nano carbon is assumed to be a cube, and the particle size of the nano carbon is represented by Equation 1 below based on the specific surface area and the density.

[Equation 1]

Particle size = 6 / (specific surface area density)

Also, in the plasma member, when yttrium oxide occupies less than about 90.0% by weight, and nanocarbon occupies more than about 10.0% by weight, it is not preferable because it is not easy to realize the densification of the plasma member due to the decrease in relative density. When yttrium oxide is more than about 99.9% by weight and nanocarbon is less than about 0.1% by weight, it is not preferable because it does not exhibit electrical properties similar to silicon, silicon carbide, and the like as described below. Thus, in the case of the aforementioned flame resistant member, it is preferable that yttrium oxide accounts for about 90.0 to 99.9% by weight and nano carbon to about 0.1 to 10.0% by weight.

In addition, since the sintered compact for application to the aforementioned plasma member must exhibit electrical properties similar to silicon, silicon carbide, etc., it is preferable to have a specific resistance of about 10 to 1,000 Ωcm.

In addition, when the sintered compact for application to the plasma member mentioned above has a relative density of less than about 85%, the plasma resistance of yttrium oxide is remarkably inferior, which is not preferable. Thus, the sintered body mentioned above preferably has a relative density of about 85 to 100%. In addition, the sintered body obtained by sintering at a temperature of less than about 1,350 ℃ for application to the above-mentioned plasma member is not preferable because it has a relative density of less than 85%, it is not preferable to sintering at a temperature above about 1,750 ℃ The sintered compact obtained by the present invention is not preferable because it does not exhibit electrical properties similar to silicon, silicon carbide and the like. Accordingly, the sintered body for application to the plasma member of the present invention is preferably obtained by sintering at a temperature of about 1,350 to 1,750 ℃.

As mentioned, the plasma member of the present invention can secure excellent plasma resistance because it contains yttrium oxide, and can have electrical properties similar to silicon, silicon carbide, etc., because it contains nano carbon.

Plasma resistance  Manufacturing method of the member

Hereinafter, a manufacturing method of the plasma member will be described with reference to FIG. 1.

1 is a process chart for explaining a method for manufacturing a plasma member according to an embodiment of the present invention.

Referring to Figure 1, yttrium oxide powder and nano carbon powder is prepared. At this time, the nano carbon powder has a particle size of about 1 to 200nm as mentioned. Then, the yttrium oxide powder and the nano carbon powder are mixed to form a liquid mixture. (S11) As described above, the yttrium oxide powder and the nano carbon powder comprise about 90.0 to 99.9 wt% of the yttrium oxide powder and the nano carbon powder. Mix so that it accounts for about 0.1 to 10.0% by weight.

In particular, the aforementioned liquid mixture can be formed by mixing yttrium oxide powder and nano carbon powder with a solvent such as ethanol, and is formed by using a ball mill having a ball made of aluminum oxide. can do.

Subsequently, the liquid mixture obtained as mentioned is formed into a spherical powder mixture. (S13) At this time, the spherical powder mixture can be formed by using a spray dryer.

And the spherical powder mixture obtained as mentioned is formed into a sintered body. (S15) Here, the sintered body can be formed by performing a sintering process using a hot press, wherein the temperature for sintering is mentioned It is preferably about 1,350 to 1,750 ° C.

Thus, by performing steps S11 to S15, it is possible to obtain a plasma member comprising yttrium oxide and nano-carbon having a particle size of about 1 to 200 nm and comprising a sintered body.

Plasma resistance  Evaluation of the microstructural properties of the members

FIG. 2 is a photograph observing the plasma member obtained by performing the method of manufacturing the plasma resistant device of FIG. 1 with an electron microscope. FIG.

First, in order to observe by electron microscopy, in Fig. 1 mentioned by limiting the sintering temperature of about 99.0% by weight of yttrium oxide, about 1.0% by weight and nano-carbon having a particle size of about 10nm and sintering temperature of about 1,600 ℃ The sintered compact for application to a plasma member was obtained by performing the same process as the manufacturing method of plasma.

Referring to FIG. 2, it can be seen that the nano carbon 21 is uniformly distributed in the matrix made of yttrium oxide. In particular, it can be seen that most of the nano-carbon 21 has a length of about 1 μm and shows a very thin plate shape.

As such, it can be seen that the plasma member of the present invention is uniformly distributed in the substrate made of yttrium oxide even if the nano carbon accounts for only about 1.0 wt%.

Therefore, the plasma member of the present invention can be seen that even if yttrium oxide occupies about 90.0 to 99.9% by weight and nanocarbon occupies about 0.1 to 10.0% by weight, the nano carbon is uniformly distributed in the substrate composed of yttrium oxide. .

Relative Density Evaluation According to Nano Carbon Content

3 is a graph showing a change in relative density according to the content of nano carbon in the plasma member of the present invention.

First, about 0.0, 0.2, 0.4, 0.6, 0.8 based on yttrium oxide in order to evaluate the relative density change according to the content of nano carbon. The nano-carbon having a particle size of 1.0 and 1.2 wt% and about 10 nm and the sintering temperature of about 1,600 ° C. were subjected to the same process as the method for producing plasma resistant in FIG. Each of the sinters for application was obtained.

In addition, about 0.0, 0.2, 0.4, 0.6, 0.8 based on yttrium oxide in order to evaluate the relative density change according to the content of nano carbon. The nano-carbon having a particle size of 1.0 and 1.2 wt% and about 10 nm and a sintering temperature of about 1,400 ° C. were subjected to the same process as the method for producing plasma resistant in FIG. Each of the sinters for application was obtained.

Referring to FIG. 3, the-mark-indicates the relative density of each of the sintered bodies obtained at a sintering temperature of about 1,600 ° C. under the process conditions, and the nano carbon occupies about 0.0 to 1.2 wt% based on the yttrium oxide. Even if the relative density is maintained at more than 98.5% it can be confirmed that.

And-■-indicates the relative density of each of the sintered bodies obtained at the sintering temperature of about 1,400 ° C. under the process conditions, and when the nano carbon occupies about 0.0 and 0.4 wt% based on the yttrium oxide, It can be seen that maintaining more than about 90%, even when the nano carbon occupies about 0.6 to 1.2% by weight can be seen that the relative density is maintained at about 85% or more.

Here, in the case of the relative density evaluation according to the content of the nano-carbon mentioned above, but limited to only about 1.2% by weight of the nano-carbon content, even if the nano-carbon occupies about 10.0% by weight of the plasma member of the present invention It may have a saturation state capable of maintaining a relative density of about 85% by weight or more.

Thus, it can be seen that the plasma member of the present invention has a relative density of about 85 to 100% even though yttrium oxide occupies about 90.0 to 99.9% by weight and nanocarbon occupies about 0.1 to 10.0% by weight. Here, the nano carbon excludes about 0.0% by weight because the plasma member may not exhibit desired electrical properties when it is composed of only yttrium oxide.

Thus, as mentioned, the plasma member of the present invention preferably contains yttrium oxide in an amount of about 90.0 to 99.9% by weight, and nano carbon in an amount of about 0.1 to 10.0% by weight.

Evaluation of resistivity according to the content of nano carbon

4 is a graph showing a change in specific resistance according to the content of nano carbon in the plasma member of the present invention.

First, in order to evaluate the change in specific resistance according to the content of nano carbon, each of the same sintered bodies as in FIG. 3 was prepared by limiting nano carbon having a particle size of about 80 nm to process conditions.

Referring to FIG. 4, the-mark-indicates the specific resistance of each of the sintered bodies obtained at a sintering temperature of about 1,600 ° C. under process conditions, and when nano carbon occupies about 0.0 to 0.5 wt% based on yttrium oxide Although it exhibits a high resistivity property, it can be seen that when the nano carbon occupies about 0.6 to 1.2% by weight, it exhibits a resistivity property of less than about 1,000 Ωcm.

And-■-indicates the specific resistance of each of the sintered bodies obtained at the sintering temperature of about 1,400 ° C. under the process conditions, and is less than about 1,000 Ωcm even though nano carbon occupies about 0.1 to 1.2 wt% based on the yttrium oxide. It can confirm that it shows a specific resistance characteristic.

Therefore, the plasma member of the present invention has a resistivity characteristic of less than 1,000 Ωcm even though yttrium oxide occupies about 90.0 to 99.9% by weight and nanocarbon occupies about 0.1 to 10.0% by weight, and particularly, the sintering temperature is about 1,600. In the case of the sintered body obtained at the process conditions having ℃, it can be seen that it exhibits a resistivity characteristic of less than about 1,000 Ωcm from occupying about 0.6% by weight or more, and the sintered body obtained at the process conditions having a sintering temperature of about 1,400 ℃ In the case of occupying about 0.1 wt% or more, it can be seen that it exhibits a resistivity characteristic of less than about 1,000Ωcm.

Therefore, on the basis of the above-mentioned, the plasma member of the present invention has a specific resistance of about 10 to 1,000 Ωcm even though yttrium oxide accounts for about 90.0 to 99.9 wt% and nano carbon accounts for about 0.1 to 10.0 wt%. In addition, it can exhibit electrical properties similar to silicon, silicon carbide, and the like.

Therefore, since the plasma member of the present invention contains yttrium oxide, excellent plasma resistance can be ensured, and since the plasma member contains nano carbon, it can have electrical properties similar to silicon, silicon carbide, and the like, and thus the plasma member of the present invention. Can be easily applied to the integrated circuit device manufacturing apparatus that performs the etching process in the high density plasma environment, and can be used as a substitute for silicon, silicon carbide, etc., which is widely applied to the integrated circuit device manufacturing equipment. Do.

Comparative example

5 is a graph showing a change in specific resistance according to the content of carbon having a particle size of the micro unit.

First, micro carbon having a particle size of about 1.0 to 5.0 wt% and a particle size of about 0.5 μm and about 1,600 ° C., based on yttrium oxide, to compare the change in specific resistance with the plasma member of the present invention having a particle size of nano units. The sintered compact of each of the comparative examples was obtained by performing the same process as the method for producing the plasma member in FIG. That is, each of the sintered bodies including carbon having a particle size of micro units was obtained.

Referring to FIG. 5, it can be seen that each of the sintered bodies corresponding to the comparative examples has a resistivity characteristic of about 10 ¹¹ Ωcm or more.

Therefore, in the case of the plasma member of the present invention it can be seen that it is preferable to obtain using a nano-carbon having a particle size of about 1 to 200nm to have a specific resistance of about 10 to 1,000Ωcm.

Corrosion Characterization

6 is a graph for explaining the corrosion characteristics evaluation of the plasma member of the present invention.

Referring to FIG. 6, Samples 1 to 7 were prepared for evaluating corrosion characteristics of the aforementioned plasma member. Here, sample 1 is a yttrium oxide in a bulk state, sample 2 is a plasma member prepared by the same manufacturing method as in FIG. 2 mentioned above, sample 3 is coated with nano carbon on an alumina base material, and sample 4 is in bulk state. An alumina base material, Sample 5 is alumina coated on the alumina base material, Sample 6 is a silicon carbide base material, Sample 7 is a silicon base material.

And about 100 sccm, about 1,000 sccm, and about 10 sccm of silicon fluoride (CF ₄ ) gas, argon gas and oxygen gas in the chamber to evaluate the corrosion characteristics for each of the samples 1 to 7 mentioned above. RF (RF) power was applied to create a plasma environment. Thus, each of Samples 1 to 7 was placed in the aforementioned plasma environment for about 1 hour.

As a result, it was confirmed that sample 1 was the least corroded, and sample 7 was the most corroded. In particular, in the case of sample 2, but more corroded than sample 1, it was confirmed that less corroded than the remaining samples 3 to 7. Here, in the case of sample 1, as mentioned above, the yttrium oxide in the bulk state does not have good electrical properties for use as a plasma member.

Therefore, as a result of the corrosion characteristic evaluation mentioned above, it can be confirmed that the same Sample 2 as the plasma member of the present invention shows the best result.

As described above, since the plasma member of the present invention includes yttrium oxide, excellent plasma resistance can be secured, and since the plasma member includes nano carbon, it can have electrical properties similar to silicon, silicon carbide, and the like. Therefore, the plasma member of the present invention can be more easily applied to an apparatus for manufacturing integrated circuit devices that perform an etching process or the like in a high-density plasma environment, and in particular, silicon, silicon carbide, etc., which are widely applied to apparatuses for manufacturing integrated circuit devices. It can also be used as a substitute for.

In other words, the plasma member of the present invention, as mentioned, contains yttrium oxide and nano carbon consisting of about 1 to 200 nm in particle size, and consists of a sintered body. In particular, the sintered body obtained by sintering at a temperature of about 1,500 to 1,750 ° C. in the plasma member of the present invention has a relative density of about 98.5% or more and at least about 0.5% by weight of nano carbon based on yttrium oxide. It can be seen that the specific resistance is about 1,000 Ωcm or less from the occupied section, and the sintered body obtained by sintering at a temperature of about 1,350 to 1,500 ° C. has a relative density of about 85% or more and nanocarbon based on yttrium oxide. From the section occupying about 0.1% by weight or more, it can be seen that the specific resistance is about 1,000Ωcm or less.

As mentioned, the plasma member of the present invention not only has electrical properties similar to silicon, silicon carbide, etc., but also excellent plasma resistance similar to yttrium oxide can be ensured. Accordingly, the plasma member of the present invention can be more easily applied to an integrated circuit device manufacturing apparatus that performs an etching process and the like on a silicon substrate in a high density plasma environment, and can be used as a substitute for silicon, silicon carbide, and the like. It is possible.

Therefore, when the plasma member of the present invention is applied to the manufacture of integrated circuit devices, the yield of integrated circuit devices can be expected to improve productivity due to the manufacture of integrated circuit devices.

Claims (9)

yttrium oxide; And
A particle size of nano carbon comprising 1 to 200 nm,
Plasma resistant member comprising a sintered body. The plasma member according to claim 1, wherein the yttrium oxide occupies 90.0 to 99.9 weight percent, and the nano carbon occupies 0.1 to 10.0 weight percent. The plasma member of claim 1, wherein the sintered body has a specific resistance of 10 to 1,000 Ωcm. The plasma member according to claim 1, wherein the sintered body has a relative density of 85 to 100%. The plasma member according to claim 1, wherein the sintered body is obtained by sintering a mixture of the yttrium oxide and the nano carbon at a temperature of 1,350 to 1,750 ° C. Mixing the yttrium oxide powder and the nano carbon powder having a particle size of 1 to 200 nm with a solvent to form a liquid mixture;
Forming the liquid mixture into a spherical powder mixture using a spray dryer; And
A method for producing a plasma member comprising the step of forming the spherical powder mixture into a sintered body by using a hot-press. 7. The method of claim 6, wherein the yttrium oxide powder comprises 90.0 to 99.9 weight percent of the yttrium oxide, and the nano carbon powder is mixed to account for 0.1 to 10.0 wt%. The method of claim 6, wherein the forming of the liquid mixture comprises performing a ball-mill process using ethanol as the solvent. The method of claim 6, wherein the forming of the sintered body comprises using a hot-press at a temperature of 1,350 to 1,750 ° C. 8.

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