Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
  • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
  • C03B5/235—Heating the glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
  • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B25/00—Annealing glass products
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B25/00—Annealing glass products
  • C03B25/02—Annealing glass products in a discontinuous way
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
  • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
  • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
  • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
  • C03C3/111—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/12—Silica-free oxide glass compositions
  • C03C3/125—Silica-free oxide glass compositions containing aluminium as glass former
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/24—Dry etching; Plasma etching; Reactive-ion etching of semiconductor materials
  • H10P50/242—Dry etching; Plasma etching; Reactive-ion etching of semiconductor materials of Group IV materials
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2201/00—Glass compositions
  • C03C2201/02—Pure silica glass, e.g. pure fused quartz
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/72—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using electrostatic chucks
  • H10P72/722—Details of electrostatic chucks
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/76—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using mechanical means, e.g. clamps or pinches
  • H10P72/7604—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using mechanical means, e.g. clamps or pinches the wafers being placed on a susceptor, stage or support
  • H10P72/7616—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using mechanical means, e.g. clamps or pinches the wafers being placed on a susceptor, stage or support characterised by a coating, a hardness or a material

Definitions

• the present invention relates to a glass block, its manufacturing method, and members for semiconductor manufacturing equipment.
• Examples of semiconductor manufacturing equipment include plasma etching equipment.
• a plasma etching apparatus is equipped with members such as a top plate (conductor type), a microwave introduction tube, lift pins, various nozzles, an edge ring, an electrostatic chuck, a shower plate, and a protective cover for sensors in the chamber. Materials such as cordierite sintered bodies have been conventionally used for these members (see Patent Document 1).
• materials used as window materials for semiconductor manufacturing equipment are required to have good plasma resistance as well as good transparency.
• the present invention has been made in view of the above points, and aims to provide a material that is excellent in plasma resistance and transparency.
• the present invention consists of the following configurations.
• [1] Contains silicon and at least one of magnesium and calcium, and is B 2 O in mole percentage expression based on oxides, where R 1 is an alkali metal element and R 2 is an alkaline earth metal element
• the content of 3 is 49.0 mol % or less
• the content of P 2 O 5 is 11.5 mol % or less
• the total amount is 10.0 mol % or more and 59.5 mol % or less
• the total content of SiO 2 , B 2 O 3 , P 2 O 5 , GeO 2 and Al 2 O 3 is 66.5 mol % or less
• the content of Ga 2 O 3 is 7.0 mol % or less
• the content of TiO2 or ZrO2 is not more than 4.8 mol%
• the content of MnO2 is not more than 9.5 mol%
• the content of ZnO is not more than 11.8 mol%
• the ratio Ta 2 O 5 /SiO 2 between the content of Ta 2 O 5 and the content of SiO 2 is 0.067 or less
• the content of the impurity element in terms of oxide is 15.0 mol % or less.
• the impurity elements are metal elements other than silicon, boron, phosphorus, germanium, aluminum, gallium, indium, alkaline earth metal elements, yttrium, alkali metal elements, titanium, zirconium, manganese, zinc and tantalum.
• a material with excellent plasma resistance and transparency can be provided.
• the glass block of the present invention contains silicon and at least one of magnesium and calcium.
• the B 2 O 3 content is 49.0 mol % or less
• the P 2 O 5 content is 11.5 mol % or less
• the total content of GeO 2 is 10.0 mol % or more and 59.5 mol % or less
• the total content of SiO 2 , B 2 O 3 , P 2 O 5 , GeO 2 and Al 2 O 3 is , 66.5 mol % or less
• the content of Ga 2 O 3 is 7.0 mol % or less
• the ratio b/a to the total a of the contents of SiO 2 , B 2 O 3 , P 2 O 5 and GeO 2 is 0.44 or less
• the content of R 2 O is 20.0 mol % or more.
• the content of MgO is 50.0 mol% or less
• the content of MgO is equal to or greater than the content of BaO
• the content of CaO is equal to or greater than the content of BaO
• the content of SrO is at least the content of BaO
• the content of MgO is at least the content of SrO
• the content of CaO is at least the content of SrO
• the content of R 1 2 O is 1.2 mol %
• the content of TiO2 or ZrO2 is not more than 4.8 mol%
• the content of MnO2 is not more than 9.5 mol%
• the content of ZnO is 11.8 mol % or less
• the ratio Ta 2 O 5 /SiO 2 between the content of Ta 2 O 5 and the content of SiO 2 is 0.067 or less
• the content of the impurity element in terms of oxide is 15.0% or less.
• the impurity elements include silicon, boron, phosphorus, germanium, aluminum, gallium, indium, alkaline earth metal elements, yttrium, alkali metal elements, titanium, zirconium, manganese, zinc and tantalum.
• the ratio F/O between the fluorine content F and the oxygen content O is 0.20 or less.
• the glass block is also simply referred to as “glass”, and the glass block of the present invention is also referred to as “this glass block” or “this glass”.
• This glass block has excellent plasma resistance. It is presumed that this is because the rate of deterioration due to plasma irradiation is reduced by adopting the above configuration.
• this glass block is excellent in transparency. This is presumed to be because the adoption of the above configuration suppresses crystallization, thereby suppressing the formation of heterogeneous phases.
• heterogeneous phases include crystalline phases, colloidal metals, ceramic particles, and the like. That is, the present glass block preferably does not contain these different phases (crystal phase, colloidal metal, ceramic particles, etc.) for the reason of excellent transparency.
• conventional transparent members used in an environment exposed to plasma include, for example, members made of quartz.
• quartz has poor plasma resistance.
• the present glass block is excellent in both plasma resistance and transparency.
• the present glass block will be described in detail below. First, the composition (glass composition) of the present glass block will be described below. That is, the contents of the elements that the present glass block can contain (in terms of mol percentages based on oxides) will be described.
• the glass block contains silicon (Si).
• the glass block may further contain boron (B), phosphorus (P) and germanium (Ge).
• the content of SiO 2 in the present glass block is preferably in the range of 17.0 mol % to 59.5 mol %.
• the content of SiO 2 is preferably 17.0 mol % or more, more preferably 22.0 mol % or more, still more preferably 27.0 mol % or more, for the reason that the transparency of the present glass block is more excellent.
• 0 mol % or more is more preferred, 35.0 mol % or more is particularly preferred, 37.0 mol % or more is more particularly preferred, 39.0 mol % or more is very preferred, and 41.0 mol % or more is most preferred. preferable.
• the content of SiO2 is preferably 59.5 mol% or less, more preferably 57.0 mol% or less, and more preferably 55.0 mol% or less, because the plasma resistance and transparency of the present glass block are more excellent. More preferably, 53.0 mol% or less is even more preferable, 51.0 mol% or less is particularly preferable, 49.0 mol% or less is more particularly preferable, 47.0 mol% or less is very preferably, 45.0 mol % or less is most preferable.
• the content of B 2 O 3 is 49.0 mol % or less, preferably 40.0 mol % or less, more preferably 30.0 mol % or less, for the reason that the present glass block has excellent plasma resistance, 20.0 mol% or less is more preferable, 15.0 mol% or less is even more preferable, 10.0 mol% or less is particularly preferable, 5.0 mol% or less is very preferable, and 1.0 mol% or less is most preferable. preferable.
• the lower limit of the content of B 2 O 3 is preferably zero.
• the content of P 2 O 5 is 11.5 mol % or less, preferably 9.0 mol % or less, more preferably 7.0 mol % or less, for the reason that the present glass block has excellent plasma resistance, 5.5 mol % or less is more preferable, 4.0 mol % or less is even more preferable, 2.0 mol % or less is particularly preferable, and 1.0 mol % or less is most preferable.
• the lower limit of the content of P 2 O 5 is preferably zero.
• the content of GeO 2 is preferably 5.5 mol % or less, more preferably 4.0 mol % or less, still more preferably 2.0 mol % or less, for the reason that the present glass block has excellent plasma resistance. 0 mol % or less is particularly preferred.
• the lower limit of the content of GeO 2 is preferably zero.
• the glass block may contain aluminum (Al), gallium (Ga) and In (indium).
• the content of Al 2 O 3 in the present glass block is preferably in the range of 0.0 mol % or more and 27.5 mol % or less.
• the content of Al 2 O 3 is preferably 27.5 mol% or less, more preferably 22.0 mol% or less, and even more preferably 18.0 mol% or less, because the transparency of the present glass block is more excellent.
• the content of Al 2 O 3 is preferably 0.0 mol% or more, more preferably 1.0 mol% or more, and 2.0 mol% or more. More preferably, 3.0 mol % or more is even more preferable, 4.0 mol % or more is particularly preferable, and 5.0 mol % or more is most preferable.
• the content of Ga 2 O 3 is 7.0 mol % or less, preferably 3.0 mol % or less, more preferably 1.0 mol % or less, for the reason that the present glass block has excellent plasma resistance and transparency. More preferably, 0.5 mol % or less is even more preferable.
• the lower limit of the content of Ga 2 O 3 is preferably zero.
• the content of In 2 O 3 is preferably 5.0 mol % or less, more preferably 3.0 mol % or less, and more preferably 1.0 mol % because the present glass block has better plasma resistance and transparency. More preferred are: The lower limit of the content of In 2 O 3 is preferably zero.
• % or more more preferably 22.0 mol% or more, still more preferably 27.0 mol% or more, even more preferably 32.0 mol% or more, particularly preferably 35.0 mol% or more, 37.0 mol % or more is more particularly preferred, 39.0 mol % or more is very preferred, and 41.0 mol % or more is most preferred.
• the total content (a) of SiO 2 , B 2 O 3 , P 2 O 5 and GeO 2 is 59.5 mol % or less, and 57.0 mol %.
• mol% or less is preferable, 55.0 mol% or less is more preferable, 53.0 mol% or less is still more preferable, 51.0 mol% or less is even more preferable, 49.0 mol% or less is particularly preferable, and 47.0 mol % or less is highly preferred, and 45.0 mol % or less is most preferred.
• a + Al2O3 sum of SiO2 , B2O3 , P2O5 , GeO2 and Al2O3 >
• the total content of SiO 2 , B 2 O 3 , P 2 O 5 , GeO 2 and Al 2 O 3 (a+Al 2 O 3 ) is 66.5 mol for the reason that the present glass block has excellent plasma resistance.
• % 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, 51.0 mol%
• the following are particularly preferred, and 48.0 mol % or less is most preferred.
• the total content of SiO 2 , B 2 O 3 , P 2 O 5 , GeO 2 and Al 2 O 3 is 10.0% because the transparency of the present glass block is more excellent.
• 0 mol % or more is preferable, 17.0 mol % or more is more preferable, and 22.0 mol % or more is still more preferable. That is, the total content of SiO 2 , B 2 O 3 , P 2 O 5 , GeO 2 and Al 2 O 3 (a + Al 2 O 3 ) is in the range of 10.0 mol% to 66.5 mol%. preferable.
• the ratio (b/a) of the O 5 and GeO 2 contents (unit: mol %) to the total a is 0.44 or less, preferably 0.36 or less, more preferably 0.29 or less, and 0 0.22 or less is more preferred, 0.16 or less is even more preferred, 0.12 or less is particularly preferred, and 0.09 or less is most preferred.
• the lower limit of the ratio (b/a) is preferably zero.
• the present glass block may contain an alkaline earth metal element (R 2 ).
• Alkaline earth metal elements (R 2 ) include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra).
• Be beryllium
• Mg magnesium
• Ca calcium
• Sr strontium
• Ba barium
• Ra radium
• the present glass block contains at least one of Mg and Ca as an essential element.
• the content of R 2 O is 20.0 mol % or more, preferably 29.0 mol % or more, more preferably 36.0 mol % or more, and 40 mol % or more, because the plasma resistance of the present glass block is excellent.
• 0 mol % or more is even more preferred, 43.0 mol % or more is particularly preferred, 46.0 mol % or more is very preferred, and 49.0 mol % or more is most preferred.
• the upper limit of the content of R 2 O 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, and 60.0 mol% or less.
• the content of R 2 O in the present glass block is preferably in the range of 0.0 mol % or more and 80.0 mol % or less.
• MgO The content of MgO is 50.0 mol % or less, preferably 40.0 mol % or less, more preferably 35.0 mol % or less, more preferably 30.0 mol %, for the reason that the present glass block has excellent transparency. % or less, even more preferably 25.0 mol % or less, particularly preferably 20.0 mol % or less, very preferably 15.0 mol % or less, most preferably 10.0 mol % or less.
• the content of MgO is preferably 1.0 mol % or more, more preferably 3.0 mol % or more, and still more preferably 5.0 mol % or more, because the plasma resistance of the present glass block is more excellent. . That is, the content of MgO in the present glass block is preferably in the range of 1.0 mol % or more and 50.0 mol % or less.
• the content of CaO in the present glass block is preferably in the range of 20.0 mol % or more and 69.0 mol % or less.
• the content of CaO is preferably 20.0 mol% or more, more preferably 29.0 mol% or more, still more preferably 36.0 mol% or more, and 40 0 mol % or more is even more preferred, 43.0 mol % or more is particularly preferred, 46.0 mol % or more is very preferred, and 49.0 mol % or more is most preferred.
• the content of CaO is preferably 69.0 mol% or less, more preferably 66.0 mol% or less, even more preferably 63.0 mol% or less, for the reason that the transparency of the present glass block is more excellent. 60.0 mol % or less is even more preferred, 57.0 mol % or less is particularly preferred, 54.0 mol % or less is very preferred, and 51.0 mol % or less is most preferred.
• the total content of MgO and CaO in the present glass block is preferably in the range of 20.0 mol % or more and 69.0 mol % or less.
• the total content of MgO and CaO is preferably 20.0 mol% or more, more preferably 29.0 mol% or more, and more preferably 36.0 mol% or more, because the present glass block has better plasma resistance. More preferably, 40.0 mol % or more is even more preferable, 43.0 mol % or more is particularly preferable, 46.0 mol % or more is very preferable, and 49.0 mol % or more is most preferable.
• the total content of MgO and CaO is preferably 69.0 mol% or less, more preferably 66.0 mol% or less, and 63.0 mol% or less. is more preferable, 60.0 mol% or less is even more preferable, 57.0 mol% or less is particularly preferable, 54.0 mol% or less is very preferable, and 51.0 mol% or less is most preferable.
• the content of SrO is preferably 60.0 mol% or less, more preferably 30.0 mol% or less, even more preferably 10.0 mol% or less, further preferably 5.0 mol% or less, because the transparency of the present glass block is excellent. mol % or less is particularly preferred, and 1.0 mol % or less is most preferred.
• the lower limit of the SrO content is preferably zero.
• the content of BaO is preferably 30.0 mol % or less, more preferably 25.0 mol % or less, even more preferably 20.0 mol % or less, because the transparency of the present glass block is more excellent. 0 mol % or less is even more preferred, 10.0 mol % or less is particularly preferred, 5.0 mol % or less is very preferred, and 1.0 mol % or less is most preferred.
• the lower limit of the BaO content is preferably zero.
• the content of MgO (unit: mol %) is equal to or greater than the content of BaO (unit: mol %), and is higher than the content of BaO (unit: mol %). is preferably large.
• the CaO content (unit: mol %) is preferably equal to or greater than the BaO content (unit: mol %) and greater than the BaO content (unit: mol %).
• the SrO content (unit: mol %) is preferably equal to or greater than the BaO content (unit: mol %) and greater than the BaO content (unit: mol %).
• the content of MgO (unit: mol %) is greater than or equal to the content of SrO (unit: mol %), and is higher than the content of SrO (unit: mol %). is preferably large.
• the CaO content (unit: mol %) is preferably equal to or greater than the SrO content (unit: mol %) and greater than the SrO content (unit: mol %).
• the glass block may contain yttrium (Y).
• Y yttrium
• the content of Y 2 O 3 in the present glass block is preferably 5.0 mol % or less, more preferably 3.0 mol % or less, even more preferably 1.0 mol % or less.
• the lower limit of the total content of Y 2 O 3 is preferably zero.
• the present glass block may contain an alkali metal element (R 1 ).
• Alkali metal elements (R 1 ) include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr). Among these, lithium (Li), sodium (Na), and potassium (K) are substantially preferred.
• R 1 2 O is 1.2 mol% or less, preferably 0.8 mol% or less, more preferably 0.4 mol% or less, for the reason that the present glass block has excellent plasma resistance, 0.1 mol % or less is even more preferred, 0.05 mol % or less is particularly preferred, 0.01 mol % or less is very preferred, and 0.002 mol % or less is most preferred.
• the lower limit of the content of R 1 2 O is preferably zero.
• the glass block may contain titanium (Ti), zirconium (Zr), manganese (Mn), zinc (Zn) and tantalum (Ta).
• TiO2 or ZrO2 The content of TiO 2 or ZrO 2 is 4.8 mol % or less, preferably 3.5 mol % or less, more preferably 2.5 mol % or less, for the reason that the present glass block has excellent plasma resistance. , 1.0 mol % or less is more preferable.
• the lower limit of the content of TiO 2 or ZrO 2 is preferably zero.
• the content of TiO 2 is preferably 4.8 mol % or less, more preferably 3.5 mol % or less, still more preferably 2.5 mol % or less, for the reason that the plasma resistance of the present glass block is excellent. 0 mol % or less is particularly preferred.
• the lower limit of the content of TiO 2 is preferably zero.
• the content of ZrO 2 is preferably 4.8 mol % or less, more preferably 3.5 mol % or less, still more preferably 2.5 mol % or less, for the reason that the plasma resistance of the present glass block is excellent. 0 mol % or less is particularly preferred.
• the lower limit of the ZrO 2 content is preferably zero.
• the content of MnO 2 is 9.5 mol % or less, preferably 6.0 mol % or less, more preferably 3.0 mol % or less, for the reason that the present glass block has excellent plasma resistance. 0 mol % or less is more preferable.
• the lower limit of the content of MnO 2 is preferably zero.
• the content of ZnO is 11.8 mol% or less, preferably 7.0 mol% or less, more preferably 4.0 mol% or less, and more preferably 1.0 mol% or less, because the present glass block has excellent plasma resistance. mol % or less is more preferable.
• the lower limit of the ZnO content is preferably zero.
• the Ta 2 O 5 content is preferably 6.0 mol % or less, more preferably 3.0 mol % or less, and even more preferably 1.0 mol % or less, because the present glass block has excellent plasma resistance. .
• the lower limit of the Ta 2 O 5 content is preferably zero.
• the ratio of the Ta 2 O 5 content (unit: mol %) to the SiO 2 content (unit: mol %) (Ta 2 O 5 /SiO 2 ) 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 0.067 or less. 010 or less is most preferred.
• the lower limit of the ratio (Ta 2 O 5 /SiO 2 ) is preferably zero.
• 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, because the present glass block has excellent plasma resistance. 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 0.05 mol% or less is most preferred. A lower bound of zero is preferred.
• Impurity elements include silicon (Si), boron (B), phosphorus (P), germanium (Ge), aluminum (Al), gallium (Ga), indium (In), alkaline earth metal elements (R 2 ), yttrium.
• impurity elements include Cu, Fe, Ni, Cr, Sn, Co, V, Bi, Se, Ce, Er and Nd.
• the content of Cu in terms of oxide specifically means the content of CuO.
• the content of Fe in terms of oxide specifically means the content of Fe 2 O 3 .
• the content of Ni in terms of oxide specifically means the content of NiO.
• the content of Cr in terms of oxide specifically means the content of Cr 2 O 3 .
• the content of Sn in terms of oxide specifically means the content of SnO 2 .
• the content of Co in terms of oxide specifically means the content of Co 3 O 4 .
• the content of V in terms of oxide specifically means the content of V 2 O 5 .
• the content of Bi in terms of oxide specifically means the content of Bi 2 O 3 .
• the content of Se in terms of oxide specifically means the content of SeO 2 .
• the content of Ce in terms of oxide specifically means the content of CeO 2 .
• the content of Er in terms of oxide specifically means the content of Er 2 O 3 .
• the content of Nd in terms of oxide specifically means the content of Nd 2 O 3 .
• the content of each of the above elements (excluding Si) in the glass block is measured using an X-ray fluorescence spectrometer (XRF) (ZSX100e, manufactured by Rigaku Corporation). That is, 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.
• XRF X-ray fluorescence spectrometer
• ROH-600 oxygen/hydrogen analyzer
• the ratio (F/O) between the fluorine content F and the oxygen content O is 0.20 or less, preferably 0.15 or less, and 0.15 or less, because the plasma resistance of the present glass block is excellent. 10 or less is more preferable, and 0.05 or less is even more preferable.
• the lower limit of the ratio (F/O) is preferably zero.
• the ratio (F/O) in the glass block is obtained as follows. First, for any one surface of the glass block, using an X-ray photoelectron spectrometer (JPS-9000MC manufactured by JEOL Ltd.), F atomic concentration (unit: atomic %) and O atomic concentration (unit: atomic %) are obtained. . The obtained ratio of the F atomic concentration and the O atomic concentration is defined as the ratio (F/O) of the glass block.
• the nitrogen (N) content (N content) of the present glass block is preferably small because the transparency of the present glass block is more excellent.
• the N content is preferably 9.0% by mass or less, more preferably 7.0% by mass or less, still more preferably 5.0% by mass or less, and even more preferably 4.0% by mass or less. 3.0% by weight or less is particularly preferred, 2.0% by weight or less is very preferred, and 1.0% by weight or less is most preferred.
• the lower limit of the N content is preferably zero.
• the N content is measured by secondary ion mass spectroscopy (SIMS). A mass spectrometer (ION-TOF, TOF.SIMS5) is used for the measurement.
• the average thermal expansion coefficient of the present glass block at 50 to 350 ° C. is preferably 9.0 ppm / ° C. or less. 0 ppm/°C or less is more preferable, 7.0 ppm/°C or less is more preferable, 6.0 ppm/°C or less is even more preferable, 5.5 ppm/°C or less is particularly preferable, and 5.0 ppm/°C or less is very preferable. , 4.5 ppm/° C. or less is most preferred.
• the expansion coefficient is measured using a differential thermal dilatometer according to the method described in JIS R 3102-1995.
• the present glass block has excellent transparency. Specifically, for example, the visible light transmittance of the present glass block is 75% or more.
• the visible light transmittance of the present glass block is preferably 78% or more, more preferably 81% or more, still more preferably 84% or more, even more preferably 87% or more, particularly preferably 90% or more, and most preferably 93% or more. preferable.
• the upper limit is preferably 100%. Visible light transmittance is measured by a method based on JIS R 3106 (1998). In order to keep the visible light transmittance within the above range, it is preferable to set the content of each component as described above and to manufacture the glass block by the method (this manufacturing method) described later.
• the porosity of the present glass block is, for example, 3.0% by volume or less. Thereby, the present glass block is more excellent in plasma resistance.
• the porosity of the glass block is preferably 2.5% by volume or less, more preferably 2.0% by volume or less, and even more preferably 1.5% by volume or less, because the plasma resistance of the glass block is further excellent. , 1.0% by volume or less is more preferable, 0.5% by volume or less is particularly preferable, and 0.1% by volume or less is most preferable. A lower bound of zero is preferred.
• the porosity is determined according to the open porosity calculation method described in JIS R 1634:1998 "Method for measuring sintered body density and open porosity of fine ceramics". In order to keep the porosity within the above range, it is preferable to set the content of each component as described above and to manufacture the glass block by the method (this manufacturing method) described later.
• the shape of the present glass block may be plate-like (for example, disc-like, flat plate-like), spherical, spheroidal, or the like, and is appropriately selected depending on the application.
• the "glass block” is a concept that does not include at least glass frit, glass powder, and glass fiber, regardless of its shape.
• the area of at least one surface (e.g., main surface) of the present glass block is preferably 25 mm 2 or more, more preferably 100 mm 2 or more, still more preferably 500 mm 2 or more, and 1,000 mm 2 .
• 5,000 mm 2 or more is particularly preferred, 10,000 mm 2 or more is even more preferred, 40,000 mm 2 or more is very preferred, and 90,000 mm 2 or more is most preferred.
• the thickness of the present glass block (the thickness of the thinnest portion) is preferably 0.3 mm or more, more preferably 0.5 mm or more, still more preferably 1 mm or more, and 3 mm or more. Even more preferred, 6 mm or more is particularly preferred, 10 mm or more is even more preferred, 15 mm or more is very preferred, and 20 mm or more is most preferred.
• the thickness of the present glass block is preferably 500 mm or less, more preferably 100 mm or less, still more preferably 80 mm or less, and 60 mm or less because crystallization of the present glass block is suppressed and transparency is more excellent. Even more preferred, 50 mm or less is very preferred, 40 mm or less is particularly preferred, and 30 mm or less is most preferred. That is, the thickness of the present glass block is preferably in the range of 0.3 mm or more and 500 mm or less.
• the present glass block can be suitably used, for example, as a window material for semiconductor manufacturing equipment.
• the application of the present glass block is not limited to this.
• the present glass block can be used, for example, as a member mounted in a plasma etching apparatus, such as a top plate, a microwave introduction tube, a lift pin, a nozzle, an edge ring, an electrostatic chuck, a shower plate, and a Examples include a protective cover for the sensor and the like.
• various glass raw materials are weighed and mixed so that the resulting glass block has the glass composition described above.
• the mixed glass raw materials are heated and melted using a glass melting furnace or the like.
• defoaming, homogenization, etc. are appropriately performed on the melt by a known method.
• molten glass is obtained.
• the obtained molten glass is formed into a desired shape and slowly cooled.
• the molding method is not particularly limited, and examples thereof include a float method, a press method, a fusion method, a down-draw method and the like.
• the obtained molten glass may be formed into a temporary shape, then slowly cooled, and the resulting temporary shape may be processed such as cutting. A glass block of desired shape is thus obtained.
• the obtained glass block may be subjected to a treatment such as grinding or polishing, if necessary.
• the temperature at which the glass raw materials are heated and melted (hereinafter also referred to as "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 the production characteristics are excellent. .
• the melting temperature is preferably 1200° C. or higher, more preferably 1300° C. or higher, and particularly preferably 1400° C. or higher. That is, the melting temperature is preferably in the range of 1200°C or higher and 1650°C or lower.
• 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, further preferably 10 hours or less, and 8 hours or less from the viewpoint of clarity. is more preferred, 6 hours or less is particularly preferred, and 4 hours or less is most preferred.
• the melting time is preferably 1 hour or longer, more preferably 2 hours or longer, and particularly preferably 3 hours or longer. That is, the melting time is preferably in the range of 1 hour or more and 24 hours or less.
• the cooling rate when cooling the molten glass is preferably 0.5° C./min or more, more preferably 1° C./min or more, still more preferably 5° C./min or more, and 10° C./min from the viewpoint of crystallization acceleration.
• the above are particularly preferred.
• 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. That is, the cooling rate is preferably in the range of 0.5° C./min or more and 30° C./min or less.
• conventional members used in an environment exposed to plasma include, for example, members made of sapphire.
• sapphire is manufactured by a single crystal growth method, its manufacturing characteristics are inferior and there is a limit to the size that can be manufactured.
• sapphire is a difficult-to-work material, so it is very expensive.
• the present glass block is obtained by the above-described present manufacturing method, the manufacturing characteristics can be improved, and the size can be changed as appropriate. Furthermore, it is low cost because it is easier to process than sapphire.
• this specification discloses the following configurations. ⁇ 1> containing silicon and at least one of magnesium and calcium,
• the alkali metal element is R 1 and the alkaline earth metal element is R 2
• the molar percentage display based on the oxide is The content of B 2 O 3 is 49.0 mol% or less
• the content of P 2 O 5 is 11.5 mol% or less
• the total content of SiO 2 , B 2 O 3 , P 2 O 5 and GeO 2 is 10.0 mol % or more and 59.5 mol % or less, the total content of SiO 2 , B 2 O 3 , P 2 O 5 , GeO 2 and Al 2 O 3 is 66.5 mol% or less
• the content of Ga 2 O 3 is 7.0 mol% or less
• the ratio b/a of the total content b of Al 2 O 3 , Ga 2 O 3 and In 2 O 3 to the total content a of SiO 2 , B 2 O 3 , P 2 O 5 and GeO 2 is , is less than
• ⁇ 2> The glass block according to ⁇ 1> above, wherein the content of SiO 2 is 17.0 mol % or more.
• ⁇ 3> The glass block according to ⁇ 1> or ⁇ 2> above, wherein the content of SiO 2 is 59.5 mol % or less.
• ⁇ 4> The glass block according to any one of ⁇ 1> to ⁇ 3> above, wherein the content of Al 2 O 3 is 27.5 mol % or less.
• ⁇ 5> The glass block according to any one of ⁇ 1> to ⁇ 4> above, wherein the total content of MgO and CaO is 20.0 mol % or more.
• ⁇ 6> The glass block according to any one of ⁇ 1> to ⁇ 5> above, wherein the total content of MgO and CaO is 69.0 mol % or less.
• ⁇ 7> The glass block according to any one of ⁇ 1> to ⁇ 6> above, wherein the CaO content is 20.0 mol % or more and 69.0 mol % or less.
• ⁇ 8> The glass block according to any one of ⁇ 1> to ⁇ 7> above, wherein the BaO content is 30.0 mol % or less.
• ⁇ 9> The glass block according to any one of ⁇ 1> to ⁇ 8> above, having an average thermal expansion coefficient of 9.0 ppm/°C or less at 50 to 350°C.
• ⁇ 10> The glass block according to any one of ⁇ 1> to ⁇ 9> above, which has a visible light transmittance of 75% or more.
• ⁇ 11> The glass block according to any one of ⁇ 1> to ⁇ 10> above, having a porosity of 3.0% by volume or less.
• ⁇ 12> A method for producing a glass block according to any one of the above ⁇ 1> to ⁇ 11>, wherein the frit is melted by heating, the resulting molten glass is shaped, and slowly cooled.
• ⁇ 13> The method for producing a glass block according to ⁇ 12> above, wherein the glass raw material is heated and melted at a temperature of 1650° C. or less.
• ⁇ 14> A member for semiconductor manufacturing equipment, comprising the glass block according to any one of ⁇ 1> to ⁇ 11> above.
• ⁇ 15> The above ⁇ 14>, the member for a semiconductor manufacturing apparatus.
• Glass raw materials were weighed and mixed so that the resulting glass block had the composition shown in Tables 1 to 6 below (indicated by mole percentage based on oxide) and weighed 400 g.
• the mixed glass raw materials were placed in a platinum crucible, put into an electric furnace, melted by heating at a temperature of 1500 to 1700° C. for about 3 hours, defoamed and homogenized to obtain molten glass.
• a portion of the obtained molten glass was poured into a metal mold, held at a temperature about 50°C higher than 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-like glass block. (Area of main surface: 10000 mm 2 , thickness: 10 mm) was obtained.
• Examples 47-49 commercial sapphire, silicon and quartz blocks were used, respectively, rather than glass blocks.
• the blocks of Examples 47 to 49 are also referred to as "glass blocks" for convenience.
• the amount of etching was determined to evaluate the plasma resistance. Specifically, a test piece having a size of 10 mm ⁇ 5 mm ⁇ 4 mm was cut out from a glass block, and a surface of 10 mm ⁇ 5 mm was mirror-finished. A part of the mirror-finished surface was masked with Kapton tape and etched with plasma gas. After that, using a stylus surface profiler (Dectak 150, manufactured by ULVAC), the amount of etching was determined by measuring the difference in level between the etched portion and the non-etched portion. EXAM (manufactured by Shinko Seiki Co., Ltd., model: POEM type) was used as a plasma etching apparatus.
• EXAM manufactured by Shinko Seiki Co., Ltd., model: POEM type
• Etching was performed in RIE mode (reactive ion etching mode) with CF 4 gas at a pressure of 10 Pa and an output of 350 W for 195 minutes. It can be evaluated that the smaller the etching amount (unit: nm), the better the plasma resistance. Specifically, when the etching amount was 1600 nm or less, the plasma resistance was evaluated to be excellent. The etching amount is preferably 1000 nm or less because plasma resistance is more excellent.

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