Glass, method for manufacturing glass, components for semiconductor manufacturing equipment, and semiconductor manufacturing equipment

Abstract

To provide a glass that exhibits excellent etching resistance in a plasma environment, has a small number of particles deposited in a plasma environment, and suppresses the deposition of particles containing components that may significantly affect the performance of semiconductor products; a method for manufacturing the glass; a component for semiconductor manufacturing equipment related to the glass; and semiconductor manufacturing equipment related to the glass. [Solution] Contains silicon, magnesium, strontium, and barium, and the alkali metal element R 1 , alkaline earth metal elements R 2 In this case, expressed as a mole percentage based on oxides, the SiO2 content is 48.0 mol% or more, the Al2O3 content is 20.0 mol% or less, the MgO content is 0.1 mol% or more, the SrO content is 0.1 mol% or more, and the BaO content is 0.1 mol% or more. 2 The O content is 22.0 mol% or more, substantially free of CaO, substantially free of TiO2, R 1 Glass that is substantially free of 2O.

Description

[Technical Field]

[0001] This invention relates to glass, a method for manufacturing glass, a component for semiconductor manufacturing equipment, and semiconductor manufacturing equipment. [Background technology]

[0002] Plasma is used in various semiconductor manufacturing equipment, such as plasma CVD equipment and plasma etching equipment, when manufacturing semiconductor devices. Components used in semiconductor manufacturing equipment are frequently exposed to plasma during operation and gradually wear out. Worn-out components are replaced with new ones. Traditionally, quartz glass has often been used for peripheral components within such semiconductor manufacturing equipment.

[0003] As products manufactured by semiconductor manufacturing equipment become taller and more complex, the plasma environment to which components are exposed is becoming increasingly harsh, leading to more frequent component replacements. Since semiconductor manufacturing equipment cannot be operated while components are being replaced, an increase in the frequency of component replacements reduces the production efficiency of the product. Thus, from the perspective of further extending the lifespan of components used in semiconductor manufacturing equipment, there is a demand for components with higher plasma resistance than quartz glass. Patent Document 1 describes a glass material for semiconductor manufacturing equipment that exhibits plasma resistance characteristics such as an etching rate of less than 10 nm / min against a mixed plasma of fluorine and argon. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 2023-508677 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The present inventors, with reference to the technology described in Patent Document 1, investigated highly plasma-resistant glass and found that while it exhibits a low etching rate in a plasma environment and is excellent in terms of etching resistance, depending on the materials contained in the glass, it may precipitate a large number of particles during plasma processing, or precipitate particles containing components that can significantly affect the performance of semiconductor products during plasma processing. In other words, it may have poor plasma resistance in terms of particle precipitation. Particles precipitated in a plasma environment within semiconductor manufacturing equipment can cause defects in the manufactured semiconductor products.

[0006] One aspect of this disclosure has been made in view of the above points, and aims to provide a glass that has excellent etching resistance in a plasma environment, a small number of particles deposited in a plasma environment, and suppresses the deposition of particles containing components that may significantly affect the performance of semiconductor products. Another aspect of this disclosure aims to provide a method for manufacturing the above glass, a component for semiconductor manufacturing equipment related to the above glass, and semiconductor manufacturing equipment related to the above glass. [Means for solving the problem]

[0007] As a result of diligent research, the inventors of this invention discovered that the above objective can be achieved by adopting the following configuration, and thus completed the present invention.

[0008] In other words, the means for solving the above problems include the following embodiments [1] to

[15] . [1] It contains silicon, magnesium, strontium, and barium, and the alkali metal element R 1 , alkaline earth metal elements R 2 In this case, expressed as a mole percentage based on oxides, the SiO2 content is 48.0 mol% or more, the Al2O3 content is 20.0 mol% or less, the MgO content is 0.1 mol% or more, the SrO content is 0.1 mol% or more, and the BaO content is 0.1 mol% or more. 2The glass has an O content of 22.0 mol% or more, substantially does not contain CaO, substantially does not contain TiO2, and substantially does not contain R 1 2O. [2] The glass according to [1], wherein the Al2O3 content is 13.5 mol% or less. [3] The glass according to [1] or [2], which substantially does not contain Al2O3. [4] The glass according to any one of [1] to [3], wherein the BaO content is 4.0 to 14.0 mol%. [5] The glass according to any one of [1] to [4], wherein the Al2O3 content is 13.5 mol% or less and the BaO content is 4.0 to 14.0 mol%. [6] The glass according to any one of [1] to [5], which is a glass block. [7] The glass according to any one of [1] to [6], which is a disc-shaped glass block. [8] The glass according to any one of [1] to [6], which is an annular glass block. [9] The glass according to any one of [1] to [8], which is used as a member for a semiconductor manufacturing apparatus mounted on a semiconductor manufacturing apparatus.

[10] The glass according to [9], wherein the member for a semiconductor manufacturing apparatus is an edge ring, a shield ring, a focus ring, a shower plate, an electrostatic chuck, a susceptor, an injector, a viewing window, a top plate or a side wall mounted on a semiconductor manufacturing apparatus.

[11] A method for manufacturing the glass according to any one of [1] to

[10] , comprising melting by heating a glass raw material at a melting temperature of 1400 to 1800 °C, and cooling the obtained molten glass at a cooling rate of 100 to 1500 °C / min to a cooling stop temperature of 500 to 700 °C.

[12] A member for a semiconductor manufacturing apparatus made of the glass according to any one of [1] to [8].

[13] The semiconductor manufacturing equipment component described in

[12] , which is mounted on semiconductor manufacturing equipment, and is an edge ring, shield ring, focus ring, shower plate, electrostatic chuck, susceptor, injector, viewing window, top plate, or side wall.

[14]

[12] A semiconductor manufacturing apparatus equipped with the semiconductor manufacturing apparatus components described above.

[15]

[13] A semiconductor manufacturing apparatus equipped with the semiconductor manufacturing apparatus components described above. [Effects of the Invention]

[0009] According to one aspect of this disclosure, it is possible to provide glass that exhibits excellent etching resistance in a plasma environment, has a small number of particles deposited in a plasma environment, and suppresses the deposition of particles containing components that can significantly affect the performance of semiconductor products. Furthermore, according to the present invention, it is possible to provide a method for manufacturing the above glass, a component for semiconductor manufacturing equipment related to the above glass, and semiconductor manufacturing equipment related to the above glass. [Brief explanation of the drawing]

[0010] [Figure 1] This graph shows the relationship between the Ca content in the glass and the number of particles with a diameter of 100 nm or more, measured after a dust generation test. [Modes for carrying out the invention]

[0011] The meanings of the terms used in this specification are as follows: A numerical range represented using "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In the numerical ranges described stepwise in this specification, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise. Furthermore, in the numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0012] [glass] A glass according to one aspect of the present disclosure contains silicon, magnesium, strontium, and barium, and an alkali metal element R 1 , alkaline earth metal elements R 2 In this case, expressed as a mole percentage based on oxides, the SiO2 content is 48.0 mol% or more, the Al2O3 content is 20.0 mol% or less, the MgO content is 0.1 mol% or more, the SrO content is 0.1 mol% or more, the BaO content is 0.1 mol% or more, and R 2 The O content is 22.0 mol% or more, substantially free of CaO, substantially free of TiO2, and R 1 It contains virtually no 2O.

[0013] Hereinafter, a glass in one aspect of this disclosure will also be referred to as "this glass."

[0014] This glass exhibits excellent etching resistance in a plasma environment (hereinafter also simply referred to as "etching resistance"). This is presumed to be because, due to the presence of a predetermined amount of alkaline earth metal elements, this glass contains many components that have high resistance to plasma processing gases (e.g., fluorine gas) that fill semiconductor manufacturing equipment during plasma processing, thereby reducing the rate at which the material is consumed by plasma processing.

[0015] Furthermore, using this glass in semiconductor manufacturing equipment components reduces the number of particles deposited in a plasma environment. When glass contains a large amount of Ca, the sublimation point of CaF2, a reaction product of Ca and atoms of the plasma processing gas, such as fluorine, is too high. As a result, CaF2 particles do not volatilize in the plasma environment and remain as particles within the semiconductor manufacturing equipment. In contrast, this glass, by substantially containing no CaO, is presumed to suppress particle deposition in a plasma environment, particularly the deposition of particles with a diameter of 100 nm or more, which can have a significant impact on the wiring of semiconductor products. Hereinafter, the performance of suppressing the number of particles deposited when exposed to a plasma environment is also referred to as "dust generation resistance".

[0016] Furthermore, by using this glass as a member for a semiconductor manufacturing apparatus, it is possible to suppress the deposition of particles containing components (hereinafter also referred to as "component X") that can significantly affect the performance of semiconductor products. Examples of such component X include alkali metal elements represented by Na, and Ti. The reason for being able to suppress the deposition of particles containing component X is presumably that this glass does not substantially contain TiO2 and does not substantially contain R 1 2O which is an oxide of an alkali metal element.

[0017] In a semiconductor manufacturing apparatus, examples of members used in an environment exposed to plasma include members made of quartz glass. However, quartz glass has insufficient etching resistance. In contrast, this glass has excellent etching resistance, can reduce the number of particles deposited in a plasma environment, and can suppress the deposition of particles containing component X.

[0018] Hereinafter, this glass will be described in detail. First, the composition (glass composition) of this glass will be described below. That is, the content (expressed as a molar percentage based on oxides) of elements that this glass may contain will be described.

[0019] 〈Si〉 This glass contains silicon (Si).

[0020] 《SiO2》 Due to the reason that the chemical durability of this glass is more excellent, the content of SiO2 is 48.0 mol% or more, preferably 50.0 mol% or more, more preferably 51.0 mol% or more, still more preferably 52.0 mol% or more, yet more preferably 53.0 mol% or more, particularly preferably 55.0 mol% or more, and most preferably 58.0 mol% or more. For the reason that the content of components that improve etching resistance in this glass can be increased, the SiO2 content is preferably 78.0 mol% or less, more preferably 75.0 mol% or less, even more preferably 70.0 mol% or less, even more preferably 68.0 mol% or less, particularly preferably 66.0 mol% or less, and most preferably 65.0 mol% or less.

[0021] <R 2 > Alkaline earth metal elements (R 2 Examples of these include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). This glass contains Mg, Sr, and Ba as essential elements. On the other hand, this glass contains virtually no CaO. Furthermore, this glass may contain either or both Be and Ra. Alkaline earth metal elements (R) contained in this glass 2 ) is preferably substantially Mg, Sr, and Ba.

[0022] 《R 2 O》 This glass has superior etching resistance, therefore, R 2 The O content is 22.0 mol% or more, preferably 24.0 mol% or more, more preferably 27.0 mol% or more, even more preferably 30.0 mol% or more, even more preferably 32.0 mol% or more, particularly preferably 34.0 mol% or more, and most preferably 35.0 mol% or more. When manufacturing this glass, R is used because it can suppress crystal precipitation due to devitrification. 2 The O content is preferably 52.0 mol% or less, more preferably 50.0 mol% or less, even more preferably 47.5 mol% or less, even more preferably 45.0 mol% or less, particularly preferably 44.0 mol% or less, even more preferably 42.0 mol% or less, and most preferably 40.0 mol% or less.

[0023] 《MgO》 For the reason that this glass has superior etching resistance, the MgO content is 0.1 mol% or more, preferably 1.0 mol% or more, more preferably 2.0 mol% or more, even more preferably 3.0 mol% or more, even more preferably 4.0 mol% or more, particularly preferably 5.0 mol% or more, and most preferably 8.0 mol% or more. When manufacturing this glass, the MgO content is preferably 50.0 mol% or less, more preferably 40.0 mol% or less, even more preferably 35.0 mol% or less, even more preferably 30.0 mol% or less, particularly preferably 25.0 mol% or less, even more preferably 20.0 mol% or less, and most preferably 18.0 mol% or less, because it can suppress the precipitation of crystals due to devitrification.

[0024] 《SrO》 For the reason that this glass has superior etching resistance, the SrO content is 0.1 mol% or more, preferably 1.0 mol% or more, more preferably 2.0 mol% or more, even more preferably 3.0 mol% or more, even more preferably 4.0 mol% or more, particularly preferably 5.0 mol% or more, and most preferably 8.0 mol% or more. When manufacturing this glass, the SrO content is preferably 50.0 mol% or less, more preferably 40.0 mol% or less, even more preferably 35.0 mol% or less, even more preferably 30.0 mol% or less, particularly preferably 25.0 mol% or less, even more preferably 20.0 mol% or less, and most preferably 18.0 mol% or less, because it can suppress the precipitation of crystals due to devitrification.

[0025] 《BaO》 For the sake of superior etching resistance of this glass, the BaO content is 0.1 mol% or more, preferably 1.0 mol% or more, more preferably 2.0 mol% or more, even more preferably 3.0 mol% or more, even more preferably 4.0 mol% or more, particularly preferably 5.0 mol% or more, even more preferably 8.0 mol% or more, and most preferably 9.0 mol% or more. When manufacturing this glass, the BaO content is preferably 50.0 mol% or less, more preferably 40.0 mol% or less, even more preferably 35.0 mol% or less, even more preferably 30.0 mol% or less, particularly preferably 25.0 mol% or less, very preferably 20.0 mol% or less, even more preferably 18.0 mol% or less, and most preferably 14.0 mol% or less, for the reason that it can suppress the precipitation of crystals due to devitrification.

[0026] 《SrO / BaO》 For the reason that this glass has superior etching resistance, the SrO / BaO ratio is preferably 3.0 or less, more preferably 2.5 or less, even more preferably 2.0 or less, even more preferably 1.5 or less, particularly preferably 1.25 or less, and most preferably 1.0 or less. When manufacturing this glass, the SrO / BaO ratio is preferably 0.1 or higher, more preferably 0.2 or higher, even more preferably 0.3 or higher, even more preferably 0.35 or higher, particularly preferably 0.4 or higher, very preferably 0.45 or higher, and most preferably 0.5 or higher, because it suppresses the precipitation of crystals due to devitrification.

[0027] 《CaO》 This glass is substantially free of CaO because it exhibits superior dust resistance. Here, substantially free of CaO means that the CaO content is less than 0.1% by mass. The CaO content is preferably 0.08% by mass or less, more preferably 0.05% by mass or less, and even more preferably 0.03% by mass or less. The CaO content may be zero.

[0028] <Al> This glass may contain aluminum (Al).

[0029] 《Al2O3》 For the reason that this glass has superior etching resistance, the Al2O3 content is 20.0 mol% or less, preferably 17.0 mol% or less, more preferably 15.0 mol% or less, even more preferably 13.5 mol% or less, even more preferably 10.0 mol% or less, particularly preferably 8.0 mol% or less, even more preferably 6.0 mol% or less, and most preferably 5.0 mol% or less. In particular, it is most preferable that the glass is substantially free of Al2O3. Here, substantially free of Al2O3 means that the Al2O3 content is less than 0.1% by mass. The Al2O3 content is preferably 0.08% by mass or less, more preferably 0.05% by mass or less, and even more preferably 0.03% by mass or less. The lower limit of the Al2O3 content is preferably zero.

[0030] <Ti(TiO2)> This glass is substantially TiO2-free because it can suppress the precipitation of particles containing component X when used in semiconductor manufacturing equipment components. Here, "substantially TiO2-free" means that the TiO2 content is less than 0.1% by mass. The TiO2 content may be zero.

[0031] <R 1 (R 1 2O)〉 This glass contains alkali metal elements (R) because it can suppress the precipitation of particles containing component X when used in semiconductor manufacturing equipment components. 1 ) oxide (R 1 It substantially does not contain 2O). Here, R 1 Substantially containing 2O means R 1 This means that the 2O content is less than 0.1% by mass. Furthermore, alkali metal elements (R 1 Examples of these elements include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).

[0032] <B, P, Ge> This glass may further contain at least one element selected from the group consisting of boron (B), phosphorus (P), and germanium (Ge).

[0033] 《B2O3》 For the sake of the excellent etching resistance of this glass, the B2O3 content is preferably 25.0 mol% or less, more preferably 20.0 mol% or less, even more preferably 15.0 mol% or less, even more preferably 13.0 mol% or less, particularly preferably 10.0 mol% or less, even more preferably 9.0 mol% or less, very preferably 6.0 mol% or less, most preferably 5.0 mol% or less, and most preferably 1.0 mol% or less. The lower limit of the B2O3 content is preferably zero.

[0034] 《P2O5》 For the sake of the excellent etching resistance of this glass, the P2O5 content is preferably 9.0 mol% or less, more preferably 7.0 mol% or less, even more preferably 5.5 mol% or less, even more preferably 4.0 mol% or less, even more preferably 3.0 mol% or less, particularly preferably 2.0 mol% or less, even more preferably 1.5 mol% or less, and most preferably 1.0 mol% or less. The lower limit of the P2O5 content is preferably zero.

[0035] 《GeO2》 For the reason that this glass has excellent etching resistance, the GeO2 content is preferably 9.0 mol% or less, more preferably 5.5 mol% or less, even more preferably 4.0 mol% or less, even more preferably 2.0 mol% or less, and particularly preferably 1.0 mol% or less. The lower limit of the GeO2 content is preferably zero.

[0036] <Impure Elements> For the sake of the excellent etching resistance of this glass, the content of impurity elements in terms of oxides is preferably 15.0 mol% or less, more preferably 10.0 mol% or less, even more preferably 7.5 mol% or less, even more preferably 5.0 mol% or less, particularly preferably 1.0 mol% or less, very preferably 0.5 mol% or less, and most preferably 0.05 mol% or less. The lower limit of the content of impurity elements in terms of oxides is preferably zero.

[0037] Impurity elements include silicon (Si) and alkaline earth metal elements (R 2 ), aluminum (Al), titanium (Ti), alkali metal elements (R 1 These are metallic elements, excluding boron (B), phosphorus (P), and germanium (Ge).

[0038] Examples of impurity elements include Cu, Fe, Ni, Cr, Sn, Co, V, Bi, Se, Ce, Er, Nd, Y, Ga, In, Zr, Mn, Zn, and Ta. The copper content, when expressed as an oxide, specifically refers to the content of CuO. The Fe content, calculated as an oxide, specifically refers to the Fe2O3 content. The Ni content, when expressed as an oxide, specifically refers to the NiO content. The Cr content, calculated as an oxide, specifically refers to the Cr2O3 content. The Sn content, calculated as an oxide, specifically refers to the SnO2 content. The Co content, calculated as an oxide, specifically refers to the Co3O4 content. The V content, when expressed as an oxide, specifically refers to the V2O5 content. The Bi content, calculated as an oxide, specifically refers to the Bi2O3 content. The Se content, calculated as an oxide, specifically refers to the SeO2 content. The Ce content, calculated as an oxide, specifically refers to the CeO2 content. The Er content, when expressed as an oxide, specifically refers to the Er2O3 content. The Nd content, when expressed as an oxide, specifically refers to the Nd2O3 content. The Y content, when expressed as an oxide, specifically refers to the Y2O3 content. The Ga content, when expressed as an oxide, specifically refers to the Ga2O3 content. The In content, when expressed as an oxide, specifically refers to the In2O3 content. The Zr content, calculated as an oxide, specifically refers to the ZrO2 content. The Mn content, calculated as an oxide, specifically refers to the MnO2 content. The Zn content, calculated as an oxide, specifically refers to the ZnO content. The Ta content, when expressed as an oxide, specifically refers to the content of Ta2O5.

[0039] As an example of a preferred embodiment of this glass, it contains silicon, magnesium, strontium, and barium, and the alkali metal element R 1 , alkaline earth metal elements R 2 In this case, expressed as a mole percentage based on oxides, the SiO2 content is 48.0 mol% or more, the MgO content is 0.1 mol% or more, the SrO content is 0.1 mol% or more, the BaO content is 0.1 mol% or more, and R 2 The O content is 22.0 mol% or more, substantially free of Al2O3, substantially free of CaO, substantially free of TiO2, R 1 Examples include glass that substantially does not contain 2O.

[0040] Another example of a preferred embodiment of this glass is one containing silicon, magnesium, strontium, and barium, with alkali metal elements R 1 , alkaline earth metal elements R 2In this case, expressed as a mole percentage based on oxides, the SiO2 content is 48.0 mol% or more, the Al2O3 content is 13.5 mol% or less, the MgO content is 0.1 mol% or more, the SrO content is 0.1 mol% or more, and the BaO content is 4.0 to 14.0 mol%, R 2 The O content is 22.0 mol% or more, substantially free of CaO, substantially free of TiO2, and R 1 Examples include glass that substantially does not contain 2O. In each of the above preferred embodiments, the embodiment in which the content of each component is within the above preferred range is a more preferred embodiment.

[0041] The content of each element mentioned above (except Si) in glass (expressed as a mole percentage based on oxides) is measured using an X-ray fluorescence spectrometer (XRF) (Rigaku Corporation's "ZSX100e"). In other words, the X-ray intensity of each element on the glass surface is measured and quantitatively analyzed to determine the content of each element.

[0042] The SiO2 content in glass can be determined as follows: First, a powdery sample is collected from the glass (for example, the central part of the glass block described later) by polishing, and the total amount of oxygen Z1 in the glass is determined by infrared absorption using an oxygen / hydrogen analyzer (LECO ROH-600). The amount of oxygen Z3 is calculated by subtracting the amount of oxygen Z2, which is bonded to the elements (excluding Si) contained in the glass in a stoichiometric composition, from the total amount of oxygen Z1 in the glass (amount of oxygen Z3 = total amount of oxygen Z1 - amount of oxygen Z2). Assuming that the entire amount of oxygen Z3 is used for bonding with silicon atoms, the amount of oxygen Z3 is converted to the amount of SiO2. The amount of SiO2 obtained in this way is taken as the SiO2 content of the glass.

[0043] The etching rate of this glass in a plasma environment is preferably 1000 nm / h or less. More preferably 900 nm / h or less, even more preferably 700 nm / h or less, particularly preferably 600 nm / h or less, very preferably 500 nm / h or less, and most preferably 300 nm / h or less. The etching rate of this glass in a plasma environment may also be 0 nm / h. The etching rate in a plasma environment as described herein is measured by the method described in the later examples.

[0044] The number of particles with a diameter of 100 nm or more deposited in the glass under a plasma environment is preferably 100 or less. More preferably 80 or less, even more preferably 50 or less, and particularly preferably 40 or less. The number of particles deposited in the glass under a plasma environment may be 0. The number of particles deposited in the plasma environment in this specification is measured by the measurement method described in the later examples.

[0045] <Glass Blocks> The glass is preferably in the form of a glass block. Furthermore, the term "glass block" refers to a solid mass of glass that does not contain any glass frit, glass powder, or glass fiber. A glass block may take any shape.

[0046] 《Shape of glass blocks》 Examples of glass block shapes include plate-like (e.g., disc-shaped, flat), spherical, elongated spherical, cylindrical, and rectangular prism-shaped. Furthermore, the glass block may have holes. Examples of shapes for glass blocks with holes include annular (e.g., ring-shaped, donut-shaped) and cylindrical shapes. The glass block may have multiple holes. The shape of the glass block is selected appropriately depending on its application. For example, when used as a focus ring or edge ring, as described later, an annular glass block is used.

[0047] If the glass is in the form of a plate, the area of ​​at least one surface of the glass (e.g., the main surface) is 25 mm². 2 The above is preferable, 100 mm 2 The above is more preferable, 500mm 2 The above is even more preferable, 1,000 mm 2 The above is even more preferable, 5,000 mm 2 The above is particularly preferred, and 10,000 mm 2 The above is particularly preferred, and 40,000 mm 2 The above is highly preferable, 90,000 mm 2 The above is the most preferable option.

[0048] If the glass is in the form of a plate, the thickness of the glass (thickness of the thinnest part) is preferably 0.3 mm or more, more preferably 0.5 mm or more, even more preferably 1 mm or more, even more preferably 3 mm or more, particularly preferably 6 mm or more, even more preferably 10 mm or more, very preferably 15 mm or more, and most preferably 20 mm or more. On the other hand, because crystallization of the glass is suppressed and transparency is improved, the thickness of the glass is preferably 500 mm or less, more preferably 100 mm or less, even more preferably 80 mm or less, even more preferably 60 mm or less, particularly preferably 50 mm or less, very preferably 40 mm or less, and most preferably 30 mm or less.

[0049] <Application> This glass can be used, for example, as a component for semiconductor manufacturing equipment, and is particularly suitable for use as a component mounted in plasma etching equipment or plasma CVD equipment. However, the applications of this glass are not limited to these. Another embodiment of the present invention is a component for semiconductor manufacturing equipment made of this glass. Components for semiconductor manufacturing equipment made from this glass are, for example, mounted in semiconductor manufacturing equipment. Examples of components for semiconductor manufacturing equipment mounted in semiconductor manufacturing equipment (such as plasma etching equipment and plasma CVD equipment) include shield rings, focus rings, edge rings, shower plates, electrostatic chucks, susceptors, injectors, viewing windows, top plates, side walls, microwave introduction tubes, lift pins, various nozzles, window materials, and protective covers for chamber sensors. This glass can be suitably used in particular as focus rings, shower plates, electrostatic chucks, susceptors, injectors, viewing windows, top plates, or side walls.

[0050] [Method of manufacturing glass] Next, the method for manufacturing this glass (hereinafter also referred to as "this manufacturing method") will be explained. In general, this manufacturing method involves heating and melting the glass raw material, shaping the resulting molten glass, and then cooling it.

[0051] More specifically, first, various glass raw materials are weighed and mixed so that the resulting glass has the composition described above. Next, the mixed glass raw materials are heated and melted using a glass melting furnace or the like. During this process, the molten material is degassed and homogenized as appropriate by known methods. In this way, molten glass is obtained. Subsequently, the obtained molten glass is molded into the desired shape and cooled. Examples of molding methods include the float method, press method, fusion method, and down-draw method. Alternatively, the obtained molten glass may be molded into a temporary shape, cooled, and then processed by cutting or other methods. In this way, glass (glass block) of the desired shape is obtained. The resulting glass may be subjected to grinding, polishing, or other treatments as needed.

[0052] The temperature at which the glass raw material is heated and melted (hereinafter also referred to as the "melting temperature") is preferably 1400 to 1800°C, more preferably 1450 to 1750°C, and even more preferably 1500 to 1700°C, for the reason that it provides excellent manufacturing characteristics.

[0053] From the viewpoint of clarity, the time for heating and melting the glass raw material (hereinafter also referred to as "melting time") is preferably 24 hours or less, more preferably 12 hours or less, even more preferably 10 hours or less, even more preferably 8 hours or less, particularly preferably 6 hours or less, and most preferably 4 hours or less. From the viewpoint of reducing undissolved raw material and bubbles in the glass, the melting time is preferably 2 hours or more, and more preferably 3 hours or more.

[0054] When cooling molten glass, the cooling rate is preferably 50°C / min or higher, more preferably 60°C / min or higher, even more preferably 70°C / min or higher, particularly preferably 80°C / min or higher, and most preferably 100°C / min or higher, from the viewpoint of accelerating crystallization. Furthermore, from the viewpoint of producing glass without breaking it, the cooling rate is preferably 3000°C / min or lower, more preferably 2000°C / min or lower, and even more preferably 1500°C / min or lower. The cooling of the molten glass at the above cooling rate is stopped when the glass reaches a predetermined temperature (hereinafter also referred to as the "cooling stop temperature"). From the viewpoint of not leaving any strain in the glass, the cooling stop temperature is preferably 0 to 1000°C, more preferably 300 to 900°C, even more preferably 400 to 800°C, and particularly preferably 500 to 700°C. The glass is obtained by allowing the glass block, cooled to the above-mentioned cooling stop temperature, to cool naturally or slowly until it reaches ambient temperature (e.g., 25°C).

[0055] As an example of a preferred embodiment of this manufacturing method, a glass raw material is melted by heating it to a melting temperature of 1400 to 1800°C, and the resulting molten glass is cooled to a cooling stop temperature of 500 to 700°C at a cooling rate of 100 to 1500°C / min. [Examples]

[0056] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples described below. Examples 1 to 22 below are examples, and Examples 23 to 29 are comparative examples.

[0057] <Examples 1-29> The glass blocks for each example were obtained as follows.

[0058] The resulting glass block had the composition shown in Tables 1 to 4 below (expressed as a molar percentage based on oxides), and the glass raw materials were weighed and mixed to a total weight of 400g. The mixed glass raw materials were placed in a platinum crucible and placed in an electric furnace. They were heated at a temperature of 1500-1700°C for about 3 hours to melt them, and then degassed and homogenized to obtain molten glass. A portion of the obtained molten glass was poured into a metal mold and cooled at a cooling rate of 100-1500°C / min until it reached a temperature of 500-700°C, which is about 50°C higher than the glass transition temperature. The glass in the metal mold was held at 500-700°C for 1 hour, then cooled to room temperature at a rate of 1°C / min to form a plate-shaped glass block (main surface area: 10,000 mm²). 2 A thickness of 10 mm was obtained.

[0059] <Content of each element> For each example of glass block, the content of each element (expressed as a mole percentage based on oxides) was determined using the method described above. The results are shown in Tables 1 to 4 below.

[0060] <Etching resistance test (etching rate)> For each example of glass block, plasma etching was performed to evaluate its etching resistance. More specifically, the fabricated glass block was cut to produce a test piece measuring 20mm x 20mm x 2mm, and the 20mm x 20mm surface of the test piece was polished with cerium oxide to a mirror finish. Next, half of the polished surface was covered with a polyimide tape (Nitto Denko Corporation's "P-222") with a total thickness of 100μm to prepare a sample for etching resistance testing. Subsequently, the sample was placed on the stage of a plasma etching apparatus (EXAM, manufactured by Shinko Seiki Co., Ltd.), and plasma etching was performed using a mixed gas of CF4 / O2 / Ar. For plasma etching, the output was 550W, the pressure was 3Pa, and the etching time was 60 minutes. After plasma etching, the polyimide tape was peeled off the sample surface, and the height of the step created between the coated surface and the exposed surface was measured using a stylus-type surface profile analyzer, dektak-XT (ULVAC, Inc.). Measurements were performed at three points, and the etching rate (unit: nm / h) was calculated from the arithmetic mean of the three measurements and the etching time. The results are shown in the table below. A lower etching rate indicates better etching resistance.

[0061] <Dust generation test> The glass blocks from each example were cut to create samples measuring 20mm x 20mm x 2mm, each with a 20mm x 20mm glass surface. Next, a 6-inch (150 mm) diameter disc-shaped silicon wafer was placed on the stage of a plasma etching apparatus (EXAM, manufactured by Shinko Seiki Co., Ltd.), and the sample was positioned at the center of the silicon wafer's surface. Subsequently, plasma etching was performed on the silicon wafer on which the sample was placed using a mixed gas of CF4 / O2 / Ar. For plasma etching, the output was 550W, the pressure was 3Pa, and the etching time was 60 minutes. After plasma etching, the silicon wafer and sample were removed from the plasma etching apparatus. Then, particles with a diameter of 100 nm or larger attached to the surface of the silicon wafer were detected using a particle inspection device (LAZIN's "LODAS"). The particles were imaged using the camera provided by the particle inspection device, and the major axis of the particles displayed in the resulting image was measured. This measured major axis was defined as the diameter of the particle. On the circular surface of the silicon wafer, the outer periphery (3 mm wide from the outer edge) and the central circular area (40 mm in diameter from the center, including the area where the sample was placed) were excluded from the count. The number of particles detected on the surface other than the outer periphery and central area was then counted. The measurement results for the number of particles in each example are shown in the table below. A lower number of particles indicates better dust resistance.

[0062] <Particle composition> The particles obtained from the dust generation test described above were collected and subjected to elemental analysis. More specifically, the elemental content of the particles was measured using an X-ray fluorescence analyzer (XRF) (Rigaku Corporation "ZSX100e"). That is, the X-ray intensity of each element on the surface of the particles was measured and quantitatively analyzed to determine the content of each element. The table below shows the content of each element as a mole percentage based on oxide. However, the units of the values ​​shown in the "SrO / BaO" column are dimensionless. For each example, if elemental analysis of the particles revealed the presence of at least one alkali metal element and Ti, "×" was written in the "Particle Composition" column of the table. If neither alkali metal element nor Ti was detected, but Al was detected, "△" was written in the "Particle Composition" column. If neither alkali metal element, Ti, nor Al was detected, "○" was written in the "Particle Composition" column. Furthermore, alkali metal elements such as Na, and Ti, are components X that can significantly affect the performance of semiconductor products. Therefore, if the particle composition is evaluated as "○" or "△", it can be evaluated as having excellent properties as a component for semiconductor manufacturing equipment used in a plasma environment. In addition, since Al may have a slight effect on the performance of semiconductor products depending on the semiconductor material, if the particle composition is evaluated as "○", it can be evaluated as having even better properties as a component for semiconductor manufacturing equipment used in a plasma environment.

[0063] [Table 1]

[0064] [Table 2]

[0065] [Table 3]

[0066] [Table 4]

[0067] <Summary of Evaluation Results> As shown in the table above, the glass blocks of Examples 1 to 22 exhibited excellent etching resistance in a plasma environment, with etching rates of 700 nm / h or less obtained from etching resistance tests. Furthermore, the dust generation tests showed that the number of particles generated by plasma etching in Examples 1 to 22 was very low (50 or less), demonstrating excellent dust generation resistance. In addition, since the deposited particles did not contain alkali metal elements or Ti, which can significantly affect the performance of semiconductor products, it was confirmed that the glass blocks of Examples 1 to 22 are composed of components that do not pose a problem even if deposited within semiconductor manufacturing equipment, and are suitable as components for semiconductor manufacturing equipment. In contrast, the glass block in Example 23, which was manufactured using quartz glass that contains no alkaline earth metal elements as a raw material, showed an etching rate exceeding 3500 nm / h in etching resistance tests, confirming its unsuitability as a component for semiconductor manufacturing equipment. Furthermore, although Examples 24 to 26 showed good etching rates, dust generation tests revealed that the number of particles exceeded 100, confirming their unsuitability as components for semiconductor manufacturing equipment. This was presumed to be due to the high calcium content of the glass blocks in Examples 24 to 26. Figure 1 is a graph showing the relationship between the calcium content (molar percentage based on oxide, horizontal axis) contained in the glass blocks of each example and the number of particles with a diameter of 100 nm or more measured after the dust generation test (vertical axis). From Figure 1, it can be seen that as the calcium content in the glass block increases, the number of particles increases and dust resistance tends to decrease. Examples 27 and 28 were found to be unsuitable as components for semiconductor manufacturing equipment, as the particle composition evaluation obtained in the dust generation test was "X". Since the glass block in Example 27 contained the alkali metal element Na, and the glass block in Example 28 contained Ti, it was presumed that particles containing components that could significantly affect the performance of semiconductor products were generated by plasma etching. In Example 29, etching resistance tests revealed an etching rate exceeding 1000 nm / h, confirming its unsuitability as a component for semiconductor manufacturing equipment. This was presumed to be due to the low alkaline earth metal content in Example 29.

Claims

1. It contains silicon, magnesium, strontium, and barium. Alkali metal elements R １ , alkaline earth metal elements R ２ In that case, expressed as a mole percentage based on oxides, SiO ２ The content is 48.0 mol% or more, Al ２ O ３ The content is 20.0 mol% or less. The MgO content is 0.1 mol% or more. The SrO content is 0.1 mol% or more. The BaO content is 0.1 mol% or more. R ２ The O content is 22.0 mol% or more. It contains virtually no CaO, TiO ２ It does not substantially contain, R １ ２ Glass that does not substantially contain O.

2. Al ２ O ３ The glass according to claim 1, wherein the content of is 13.5 mol% or less.

3. Al ２ O ３ The glass according to claim 1, which substantially does not contain.

4. The glass according to claim 1, wherein the BaO content is 4.0 to 14.0 mol%.

5. Al ２ O ３ The content is 13.5 mol% or less. The glass according to claim 1, wherein the BaO content is 4.0 to 14.0 mol%.

6. The glass according to claim 1, which is a glass block.

7. The glass according to claim 1, which is a disc-shaped glass block.

8. The glass according to claim 1, which is an annular glass block.

9. A glass according to any one of claims 1 to 8, used as a component for semiconductor manufacturing equipment mounted on semiconductor manufacturing equipment.

10. The glass according to claim 9, wherein the semiconductor manufacturing apparatus component is an edge ring, shield ring, focus ring, shower plate, electrostatic chuck, susceptor, injector, viewing window, top plate, or side wall mounted on the semiconductor manufacturing apparatus.

11. A method for manufacturing glass according to any one of claims 1 to 8, The glass raw material is melted by heating it to a melting temperature of 1400 to 1800°C. A method for manufacturing glass, comprising cooling the obtained molten glass to a cooling stop temperature of 500 to 700°C at a cooling rate of 100 to 1500°C / min.

12. A component for semiconductor manufacturing equipment, comprising the glass described in any one of claims 1 to 8.

13. The semiconductor manufacturing apparatus component according to claim 12, which is mounted on a semiconductor manufacturing apparatus and is an edge ring, shield ring, focus ring, shower plate, electrostatic chuck, susceptor, injector, viewing window, top plate, or side wall.

14. A semiconductor manufacturing apparatus equipped with the semiconductor manufacturing apparatus component described in claim 12.

15. A semiconductor manufacturing apparatus equipped with the semiconductor manufacturing apparatus component described in claim 13.

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