WO2024080532A2 - Plasma-resistant glass, inner chamber component for semiconductor manufacturing process, and manufacturing methods therefor - Google Patents

Abstract

The present invention relates to plasma-resistant glass, an inner chamber component for a semiconductor manufacturing process, and manufacturing methods therefor and, particularly, to plasma-resistant glass, an inner chamber component for a semiconductor manufacturing process, and manufacturing methods therefor, wherein the contents of components in the plasma-resistant glass are adjusted, and a Ge-based oxide is added to achieve a low melting temperature, a thermal expansion coefficient of the plasma-resistant glass is reduced to prevent damage from thermal shock during use at high temperatures, and light transmittance and durability of the plasma-resistant glass can be improved.

Description

Plasma-resistant glass, chamber interior components for semiconductor manufacturing processes, and their manufacturing methods

The present invention claims the benefit of Korean Patent Application No. 10-2022-0131088, filed with the Korea Intellectual Property Office on October 13, 2022, the entire contents of which are included in the present invention.

The present invention relates to plasma-resistant glass, chamber interior parts for a semiconductor manufacturing process, and their manufacturing method. Specifically, the content of the plasma-resistant glass components is controlled, the melting temperature is low by including Ge-based oxide, and the melting temperature is low. It relates to plasma-resistant glass that can prevent damage from thermal shock when used at high temperatures by reducing the coefficient of thermal expansion and improve light transmittance and durability, parts for the interior of the chamber for the semiconductor manufacturing process, and methods of manufacturing them.

Plasma etching processes are applied when manufacturing semiconductors and/or displays. Recently, with the application of nano-processing, the difficulty of etching has increased, and the internal parts of the process chamber exposed to the high-density plasma environment are made of oxide-based ceramics such as alumina (Al ₂ O ₃ ) and yttria (Y ₂ O ₃ ), which have corrosion resistance. It is mainly used.

When a polycrystalline material is exposed to a high-density plasma etching environment using fluorine-based gas for a long period of time, particles are eliminated due to local erosion, thereby increasing the probability of generating contaminating particles. This causes defects in semiconductors/displays and adversely affects production yield. In addition, oxide-based ceramic materials have a problem of low workability due to their high melting temperature.

Therefore, there is a need to develop technology that can prevent thermal shock damage to existing plasma-resistant glass while having a low melting temperature.

The technical problem to be achieved by the present invention is to provide excellent resistance due to the plasma inside the chamber used in the semiconductor manufacturing process, and excellent heat resistance under high temperature conditions to prevent damage to components used inside the chamber and to achieve a low melting temperature. To provide plasma-resistant glass, chamber interior parts for semiconductor manufacturing processes, and their manufacturing methods.

However, the problem to be solved by the present invention is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One embodiment of the present invention is 20 to 50% by weight of SiO ₂ , 5 to 25% by weight of Al ₂ O ₃ , 10 to 74% by weight of CaO, and 0.01 to 50% by weight. Provided is a plasma-resistant glass formed by melting a composition containing % or less of Ge-based oxide.

According to one embodiment of the present invention, the composition contains only SiO ₂ , Al ₂ O ₃ , CaO, Ge-based oxides and inevitable impurities, and the content of SiO ₂ is 45.00% by weight or more and 50.00% by weight or less, and the Al The content of ₂ O ₃ may be 5.00 wt% or more and 20.00 wt% or less, the CaO content may be 10.00 wt% or more and 25.00 wt% or less, and the Ge-based oxide content may be 10.00 wt% or more and 30.00 wt% or less.

According to one embodiment of the present invention, the light transmittance may be 80% or more and 100% or less.

According to one embodiment of the present invention, the Vickers hardness may be 650 HV or more and 1,000 HV or less.

According to an exemplary embodiment of the present invention, the glass transition temperature may be 600°C or more and 850°C or less.

^{According to} an exemplary embodiment of the present invention, the thermal expansion coefficient may be 4.0

According to an exemplary embodiment of the present invention, the etching rate by mixed plasma of fluorine and argon (Ar) may be greater than 0 nm/min and less than or equal to 20 nm/min.

According to an exemplary embodiment of the present invention, the melting point may be 1,500°C or more and 1,750°C or less.

One embodiment of the present invention provides parts for the interior of a chamber for a semiconductor manufacturing process made of the plasma-resistant glass.

According to one embodiment of the present invention, the internal components include a focus ring, an edge ring, a cover ring, a ring shower, an insulator, and an EPD window. (window), electrode, view port, inner shutter, electro static chuck, heater, chamber liner, shower head, CVD Boat, wall liner, shield, cold pad, source head, outer liner, deposition shield for (Chemical Vapor Deposition) ), it may be any one of an upper liner, an exhaust plate, and a mask frame.

One embodiment of the present invention is 20 to 50% by weight of SiO ₂ , 5 to 25% by weight of Al ₂ O ₃ , 10 to 74% by weight of CaO, and 0.01 to 50% by weight. melting a composition comprising less than or equal to % Ge-based oxide; and cooling the molten composition. It provides a method for manufacturing plasma-resistant glass including a.

According to one embodiment of the present invention, the melting temperature in the step of melting the composition may be 1,400°C or more and 1,700°C or less.

One embodiment of the present invention includes melting the plasma-resistant glass; Injecting the molten plasma-resistant glass into a mold; and annealing the injected plasma-resistant glass.

According to one embodiment of the present invention, the melting temperature in the step of melting the plasma-resistant glass may be 1,550 ℃ or more and 1,750 ℃ or less.

According to an exemplary embodiment of the present invention, the temperature of the annealing step may be 400°C or more and 900°C or less.

The plasma-resistant glass according to an exemplary embodiment of the present invention improves processability by implementing a low melting temperature, and can easily manufacture parts for the interior of a chamber for a semiconductor manufacturing process.

The plasma-resistant glass according to an exemplary embodiment of the present invention exhibits a low thermal expansion coefficient and can prevent damage due to thermal shock in a high-temperature atmosphere.

The plasma-resistant glass according to an exemplary embodiment of the present invention has improved light transmittance and improved mechanical properties by improving hardness, thereby improving durability in a plasma etching environment.

Components used inside a chamber for a semiconductor manufacturing process according to an embodiment of the present invention can improve usage time in the semiconductor manufacturing process by implementing a low etch rate for plasma, and can improve durability by preventing damage to components due to thermal shock. You can.

The method for manufacturing plasma-resistant glass according to an embodiment of the present invention can easily manufacture plasma-resistant glass and prevent damage due to thermal shock in a high-temperature atmosphere.

The method of manufacturing components for the interior of a chamber for a semiconductor manufacturing process according to an embodiment of the present invention can manufacture components with various shapes, prevent damage due to thermal shock in a high temperature atmosphere, and easily manufacture the components.

The effect of the present invention is not limited to the above-mentioned effect, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and the attached drawings.

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

Figure 2 is a flowchart of a method of manufacturing components for the interior of a chamber for a semiconductor manufacturing process according to an exemplary embodiment of the present invention.

Figure 3 is a photograph taken of the plasma-resistant glass of Examples 1 to 3, which is an embodiment of the present invention.

[Explanation of symbols]

S 11: Composition melting step

S 13: Cooling stage

S 21: Plasma-resistant glass melting step

S 23: Mold injection step

S 25: Annealing step

S 27: Processing steps

Throughout the specification of the present application, when a part is said to “include” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.

Throughout this specification, “A and/or B” means “A and B, or A or B.”

Hereinafter, the present invention will be described in more detail.

One embodiment of the present invention is 20 to 50% by weight of SiO ₂ , 5 to 25% by weight of Al ₂ O ₃ , 10 to 74% by weight of CaO, and 0.01 to 50% by weight. Provided is a plasma-resistant glass formed by melting a composition containing % or less of Ge-based oxide.

The plasma-resistant glass according to an embodiment of the present invention improves processability by implementing a low melting temperature, can easily manufacture parts for the interior of the chamber for the semiconductor manufacturing process, and exhibits low thermal expansion coefficient characteristics in a high temperature atmosphere. Damage caused by thermal shock can be prevented, light transmittance is improved, and mechanical properties are improved by improving hardness, thereby improving durability in a plasma etching environment.

According to one embodiment of the present invention, the composition includes 20% by weight or more and 50% by weight or less of SiO ₂ . Specifically, the content of SiO ₂ in the composition is 21% by weight or more and 49% by weight or less, 22% by weight or more and 48% by weight or less, 23% by weight or more and 47% by weight or less, 24% by weight or more and 46% by weight or less, and 25% by weight or more. 45 wt% or less, 26 wt% or more but 44 wt% or less, 27 wt% or more but 43 wt% or less, 28 wt% or more but 42 wt% or less, 29 wt% or more and 41 wt% or less, 30 wt% or more and 40 wt% or less, It may be 31 weight% or more and 39 weight% or less, 32 weight% or more and 38 weight% or less, 33 weight% or more and 37 weight% or less, or 34 weight% or more and 36 weight% or less. As described above, by including the SiO ₂ and controlling the content of the SiO 2 in the above-mentioned range, the basic physical properties of the plasma-resistant glass can be secured, durability and reliability can be improved, and the plasma-resistant glass can be processed. It is possible to easily reduce the production cost of parts.

According to one embodiment of the present invention, the composition includes 5% by weight or more and 25% by weight or less of Al ₂ O ₃ . Specifically, the content of Al ₂ O ₃ in the composition is 6 wt% or more and 24 wt% or less, 7 wt% or more and 23 wt% or less, 8 wt% or more and 22 wt% or less, 9 wt% or more and 21 wt% or less, and 10 wt. % or more and 20 weight% or less, 11 weight% or more and 19 weight% or less, 12 weight% or more and 18 weight% or less, 13 weight% or more and 17 weight% or less, or 14 weight% or more and 16 weight% or less. As described above, it contains Al ₂ O ₃ and by adjusting the content of Al ₂ O ₃ in the above-mentioned range, outgassing can be prevented and the generation of particles can be suppressed. , the wear resistance of the internal parts of the chamber for the semiconductor manufacturing process can be improved, and the composition can be easily melted by lowering the melting temperature even if it contains Ge-based oxide, which will be described later.

According to one embodiment of the present invention, the composition contains 10% by weight or more and 74% by weight or less of CaO. Specifically, the content of CaO in the composition is 11% by weight or more and 73% by weight or less, 12% or more and 72% by weight or less, 13% or more and 71% by weight or less, 14% by weight or more and 70% by weight or less, and 15% by weight or more 69 Weight% or less, 16% or more and 68% or less by weight, 17% or more and 67% by weight or less, 18% or more and 66% by weight or less, 19% or more and 65% by weight or less, 20% or more and 64% by weight or less, 21 Weight% or more 63% by weight or less, 22% or more but 62% by weight or less, 23% or more and 61% by weight or less, 24% or more and 60% by weight or less, 25% or more and 59% by weight or less, 26% or more and 58% by weight % or less, 27% by weight or more, 57% by weight or less, 28% by weight or more, 56% by weight or less, 29% by weight or more, 55% by weight or less, 30% by weight or more, 54% by weight or less, 31% by weight or more, 53% by weight or less, 32% by weight % or more 52% by weight or less, 33% or more but 51% by weight or less, 34% or more but 50% by weight, 35% or more but 49% by weight or less, 36% by weight or more and 48% by weight or less, 37% by weight or more 47% by weight Hereinafter, it may be 38 wt% or more and 46 wt% or less, 39 wt% or more and 45 wt% or less, 40 wt% or more and 44 wt% or less, or 41 wt% or more and 43 wt% or less. As described above, it contains the CaO, and by adjusting the content of the CaO within the above-mentioned range, the thermal expansion coefficient and glass transition temperature of the glass are realized to be low, thereby minimizing thermal shock at high temperatures and inside the chamber for the semiconductor manufacturing process. The durability of parts can be improved.

According to one embodiment of the present invention, the composition includes 0.01% by weight or more and 50% by weight or less of Ge-based oxide. Specifically, the content of Ge-based oxide in the composition is 1% by weight to 49% by weight, 2% to 48% by weight, 3% to 47% by weight, 4% to 46% by weight, and 5% by weight. Not less than 46% by weight but not more than 45% by weight, not less than 7% by weight but not more than 44% by weight, not less than 8% by weight but not more than 43% by weight, not less than 9% by weight but not more than 42% by weight, not less than 10% by weight but not more than 41% by weight , 11 weight% or more and 40 weight% or less, 12 weight% or more and 39 weight% or less, 13 weight% or more and 38 weight% or less, 14 weight% or more and 37 weight% or less, 15 weight% or more and 36 weight% or less, 16 weight% or more 35 wt% or less, 17 wt% or more and 34 wt% or less, 18 wt% or more and 33 wt% or less, 19 wt% or more and 32 wt% or less, 20 wt% or more and 31 wt% or less, 21 wt% or more and 30 wt% or less, It may be 22% by weight or more and 29% by weight or less, 23% by weight or more and 28% by weight or less, 24% by weight or more and 27% by weight or less, or 25% by weight or more and 26% by weight or less. As described above, when the composition contains the Ge-based oxide, it has the same outermost electrons as the Si atoms, so that the glass cooled after melting has characteristics similar to Si, and the low melting point of Ge is achieved during the melting process. Although this is not easy, it is possible to achieve a low dielectric constant by including the Ge-based oxide. In addition, by adjusting the content of the Ge-based oxide within the above-mentioned range, the melting temperature of the plasma-resistant glass can be lowered to enable melting, and the dielectric constant can be realized low. Furthermore, as described above, when the composition contains the Ge-based oxide, the fluorine (F ₂ ) gas used in the etching process reacts with the Ge-based oxide to produce GeF ₂ (Boiling point: 130 ℃, Melting point: 120 ℃). Alternatively, it generates GeF ₄ (Boiling point: -15 ℃, Melting point: -36.5 ℃), and since these fluorine compounds have low BP and MP, they fly away during the gas etching process, so particles may not be formed.

According to one embodiment of the present invention, the plasma-resistant glass is formed by melting the composition. As described above, by melting the composition and cooling it to form the plasma-resistant glass, the composition can be melted at a relatively low temperature and the plasma-resistant glass can be easily formed, preventing damage to thermal shock. It can be prevented.

According to one embodiment of the present invention, the plasma-resistant glass may have a dielectric constant of 6.65 or more and 8.80 or less. Specifically, the plasma-resistant glass has a dielectric constant of 6.70 to 8.75, 6.75 to 8.00, 6.80 to 7.95, 6.85 to 7.90, 6.90 to 7.85, 6.95 to 7.80, 7.00 to 7.75, 7.05 to 7.70. , 7.10 or more and 7.65 or less, 7.15 or more and 7.60 or less, 7.20 or more and 7.55 or less, 7.25 or more and 7.50 or less, 7.30 or more and 7.45 or less, or 7.35 or more and 7.40 or less. More specifically, the plasma resistant glass has a dielectric constant of 6.79 to 6.99, 6.79 to 7.19, 6.79 to 7.39, 6.79 to 7.59, 6.99 to 7.19, 6.99 to 7.39, 6.99 to 7.59, 7.19 to 7.39. Hereinafter, it may be 7.19 or more and 7.59 or less, or 7.39 or more and 7.59 or less. Dielectric constant measurement methods include the capacitance method using an LCR meter, the reflection coefficient method using a network analyzer, and the resonant frequency method. As an example of a dielectric constant measurement method, the capacitance method using an LCR meter is mainly used to measure low frequency characteristics (kHZ, MHz), and the dielectric constant can be determined from the physical size and electrostatic capacity of the capacitor. By implementing the dielectric constant of the plasma-resistant glass in the above-described range, thermal shock at high temperatures can be minimized, durability of components used inside the chamber for the semiconductor manufacturing process can be improved, and light transmittance and durability can be improved.

According to an exemplary embodiment of the present invention, the Ge-based oxide may be one selected from the group consisting of GeO, GeO ₂ , Ge ₂ O ₃ and combinations thereof. Preferably, the Ge-based oxide may be GeO ₂ . By selecting the Ge-based oxide from the above, the melting temperature of the plasma-resistant glass can be realized low, enabling melting, and the dielectric constant can be realized low.

According to an exemplary embodiment of the present invention, the composition may include only SiO ₂ , Al ₂ O ₃ , CaO, and Ge-based oxide. That is, the composition may be composed of SiO ₂ , Al ₂ O ₃ , CaO, and Ge-based oxide. Specifically, the composition may be composed of SiO ₂ , Al ₂ O ₃ , CaO, and Ge-based oxide and may not contain any other components. More specifically, the composition contains only SiO ₂ , Al ₂ O ₃ , CaO, Ge-based oxides, and inevitable impurities, and is a composition composed of SiO ₂ , Al ₂ O ₃ , CaO, and Ge-based oxides, and other than inevitable impurities. It may not contain any ingredients. As described above, since the composition contains only SiO ₂ , Al ₂ O ₃ , CaO, and Ge-based oxides, a low melting temperature can be achieved and plasma resistance can be improved to achieve a low etch rate in the etching process using plasma.

According to an exemplary embodiment of the present invention, the content of SiO ₂ in the composition may be 45.00% by weight or more and 50.00% by weight or less. By controlling the content of SiO ₂ in the above-mentioned range, the basic physical properties of the plasma-resistant glass can be secured, durability and reliability can be improved, and the production cost of parts can be reduced by facilitating processing of the plasma-resistant glass. You can.

According to an exemplary embodiment of the present invention, the content of Al ₂ O ₃ in the composition may be 5.00% by weight or more and 20.00% by weight or less. By adjusting the content of Al ₂ O ₃ within the above-mentioned range, outgassing can be prevented, particle generation can be suppressed, and the wear resistance of chamber internal parts for the semiconductor manufacturing process is improved. It can be melted easily by lowering the melting temperature of the composition.

According to one embodiment of the present invention, the content of CaO in the composition may be 10.00% by weight or more and 25.00% by weight or less. By adjusting the content of CaO within the above-mentioned range, the thermal expansion coefficient and glass transition temperature of the glass can be lowered, thereby minimizing thermal shock at high temperatures and improving the durability of components used inside the chamber for the semiconductor manufacturing process.

According to one embodiment of the present invention, the content of the Ge-based oxide may be 10.00% by weight or more and 30.00% by weight or less. By adjusting the content of the Ge-based oxide within the above-mentioned range, the melting temperature of the plasma-resistant glass can be realized low, enabling melting, and the dielectric constant can be realized low.

According to one embodiment of the present invention, the light transmittance may be 80% or more and 100% or less. Specifically, the light transmittance of the plasma-resistant glass may be 82% or more and 98% or less, 85% or more and 95% or less, or 87% or more and 92% or less. In this specification, “light transmittance” may refer to a value measured using a haze meter (JCH-300S, Oceanoptics). By implementing the light transmittance of the plasma-resistant glass in the above-described range, it is possible to improve the meltability of the plasma-resistant glass and at the same time achieve high vitrification.

According to one embodiment of the present invention, the Vickers hardness may be 650 HV or more and 1,000 HV or less. The Vickers hardness of the plasma-resistant glass is 670 HV or more and 980 HV or less, 650 HV or more and 950 HV or less, 680 HV or more and 930 HV or less, 700 HV and 900 HV or less, 720 HV and 880 HV or less, 750 HV and 850 HV or It may be above 780 HV and below 820 HV. As used herein, “Vickers hardness” may refer to a value measured using a Vickers hardness meter (Helmut Fischer, FISCHERSCOPE HM-2000). By implementing the Vickers hardness of the plasma-resistant glass in the above-described range, mechanical properties can be increased and durability in a plasma etching environment can be improved.

According to one embodiment of the present invention, the glass transition temperature may be 600°C or more and 850°C or less. Specifically, the glass transition temperature of the plasma-resistant glass may be 620 ℃ or higher and 830 ℃ or lower, 650 ℃ or higher and 800 ℃ or lower, 670 ℃ or higher and 780 ℃ or lower, or 700 ℃ or higher and 750 ℃ or lower. By adjusting the glass transition temperature of the plasma-resistant glass within the above-mentioned range, thermal shock at high temperatures of components used inside the chamber for the semiconductor manufacturing process can be minimized and durability can be improved.

^{According to} an exemplary embodiment of the present invention, the thermal expansion coefficient may be 4.0 ^Specifically , ^the thermal expansion coefficient of ^the plasma-resistant glass is 4.1 X 10 ^-6 m/(m℃) ^or less, 4.3 X ^{10 -6} m/(m℃) or more 5.7 X ^{10 -6} m/(m℃) ^or less, ^4.5 X 10 ^-6 m/(m℃) ^or less, 4.7 X ^{10 -6} m/(m℃) or more 5.3 It may be below X ^{10 -6} m/(m℃) ^or between 4.9 By adjusting the thermal expansion coefficient of the plasma-resistant glass within the above-mentioned range, durability can be improved by preventing damage to components due to thermal shock.

According to an exemplary embodiment of the present invention, the etching rate by mixed plasma of fluorine and argon (Ar) may be greater than 0 nm/min and less than or equal to 20 nm/min. Specifically, the etching rate by mixed plasma of fluorine and argon is more than 0 nm/min but less than 18 nm/min, more than 1 nm/min but less than 16 nm/min, and more than 2 nm/min and less than 15 nm/min. or less, 3 nm/min or more but 14 nm/min or less, 4 nm/min or more but 13 nm/min or less, 5 nm/min or more but 12 nm/min or less, 6 nm/min or more and 11 nm/min or less or 7 nm/min It may be more than 10 nm/min or less. By implementing an etching rate by the mixed plasma of fluorine and argon (Ar) in the above-mentioned range, the parts used inside the chamber for the semiconductor manufacturing process realize a low etching rate for plasma, thereby reducing the usage time in the semiconductor manufacturing process. It can be improved.

According to one embodiment of the present invention, the etch step of the plasma-resistant glass may be 150 nm or more and 600 nm or less. Specifically, the etch step of the plasma-resistant glass may be 160 nm or more and 590 nm or less, 200 nm or more and 580 nm or less, 300 nm or more and 560 nm or less, or 350 nm or more and 550 nm or less. By implementing the etching step of the plasma-resistant glass in the above-mentioned range, the parts for the interior of the chamber for the semiconductor manufacturing process can improve the usage time in the semiconductor manufacturing process by implementing a low etch rate for plasma.

According to an exemplary embodiment of the present invention, the melting point may be 1,500°C or more and 1,750°C or less. In this specification, the melting point may mean melting temperature. Specifically, the melting point of the plasma-resistant glass is 1,560 ℃ or higher and 1,740 ℃ or lower, 1,570 ℃ or higher and 1,730 ℃ or lower, 1,580 ℃ or higher and 1,720 ℃ or lower, 1,590 ℃ or higher and 1,710 ℃ or lower, 1,600 ℃ or higher and 1,700 ℃ or lower, or 1,610 ℃ or lower. ℃ Hereinafter, it may be 1,620 ℃ or higher and 1,680 ℃ or lower, 1,630 ℃ or higher and 1,670 ℃ or lower, or 1,640 ℃ or higher and 1,660 ℃ or lower. By adjusting the melting point of the plasma-resistant glass in the above-mentioned range, the viscosity of the melt of the plasma-resistant glass can be adjusted and the workability of the process using the plasma-resistant glass can be improved.

According to one embodiment of the present invention, the plasma-resistant glass may be amorphous. As described above, by implementing the structure of the plasma-resistant glass as amorphous, the durability of parts using the plasma-resistant glass can be improved while simultaneously reducing the etching rate by plasma.

One embodiment of the present invention provides parts for the interior of a chamber for a semiconductor manufacturing process made of the plasma-resistant glass.

Components for use inside a chamber for a semiconductor manufacturing process according to an embodiment of the present invention can improve usage time in the semiconductor manufacturing process by implementing a low etch rate for plasma, and can improve durability by preventing damage to components due to thermal shock. You can.

According to one embodiment of the present invention, the internal components include a focus ring, an edge ring, a cover ring, a ring shower, an insulator, and an EPD window. (window), electrode, view port, inner shutter, electro static chuck, heater, chamber liner, shower head, CVD Boat, wall liner, shield, cold pad, source head, outer liner, deposition shield for (Chemical Vapor Deposition) ), it may be any one of an upper liner, an exhaust plate, and a mask frame. From the above, by using the internal components, the resistance to plasma in the semiconductor manufacturing process is improved and the usage time is extended, thereby minimizing the cost required for semiconductor manufacturing.

One embodiment of the present invention is 20 to 50% by weight of SiO ₂ , 5 to 25% by weight of Al ₂ O ₃ , 10 to 74% by weight of CaO, and 0.01 to 50% by weight. melting a composition comprising less than or equal to % Ge-based oxide; and cooling the molten composition. It provides a method for producing plasma-resistant glass, including a step of cooling the molten composition.

The method for manufacturing plasma-resistant glass according to an embodiment of the present invention can easily manufacture plasma-resistant glass and prevent damage due to thermal shock in a high-temperature atmosphere, and can produce glass with higher hardness than existing glass, thereby producing mechanical glass. By increasing the characteristics, durability in a plasma etching environment can be improved.

In the method for manufacturing plasma-resistant glass, which is an exemplary embodiment of the present invention, description of content that overlaps with the plasma-resistant glass is omitted.

According to an exemplary embodiment of the present invention, 20 to 50% by weight of SiO ₂ , 5 to 25% by weight of Al ₂ O ₃ , 10 to 74% by weight of CaO, and 0.01% by weight or more. It includes a step (S11) of melting a composition containing 50% by weight or less of Ge-based oxide. From the above, by controlling the components of the plasma-resistant glass and controlling the content of the components, it is possible to prevent damage due to thermal shock in a high-temperature atmosphere of the plasma-resistant glass, achieve a low melting temperature, and achieve light transparency and durability. can be improved.

According to one embodiment of the present invention, the melting step may be melting the platinum crucible. As described above, by melting the composition in a platinum crucible, the components eluted from the crucible can be minimized and the physical properties of the plasma-resistant glass can be realized.

According to an exemplary embodiment of the present invention, a step (S13) of cooling the molten glass composition is included. By including the step of cooling the molten glass composition as described above, crystals of the plasma-resistant glass can be controlled and damage due to rapid thermal change can be prevented.

According to one embodiment of the present invention, the temperature of the cooling step may be room temperature. By adjusting the temperature of the cooling step within the above-described range, crystals of the plasma-resistant glass can be controlled, and melting can be easily performed in the process of manufacturing components for the interior of the chamber for the semiconductor manufacturing process.

According to one embodiment of the present invention, the melting temperature in the step of melting the plasma-resistant glass may be 1,500 ℃ or more and 1,750 ℃ or less. Specifically, the melting temperature in the step of melting the composition may be a melting point of 1,500°C or more and 1,750°C or less. In this specification, the melting point may mean melting temperature. Specifically, the melting point of the plasma-resistant glass is 1,560 ℃ or higher and 1,740 ℃ or lower, 1,570 ℃ or higher and 1,730 ℃ or lower, 1,580 ℃ or higher and 1,720 ℃ or lower, 1,590 ℃ or higher and 1,710 ℃ or lower, 1,600 ℃ or higher and 1,700 ℃ or lower, or 1,610 ℃ or lower. ℃ Hereinafter, it may be 1,620 ℃ or higher and 1,680 ℃ or lower, 1,630 ℃ or higher and 1,670 ℃ or lower, or 1,640 ℃ or higher and 1,660 ℃ or lower. By controlling the melting temperature in the step of melting the composition within the above-mentioned range, the workability of the process of manufacturing the plasma-resistant glass can be improved by controlling the viscosity of the molten composition.

One embodiment of the present invention includes melting the plasma-resistant glass; Injecting the molten plasma-resistant glass into a mold; and annealing the injected plasma-resistant glass.

The method of manufacturing components for the interior of a chamber for a semiconductor manufacturing process according to an embodiment of the present invention can manufacture components with various shapes, prevent damage due to thermal shock in a high temperature atmosphere, and easily manufacture the components.

According to one embodiment of the present invention, the method of manufacturing components for the interior of the chamber for the semiconductor manufacturing process includes melting the plasma-resistant glass (S21). By including the step of melting the plasma-resistant glass as described above, the workability of the process of manufacturing parts for the interior of the chamber for the semiconductor manufacturing process is improved, and at the same time, the molten metal in which the plasma-resistant glass is melted is injected into the mold. By doing so, it can be molded into various shapes.

According to one embodiment of the present invention, the method of manufacturing components for the interior of a chamber for the semiconductor manufacturing process includes the step of injecting the molten plasma-resistant glass into a mold (S23). As described above, parts of various shapes can be manufactured by injecting the molten plasma-resistant glass into a mold.

According to one embodiment of the present invention, the mold includes a focus ring, an edge ring, a cover ring, a ring shower, an insulator, and an EPD window. ), electrode, view port, inner shutter, electro static chuck, heater, chamber liner, shower head, CVD (Chemical Vapor Deposition boat, wall liner, shield, cold pad, source head, outer liner, deposition shield, It may have one of the following shapes: an upper liner, an exhaust plate, and a mask frame. As described above, by implementing various shapes of the mold, it is possible to easily implement the shape of the part and reduce manufacturing time.

According to one embodiment of the present invention, the method of manufacturing components for the interior of the chamber for the semiconductor manufacturing process includes the step of annealing the injected plasma-resistant glass (S25). By including the step of annealing the injected plasma-resistant glass as described above, the stress caused by heat generated in the part manufactured by injecting into the mold can be minimized to improve the durability of the part and minimize thermal shock at high temperatures. there is.

According to one embodiment of the present invention, the melting temperature in the step of melting the plasma-resistant glass may be 1,500 ℃ or more and 1,750 ℃ or less. Specifically, the melting temperature in the step of melting the plasma-resistant glass may be 1,500°C or more and 1,750°C or less. In this specification, the melting point may mean melting temperature. Specifically, the melting point of the plasma-resistant glass is 1,560 ℃ or higher and 1,740 ℃ or lower, 1,570 ℃ or higher and 1,730 ℃ or lower, 1,580 ℃ or higher and 1,720 ℃ or lower, 1,590 ℃ or higher and 1,710 ℃ or lower, 1,600 ℃ or higher and 1,700 ℃ or lower, or 1,610 ℃ or lower. ℃ Hereinafter, it may be 1,620 ℃ or higher and 1,680 ℃ or lower, 1,630 ℃ or higher and 1,670 ℃ or lower, or 1,640 ℃ or higher and 1,660 ℃ or lower. By controlling the melting temperature in the step of melting the plasma-resistant glass within the above-described range, workability can be improved by controlling the viscosity of the molten plasma-resistant glass.

According to an exemplary embodiment of the present invention, the temperature of the annealing step may be 400°C or more and 900°C or less. Specifically, the temperature of the annealing step is 430 ℃ or more and 890 ℃ or less, 450 ℃ or more and 880 ℃ or less, 470 ℃ or more and 870 ℃ or less, 500 ℃ or more and 860 ℃ or less, 550 ℃ or more and 850 ℃ or less, 560 ℃ or more and 840 ℃ Below, 570 ℃ and below 830 ℃, 580 ℃ and below 820 ℃, 590 ℃ and below 810 ℃, 600 ℃ and below 800 ℃, 610 ℃ and below 790 ℃, 620 ℃ and below 780 ℃, 630 ℃ and below 770 ℃ , 640 ℃ or more and 760 ℃ or less, 650 ℃ or more and 750 ℃ or less, 660 ℃ or more and 740 ℃ or less, 670 ℃ or more and 730 ℃ or less, 680 ℃ or more and 720 ℃ or less, or 690 ℃ or more and 710 ℃ or less. By controlling the temperature of the annealing step within the above-mentioned range, stress caused by heat formed within the components used inside the chamber for the semiconductor manufacturing process can be reduced, and thermal shock at high temperatures can be minimized to improve the durability of the components.

According to one embodiment of the present invention, it may include a step (S27) of processing a precursor of a component for the interior of a chamber for a semiconductor manufacturing process manufactured by the annealed plasma-resistant glass. As described above, sophisticated components can be manufactured by processing precursors for components used inside the chamber for the semiconductor manufacturing process.

Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain the present invention to those skilled in the art.

<Example 1>

A composition was prepared comprising 50% by weight SiO ₂ , 15% by weight Al ₂ O ₃ , 20% by weight CaO and 15% by weight GeO ₂ . Specifically, the composition was placed in a weight of 600 g and mixed for approximately 1 hour using a zirconia ball milling method. That is, 600 g of the composition: 1,800 g of zirconia balls (weight ratio 1:3) were mixed in a dry manner and then dried for 24 hours. Thereafter, the temperature of the dried composition was increased at a rate of 10 °C/min until it reached a temperature of 1,650 °C using a supercatalyst, and the composition was melted by maintaining the temperature at 1,650 °C for approximately 2 hours.

The molten composition was cooled to room temperature to prepare plasma-resistant glass.

<Example 2>

In the same manner as Example 1, except that the composition was prepared to include 50% by weight of SiO ₂ , 10% by weight of Al ₂ O ₃ , 15% by weight of CaO, and 25% by weight of GeO ₂ Plasma-resistant glass was manufactured.

<Example 3>

In the same manner as Example 1, except that the composition was prepared to include 50% by weight of SiO ₂ , 10% by weight of Al ₂ O ₃ , 10% by weight of CaO, and 30% by weight of GeO ₂ Plasma-resistant glass was manufactured.

<Comparative Example 1>

Plasma-resistant glass was prepared in the same manner as in Example 1, except that the composition was prepared to include 50% by weight of SiO ₂ , 10% by weight of Al ₂ O ₃ and 40% by weight of CaO. .

<Experimental Example 1: Measurement of melting state of plasma-resistant glass>

Examples 1 to 3 were placed in a platinum crucible, heated at 1,650°C and 1 atm for 4 hours, and then the appearance was measured.

Figure 3 is a photograph taken of the plasma-resistant glass of Examples 1 to 3, which is an embodiment of the present invention. Referring to FIG. 3, it was confirmed that Examples 1 to 3 were all melted and vitrified without any unmelted portions.

<Experimental Example 2: Measurement of dielectric constant of plasma-resistant glass>

Examples 1 to 3 and Comparative Example 1 were set at a measurement frequency of 1 MHz, and the dielectric constants were measured using a Keysight E4990A Impedence Analyzer and are summarized in Table 1 below.

	Example 1	Example 2	Example 3	Comparative Example 1
Dielectric constant @1MHz	8.72	8.08	7.07	10.13

Referring to Table 1, it was confirmed that Examples 1 to 3 including SiO ₂ , Al ₂ O ₃ , CaO and GeO ₂ were implemented with low dielectric constants.

In contrast, Comparative Example 1, which did not contain GeO ₂ , confirmed that the dielectric constant increased.

<Experimental Example 3: Measurement of etch step and etch rate>

Examples 1 to 3 and Reference Example 1 made of quartz were partially exposed to a mixed plasma of fluorine and argon (Ar) for 1 hour, and the exposed portion and the unexposed portion were exposed to the plasma. The etch step difference, which is the difference between , was measured with a confocal laser microscope (Olympus OLS 5100 equipment, 400 magnification), and the etching rate was calculated by dividing the etching time from the etch step difference and summarized in Table 2 below.

	Example 1	Example 2	Example 3	Reference example 1
Etching step (nm)	380.8	470.6	545.0	14144
Etch rate (nm/min)	6.3	7.8	9.1	235.7

In comparison, it can be confirmed that Reference Example 1 corresponds to quartz and has high etch steps and high etch rates, but Examples 1 to 3 including GeO ₂ have low etch steps and low etch rates.

Therefore, one embodiment of the present invention satisfies the content of SiO ₂ , Al ₂ O ₃ , CaO and Ge-based oxide in the plasma-resistant glass, thereby realizing a low etch rate and glass transition temperature, and at the same time implementing a low thermal expansion coefficient to achieve high temperature Thermal shock can be prevented, the melting temperature is low, and mechanical properties are improved by realizing light transmittance and high hardness, thereby improving durability.

Although the present invention has been described in terms of limited embodiments in the above, the present invention is not limited thereto, and the technical idea of the present invention and the patent claims described below will be understood by those skilled in the art in the technical field to which the present invention pertains. Of course, various modifications and variations are possible within the scope of equality.

Claims (15)

1. SiO ₂ of 20% to 50% by weight, Al ₂ O ₃ of 5% to 25% by weight, CaO of 10% to 74% by weight, and Ge-based oxide of 0.01% to 50% by weight. Formed by melting a composition comprising

   Plasma resistant glass.
2. In claim 1,

   The composition contains only SiO ₂ , Al ₂ O ₃ , CaO, Ge-based oxides and inevitable impurities,

   The content of SiO ₂ is 45.00% by weight or more and 50.00% by weight or less,

   The content of Al ₂ O ₃ is 5.00% by weight or more and 20.00% by weight or less,

   The content of CaO is 10.00% by weight or more and 25.00% by weight or less,

   The content of the Ge-based oxide is 10.00% by weight or more and 30.00% by weight or less,

   Plasma resistant glass.
3. In claim 1,

   A light transmittance of 80% or more and 100% or less,

   Plasma resistant glass.
4. In claim 1,

   Vickers hardness is 650 HV or more and 1,000 HV or less,

   Plasma resistant glass.
5. In claim 1,

   The glass transition temperature is 600 ℃ or more and 850 ℃ or less,

   Plasma resistant glass.
6. In claim 1,

   The thermal ^expansion coefficient is ^4.0

   Plasma resistant glass.
7. In claim 1,

   The etching rate by the mixed plasma of fluorine and argon is greater than 0 nm/min and less than 20 nm/min,

   Plasma resistant glass.
8. In claim 1,

   With a melting point of 1,500 ℃ or more and 1,750 ℃ or less,

   Plasma resistant glass.
9. Manufactured from the plasma-resistant glass of claim 1,

   Parts for the interior of the chamber for the semiconductor manufacturing process.
10. In claim 9,

    The internal components include a focus ring, edge ring, cover ring, ring shower, insulator, EPD window, electrode, View port, inner shutter, electro static chuck, heater, chamber liner, shower head, boat for CVD (Chemical Vapor Deposition) ), wall liner, shield, cold pad, source head, outer liner, deposition shield, upper liner, One of an exhaust plate and a mask frame,

    Parts for the interior of the chamber for the semiconductor manufacturing process.
11. SiO ₂ of 20% to 50% by weight, Al ₂ O ₃ of 5% to 25% by weight, CaO of 10% to 74% by weight, and Ge-based oxide of 0.01% to 50% by weight. melting the composition comprising; and

    Including, cooling the molten composition.

    Method for manufacturing plasma-resistant glass.
12. In claim 11,

    The melting temperature in the step of melting the composition is 1,400 ℃ or more and 1,700 ℃ or less,

    Method for manufacturing plasma-resistant glass.
13. Melting the plasma-resistant glass of claims 1 to 8;

    Injecting the molten plasma-resistant glass into a mold; and

    Comprising the step of annealing the injected plasma-resistant glass,

    Method for manufacturing chamber internal parts for the semiconductor manufacturing process.
14. In claim 13,

    The melting temperature in the step of melting the plasma-resistant glass is 1,550 ℃ or more and 1,750 ℃ or less,

    Method for manufacturing chamber internal parts for the semiconductor manufacturing process.
15. In claim 13,

    The temperature of the annealing step is 400 ℃ or more and 900 ℃ or less,

    Method for manufacturing chamber internal parts for the semiconductor manufacturing process.

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