WO2022035111A1 - Plasma-resistant glass, and method for manufacturing same - Google Patents

Abstract

An embodiment of the present invention relates to a plasma-resistant glass, and a method for manufacturing same. The present invention is intended to solve the technical problem of providing a plasma-resistant glass having improved plasma resistance, and a method for manufacturing same. To this end, the present invention provides: a plasma glass including 40-75 mol% of SiO₂, 5-20 mol% of Al₂O₃, 5-30 mol% of CaO, and 0.01-10 mol% of a plasma-resistant Y-based compound; and a method for manufacturing same.

Description

Plasma-resistant glass and its manufacturing method

An embodiment of the present invention relates to a plasma-resistant glass and a method for manufacturing the same.

A plasma etching process is being applied in the manufacture of semiconductors and/or displays. Recently, as the nano process is applied, the difficulty of etching is increased and the internal parts of the process chamber exposed to the high-density plasma environment have corrosion resistance oxide-based ceramics such as alumina (Al ₂ O ₃ ) and yttria (Y ₂ O ₃ ). It is mainly used.

When the polycrystalline material is exposed to a high-density plasma etching environment using a fluorine-based gas for a long period of time, particles are dropped due to local erosion, and thus the probability of occurrence of contaminant particles increases. This causes defects in the semiconductor/display and adversely affects the production yield.

The above-described information disclosed in the background technology of the present invention is only for improving the understanding of the background of the present invention, and thus may include information that does not constitute the prior art.

An object to be solved according to an embodiment of the present invention is to provide a plasma glass having improved plasma resistance and a method for manufacturing the same.

The method of manufacturing a plasma glass according to an embodiment of the present invention comprises the steps of preparing a plasma glass raw material by mixing SiO ₂ powder, Al ₂ O ₃ precursor, CaO precursor and Y-based compound powder; melting the plasma glass raw material in an oxidizing atmosphere; Rapid cooling of the molten plasma-resistant glass material; and heat-treating and annealing the rapidly cooled resultant at a temperature higher than the glass transition temperature (Tg) to obtain a plasma-resistant glass, wherein the obtained plasma-resistant glass is SiO ₂ 40 to 75 mol%, Al ₂ O ₃ 5 to 20 mol%, CaO 5 to 30 mol%, and a plasma-resistant Y-based compound may contain 0.01 to 10 mol%.

The Al ₂ O ₃ precursor may include Al(OH) ₃ powder, and the CaO precursor may include a CaCO ₃ powder.

The Y-based compound may include YF ₃ , YOF or Y(NO ₃ ) ₃ ·6H ₂ O.

The obtained plasma glass may contain 4 to 6 At% of fluorine (F).

The obtained plasma glass may contain 1-3 At% of nitrogen (N).

The obtained plasma-resistant glass is a glass used in a mixed plasma environment of fluorine and argon (Ar), and the obtained plasma-resistant glass has an etching rate of 5 nm/min to 10 nm with respect to a mixed plasma of fluorine and argon It can have a plasma resistance of /min.

The melting step may be performed at a temperature of 1300 °C to 1800 °C.

Annealing at a temperature of 700°C to 1000°C may be further included between the melting step and the rapid cooling step.

The glass transition temperature (Tg) of the obtained plasma-resistant glass may be 700 ℃ ~ 900 ℃.

The softening point (Tdsp) of the obtained plasma glass may be 800 ℃ ~ 1000 ℃.

Plasma glass according to an embodiment of the present invention contains SiO ₂ 40 to 75 mol%, Al ₂ O ₃ 5 to 20 mol%, CaO 5 to 30 mol% and plasma-resistant Y-based compound 0.01 to 10 mol% can do.

The Y-based compound may include YF ₃ , YOF or YN.

An embodiment of the present invention provides a plasma-resistant glass with improved plasma resistance and a method for manufacturing the same. As an example, an embodiment of the present invention provides a plasma glass having a plasma resistance with an etching rate of 5 nm/min to 10 nm/min with respect to a mixed plasma of fluorine and argon, and a method for manufacturing the same.

1 is a flowchart illustrating a method of manufacturing a plasma-resistant glass according to an embodiment of the present invention.

Figures 2a and 2b is a table showing the composition ratio for the manufacture of plasma-resistant glass according to an embodiment of the present invention.

Figures 3a to 3d is a photograph showing a plasma-resistant glass according to an embodiment of the present invention.

Figure 4 is a table showing the atomic % in the mixture of plasma-resistant glass raw material and plasma-resistant glass according to an embodiment of the present invention.

5 is a table showing the thermal properties of the plasma glass according to an embodiment of the present invention.

Figure 6 is a photograph showing the plasma characteristics of the plasma-resistant glass according to an embodiment of the present invention.

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

Examples of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art, and the following examples may be modified in various other forms, and the scope of the present invention is as follows It is not limited to an Example. Rather, these examples are provided so that this disclosure will be more thorough and complete, and will fully convey the spirit of the invention to those skilled in the art.

As used herein, the term “and/or” includes any one and all combinations of one or more of those listed items. In addition, the terminology used in this specification is used to describe specific embodiments, and is not intended to limit the present invention. As used herein, the singular form may include the plural form unless the context clearly dictates otherwise. Also, as used herein, “comprise, include” and/or “comprising, including” refer to the referenced shapes, numbers, steps, actions, members, elements, and/or groups thereof. It specifies the presence and does not exclude the presence or addition of one or more other shapes, numbers, movements, members, elements and/or groups.

Although the terms first, second, etc. are used herein to describe various members, parts, regions, layers and/or parts, these members, parts, regions, layers, and/or parts are limited by these terms so that they It is self-evident that These terms are used only to distinguish one member, component, region, layer or portion from another region, layer or portion. Accordingly, a first member, component, region, layer, or portion described below may refer to a second member, component, region, layer or portion without departing from the teachings of the present invention.

Referring to Figure 1, there is shown a flowchart for a method of manufacturing a plasma-resistant glass according to an embodiment of the present invention.

As shown in Figure 1, the plasma glass manufacturing method according to an embodiment of the present invention is a plasma glass raw material preparation step (S1), melting step (S2), annealing step (S3), cooling step (S4) and It may include a plasma glass obtaining step (S5).

In the plasma glass raw material preparation step (S1), SiO ₂ powder, Al ₂ O ₃ precursor powder, CaO precursor powder and Y-based compound powder may be mixed to prepare a plasma glass raw material.

In some examples, the Al ₂ O ₃ precursor powder may include Al(OH) ₃ powder, and the CaO precursor powder may include CaCO ₃ powder.

In some examples, the Y-based compound powder may include YF ₃ powder, YOF powder, or Y(NO ₃ ) ₃ .6H ₂ O powder.

In the melting step (S2), the plasma glass raw material may be melted in an oxidizing atmosphere.

In some examples, the melting step may be performed at a temperature of about 1300° C. to about 1800° C. in an oxidizing atmosphere.

In the annealing step (S3), the molten plasma-resistant glass material may be annealed in an oxidizing atmosphere (optional).

In some examples, the annealing step may be performed at a temperature of about 700° C. to about 1000° C. in an oxidizing atmosphere.

In the cooling step (S4), the annealed plasma-resistant glass material may be rapidly cooled.

In the plasma glass obtaining step (S5), a plasma glass can be obtained by heat-treating and annealing the rapidly cooled product at a temperature higher than the glass transition temperature (Tg).

In some examples, the glass transition temperature (Tg) of the obtained plasma glass may be about 700 ℃ ~ about 900 ℃.

In some examples, the obtained plasma glass may have a softening point (Tdsp) of approximately 800°C to approximately 1000°C.

In some examples, the plasma-resistant glass obtained is from about 40 mol% to about 75 mol% of SiO ₂ , about 5 mol% to about 20 mol% of Al ₂ O ₃ , about 5 mol% to about 30 mol% of CaO and plasma resistance It may contain about 0.01 mol% to about 10 mol% of the Y-based compound.

In some examples, the obtained plasma glass may contain about 4 At% to about 6 At% of fluorine (F).

In some examples, the obtained plasma glass may contain about 1 to about 3 At% nitrogen (N).

In some examples, the obtained plasma-resistant glass is a glass used in a mixed plasma environment of fluorine and argon (Ar), and the obtained plasma-resistant glass has an etching rate of about 5 nm/min with respect to a mixed plasma of fluorine and argon ˜10 nm/min. More specifically, the obtained plasma-resistant glass may have an etching rate of about 8.0 nm/min to about 8.3 nm/min with respect to a mixed plasma of fluorine and argon.

Referring to Figures 2a and 2b, there is shown a table for the composition ratio for the manufacture of plasma-resistant glass according to an embodiment of the present invention.

Example 1

In the plasma glass raw material preparation step (S1), 65.909 mol% of SiO ₂ powder, 10.356 mol% of Al ₂ O ₃ precursor powder, 20.006 mol% of CaO precursor powder, and 3.730 mol% of YOF powder are mixed to prepare a plasma glass raw material (see Fig. 2a).

Here, the plasma glass raw material was mixed using a dry mixing method.

As an example, the total amount of chemical components was placed in a weight of 100 g, and the plasma glass raw material was mixed for about 1 hour by a zirconia ball milling method. In some examples, 100 g of raw material: 300 g of zirconia balls (weight ratio 1:3) was dry-mixed with the plasma glass raw material, and then dried for 24 hours.

In the melting step (S2), the temperature was increased at a rate of 10°C/min until the plasma glass raw material mixed in the dry mixing manner reached a temperature of 1500°C, and the temperature was maintained at 1500°C for approximately 2 hours. . Then, by performing the annealing step (S3), cooling step (S4) and plasma glass obtaining step (S5) in the same manner as described above, to obtain a plasma glass containing a YOF compound.

Example 2

The plasma glass raw material preparation step (S1) is the same as or similar to Example 1 described above (see FIG. 2A).

Here, the plasma glass raw material was mixed using a wet mixing method.

As an example, the total amount of chemical components was placed in a weight of 100 g, and the plasma glass raw material was mixed for about 1 hour by a zirconia ball milling method. In some examples, the plasma glass raw material was wet-mixed with 100 g of raw material: 400 g of ethanol: 900 g of zirconia balls (weight ratio 1:4:9), and then dried for 24 hours.

In the melting step (S2), the Naplesma glass raw material mixed by the wet mixing method was increased in temperature at a rate of 10°C/min until it reached a temperature of 1500°C, and was maintained at a temperature of 1500°C for approximately 2 hours. . Then, by performing the annealing step (S3), cooling step (S4) and plasma glass obtaining step (S5) in the same manner as described above, to obtain a plasma glass containing a YOF compound.

Example 3

Most of the processes are the same or similar to those of Example 2, but in the melting step (S2), the Naplesma glass raw material mixed by the wet mixing method is heated at a rate of 10°C/min until it reaches a temperature of 1500°C and maintained at a temperature of 1500° C. for approximately 4 hours.

Example 4

In the plasma-resistant glass raw material preparation step (S1), 67.615 mol% of SiO ₂ powder, 20.523 mol% of Al ₂ O ₃ precursor powder, 10.624 mol% of CaO precursor powder, and 5.75 mol% of Y(NO ₃ ) ₃ .6H ₂ O powder By mixing, a plasma glass raw material was prepared (see FIG. 2b).

Here, the plasma glass raw material was mixed using a dry mixing method. As an example, the total amount of chemical components was placed in a weight of 100 g, and the plasma glass raw material was mixed for about 1 hour by a zirconia ball milling method. In some examples, 100 g of raw material: 300 g of zirconia balls (weight ratio 1:3) was dry-mixed with the plasma glass raw material, and then dried for 24 hours.

In the melting step (S2), the temperature was increased at a rate of 10°C/min until the plasma glass raw material mixed in the dry mixing manner reached a temperature of 1500°C, and the temperature was maintained at 1500°C for approximately 2 hours. . Then, by performing the annealing step (S3), cooling step (S4) and plasma glass obtaining step (S5) in the same manner as described above, to obtain a plasma glass containing a YN compound.

Referring to Figure 3a to Figure 3d, there is shown a photograph for the plasma glass according to an embodiment of the present invention.

Here, the photograph of Figure 3a is the plasma-resistant glass prepared by Example 1, the photograph of Figure 3b is the plasma-resistant glass prepared by Example 2, and the photograph of Figure 3c is the plasma-resistant glass prepared by Example 3 It is glass, and the photograph of FIG. 3d is a plasma-resistant glass prepared in Example 4.

The plasma-resistant glass prepared in Example 1 was generally transparent in appearance, but a large amount of air bubbles and unmelted particles were observed. On the other hand, as a result of EDS (Energy Dispersive X-ray Spectroscopy) analysis, each element of the plasma glass was observed to be in a homogeneous mixed state, and fluorine (F) element was also detected.

The plasma-resistant glass prepared in Example 2 was also substantially transparent in appearance, but a large amount of air bubbles was observed. However, unmelted particles were not observed. As a result of EDS analysis, each element of the plasma glass was observed to be in a homogeneous mixed state, and elemental fluorine (F) was also detected.

The plasma-resistant glass prepared in Example 3 was also substantially transparent in appearance, but a large amount of air bubbles were observed. However, unmelted particles were not observed. As a result of EDS analysis, each element of the plasma glass was observed to be in a homogeneous mixed state, and elemental fluorine (F) was also detected. Here, in the case of the glass maintained for 4 hours, the appearance of the glass (Example 1) after dry mixing was similar.

As a result of EDS analysis, it was observed that both the plasma-resistant glass prepared by the dry mixing method and the wet mixing method had similar chemical component contents.

The plasma-resistant glass prepared in Example 4 was generally opaque (ivory color), and a large amount of air bubbles were observed. As a result of EDS analysis, each element of the plasma glass was observed to be in a homogeneous mixed state.

Referring to FIG. 4 , a table for atomic (At)% in the plasma glass raw material mixture and the plasma glass according to an embodiment of the present invention is shown.

Here, the plasma glass raw material mixture refers to the mixture before performing the melting step, Example 1 (plasma-resistant glass by dry mixing method) and Example 2 (plasma-resistant glass by wet mixing method) after the melting step It means commercialized plasma-resistant glass.

As shown in FIG. 4 , as a result of EDS analysis, yttrium (Y) element and fluorine (F) element were detected in common in the plasma glass raw material mixture and the plasma glass manufactured by Examples 1 and 2 . That is, the yttrium (Y) element was detected at 1.61 At% in the plasma glass raw material mixture, 2.23 At% in Example 1, and 2.94 At% in Example 2, respectively. In addition, the element fluorine (F) was detected at 5.47 At% in the plasma glass raw material mixture, 5.98 At% in Example 1, and 4.71 At% in Example 2, respectively.

Therefore, the yttrium (Y) element and the fluorine (F) element are detected in the plasma-resistant glass raw material mixture before the melting step and the plasma-resistant glass after the melting step, respectively, so that the yttrium (Y) element and the fluorine (F) element during the manufacturing process It can be confirmed that is not lost.

Here, since the element fluorine (F) affects plasma resistance (eg, etch rate), it is preferable to remain in the commercialized plasma glass.

Referring to Figure 5, there is shown a table for the thermal properties of the plasma glass according to an embodiment of the present invention.

As shown in FIG. 5, the plasma-resistant glass to which YOF was added according to Example 1 had a CTE of 4.75 * 10 ^-6 m/(m ° C.), a glass transition temperature of 763.7 ° C., and a softening point of 845.2 ° C., The plasma glass to which YOF according to Example 2 was added had a CTE of 4.92*10 ^-6 m/(m°C), a glass transition temperature of 769.9°C, and a softening point of 830.9°C, and YN according to Example 4 was added. The plasma-resistant glass was measured to have a CTE of 4.83*10 ^-6 m/(m°C), a glass transition temperature of 824.3°C, and a softening point of 936.2°C.

In this way, when the plasma glass contains a fluorine (F) element rather than a nitrogen (N) element, it can be seen that the glass transition temperature and softening point are lowered. Therefore, since the plasma glass containing YOF reduces the viscosity and melting point, it provides a low melting point plasma glass that is easy to process in the end.

In addition, when the plasma glass contains a fluorine (F) element rather than a nitrogen (N) element, plasma resistance is improved. For example, when the plasma glass is exposed to a CF ₄ based plasma environment, a fluorine compound layer is formed on the plasma glass by reacting with each other. Such a fluorine compound layer reduces the etching rate. However, in an embodiment of the present invention, since the fluorine (F) element is already contained in the plasma-resistant glass, the fluorine compound layer on the surface of the plasma-resistant glass becomes faster and thicker when the plasma glass is exposed to a CF ₄ -based plasma environment. formed, and thus plasma resistance can be further improved.

Figure 6 is a photograph showing the plasma characteristics of the plasma-resistant glass according to an embodiment of the present invention. In FIG. 6, CAS means Ca, Al and Si, YO means Y ₂ O ₃ (see photo 1), YOF literally means YOF (see photo 2), and YN is Y (NO ₃ ) It means ₃ ·6H ₂ O (refer to the 3rd picture). In addition, photos 1, 2, and 3 in FIG. 6 show the etch depth before and after etching and the surface roughness before and after etching. In some examples, conditions of an Inductively Coupled Plasma (ICP) etching system are shown in Table 1 below.

Power 600 W Bias 200 W CF ₄ 30 sccm Ar 10 sccm O ₂ 5 sccm Pressure 10 mTorr Time 60 min

In addition, a comparison of the etch depth and surface roughness after etching is shown in Table 2 below.

Thickness [um] (1) CAS+YO (2) CAS+YOF (3) CAS+YN etch depth
(Etching Depth) 0.83 0.482 0.5 Ra @ Before 0.036 0.028 0.032 Ra @ After 0.069 0.031 0.036

As can be seen in FIG. 6 and Tables 1 and 2, it can be seen that the etch rate of the plasma glass containing YOF and/or YN is lower than that of the plasma glass containing YO. That is, in the case of plasma-resistant glass containing YO, the etching rate is 830 nm/60 min (ie, 13.8 nm/min), whereas in the case of plasma-resistant glass containing YOF, the etching rate is 8.0 nm/min, and plasma resistance containing YN In the case of glass, the etching rate is 8.3 nm/min. In addition, it can be seen that the roughness of the plasma-resistant glass containing YOF and/or YN is lower than the surface roughness of the plasma-resistant glass containing YO. That is, in the case of plasma-resistant glass containing YO, the roughness after etching increased by 60 nm-36 nm (ie, 33 nm), whereas the post-etch roughness of plasma-resistant glass containing YOF increased by 3 nm, and plasma glass containing YN In the case of , the roughness increased by 4 nm after etching.

In this way, an embodiment of the present invention can provide a plasma glass with improved plasma resistance and a method for manufacturing the same. As an example, an embodiment of the present invention may provide a plasma glass having a plasma resistance of about 5 nm/min to about 10 nm/min with respect to a mixed plasma of fluorine and argon and a method for manufacturing the same.

What has been described above is only one embodiment for carrying out the plasma-resistant glass and its manufacturing method according to the present invention, the present invention is not limited to the above-described embodiment, and as claimed in the claims below Without departing from the gist of the invention, it will be said that the technical spirit of the present invention exists to the extent that various modifications can be made by anyone with ordinary knowledge in the field to which the invention pertains.

Claims (17)

Preparing a plasma glass raw material by mixing SiO ₂ powder, Al ₂ O ₃ precursor, CaO precursor and Y-based compound powder; melting the plasma glass raw material in an oxidizing atmosphere; Rapid cooling of the molten plasma-resistant glass material; and Comprising the step of heat-treating and annealing the rapidly cooled result at a temperature higher than the glass transition temperature (Tg) to obtain a plasma glass, Plasma-resistant glass obtained above is SiO ₂ 40 to 75 mol%, Al ₂ O ₃ 5 to 20 mol%, CaO 5 to 30 mol% and plasma-resistant Y-based compound 0.01 to 10 mol% containing, plasma resistance A method of manufacturing glass. The method of claim 1, The Al ₂ O ₃ precursor includes Al(OH) ₃ powder, and the CaO precursor is CaCO ₃ A method of manufacturing a plasma-resistant glass comprising a powder. The method of claim 1, The Y-based compound is YF ₃ , YOF or Y (NO ₃ ) ₃ ·6H ₂ O, including a plasma glass manufacturing method. The method of claim 1, The obtained plasma glass is fluorine (F) 4 to 6 At% containing, a method for producing a plasma glass. The method of claim 1, The obtained plasma-resistant glass comprises nitrogen (N) 1-3 At%, a method for producing a plasma-resistant glass. The method of claim 1, The obtained plasma-resistant glass is a glass used in a mixed plasma environment of fluorine and argon (Ar), and the obtained plasma-resistant glass has an etching rate of 5 nm/min to 10 nm with respect to a mixed plasma of fluorine and argon /min having a plasma property that is, a method for producing a plasma glass. The method of claim 1, The melting step is performed at a temperature of 1300 °C to 1800 °C, a method for producing a plasma glass. The method of claim 1, Further comprising the step of annealing at a temperature of 700 ℃ ~ 1000 ℃ between the melting step and the rapid cooling step, plasma glass manufacturing method. The method of claim 1, The glass transition temperature (Tg) of the obtained plasma-resistant glass is 700 ℃ ~ 900 ℃, the plasma glass manufacturing method. The method of claim 1, The softening point (Tdsp) of the obtained plasma glass is 800 ℃ ~ 1000 ℃, a method for producing a plasma glass. SiO ₂ 40 to 75 mol%, Al ₂ O ₃ 5 to 20 mol%, CaO 5 to 30 mol% and plasma-resistant Y-based compound 0.01 to 10 mol% containing, plasma-resistant glass. 12. The method of claim 11, The Y-based compound is YF ₃ , YOF or YN, including plasma glass. 12. The method of claim 11, The plasma glass is fluorine (F) containing 4 to 6 At%, plasma glass. 12. The method of claim 11, The obtained plasma glass is nitrogen (N) containing 1-3 At%, plasma glass. 12. The method of claim 11, The plasma glass is a glass used in a mixed plasma environment of fluorine and argon (Ar), and the plasma glass has an etching rate of 5 nm/min to 10 nm/min with respect to a mixed plasma of fluorine and argon. Plasma-resistant glass with plasma properties. 12. The method of claim 11, The glass transition temperature (Tg) of the plasma glass is 700 ℃ ~ 900 ℃, plasma glass. 12. The method of claim 11, The softening point (Tdsp) of the plasma glass is 800 ℃ ~ 1000 ℃, plasma glass.

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