Glass block, method for manufacturing the same, and component for semiconductor manufacturing equipment

Abstract

The present invention provides a glass block having excellent plasma resistance and transparency. The glass block according to the present invention contains Si and at least one of Mg and Ca, in which, in mol%, the content of B2O3 is 49.0% or less, the content of P2O5 is 11.5% or less, the content of a (= SiO2+B2O3+P2O5+GeO2) is 10.0 to 59.5%, the content of a+Al2O3 is 66.5% or less, the content of Ga2O3 is 7.0% or less, the content of [b (= Al2O3+Ga2O3+In2O3)] / a is 0.44 or less, the content of R2O (wherein R2: an alkaline earth metal) is 20.0% or more, the content of MgO is 50.0% or less, MgO ≥ BaO, CaO ≥ BaO, SrO ≥ BaO, MgO ≥ SrO, CaO ≥ SrO, the content of R1 2O (wherein R1: an alkali metal) is 1.2% or less, the content of TiO2 or ZrO2 is 4.8% or less, the content of MnO2 is 9.5% or less, the content of ZnO is 11.8% or less, the content of Ta2O5 / SiO2 is 0.067 or less, the content of impurity elements is 15.0% or less, and the content of F / O is 0.20 or less.

Description

[Technical Field]

[0001] This invention relates to glass blocks, a method for manufacturing the same, and components for semiconductor manufacturing equipment. [Background technology]

[0002] Components used in semiconductor manufacturing equipment are often exposed to plasma during operation and gradually wear out. Components that have become worn out are replaced with new ones. In recent years, as products manufactured by semiconductor manufacturing equipment have become taller and more complex, the plasma environment to which components are exposed has become increasingly harsh, leading to frequent need to replace components. However, semiconductor manufacturing equipment cannot be operated while components are being replaced. Therefore, an increase in the frequency of component replacement leads to a decrease in product production efficiency.

[0003] Therefore, components used in semiconductor manufacturing equipment are required to have an even longer lifespan. In other words, good plasma resistance is required.

[0004] Examples of semiconductor manufacturing equipment include plasma etching equipment. Plasma etching equipment is equipped with components such as a top plate (conductor type), microwave introduction tube, lift pins, various nozzles, edge rings, electrostatic chucks, shower plates, and protective covers for sensors inside the chamber. Conventionally, materials such as cordierite sintered bodies have been used as these components (see Patent Document 1). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 9-295863 [Overview of the project] [Problems that the invention aims to solve]

[0006] For example, materials used as window materials for semiconductor manufacturing equipment (components used to view the inside of the equipment from the outside) require not only good plasma resistance but also good transparency.

[0007] This invention has been made in view of the above points, and aims to provide a material with excellent plasma resistance and transparency. [Means for solving the problem]

[0008] 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.

[0009] In other words, the present invention consists of the following configuration. [1] A material containing silicon, and at least one of magnesium and calcium, 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 content of B2O3 is 49.0 mol% or less, the content of P2O5 is 11.5 mol% or less, the total content of SiO2, B2O3, P2O5, and GeO2 is 10.0 mol% or more and 59.5 mol% or less, the total content of SiO2, B2O3, P2O5, GeO2, and Al2O3 is 66.5 mol% or less, the content of Ga2O3 is 7.0 mol% or less, the ratio b / a of the total content of Al2O3, Ga2O3, and In2O3 to the total content of SiO2, B2O3, P2O5, and GeO2 is 0.44 or less, and R 2 The O content is 20.0 mol% or more, the MgO content is 50.0 mol% or less, the MgO content is greater than or equal to the BaO content, the CaO content is greater than or equal to the BaO content, and the SrO content is greater than or equal to the BaO content, the MgO content is greater than or equal to the SrO content, and the CaO content is greater than or equal to the SrO content, R 1The content of 2O is 1.2 mol% or less, the content of TiO2 or ZrO2 is 4.8 mol% or less, the content of MnO2 is 9.5 mol% or less, the content of ZnO is 11.8 mol% or less, the ratio Ta2O5 / SiO2 of the content of Ta2O5 to the content of SiO2 is 0.067 or less, the content of the impurity elements in terms of oxide conversion is 15.0 mol% or less. However, the above-mentioned impurity elements are metal elements excluding silicon, boron, phosphorus, germanium, aluminum, gallium, indium, alkaline earth metal elements, yttrium, alkali metal elements, titanium, zirconium, manganese, zinc, and tantalum, and the ratio F / O of the content of fluorine F to the content of oxygen O is 0.20 or less. A glass block. [2] A method for manufacturing the glass block according to [1] above, comprising melting by heating a glass raw material, shaping the obtained molten glass, and gradually cooling it. A method for manufacturing a glass block. [3] A member for a semiconductor manufacturing apparatus, comprising the glass block of [1] above.

Effects of the Invention

[0010] According to the present invention, a material excellent in plasma resistance and transparency can be provided.

Modes for Carrying Out the Invention

[0011] The meanings of the terms in the present invention are as follows. A numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. Also, in this specification, "mass" is synonymous with "weight".

[0012] [Glass block] The glass block of the present invention contains silicon and at least one of magnesium and calcium, and the alkali metal element is R 1 , the alkaline earth metal element is R 2In this case, expressed as a mole percentage based on oxides, the content of B2O3 is 49.0 mol% or less, the content of P2O5 is 11.5 mol% or less, the total content of SiO2, B2O3, P2O5, and GeO2 is 10.0 mol% or more and 59.5 mol% or less, the total content of SiO2, B2O3, P2O5, GeO2, and Al2O3 is 66.5 mol% or less, the content of Ga2O3 is 7.0 mol% or less, the ratio b / a of the total content of Al2O3, Ga2O3, and In2O3 to the total content of SiO2, B2O3, P2O5, and GeO2 is 0.44 or less, and R 2 The O content is 20.0 mol% or more, the MgO content is 50.0 mol% or less, the MgO content is greater than or equal to the BaO content, the CaO content is greater than or equal to the BaO content, and the SrO content is greater than or equal to the BaO content, the MgO content is greater than or equal to the SrO content, and the CaO content is greater than or equal to the SrO content, R 1 The content of 2O is 1.2 mol% or less, the content of TiO2 or ZrO2 is 4.8 mol% or less, the content of MnO2 is 9.5 mol% or less, the content of ZnO is 11.8 mol% or less, the ratio of Ta2O5 content to SiO2 content (Ta2O5 / SiO2) is 0.067 or less, the content of impurity elements on an oxide basis is 15.0 mol% or less, provided that the above impurity elements are metal elements excluding silicon, boron, phosphorus, germanium, aluminum, gallium, indium, alkaline earth metal elements, yttrium, alkali metal elements, titanium, zirconium, manganese, zinc, and tantalum, and the ratio of fluorine content (F) to oxygen content (O) (F / O) is 0.20 or less.

[0013] Hereinafter, glass blocks will also be simply referred to as "glass," and the glass blocks of the present invention will also be referred to as "this glass block" or "this glass."

[0014] This glass block exhibits excellent plasma resistance. This is presumably because the above configuration reduces the rate of degradation caused by plasma irradiation.

[0015] Furthermore, this glass block exhibits excellent transparency. This is presumed to be because the above-mentioned structure suppresses crystallization and thus inhibits the formation of other phases. In this context, examples of different phases include not only crystalline phases, but also colloidal metals and ceramic particles. In other words, it is preferable that this glass block does not contain these other phases (crystalline phase, colloidal metal, ceramic particles, etc.) because of its excellent transparency.

[0016] In semiconductor manufacturing equipment, conventional transparent components used in environments exposed to plasma include, for example, components made of quartz. However, quartz has insufficient plasma resistance. In contrast, this glass block excels in both plasma resistance and transparency.

[0017] The following provides a detailed explanation of this glass block. First, the composition (glass composition) of this glass block will be explained below. Specifically, the elemental content (expressed as molar percentages based on oxides) that this glass block may contain will be explained.

[0018] <Si, B, P, and Ge> This glass block contains silicon (Si). This glass block may further contain boron (B), phosphorus (P), and germanium (Ge).

[0019] 《SiO2》 The SiO2 content of this glass block is preferably in the range of 17.0 mol% to 59.5 mol%. For the sake of superior transparency of the glass block, the SiO2 content is preferably 17.0 mol% or more, more preferably 22.0 mol% or more, even more preferably 27.0 mol% or more, even more preferably 32.0 mol% or more, particularly preferably 35.0 mol% or more, even more preferably 37.0 mol% or more, very preferably 39.0 mol% or more, and most preferably 41.0 mol% or more.

[0020] For the reason that this glass block has superior plasma resistance and transparency, the SiO2 content is preferably 59.5 mol% or less, more preferably 57.0 mol% or less, even more preferably 55.0 mol% or less, even more preferably 53.0 mol% or less, particularly preferably 51.0 mol% or less, even more preferably 49.0 mol% or less, very preferably 47.0 mol% or less, and most preferably 45.0 mol% or less.

[0021] 《B2O3》 For the sake of the excellent plasma resistance of this glass block, the B2O3 content is 49.0 mol% or less, preferably 40.0 mol% or less, more preferably 30.0 mol% or less, even more preferably 20.0 mol% or less, even more preferably 15.0 mol% or less, particularly preferably 10.0 mol% or less, very preferably 5.0 mol% or less, and most preferably 1.0 mol% or less. The lower limit of the B2O3 content is preferably zero.

[0022] 《P2O5》 For the sake of the excellent plasma resistance of this glass block, the P2O5 content is 11.5 mol% or less, 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, particularly preferably 2.0 mol% or less, and most preferably 1.0 mol% or less. The lower limit of the P2O5 content is preferably zero.

[0023] 《GeO2》 For the sake of the excellent plasma resistance of this glass block, the GeO2 content is preferably 5.5 mol% or less, 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.

[0024] <Al, Ga, and In> This glass block may contain aluminum (Al), gallium (Ga), and indium (In).

[0025] 《Al2O3》 The Al2O3 content of this glass block is preferably in the range of 0.0 mol% to 27.5 mol%. For the sake of superior transparency of the glass block, the Al2O3 content is preferably 27.5 mol% or less, more preferably 22.0 mol% or less, even more preferably 18.0 mol% or less, even more preferably 13.0 mol% or less, particularly preferably 9.0 mol% or less, very preferably 5.0 mol% or less, and most preferably 1.0 mol% or less. From the viewpoint of suppressing the precipitation of foreign matter on the glass block, the Al2O3 content is preferably 0.0 mol% or more, more preferably 1.0 mol% or more, even more preferably 2.0 mol% or more, even more preferably 3.0 mol% or more, particularly preferably 4.0 mol% or more, and most preferably 5.0 mol% or more.

[0026] 《Ga2O3》 For the sake of the excellent plasma resistance and transparency of this glass block, the Ga2O3 content is 7.0 mol% or less, preferably 3.0 mol% or less, more preferably 1.0 mol% or less, and even more preferably 0.5 mol% or less. The lower limit of the Ga2O3 content is preferably zero.

[0027] 《In2O3》 For the sake of superior plasma resistance and transparency of this glass block, the In2O3 content is preferably 5.0 mol% or less, more preferably 3.0 mol% or less, and even more preferably 1.0 mol% or less. The lower limit of the In2O3 content is preferably zero.

[0028] <a: Total of SiO2, B2O3, P2O5, and GeO2> The total content (a) of SiO2, B2O3, P2O5, and GeO2 in this glass block is between 10.0 mol% and 59.5 mol%. For the sake of the excellent transparency of this glass block, the total content (a) of SiO2, B2O3, P2O5, and GeO2 is 10.0 mol% or more, preferably 17.0 mol% or more, more preferably 22.0 mol% or more, even more preferably 27.0 mol% or more, even more preferably 32.0 mol% or more, particularly preferably 35.0 mol% or more, even more preferably 37.0 mol% or more, very preferably 39.0 mol% or more, and most preferably 41.0 mol% or more.

[0029] For the sake of the excellent plasma resistance of this glass block, the total content (a) of SiO2, B2O3, P2O5, and GeO2 is 59.5 mol% or less, preferably 57.0 mol% or less, more preferably 55.0 mol% or less, even more preferably 53.0 mol% or less, even more preferably 51.0 mol% or less, particularly preferably 49.0 mol% or less, very preferably 47.0 mol% or less, and most preferably 45.0 mol% or less.

[0030] <a + Al2O3: sum of SiO2, B2O3, P2O5, GeO2, and Al2O3> Since the glass block has excellent plasma resistance, the total content (a + Al2O3) of SiO2, B2O3, P2O5, GeO2 and Al2O3 is 66.5 mol% or less, preferably 63.0 mol% or less, more preferably 60.0 mol% or less, still more preferably 57.0 mol% or less, even more preferably 54.0 mol% or less, particularly preferably 51.0 mol% or less, and most preferably 48.0 mol% or less.

[0031] On the other hand, since the glass block has more excellent transparency, the total content (a + Al2O3) of SiO2, B2O3, P2O5, GeO2 and Al2O3 is preferably 10.0 mol% or more, more preferably 17.0 mol% or more, and still more preferably 22.0 mol% or more. That is, the total content (a + Al2O3) of SiO2, B2O3, P2O5, GeO2 and Al2O3 is preferably in the range of 10.0 mol% or more and 66.5 mol% or less.

[0032] 〈Ratio (b / a)〉 Since the glass block has excellent transparency, the ratio (b / a) of the total content b (unit: mol%) of Al2O3, Ga2O3 and In2O3 to the total content a (unit: mol%) of SiO2, B2O3, P2O5 and GeO2 is 0.44 or less, preferably 0.36 or less, more preferably 0.29 or less, still more preferably 0.22 or less, even more preferably 0.16 or less, particularly preferably 0.12 or less, and most preferably 0.09 or less. The lower limit of the ratio (b / a) is preferably zero.

[0033] 〈R 2 〉 The glass block may contain an alkaline earth metal element (R 2 ). Examples of the alkaline earth metal element (R 2 ) include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra). However, this glass block contains at least one of Mg and Ca as essential elements.

[0034] 《R 2 O》 This glass block has excellent plasma resistance, therefore, R 2 The O content is 20.0 mol% or more, preferably 29.0 mol% or more, more preferably 36.0 mol% or more, even more preferably 40.0 mol% or more, particularly preferably 43.0 mol% or more, very preferably 46.0 mol% or more, and most preferably 49.0 mol% or more. R 2 The upper limit of the O content is not particularly limited, but is, for example, 80.0 mol% or less, preferably 70.0 mol% or less, more preferably 65.0 mol% or less, even more preferably 60.0 mol% or less, particularly preferably 56.0 mol% or less, and most preferably 52.0 mol% or less. In other words, the R of this glass block 2 The O content is preferably in the range of 0.0 mol% to 80.0 mol%.

[0035] 《MgO》 For the sake of the excellent transparency of this glass block, the MgO content is 50.0 mol% or less, preferably 40.0 mol% or less, more preferably 35.0 mol% or less, even more preferably 30.0 mol% or less, even more preferably 25.0 mol% or less, particularly preferably 20.0 mol% or less, very preferably 15.0 mol% or less, and most preferably 10.0 mol% or less.

[0036] On the other hand, for the sake of superior plasma resistance of this glass block, the MgO content is preferably 1.0 mol% or more, more preferably 3.0 mol% or more, and even more preferably 5.0 mol% or more. In other words, the MgO content of this glass block is preferably in the range of 1.0 mol% to 50.0 mol%.

[0037] 《CaO》 The CaO content of this glass block is preferably in the range of 20.0 mol% to 69.0 mol%. For the sake of superior plasma resistance of this glass block, the CaO content is preferably 20.0 mol% or more, more preferably 29.0 mol% or more, even more preferably 36.0 mol% or more, even more preferably 40.0 mol% or more, particularly preferably 43.0 mol% or more, very preferably 46.0 mol% or more, and most preferably 49.0 mol% or more.

[0038] On the other hand, for the sake of superior transparency of the glass block, the CaO content is preferably 69.0 mol% or less, more preferably 66.0 mol% or less, even more preferably 63.0 mol% or less, even more preferably 60.0 mol% or less, particularly preferably 57.0 mol% or less, very preferably 54.0 mol% or less, and most preferably 51.0 mol% or less.

[0039] Total amount of MgO and CaO The total content of MgO and CaO in this glass block is preferably in the range of 20.0 mol% to 69.0 mol%. For the sake of superior plasma resistance of this glass block, the total content of MgO and CaO is preferably 20.0 mol% or more, more preferably 29.0 mol% or more, even more preferably 36.0 mol% or more, even more preferably 40.0 mol% or more, particularly preferably 43.0 mol% or more, very preferably 46.0 mol% or more, and most preferably 49.0 mol% or more.

[0040] On the other hand, for the sake of superior transparency of the glass block, the total content of MgO and CaO is preferably 69.0 mol% or less, more preferably 66.0 mol% or less, even more preferably 63.0 mol% or less, even more preferably 60.0 mol% or less, particularly preferably 57.0 mol% or less, very preferably 54.0 mol% or less, and most preferably 51.0 mol% or less.

[0041] 《SrO》 For the sake of the excellent transparency of this glass block, the SrO content is preferably 60.0 mol% or less, more preferably 30.0 mol% or less, even more preferably 10.0 mol% or less, particularly preferably 5.0 mol% or less, and most preferably 1.0 mol% or less. The lower limit of the SrO content is preferably zero.

[0042] 《BaO》 For the sake of superior transparency of the glass block, the BaO content is preferably 30.0 mol% or less, more preferably 25.0 mol% or less, even more preferably 20.0 mol% or less, even more preferably 15.0 mol% or less, particularly preferably 10.0 mol% or less, very preferably 5.0 mol% or less, and most preferably 1.0 mol% or less. The lower limit of the BaO content is preferably zero.

[0043] 《MgO≧BaO, CaO≧BaO, and SrO≧BaO》 For the sake of the excellent plasma resistance of this glass block, the MgO content (in moles) is preferably greater than or equal to the BaO content (in moles), and greater than the BaO content (in moles). For similar reasons, the CaO content (in moles) is preferably greater than or equal to the BaO content (in moles), and greater than the BaO content (in moles). For similar reasons, the SrO content (in moles) is preferably greater than or equal to the BaO content (in moles), and greater than the BaO content (in moles).

[0044] 《MgO≧SrO and CaO≧SrO》 For the sake of superior plasma resistance of this glass block, the MgO content (in moles) is preferably greater than or equal to the SrO content (in moles), and greater than the SrO content (in moles). For similar reasons, the CaO content (in moles) is preferably greater than or equal to the SrO content (in moles), and greater than the SrO content (in moles).

[0045] <Y> This glass block may contain yttrium (Y). The Y2O3 content of this glass block is preferably 5.0 mol% or less, more preferably 3.0 mol% or less, and even more preferably 1.0 mol% or less. The lower limit of the total Y2O3 content is preferably zero.

[0046] <R 1 > This glass block contains alkali metal elements (R 1 ) may contain. Alkali metal elements (R 1 Examples of these elements include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). Of these, lithium (Li), sodium (Na), and potassium (K) are substantially preferred.

[0047] 《R 1 2O》 This glass block has excellent plasma resistance, therefore, R 1 The 2O content is 1.2 mol% or less, preferably 0.8 mol% or less, more preferably 0.4 mol% or less, even more preferably 0.1 mol% or less, particularly preferably 0.05 mol% or less, very preferably 0.01 mol% or less, and most preferably 0.002 mol% or less. R 1 The lower limit of the 2O content is preferably zero.

[0048] <Ti, Zr, Mn, Zn, and Ta> This glass block may contain titanium (Ti), zirconium (Zr), manganese (Mn), zinc (Zn), and tantalum (Ta).

[0049] 《TiO2 or ZrO2》 For the sake of the excellent plasma resistance of this glass block, the TiO2 or ZrO2 content is 4.8 mol% or less, preferably 3.5 mol% or less, more preferably 2.5 mol% or less, and even more preferably 1.0 mol% or less. The lower limit of the TiO2 or ZrO2 content is preferably zero.

[0050] 《TiO2》 For the sake of the excellent plasma resistance of this glass block, the TiO2 content is preferably 4.8 mol% or less, more preferably 3.5 mol% or less, even more preferably 2.5 mol% or less, and particularly preferably 1.0 mol% or less. The lower limit of the TiO2 content is preferably zero.

[0051] 《ZrO2》 For the sake of the excellent plasma resistance of this glass block, the ZrO2 content is preferably 4.8 mol% or less, more preferably 3.5 mol% or less, even more preferably 2.5 mol% or less, and particularly preferably 1.0 mol% or less. The lower limit of the ZrO2 content is preferably zero.

[0052] 《MnO2》 For the sake of the excellent plasma resistance of this glass block, the MnO2 content is 9.5 mol% or less, preferably 6.0 mol% or less, more preferably 3.0 mol% or less, and even more preferably 1.0 mol% or less. The lower limit of the MnO2 content is preferably zero.

[0053] 《ZnO》 For the sake of the excellent plasma resistance of this glass block, the ZnO content is 11.8 mol% or less, preferably 7.0 mol% or less, more preferably 4.0 mol% or less, and even more preferably 1.0 mol% or less. The lower limit of the ZnO content is preferably zero.

[0054] 《Ta2O5》 For the sake of the excellent plasma resistance of this glass block, the Ta2O5 content is preferably 6.0 mol% or less, more preferably 3.0 mol% or less, and even more preferably 1.0 mol% or less. The lower limit of the Ta2O5 content is preferably zero.

[0055] <Ratio (Ta2O5 / SiO2)> For the sake of the excellent transparency of this glass block, the ratio of the Ta2O5 content (unit: mol%) to the SiO2 content (unit: mol%) (Ta2O5 / SiO2) is 0.067 or less, preferably 0.060 or less, more preferably 0.050 or less, even more preferably 0.040 or less, even more preferably 0.030 or less, particularly preferably 0.020 or less, and most preferably 0.010 or less. The lower limit of the ratio (Ta2O5 / SiO2) is preferably zero.

[0056] <Impure Elements> For the sake of the excellent plasma resistance of this glass block, the content of impurity elements in terms of oxides is 15.0 mol% or less, preferably 12.5 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 should preferably be zero.

[0057] Impurity elements include silicon (Si), boron (B), phosphorus (P), germanium (Ge), aluminum (Al), gallium (Ga), indium (In), and alkaline earth metal elements (R). 2 ), yttrium (Y), alkali metal elements (R 1 ), Titanium (Ti), Zirconia These are metallic elements excluding um (Zr), manganese (Mn), zinc (Zn), and tantalum (Ta).

[0058] Examples of impurity elements include Cu, Fe, Ni, Cr, Sn, Co, V, Bi, Se, Ce, Er, and Nd. 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.

[0059] The content of each element (excluding Si) in the glass block (expressed as a mole percentage based on oxides) is measured using an XRF (X-ray fluorescence) spectrometer (Rigaku Corporation, ZSX100e). Specifically, the X-ray intensity of each element on the surface of the glass block is measured and quantitatively analyzed to determine the content of each element.

[0060] The SiO2 content in a glass block can be determined as follows: First, a powdery sample is collected from the center of the glass block by polishing, and the total amount of oxygen Z1 in the glass block 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 block in a stoichiometric composition, from the total amount of oxygen Z1 in the glass block (amount of oxygen Z3 = total amount of oxygen Z1 - amount of oxygen Z2). Assuming that the entire amount of oxygen Z3 was 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 block.

[0061] <Ratio (F / O)> For the sake of the excellent plasma resistance of this glass block, the ratio of fluorine content F to oxygen content O (F / O) is 0.20 or less, preferably 0.15 or less, more preferably 0.10 or less, and even more preferably 0.05 or less. The lower limit of the ratio (F / O) is preferably zero.

[0062] The ratio (F / O) in a glass block is calculated as follows: First, the fluorine (F) atom concentration (unit: atomic %) and oxygen (O) atom concentration (unit: atomic %) are determined for any one face of the glass block using an X-ray photoelectron spectrometer (JEOL Ltd., JPS-9000MC). The ratio of the determined F atom concentration to the O atom concentration is defined as the ratio (F / O) of that glass block.

[0063] <N content> For the sake of superior transparency, it is preferable that the nitrogen (N) content (N content) of this glass block be low. Specifically, the N content is preferably 9.0% by mass or less, more preferably 7.0% by mass or less, even more preferably 5.0% by mass or less, even more preferably 4.0% by mass or less, particularly preferably 3.0% by mass or less, very preferably 2.0% by mass or less, and most preferably 1.0% by mass or less. The lower limit of the N content is preferably zero. The nitrogen content is measured by secondary ion mass spectrometry (SIMS). A mass spectrometer (ION-TOF, TOF.SIMS5) is used for the measurement.

[0064] <Coefficient of thermal expansion> From the viewpoint of suppressing cracking during the manufacturing of this glass block, the average thermal expansion coefficient of this glass block at 50 to 350°C (hereinafter also simply referred to as the "expansion coefficient") is preferably 9.0 ppm / °C or less, more preferably 8.0 ppm / °C or less, even more preferably 7.0 ppm / °C or less, even more preferably 6.0 ppm / °C or less, particularly preferably 5.5 ppm / °C or less, very preferably 5.0 ppm / °C or less, and most preferably 4.5 ppm / °C or less. The coefficient of thermal expansion is measured using a differential thermal expander in accordance with the method described in JIS R 3102-1995.

[0065] <Visible light transmittance> This glass block exhibits excellent transparency. Specifically, for example, the visible light transmittance of this glass block is 75% or higher. The visible light transmittance of this glass block is preferably 78% or higher, more preferably 81% or higher, even more preferably 84% or higher, even more preferably 87% or higher, particularly preferably 90% or higher, and most preferably 93% or higher. The upper limit is preferably 100%. Visible light transmittance is measured according to the method compliant with JIS R 3106 (1998). In order to achieve the visible light transmittance within the above range, it is preferable to use the above-mentioned content for each component and to manufacture the glass block using the method described later (this manufacturing method).

[0066] <Porosity> The porosity of this glass block is, for example, 3.0% by volume or less. This gives the glass block superior plasma resistance. For the reason that this glass block has even better plasma resistance, the porosity of this glass block is preferably 2.5 volume% or less, more preferably 2.0 volume% or less, even more preferably 1.5 volume% or less, even more preferably 1.0 volume% or less, particularly preferably 0.5 volume% or less, and most preferably 0.1 volume% or less. The lower limit is preferably zero. Porosity is determined in accordance with the method for calculating open porosity described in JIS R 1634:1998 "Method for measuring density and open porosity of sintered fine ceramics". In order to achieve the above-mentioned porosity, it is preferable to use the above-mentioned content of each component and to manufacture the glass block using the method described later (this manufacturing method).

[0067] <shape> The shapes of these glass blocks include plate-like (e.g., disc-like, flat), spherical, and elongated spherical shapes, and are selected appropriately depending on the application. Furthermore, the term "glass block," regardless of its shape, is a concept that does not include glass frit, glass powder, or glass fiber.

[0068] If the glass block is in the form of a plate, the area of ​​at least one surface of the glass block (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.

[0069] If the glass block is in the form of a plate, the thickness of the glass block (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 block is suppressed and transparency is improved, the thickness of the glass block 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, very preferably 50 mm or less, especially preferably 40 mm or less, and most preferably 30 mm or less. In other words, the thickness of the glass block is preferably in the range of 0.3 mm to 500 mm.

[0070] <Application> This glass block can be suitably used, for example, as a window material for semiconductor manufacturing equipment. However, the applications of this glass block are not limited to this. For example, this glass block can be used as a component mounted in a plasma etching apparatus, such as a top plate, microwave introduction tube, lift pin, nozzle, edge ring, electrostatic chuck, shower plate, and protective cover for a chamber sensor.

[0071] [Method for manufacturing glass blocks] Next, the method for manufacturing this glass block (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 slowly cooling it.

[0072] More specifically, first, various glass raw materials are weighed and mixed so that the resulting glass block has the glass 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 slowly cooled. The molding method is not particularly limited and includes, for example, the float method, press method, fusion method, and down-draw method. Alternatively, the obtained molten glass may be molded into a temporary shape, slowly cooled, and then processed by cutting or other methods. In this way, a glass block of the desired shape is obtained. The resulting glass blocks may be subjected to grinding, polishing, or other treatments as needed.

[0073] The temperature at which the glass raw material is heated and melted (hereinafter also referred to as the "melting temperature") is preferably 1650°C or lower, more preferably 1600°C or lower, and even more preferably 1550°C or lower, for the reason that it provides excellent manufacturing characteristics. Furthermore, from the viewpoint of improving the heat resistance of the glass itself, the melting temperature is preferably 1200°C or higher, more preferably 1300°C or higher, and particularly preferably 1400°C or higher. In other words, the melting temperature is preferably in the range of 1200°C to 1650°C.

[0074] 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. Furthermore, from the viewpoint of glass homogeneity, the melting time is preferably 1 hour or more, more preferably 2 hours or more, and particularly preferably 3 hours or more. In other words, the melting time is preferably in the range of 1 hour to 24 hours.

[0075] From the viewpoint of crystallization acceleration, the cooling rate when cooling molten glass is preferably 0.5°C / min or more, more preferably 1°C / min or more, even more preferably 5°C / min or more, and particularly preferably 10°C / min or more. Furthermore, from the viewpoint of preventing the glass from breaking, the cooling rate is preferably 30°C / min or less, more preferably 20°C / min or less, and particularly preferably 15°C / min or less. In other words, the cooling rate is preferably in the range of 0.5°C / min to 30°C / min.

[0076] In semiconductor manufacturing equipment, conventional components used in environments exposed to plasma include, for example, sapphire components. However, because sapphire is produced using the single-crystal growth method, its manufacturing properties are inferior, and there are limitations to the size it can be produced in. Furthermore, sapphire is a difficult material to process, making it extremely expensive. In contrast, since this glass block is obtained by the manufacturing method described above, it has good manufacturing characteristics and its size can be changed as needed. Furthermore, it is easier to process than sapphire, resulting in lower costs.

[0077] As described above, the following configuration is disclosed in this specification. <1> It contains silicon and at least one of magnesium and calcium, Alkali metal elements R 1 , alkaline earth metal elements R 2 In that case, expressed as a mole percentage based on oxides, The B2O3 content is 49.0 mol% or less. The P2O5 content is 11.5 mol% or less. The total content of SiO2, B2O3, P2O5, and GeO2 is between 10.0 mol% and 59.5 mol%, The total content of SiO2, B2O3, P2O5, GeO2, and Al2O3 is 66.5 mol% or less. The Ga2O3 content is 7.0 mol% or less. The ratio b / a, which is the sum of the contents of Al2O3, Ga2O3, and In2O3 (b) and the sum of the contents of SiO2, B2O3, P2O5, and GeO2 (a), is 0.44 or less. R 2 The O content is 20.0 mol% or more. The MgO content is 50.0 mol% or less. The MgO content is greater than or equal to the BaO content, the CaO content is greater than or equal to the BaO content, and the SrO content is greater than or equal to the BaO content. The MgO content is greater than or equal to the SrO content, and the CaO content is greater than or equal to the SrO content. R 1 The 2O content is 1.2 mol% or less. The TiO2 or ZrO2 content is 4.8 mol% or less. The MnO2 content is 9.5 mol% or less. The ZnO content is 11.8 mol% or less. The ratio of Ta2O5 content to SiO2 content (Ta2O5 / SiO2) is 0.067 or less. The content of impurity elements in terms of oxides is 15.0 mol% or less, provided that the above impurity elements are metallic elements excluding silicon, boron, phosphorus, germanium, aluminum, gallium, indium, alkaline earth metal elements, yttrium, alkali metal elements, titanium, zirconium, manganese, zinc, and tantalum. A glass block in which the ratio of fluorine content F to oxygen content O, F / O, is 0.20 or less. <2> The above, which has an SiO2 content of 17.0 mol% or more. <1> The glass block described above. <3> The above, the SiO2 content is 59.5 mol% or less. <1> or <2> The glass block described above. <4> The above-mentioned Al2O3 content is 27.5 mol% or less. <1> ~ <3> A glass block described in any one of the following. <5> The above, where the total content of MgO and CaO is 20.0 mol% or more. <1> ~ <4> A glass block described in any one of the following. <6> The total content of MgO and CaO is 69.0 mol% or less, as described above. <1> ~ <5> A glass block described in any one of the following. <7> The above-mentioned CaO content is 20.0 mol% or more and 69.0 mol% or less. <1> ~ <6> A glass block described in any one of the following. <8> The above, the BaO content is 30.0 mol% or less. <1> ~ <7> A glass block described in any one of the following. <9> The average thermal expansion coefficient at 50-350°C is 9.0 ppm / °C or less, as described above. <1> ~ <8> A glass block described in any one of the following. <10> The above, which has a visible light transmittance of 75% or more. <1> ~ <9> A glass block described in any one of the following. <11> The above, the porosity is 3.0% by volume or less. <1> ~ <10> A glass block described in any one of the following. <12> the above <1> ~ <11> A method for manufacturing a glass block as described in any one of the above, comprising heating a glass raw material to melt it, shaping the resulting molten glass, and slowly cooling it. <13> The temperature at which the above glass raw material is heated and melted is 1650°C or lower. <12> The method for manufacturing glass blocks as described above. <14> the above <1> ~ <11> A component for semiconductor manufacturing equipment, comprising a glass block as described in any one of the following. <15> A component mounted on a plasma etching apparatus, which is a top plate, microwave introduction tube, lift pin, nozzle, edge ring, electrostatic chuck, shower plate, or protective cover for a chamber sensor, as described above. <14> Components for semiconductor manufacturing equipment as described above. [Examples]

[0078] 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 33 below are examples, and Examples 34 to 53 are comparative examples.

[0079] <Examples 1-53> The glass blocks for each example were obtained as follows.

[0080] The resulting glass block had the composition shown in Tables 1 to 6 below (expressed as a molar percentage based on oxides), and the glass raw materials were weighed and mixed to a total weight of 400 g. 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 is poured into a metal mold, held at a temperature approximately 50°C above the glass transition point for 1 hour, and then cooled to room temperature at a rate of 0.5°C / min to form a plate-shaped glass block (main surface area: 10,000 mm²). 2A thickness of 10 mm was obtained.

[0081] However, in Examples 47 to 49, commercially available blocks of sapphire, silicon, and quartz were used instead of glass blocks. For convenience, the blocks in Examples 47 to 49 will also be referred to as "glass blocks" below.

[0082] <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 6 below. The impurity elements were Cu, Fe, Ni, Cr, Sn, Co, V, Bi, Se, Ce, Er, and Nd. For example 48 (silicon), the content of impurity elements (in oxide terms) is expressed as 100 mol% for convenience.

[0083] <Coefficient of thermal expansion> The coefficient of thermal expansion was determined for each example of glass block using the method described above. The results are shown in Tables 1 to 6 below.

[0084] <Visible light transmittance> The visible light transmittance of each example glass block was determined using the method described above. The results are shown in Tables 1 to 6 below.

[0085] <Porosity> The porosity of each glass block was determined using the method described above. As a result, at least the glass blocks in Examples 1 to 33 all had a porosity of 0.5 volume% or less.

[0086] <Manufacturing characteristics> In each example, "A" was indicated if the temperature at which the glass raw material was melted (melting temperature) was 1600°C or lower, "B" if it was between 1600°C and 1650°C, and "C" if it was above 1650°C. A rating of "A" or "B" indicates superior manufacturing characteristics.

[0087] <Etching amount> For each example of glass block, the amount of etching was determined, and its plasma resistance was evaluated. Specifically, a test piece measuring 10mm x 5mm x 4mm was cut from a glass block, and the 10mm x 5mm surface was polished to a mirror finish. A portion of the mirror-polished surface was masked with Kapton tape, and then etched with plasma gas. Subsequently, the amount of etching was determined by measuring the step difference between the etched and unetched areas using a stylus-type surface shape measuring instrument (ULVAC, Decak150). An EXAM plasma etching system (manufactured by Shinko Seiki Co., Ltd., model: POEM) was used. Etching was performed in RIE mode (reactive ion etching mode) with CF4 gas for 195 minutes at a pressure of 10 Pa and an output of 350 W. The smaller the etching amount (in nm), the better the plasma resistance can be evaluated. Specifically, it was evaluated that the plasma resistance was excellent if the etching amount was 1600 nm or less. For even better plasma resistance, an etching amount of 1000 nm or less is preferred.

[0088] <Presence or absence of abnormalities> Each example of glass block was visually inspected to check for the presence or absence of other phases (crystalline phase, colloidal metal, ceramic particles, etc.). Tables 1 to 6 below indicate the following: "A" if there were no phase differences, "B" if the phase difference was 10% or less of the main surface area of ​​the glass block, and "C" if the phase difference was more than 10% of the main surface area of ​​the glass block. A rating of "A" or "B" indicates superior transparency. "A" is preferred because it indicates superior transparency.

[0089] [Table 1]

[0090] [Table 2]

[0091] [Table 3]

[0092] [Table 4]

[0093] [Table 5]

[0094] [Table 6]

[0095] <Summary of Evaluation Results> As shown in Tables 1 to 6 above, the glass blocks in Examples 1 to 33 exhibited excellent plasma resistance and transparency. In contrast, the glass blocks in Examples 34 to 53 were insufficient in at least one of the following: plasma resistance and transparency.

[0096] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2021-149104 filed on 14 September 2021, Japanese Patent Application No. 2021-167594 filed on 12 October 2021, and Japanese Patent Application No. 2021-192308 filed on 26 November 2021, the contents of which are incorporated herein by reference.

Claims

1. It contains silicon and at least one of magnesium and calcium, Alkali metal elements R １ , alkaline earth metal elements R ２ In that case, expressed as a mole percentage based on oxides, B ２ O ３ The content is 49.0 mol% or less. P ２ O ５ The content is 11.5 mol% or less. SiO ２ 、 B ２ O ３ 、 P ２ O ５ and GeO ２ the total content of which is 10.0 mol% or more and 59.5 mol% or less, SiO ２ , B ２ O ３ , P ２ O ５ , GeO ２ and Al ２ O ３ The total content of is 66.5 mol% or less. Ga ２ O ３ The content is 7.0 mol% or less. Al ２ O ３ Ga ２ O ３ and In ２ O ３ The total content b and SiO ２ , B ２ O ３ , P ２ O ５ and Geo ２ The ratio b / a to the total content a is 0.44 or less. R ２ The O content is 20.0 mol% or more. The MgO content is 50.0 mol% or less. The MgO content is greater than or equal to the BaO content, the CaO content is greater than or equal to the BaO content, and the SrO content is greater than or equal to the BaO content. The MgO content is greater than or equal to the SrO content, and the CaO content is greater than or equal to the SrO content. R １ ２ The O content is 1.2 mol% or less. TiO ２ or ZrO ２ The content is 4.8 mol% or less. MnO ２ The content is 9.5 mol% or less. The ZnO content is 11.8 mol% or less. Ta ２ O ５ The content and SiO ２ Ratio of content to Ta ２ O ５ / SiO ２ However, it is less than or equal to 0.

067. The content of impurity elements in terms of oxides is 15.0 mol% or less, provided that the impurity elements are metallic elements excluding silicon, boron, phosphorus, germanium, aluminum, gallium, indium, alkaline earth metal elements, yttrium, alkali metal elements, titanium, zirconium, manganese, zinc, and tantalum. A component for semiconductor manufacturing equipment, made of a glass block, wherein the ratio of fluorine content F to oxygen content O (F / O) is 0.20 or less.

2. SiO in the glass block ２ The semiconductor manufacturing apparatus component according to claim 1, wherein the content of is 17.0 mol% or more.

3. SiO in the glass block ２ The semiconductor manufacturing apparatus component according to claim 1, wherein the content of is 59.5 mol% or less.

4. Al in the glass block ２ O ３ The semiconductor manufacturing apparatus component according to claim 1, wherein the content of is 27.5 mol% or less.

5. The semiconductor manufacturing apparatus component according to Claim 1, wherein the total content of MgO and CaO in the glass block is 20.0 mol% or more.

6. The semiconductor manufacturing apparatus component according to Claim 1, wherein the total content of MgO and CaO in the glass block is 69.0 mol% or less.

7. The semiconductor manufacturing apparatus component according to Claim 1, wherein the CaO content in the glass block is 20.0 mol% or more and 69.0 mol% or less.

8. The semiconductor manufacturing apparatus component according to claim 1, wherein the BaO content in the glass block is 30.0 mol% or less.

9. The semiconductor manufacturing apparatus component according to claim 1, wherein the average thermal expansion coefficient of the glass block at 50 to 350°C is 9.0 ppm / °C or less.

10. The semiconductor manufacturing apparatus component according to claim 1, wherein the visible light transmittance of the glass block is 75% or more.

11. The semiconductor manufacturing apparatus component according to claim 1, wherein the porosity of the glass block is 3.0 volume% or less.

12. A component mounted in a plasma etching apparatus, A component for a semiconductor manufacturing apparatus according to any one of claims 1 to 11, which is a top plate, microwave introduction tube, lift pin, nozzle, edge ring, electrostatic chuck, shower plate, or protective cover for a chamber sensor.

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