EP4308512A1 - Composant de précision euvl ayant un comportement de dilatation thermique spécifique - Google Patents

Composant de précision euvl ayant un comportement de dilatation thermique spécifique

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Publication number
EP4308512A1
EP4308512A1 EP22715032.3A EP22715032A EP4308512A1 EP 4308512 A1 EP4308512 A1 EP 4308512A1 EP 22715032 A EP22715032 A EP 22715032A EP 4308512 A1 EP4308512 A1 EP 4308512A1
Authority
EP
European Patent Office
Prior art keywords
ppm
mol
euvl
cte
temperature range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22715032.3A
Other languages
German (de)
English (en)
Inventor
Florian KANAL
Ralf Jedamzik
Ina Mitra
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schott AG
Original Assignee
Schott AG
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Filing date
Publication date
Application filed by Schott AG filed Critical Schott AG
Publication of EP4308512A1 publication Critical patent/EP4308512A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • 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
    • C03C3/06—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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
    • G03F1/24—Reflection masks; Preparation thereof
    • 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
    • C03C2203/00—Production processes
    • C03C2203/50—After-treatment
    • C03C2203/52—Heat-treatment
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties

Definitions

  • the present invention relates to a precision EUVL component with a specific thermal expansion behavior.
  • EUV lithography is a photolithographic process in which electromagnetic radiation between usually 5 nm and 50 nm (soft X-ray radiation), in particular electromagnetic radiation with a wavelength of 13.5 nm (91.82 eV) is used. This is what is known as “extreme ultraviolet radiation” (EUV). This part of the electromagnetic spectrum is completely absorbed by almost all materials.
  • EUV extreme ultraviolet radiation
  • a disadvantage of using reflective photomasks is the comparatively poor maximum reflectivity of the multilayer stack in the EUV radiation range of typically less than 70%.
  • the radiation that is not reflected by the photomask is absorbed by it and, in the form of heat, enters the photomask substrate and possibly also the photomask carrier (hereinafter also referred to as the “reticle carrier” or “table” or “Mask carrier” or “table” called, English “Reticle Stage” or Photomask Stage” or “Mask Stage”), which can increase their temperature, especially with increasing irradiation time.
  • thermally induced deformations mentioned can be compensated for in part by compensating mechanisms within the overall optical system of an EUVL lithography system, for example in the beam shaping of the illumination:
  • this compensation is limited, so it is therefore advantageous to to keep as low as possible.
  • thermal hysteresis not only thermally induced deformation of the material during illumination must be taken into account, but also the thermal behavior over time (thermal hysteresis). Materials with a comparatively high thermal hysteresis, however, make the mentioned compensation more difficult and thus also the prevention of unwanted thermal imaging errors of the photomask.
  • EUVL precision components with high requirements in terms of their thermal properties are, in particular, EUVL mirrors in the optical system of the EUVL device and wafer carriers (also referred to below as “wafer tables”, English: “wafer stage”) where the (Si) wafers to be exposed are placed.
  • Ceramics, Ti-doped quartz glass and glass ceramics are known as materials for precision components with low thermal expansion in the temperature range around room temperature.
  • Glass ceramics with low thermal expansion are, in particular, lithium aluminum silicate glass ceramics (LAS glass ceramics), which are described, for example, in US Pat. No. 4,851,372, US Pat .
  • Other materials for precision components are cordierite ceramics or cordierite glass ceramics. Such materials are often used for precision components that have to meet particularly stringent requirements in terms of their properties (e.g. mechanical, physical, optical properties).
  • the thermal expansion of a material is determined using a static method in which the length of a test specimen is determined at the beginning and at the end of the specific temperature interval and the mean expansion coefficient a or CTE (Coefficient of Thermal Expansion) is calculated from the difference in length becomes.
  • the CTE is then given as an average for this temperature interval, e.g. for the temperature interval from 0°C to 50°C as CTE(0;50) or a(0;50).
  • the mean CTE can be optimized not only for the standard temperature interval CTE(0;50), but for example for a temperature interval around the actual application temperature, for example the interval from 19°C to 25°C, ie CTE(19;25) for certain Lithography applications such as EUV lithography.
  • the thermal expansion of a test specimen can also be determined in very small temperature intervals and thus displayed as a CTE-T curve.
  • a CTE-T curve may exhibit a zero crossing at one or more temperatures, preferably at or near the intended use temperature.
  • the relative change in length with a change in temperature is particularly small.
  • a zero crossing of the CTE-T curve can be shifted to the application temperature of the component through suitable heat treatment.
  • the gradient of the CTE-T curve around the application temperature should also be as small as possible in order to cause the smallest possible change in length of the component in the event of minor temperature changes.
  • the above-described optimizations of the CTE or thermal expansion are usually carried out with these special zero-expansion glass ceramics while the composition remains the same by varying the ceramization conditions.
  • hysteresis means that the change in length of a test specimen when heated at a constant heating rate differs from the change in length of the test specimen when it is subsequently cooled at a constant cooling rate, even if the amount of cooling rate and heating rate is the same. If the change in length as a function of the temperature for heating up or cooling down is shown graphically, a classic hysteresis loop results. The form of the hysteresis loop also depends on the rate of temperature change.
  • the material or a precision component made from it exhibits a disruptive isothermal change in length, i.e. after a change in temperature, a change in length of the material also occurs at the time when the temperature is already kept constant (so-called “isothermic holding”) until a stable state is reached. If the material is subsequently heated and cooled again, the same effect occurs again.
  • a temperature range from 0°C to 50°C, in particular from 10°C to 35°C or from 10°C to 25°C or from 19°C to 25°C, with a temperature of 22°C usually being relevant referred to as room temperature.
  • Some well-known materials such as ceramics, Ti-doped quartz glass and certain glass ceramics are characterized by an average thermal expansion coefficient CTE (0:50) of 0 ⁇ 0.1x10 _6 /K (corresponding to 0 ⁇ 0.1 ppm/K). Materials that have such a low average CTE in the temperature range mentioned are referred to as zero-elongation materials within the meaning of this invention.
  • glass ceramics, in particular LAS glass ceramics, whose average CTE is optimized in this way generally have a thermal hysteresis in the temperature range from 10°C to 35°C.
  • EUVL precision components such as photomask carrier or photomask
  • the cooling of EUVL photomasks or photomask carriers is described, for example, in EP 1411391 A2, US 2015/0241796 A1 and US 20212/0026474 A1. In order to characterize the thermal hysteresis of a material in a specific temperature range, the thermal behavior of the materials for different temperature points in this considered in this area.
  • a further requirement of a glass-ceramic material is that the glass components can be melted well and that the melting process and homogenization of the underlying glass melt in industrial-scale production plants is simple, in order - after the glass has been ceramized - to meet the high demands placed on the glass-ceramic or a precision component, comprising the glass-ceramic, with regard to CTE homogeneity, inner quality - in particular a small number of inclusions (particularly bubbles), low level of streaks - and polishability, etc.
  • a further object was to produce a glass ceramic that could be produced on an industrial scale with zero expansion and reduced thermal hysteresis, preferably at least in the temperature range from 19 to 25° C., preferably at least in the temperature range from 10° C. to 25° C., and particularly preferably at least in the temperature range from 10°C to 35°C, in particular for an EUVL precision component.
  • a further object was to produce a glass ceramic that could be produced on an industrial scale with zero expansion and reduced thermal hysteresis, in particular at least in the temperature range from 19 to 25° C., preferably at least in the temperature range from 10° C. to 25° C. and particularly preferably at least in the temperature range from 10° C. to 35° C., in particular for an EUVL precision component.
  • the invention relates to an EUVL precision component which has an average coefficient of thermal expansion CTE in the range from 0 to 50° C. of at most 0 ⁇ 0.1 ⁇ 10 _6 /K and a thermal hysteresis of ⁇ 0.1 ppm at least in the temperature range from 19 to 25 °C, preferably at least in the temperature range from 10 °C to 25 °C, particularly preferably at least in the temperature range from 10 °C to 35 °C and an alternative parameter fn, selected from the Group consisting of alternative parameter f ( 2o ; 40 ) ⁇ 0.024 ppm/K, alternative parameter f ⁇ oo ) ⁇ 0.039 ppm/K, alternative parameter f ( -io ; 30 ) ⁇ 0.015 ppm/K, preferably an alternative parameter f ( 2o ; 40 ) ⁇ 0.024 ppm/K.
  • and at least one inorganic material selected from the group consisting of doped quartz glass, glass ceramic and ceramic, preferably Ti-doped quartz glass, LAS glass ceramic and cordierite.
  • the invention relates to an EUVL precision component which has an average thermal expansion coefficient CTE in the range from 0 to 50°C of at most 0 ⁇ 0.1 x 10_6 /K and a thermal hysteresis of ⁇ 0.1 ppm at least in the temperature range of 19 to 25°C, preferably at least in the temperature range of 10° C to 25°C, particularly preferably at least in the temperature range from 10°C to 35°C and an alternative parameter f . , .
  • alternative parameter f ( 2o ; 40 ) selected from the group consisting of alternative parameter f ( 2o ; 40 ) ⁇ 0.024 ppm/K, alternative parameter f ( 2o ; 70 ) ⁇ 0.039 ppm/K, alternative parameter f ( -io ; 30 ) ⁇ 0.015 ppm/K , preferably an alternative parameter f ( 2o ; 40 ) ⁇ 0.024 ppm/K, and at least one inorganic material selected from the group consisting of doped quartz glass, glass ceramic and ceramic, preferably Ti-doped quartz glass, LAS glass ceramic and cordierite takes.
  • the precision component comprises a LAS glass ceramic according to the invention.
  • the invention relates to an EUVL precision component which has an average coefficient of thermal expansion CTE in the range from 0 to 50° C. of at most 0 ⁇ 0.1 ⁇ 10 _6 /K and a thermal hysteresis of ⁇ 0.1 ppm at least in the temperature range from 19 to 25°C, preferably at least in the temperature range from 10°C to 25°C, particularly preferably at least in the temperature range from 10°C to 35°C and an alternative parameter fn selected from the group consisting of alternative parameter f (2 o ; 40 ) ⁇ 0.024 ppm/K, alternative parameter f (2 o ; 70 ) ⁇ 0.039 ppm/K, alternative parameter f ( -io ; 30 ) ⁇ 0.015 ppm/K, preferably an alternative Parameter f (2 o ; 40 ) ⁇ 0.024 ppm/K, the precision component comprising a LAS glass ceramic according to the invention.
  • the invention relates to an EU VL precision component according to the invention, which is selected from the group consisting of photomasks or reticles, photomask substrates or reticle mask blanks or mask blanks, photomask carriers or reticle stages, mirrors, Mirror carriers and wafer carriers or wafer stages, in particular on a photomask or reticle, and/or a photomask substrate or reticle mask blank or mask blank and/or a photomask carrier or reticle stage.
  • the invention relates to a substrate for an EUV (micro)lithographic mirror (also called “EUVL mirror”) comprising a precision component according to the invention.
  • EUV microlithographic mirror
  • the invention relates to a substrate for an EUV photomask (also called “(EUVL) photomask blank” or “reticle mask blank”) comprising an EUVL precision component according to the invention.
  • the invention relates to an EUV photomask carrier (also called “reticle stage”) comprising an EUV precision component according to the invention.
  • the invention relates to a substrate for an EUVL photomask and/or a photomask carrier, comprising a precision component according to the invention, this having a relative change in length (dl/lo) of ⁇
  • a LAS glass-ceramic is provided, in particular for an EUVL precision component according to an aspect of the invention, which has an average coefficient of thermal expansion CTE in the range from 0 to 50° C. of at most 0 ⁇ 0.1 x 10 _6 /K and a thermal hysteresis of ⁇ 0.1 ppm at least in the temperature range from 19 to 25 °C, preferably at least in the temperature range from 10 °C to 25 °C, particularly preferably at least in the temperature range from 10 °C to 35 °C and which comprises the following components (in mole % on an oxide basis):
  • MgO+ZnO 0 0.6 at least one component selected from the group consisting of P 2 O 5 , R 2 O, where R 2 O is Na 2 0 and/or K 2 O and/or CS 2 O and/or Rb 2 can be 0, and RO, where RO can be CaO and/or BaO and/or SrO,
  • nucleating agent with a content of 1.5 to 6 mol%, wherein the nucleating agent is at least one component selected from the group consisting of PO2 , ZrÜ2 , Ta 2 0s, Nb 2 0s, Sn02, M0O3, WO3.
  • FIG. 1 shows CTE-T curves of materials known from the prior art with low linear thermal expansion for, for example, precision components.
  • FIG. 2 shows the hysteresis behavior of three glass-ceramic samples determined using the same method that is also used in the present invention. This figure is taken from R. Jedamzik et al., "Modeling of the thermal expansion behavior of ZERODUR ® at arbitrary temperature profiles", Proc. SPIE Vol. 7739, 2010.
  • Figures 12 and 13 show normalized DI / Io-T curves (also called dl / lo curves) fiction, contemporary precision components and advantageous glass ceramics (compositions according to Ex. 6 and 7 in Table 1a) and auxiliary lines for determining the parameter F as a measure for the flatness of the expansion curve in the temperature range from 0°C to 50°C.
  • FIGS. 14 to 17 show normalized DI/lo-T curves of known materials which can be used to manufacture known precision components, and auxiliary lines for determining the parameter F as a measure of the flatness of the expansion curve in the temperature ranges of -20°C or -10°C to 70°C or 80°C.
  • FIG. 18 shows normalized DI/Io-T curves of the precision components or glass ceramics of FIGS. 12 and 13 in the temperature range from -30.degree. C. to +70.degree.
  • FIG. 19 shows normalized DI/lo-T curves of known materials in the temperature range from -30°C to +70°C.
  • FIGS. 20 and 21 show that the CTE-T curves of advantageous precision components or advantageous glass ceramics of FIGS. 12 and 13 advantageously have a CTE plateau.
  • Figures 22 and 23 show the slopes of CTE-T curves from Figures 24 and 25.
  • FIGS. 24 and 25 show different CTE curves for two composition examples of the invention, set by different ceramization parameters.
  • FIG. 26 shows the gradient of a CTE-T curve of an advantageous precision component or advantageous glass ceramic, the glass ceramic having a composition according to Example 17 in Table 1a.
  • FIG. 27 shows a normalized DI/lo-T curve of a precision component according to the invention or an advantageous glass ceramic (composition according to Example 17 in Table 1a) and auxiliary lines for determining the alternative parameter f ( 20 ; 40 ) as a measure of the flatness of the extension voltage curve in the temperature range from 20°C to 40°C.
  • Figure 28 shows a normalized DI / lo-T curve of the precision component or glass ceramic of Figure 13 and auxiliary lines for determining the alternative parameter f ( -io ; 30 ) as a measure of the flatness of the expansion curve in the temperature range from -10 ° C to 30 °C
  • FIG. 29 shows a normalized DI/lo-T curve of the precision component or glass ceramic of FIG. 13 and auxiliary lines for determining the alternative parameter fpo j o ) as a measure of the flatness of the expansion curve in the temperature range from 20° C. to 70° C.
  • Figure 30 shows a normalized DI / lo-T curve of a precision component according to the invention or advantageous glass ceramic (composition according to Example 14 in Table 1a) and auxiliary lines for determining the alternative parameter f ( -io ; 30 ) as a measure of the flatness of the Expansion curve in the temperature range from -10°C to 30°C.
  • FIG. 34 shows a normalized DI/lo-T curve (also called dl/l 0 curves) of a precision component or advantageous glass ceramic according to the invention (composition according to example 7b in Table 1b) and auxiliary lines for determining the parameter F as a measure of the flatness of the expansion curve in the temperature range from 0°C to 50°C.
  • 35 shows another normalized DI/lo-T curve of a precision component or advantageous glass ceramic according to the invention (composition according to Example 7b in Table 1b) based on a different ceramization and auxiliary lines for determining the alternative parameter f ( 2o ; 70 ) as a measure of the flatness of the expansion curve in the temperature range from 20°C to 70°C.
  • FIG. 36 shows a normalized DI/lo-T curve (also called dl/l 0 curves) of a precision component according to the invention or an advantageous glass ceramic (composition according to Example 6b in Table 1b) and auxiliary lines for determining the alternative parameter f ( ⁇ io ; 30 ) as a measure of the flatness of the expansion curve in the temperature range from -10°C to 30°C.
  • Figures 37, 39 and 41 show that the CTE-T curves of advantageous precision components or advantageous glass ceramics (compositions according to Ex. 6b, Ex. 7b and Ex. 9b in Table 1b), which are used to produce advantageous EUVL precision components can advantageously have a CTE “plateau”.
  • Figures 38 and 40 show details of Figures 37 and 39.
  • FIGS. 42 and 43 show gradients of CTE-T curves of advantageous precision components or advantageous glass ceramics with compositions according to example 6b and example 7b in table 1b.
  • FIGS. 44 and 45 show different expansion curves for advantageous precision components or advantageous glass ceramics with compositions according to example 6b and example 7b in table 1b, set by different ceramization parameters.
  • an EUVL precision component is provided for the first time, which combines several relevant properties: it has an average thermal expansion coefficient CTE in the range from 0 to 50° C. of at most 0 ⁇ 0.1 x 10 _6 /K, ie it is zero-stretching. In addition, it has a thermal hysteresis of ⁇
  • hysteresis-free A precision EUVL component with such a small hysteresis effect is called hysteresis-free.
  • a thermal Have a hysteresis of ⁇ 0.1 ppm, i.e. are hysteresis-free, can also be used to advantage in other applications, especially in applications in measurement technology that take place at or around room temperature, for example in precision scales or positioning systems.
  • F TCL (0; 50°C) /
  • the EUVL precision component also has an alternative parameter fn . on, selected from the group consisting of alternative parameter f ( 2o ; 40 ) ⁇ 0.024 ppm/K, alternative parameter fpojo ) ⁇ 0.039 ppm/K, alternative parameter f ( -io ; 30 ) ⁇ 0.015 ppm/K (see eg Figures 27 to 30, 35 and 36).
  • the EUVL precision components and glass ceramics according to the invention are zero-expansion, ie they have an average thermal expansion coefficient CTE in the range from 0 to 50° C. of at most 0 ⁇ 0.1 ⁇ 10 ⁇ 6 /K. Some advantageous variants even have an average CTE in the range from 0 to 50°C of at most 0 ⁇ 0.05 ⁇ 10- 6 /K. For certain applications it can be advantageous if the mean CTE is at most 0 ⁇ 0 in a larger temperature range, for example in the range from -30°C to +70°C, preferably in the range from -40°C to +80°C. 1 x 10 _6 /K, ie there is zero strain.
  • the differential CTE(T) is first determined.
  • the differential CTE(T) is determined as a function of temperature.
  • the CTE is then defined according to the following formula (1):
  • the temperature-dependent change in length of a test specimen can be used can be measured from the initial length l 0 at the initial temperature t 0 to the length l t at the temperature t. Small temperature intervals of, for example, 5° C. or 3° C. or 1° C. are preferably selected for determining a measuring point. Such measurements can be carried out, for example, by dilatometric methods, interferometric methods, for example the Fabry-Perot method, ie the evaluation of the displacement of the resonance peak of a laser beam coupled into the material, or other suitable methods.
  • the dila tometric method with a temperature interval of 1° C. was selected for the determination of the CTE on rod-shaped specimens of the test bodies with a length of 100 mm and a diameter of 6 mm.
  • the method selected for determining the CTE has an accuracy of preferably at least ⁇ 0.05 ppm/K, preferably at least ⁇ 0.03 ppm/K.
  • the CTE can also be determined using methods that have an accuracy of at least ⁇ 0.01 ppm/K, preferably at least ⁇ 0.005 ppm/K or, according to some embodiments, even at least ⁇ 0.003 ppm/K or at least ⁇ 0.001 ppm/K. have K.
  • the average CTE for a specific temperature interval is calculated from the DI/lo-T curve.
  • a CTE-T curve is obtained by deriving the Al/I 0 -T curve. From the CTE-T curve, the zero crossing and the slope of the CTE-T curve can be determined within a temperature interval. The extent and position of an advantageous CTE plateau formed in some variants is determined using the CTE-T curve (see below and FIGS. 20 and 21 as well as FIGS. 37, 39 and 41).
  • An advantageous version of the EUVL precision component has a high CTE homogeneity.
  • the value of the CTE homogeneity (“total spatial variation of CTE”) is understood as the so-called peak-to-valley value, i.e. the difference between the respective highest and the respective lowest CTE value of a precision component samples taken.
  • the thermal expansion or the CTE value of a sample taken is typically determined using the static method already mentioned above, in which the length of a test specimen is determined at the beginning and at the end of the specific temperature interval and the mean expansion coefficient a or .CTE (Coefficient of Thermal Expansion) is calculated.
  • the CTE is then given as an average for this temperature interval, eg for the temperature interval from 0°C to 50°C as CTE(0;50) or a(0;50) or for the temperature interval from 19°C to 25°C as CTE(19;25).
  • the CTE homogeneity thus does not refer to the CTE of the material of the component, but to the spatial variation of the CTE over the considered section or the entire precision component. If the CTE homogeneity of a certain component is to be determined for several temperature ranges, e.g. B. for the range 19 °C to 25 °C as well as 0 °C to 50 °C, the CTE homogeneity for both temperature ranges can generally be determined on the same samples. In this case, however, it is advantageous to measure the CTE of the narrower temperature range, e.g. B. the CTE(19;25) and then the CTE of the further temperature range, e.g. to determine the CTE(0;50). However, it is particularly advantageous if CTE homogeneities of a component are determined for different temperature ranges using different samples of these components.
  • the CTE homogeneity for the temperature range from 0°C to 50°C i.e. the spatial variation of the CTE(0;50) is also called CTE homogeneity(0;50) in the following.
  • the naming of the CTE homogeneities for other temperature ranges can be done analogously.
  • the CTE homogeneity for the temperature range from 19°C to 25°C, i.e. the spatial variation of the CTE(19;25) is also called CTE homogeneity(19;25) in the following.
  • the EUVL precision component according to the invention has a CTE homogeneity (0;50) over the entire precision component of at most 5 ppb/K, preferably at most 4 ppb/K, most preferably at most 3 ppb/K and/or one CTE homogeneity (19;25) over the entire precision component of no more than 5 ppb/K, preferably no more than 4.5 ppb/K, preferably no more than 4 ppb/K, further preferably no more than 3.5 ppb/K, further preferably no more than ten 3 ppb/K, more preferably at most 2.5 ppb/K.
  • a method of investigation of the CTE homogeneity and measures to achieve the CTE homogeneity are described in WO 2015/124710 A, the disclosure content of which is fully incorporated into this application.
  • the EUVL precision components and glass ceramics have a thermal hysteresis of at least in the temperature range from 19 to 25 °C, preferably at least in the temperature range from 10 °C to 25 °C, particularly preferably at least in the temperature range from 10 to 35 °C ⁇ 0.1 ppm.
  • the glass ceramic after Temperature change was subjected to an isothermal change in length of less than 0.1 ppm with subsequent constant temperature.
  • this freedom from hysteresis is at least in a temperature range from 5°C to 35°C, preferably at least in the temperature range from 5°C to 45°C, preferably at least in the temperature range from >0°C to 45°C at least in the temperature range from -5°C to 50°C.
  • the temperature range of freedom from hysteresis is even wider.
  • Preferred application temperatures are in the range from -60°C to 100°C, preferably from -40°C to +80°C.
  • glass ceramics and EUVL precision components for application temperatures T A for example in the range 5°C to 20°C or T A of 22°C, 40°C, 60°C, 80°C and 100°C, which are preferably also free of hysteresis at these temperatures.
  • Further preferred variants of the present invention relate to glass ceramics and EUVL precision components for application temperatures T A , for example in the range from 5° C. to 40° C., preferably from 10° C. to 35° C., more preferably from 10° C. to 25° C. more preferably in the range of 19°C to 25°C or T A of 22°C.
  • the thermal hysteresis was for the EUVL precision components and glass ceramics according to the invention and for the comparative examples on a precision dilatometer, which can determine the CTE with a reproducibility of ⁇ 0.001 ppm / K and ⁇ 0.003 ppm / K absolute, with a temperature interval of 1 ° C on rod-shaped gene samples with a length of 100 mm and a diameter of 6 mm of the test specimen (ie sample of the precision component or sample of the glass ceramic) determined according to the method and apparatus structure disclosed in DE 102015 113 548 A, the open cash content is fully included in this application.
  • the change in length DI/Io was determined as a function of the temperature between 50°C and a cooling rate of 36K/h, cooling down to -10°C. After an isothermal holding time of 5 hours at -10°C, the sample was heated to 50°C at a heating rate of 36K/h and the change in length DI/Io as a function of temperature was recorded.
  • the thermal hysteresis behavior of a test specimen is considered at -5°C, 0°C, 5°C, 10°C, 22°C, 35°C, 40°C. These points are representative of the temperature range from -10°C to 50°C, since the hysteresis in the stated temperature interval decreases as the temperature rises.
  • a sample that is hysteresis-free at 22°C or 35°C also shows no hysteresis in the range up to 50°C.
  • other temperature points can advantageously be considered, in particular 19°C and/or 25°C.
  • the individual measured values of the change in length for the five temperatures 8°C, 9°C, 10°C, 11°C and 12°C were taken, i.e. two temperature points above and below 10°C , both when heating and when cooling the sample in the range -10°C to 50°C at a rate of 36K/h.
  • the mean value was formed from the differences in the measured values for the heating curve and cooling curve at these five temperature measuring points and listed in the tables as "Hyst.@10°C" in the unit [ppm].
  • the individual measured values of the change in length for the five temperatures 33°C, 34°C, 35°C, 36°C and 37°C were taken, i.e. two temperature points above and below 35° C, both when heating and when cooling the sample in the range -10°C to 50°C at the rate of 36K/h.
  • the mean value was formed from the differences in the measured values for the heating curve and cooling curve at these five temperature measuring points and listed in the tables as "Hyst.@35°C" in the unit [ppm].
  • Figures 2 through 8 show the thermal hysteresis curves of known materials used for precision components. For better comparability, a range of 6 ppm on the y-axis was always selected for the representation in the figures.
  • the cooling curves (dashed) and heating curves (dotted) are each clearly spaced apart from one another, especially at lower temperatures, ie they run clearly Cut. At 10°C the difference is more than 0.1 ppm, depending on the comparative example up to approx. 1 ppm. This means that the materials and the precision components made from them show considerable thermal hysteresis in the relevant temperature range of at least 10° to 35°C.
  • EUVL precision components and glass ceramics according to the invention are hysteresis-free (see, for example, FIGS. 10 and 11 and FIGS. 31 to 33, also shown with a range of 6 ppm on the y-axis), not only in the range from 19° C. to 25° C and from 10°C to 35°C, but also advantageously at least in the range from 5°C to 35°C or at least in the range from 5°C to 45°C, preferably at least in the range >0°C to 45°C , preferably at least in the temperature range from ⁇ 5° C. to 50° C., preferably also at even higher and even lower temperatures.
  • TCL value is often given, with TCL meaning "Total Change of Length".
  • TCL value for the temperature range 0°C and 50°C is given. It is determined from the normalized DI/lo-T curve (also dl/lo-T curve in the illustrations) of the respective test specimen, with “normalized” meaning that the change in length at 0°C is 0 ppm.
  • the DI/lo-T curve for the TCL determination is constructed using the same method as described above in connection with the CTE determination in the context of the invention.
  • the TCL value is the difference between the highest dl/lo value and the lowest dl/lo value in this temperature range:
  • TCL (0;50°C)
  • dl denotes the change in length at the respective temperature
  • Io denotes the length of the specimen at 0°C. The calculation is based on the amounts of the dl/l 0 values.
  • Figures 14 to 17 show expansion curves of known materials from which the dl/lo max values and dl/lo min values for the calculation of the TCL value are respectively read (see also below).
  • the expansion curves each show a curved course in the temperature range from 0°C to 50°C.
  • a flat course of the expansion curve in the temperature range from 0° C. to 50° C. is another feature of the first variant of the EUVL precision component according to the invention and an advantageous feature of the glass ceramic, in particular a glass ceramic for such an EUVL precision component .
  • the parameter F is introduced as a measure of the flatness of the expansion curve, which makes it possible to classify CTE curves:
  • the parameter F is calculated by forming the quotient of the TCL (0;50) value [in ppm] (see above) and the expansion difference between the temperature points of 0°C and 50°C [in ppm]. Since the expansion curve for the TCL determination is standardized by definition in such a way that at 0 °C the change in length is 0 ppm, the "expansion difference between the temperature points of 0 °C and 50 °C" corresponds to the "expansion at 50 °C", as indicated in the tables. The amount of expansion at 50°C is used to calculate the parameter F.
  • the parameter F is ⁇ 1.2, preferably ⁇ 1.1, preferably at most 1.05. The closer the parameter F is to 1, the flatter the expansion curve.
  • FIG. 12 shows the expansion curve of a precision component or an advantageous glass ceramic based on an advantageous ceramization of composition example 6 as an example of the invention.
  • a section of 1.6 ppm on the y-axis was selected for the display.
  • the highest expansion value (dl/lo max.) is at +50°C (dl/lo is +0.57 ppm, i.e.
  • FIG. 13 shows a further example of the invention (composition according to example 7 from Table 1a), in which the parameter F is also 1.
  • FIG. 34 shows an example of the expansion curve of a further precision component or advantageous glass ceramic based on an advantageous ceramization (maximum temperature 830° C., duration 3 days) of example 7b. A section of 2.4 ppm on the y-axis was selected for the display. The highest expansion value (dl/lo max.) is at +50°C (dl/lo is +0.57 ppm, ie
  • FIG. 35 also shows an advantageously flat extension curve in the temperature range from -10° C. to 80° C. for another precision component or glass ceramic with a different ceramization of the glass ceramic of example 7b from Table 1b (maximum temperature 825° C., duration 3 days). .
  • the EUVL precision components and advantageous glass ceramics of the first variant of the invention thus have a very flat course of their expansion curves in the temperature range from 0 °C to 50 °C, i.e. they are not only zero-expansion in the temperature range under consideration, but also have a low fluctuation in the Change in length expansion and thus the differential CTE in this area.
  • advantageous examples of the invention also have a flat course of their expansion curves over an even broader temperature range (in this case from ⁇ 30° C. to +70° C., for example). In comparison, see the much steeper gradients of the expansion curves of known materials in relation to the same temperature range in Figure 19.
  • FIGS. 14 to 17 show the expansion behavior of known materials and EUVL precision components made from them, from which the parameter F can be calculated in each case.
  • the known materials show a curved course of the strain curves:
  • FIG. 14 shows the expansion curve of a commercially available titanium-doped quartz glass in the same dl/l 0 section as in FIGS.
  • the EUVL precision components according to the invention and advantageous glass ceramics with flat expansion curves are very advantageous, since a component can now not only be optimized for the later application temperature, but also, for example, at higher and/or lower temperature loads, e.g. has an equally low thermal expansion.
  • Precision components for microlithography, EUV (extreme UV) lithography or microlithography (also “EUV lithography” or “EUVL” for short) and metrology are usually used under standard clean room conditions, in particular a room temperature of 22°C. The CTE can be adjusted to this application temperature.
  • such components are subjected to various process steps, such as coating with metallic layers, cleaning, structuring and/or exposure processes, in which higher or in some cases lower temperatures prevail than the temperatures prevailing during later use in the clean room be able.
  • higher or lower temperatures than the typical T A 22°C occur, for example higher temperatures in the photomask and/or substrate when the photomask is illuminated with EUVL radiation or lower temperatures when the photomask and/or substrate is cooled.
  • the EUVL precision components according to the invention and advantageous glass ceramics which have a parameter F of ⁇ 1.2 and thus have an optimized zero expansion not only at the application temperature, but also at possibly higher and/or lower temperatures during production, are therefore very advantageous.
  • Properties such as freedom from hysteresis and a parameter F ⁇ 1.2 are particularly advantageous since the EUVL precision component or a glass ceramic is used in EUV lithography, i.e.
  • the precision component is an EUV lithography mirror (also abbreviated " EUVL mirror”) or EUVL photomask or a corresponding substrate for this or a photomask carrier
  • EUVL mirror also abbreviated " EUVL mirror”
  • EUVL photomask or a corresponding substrate for this or a photomask carrier
  • the heat can be dissipated into the photomask carrier, which can also cause it to heat up.
  • the EUVL precision component or glass-ceramic exhibits a low gradient of the CTE-T curve in a temperature range around the application temperature (see below).
  • Advantageous EUVL precision components of the first variant and advantageous glass ceramics in particular for the first variant of the EUVL precision component, which is even better suited to a subsequent application temperature in the range of 20°C to 25°C, e.g. B. are optimized at 20 or 22 ° C, are characterized in that they have a relative length change (dl / lo) of ⁇
  • such optimized glass ceramics and precision components can be characterized in that they have a relative change in length (dl/lo) of ⁇
  • the characteristics of the relative change in length in relation to the different temperature intervals can preferably be taken from the dl/lo curves, for example in FIGS. 12 to 19.
  • the information obviously refers to the amount of the respective value.
  • a zero-stretching and hysteresis-free EUVL precision component with such an advantageous stretching behavior is particularly suitable for use as an EUVL mirror or as a substrate for an EUVL mirror that has different strengths in the light and shadow areas during operation, e.g. due to the respective exposure mask is warmed up.
  • a zero-stretching and hysteresis-free EUVL precision component with such an advantageous stretching behavior is also particularly suitable for use as an EUVL photomask substrate and/or as a photomask carrier, which are heated to different degrees during operation. Due to the small relative change in length mentioned above, the listed EUVL precision components made of the advantageous glass ceramic have lower local gradients (local gradients or local slopes) in the topography of the surface than corresponding EUVL precision components made with known materials.
  • the invention also relates to an EUVL photomask substrate and an EUVL photomask carrier comprising a precision component according to the invention, the EUVL photomask substrate and EUVL photomask carrier having an advantageous relative length change as described above.
  • An EUVL precision component according to the second variant according to the invention and advantageous glass ceramics, in particular for such a precision component, are characterized by an alternative parameter fn . characterized as described below.
  • TCL Total Change of Length
  • the expansion behavior can be observed in a temperature interval (Ti), preferably in the temperature range (20; 40), (20; 70) and/or (-10; 30).
  • Ti a temperature interval
  • the expansion behavior can be observed in a temperature interval (Ti), preferably in the temperature range (20; 40), (20; 70) and/or (-10; 30).
  • the TCL (Ti) value is the distance between the highest dl/lo value and the lowest dl/lo value in the relevant temperature range (Ti) under consideration, with the extension curve also for the TCL (Ti) - Determination is standardized according to definition in such a way that at 0°C the change in length is 0 ppm. So for example:
  • TCL (20;4o°c)
  • dl denotes the change in length at the respective temperature
  • Io denotes the length of the specimen at 0°C.
  • the calculation is based on the amounts of the dl/l 0 values if the curve fluctuates around zero in the temperature interval under consideration (eg FIGS. 30, 35, 36). Otherwise the TCL (Ti) is the difference between the highest dl/l 0 value and the lowest dl/l 0 value in the considered temperature interval (Ti), which is self-evident and can be seen from the figures (e.g. Figures 27, 29).
  • the TCLp- .i. can be calculated as follows:
  • TCL (Ti) dl/lo max - dl/lo min (6)
  • the alternative parameter fn . is calculated according to formula (4) by forming the quotient of the TCL (Ti) value [in ppm] (see above) and the width of the temperature interval (Ti) specified in [K], in which the expansion difference is considered .
  • EUVL precision components according to the invention and advantageous glass ceramics with a very flat strain curve are very advantageous, since the EUVL precision component can now be optimized not only for the later application temperature, but also, for example, for higher and/or lower temperature loads that are expected can be.
  • the alternative parameter fn . is suitable for defining a suitable material according to the specifications required for certain component applications and for providing a corresponding EUVL precision component. Special precision components and their applications are described below and are included here.
  • An EUVL precision component according to the invention of the second variant or an advantageous glass ceramic can have an alternative parameter f ( 20 ; 40 ) ⁇ 0.024 ppm/K, preferably ⁇ 0.020 ppm/K, preferably ⁇ 0.015 ppm/K.
  • a hysteresis-free, zero-expansion component or glass ceramic with such an expansion behavior in the temperature range (20;40) can be used particularly well as an EUVL precision component at room temperature. Examples of such precision components and advantageous glass ceramics are shown in FIG. 27 and, for example, also in FIG. 35 to recognize.
  • An EUVL precision component according to the invention of the second variant or an advantageous glass ceramic can have an alternative parameter f (2 o ; 70 ) ⁇ 0.039 ppm/K, preferably ⁇ 0.035 ppm/K, preferably ⁇ 0.030 ppm/K, preferably ⁇ 0.025 ppm/ K, preferably ⁇ 0.020 ppm/K.
  • a hysteresis-free, zero-expansion component or glass ceramic with such an expansion behavior in the temperature range (20;70) can also be used particularly well as an EUVL precision component. It is particularly advantageous if the component has just as little thermal expansion even under higher temperature loads, which can occur locally or over a large area, for example during the manufacture of the EUVL precision component, but also during operation. Further details on the temperature loads occurring in EUVL precision components have already been described above in connection with parameter F, to which reference is made here to avoid repetition. An example of such a precision component and advantageous glass-ceramic is shown in Figure 29, also in Figure 35.
  • An EUVL precision component according to the invention of the second variant or an advantageous glass ceramic can have an alternative parameter f ( ⁇ 10 ; 30 ) ⁇ 0.015 ppm/K, preferably ⁇ 0.013 ppm/K, preferably ⁇ 0.011 ppm/K.
  • a hysteresis-free, zero-stretching Components or glass ceramics with such an expansion behavior in the temperature range (-10;30) can be replaced particularly well as precision components, in particular as mirror substrates for applications in which temperatures lower than room temperature can also occur, for example as mirror substrates in astronomy or earth observation in space and, for the purposes of the present invention, in particular in cooled EUVL photomasks or photomask carriers.
  • Corresponding components are described further below. Examples of such precision components and advantageous glass ceramics are shown in Figures 28 and 30, as well as in Figure 36.
  • a particularly advantageous embodiment of an EUVL precision component or glass ceramic has at least 2 alternative parameters f ( n .) .
  • a particularly advantageous embodiment of a precision component or glass ceramic has the parameter F and at least one alternative parameter f (.i.) .
  • Some advantageous EUVL precision components and glass ceramics can even have a so-called CTE plateau (see FIGS. 20 and 21 as well as FIGS. 37, 39 and 41). It is advantageous if the differential CTE has a plateau close to 0 ppm/K, ie the differential CTE in a temperature interval T P with a width of at least 40 K, preferably at least 50 K, is less than 0 ⁇ 0.025 ppm/K.
  • the temperature interval of the CTE plateau is denoted by T P .
  • a CTE plateau is thus understood to mean an area extending over a section of the CTE-T curve, in which the differential CTE has a value of 0 ⁇ 0.025 ppm/K, preferably 0 ⁇ 0.015 ppm/K, more preferably 0 ⁇ 0.010 ppm/K, more preferably 0 ⁇ 0.005 ppm/K, i.e. a CTE close to 0 ppb/K.
  • the differential CTE can advantageously be less than 0 ⁇ 0.015 ppm/K, ie 0 ⁇ 15 ppb/K, in a temperature interval T P with a width of at least 40 K.
  • a CTE plateau of 0 ⁇ 0.01 ppm/K, ie 0 ⁇ 10 ppb/K may be established over a temperature interval of at least 50K.
  • the middle curve between 7° C. and 50° C., ie over a width of more than 40 K even shows a CTE plateau of 0 ⁇ 0.005 ppm/K, ie 0 ⁇ 5 ppb/K.
  • the temperature interval T P is in a range from -10 to +100.degree. C., preferably from 0 to 80.degree.
  • the position of the CTE plateau is preferably adapted to the application temperature T A of the precision component.
  • Preferred application temperatures for precision components T A are in the range from -60°C to +100°C, more preferably from -40°C to +80°C.
  • Be special variants of the present invention relate to EUVL precision components and glass ceramics for application temperatures T A of 0 ° C, 5 ° C, 10 ° C, 22 ° C, 40 ° C, 60 ° C, 80 ° C and 100 ° C, preferably T A 22°C, or in the temperature range from 10°C to 35°C, preferably from 10°C to 25°C, more preferably from 19°C to 25°C.
  • the CTE plateau ie the curve area with the small deviation of the differential CTE in the temperature interval T p can also occur in the temperature range from [-10;100]; [0;80], [0;30°C], [10;40°C], [20;50°C], [30;60°C], [40;70°C]; and/or [50;80°C].
  • the CTE plateau can also range from [-10; 30], [0;50], [10;25°C], [19;25°C]; [20;40] and/or [20;70].
  • Figure 37 shows that this precision component or glass ceramic has a CTE of 0 ⁇ 0.010 ppm/K, i.e. a 10 ppb plateau, over the entire temperature range shown from -10°C to 90°C.
  • a detailed examination of a section of this curve shows that the glass ceramic has a CTE of 0 ⁇ 0.005 ppm / K in the temperature range from -5°C to 32°C.
  • This glass-ceramic meets the requirements for the mean CTE (19;25) specified in the SEMI P37-1109 standard for EUVL substrates and blanks.
  • Figure 39 shows for example 7b from Table 1b, which was ceramized at temperatures of a maximum of 825 ° C for 3 days, that the precision components or glass ceramic from 12 ° C a CTE of 0 ⁇ 0.010 ppm / K, i.e. a 10-ppb -plateau whose width is > 40K.
  • the example range between 16°C and 40°C even has a CTE of 0 ⁇ 0.005 ppm / K and thus also meets the requirements for the mean CTE (19;25) specified in standard SEMI P37-1109 for EUVL substrates and blanks.
  • FIG. 41 shows for example 9b from table 1b, which was ceramized at temperatures of a maximum of 830° C. for 3 days, that the precision component or glass ceramic has a CTE of 0 ⁇ 0.010 ppm in the range shown between ⁇ 5° C. and 45° C / K, i.e. having a 10 ppb plateau.
  • EUVL precision components and glass ceramics with a plateau, ie with an opti mized zero expansion offer the same advantages that have already been mentioned above in connection with the flat course of the expansion curves and the parameter F or the alternative parameter fn . have been described.
  • the CTE-T curve of the EUVL precision component or glass ceramic has a temperature interval which is at least 30 K wide, preferably at least 40 K wide, more preferably at least 50 K wide , At least one curve section with a low slope, in particular a slope of at most 0 ⁇ 2.5 ppb/K 2 , advantageously of at most 0 ⁇ 2 ppb/K 2 , advantageously of at most 0 ⁇ 1.5 ppb/K 2 , preferably of at most 0 ⁇ 1 ppb/K 2 , preferably of at most 0 ⁇ 0.8 ppb/K 2 , according to special variants even of at most 0 ⁇ 0.5 ppb/K 2 .
  • the temperature interval with a small gradient is preferably adapted to the application temperature T A of the EUVL precision component.
  • Preferred application temperatures T A for precision components are in the range from -60°C to +100°C, more preferably from -40°C to +80°C.
  • Particular variants of the present invention relate to EUVL precision components and glass ceramics for application temperatures in the temperature range from 10 to 35°C, preferably from 10°C to 25°C, more preferably from 19°C to 25°C and T A of 0°C , 5°C, 10°C, 22°C, 40°C, 60°C, 80°C and 100°C.
  • the temperature interval with a small slope can also be used in the temperature range from [-10;100]; [0;80], [0; 30°C], [10;40°C], [20;50°C], [30;60°C], [40;70°C], [10;25°C], [19;25° C] and/or [50; 80°C].
  • the temperature interval with a slight increase can also be in the temperature range of [-10;30], [0;50], [10;25°C], [19;25°C]; [20;40] and/or [20;70].
  • FIG. 22 shows the gradient of the CTE-T curve in the temperature range from 0° C. to 45° C. of an advantageous EUVL precision component or glass ceramic based on the composition of example 6 from table 1a.
  • the CTE slope is below 0 ⁇ 2.5 ppb/K 2 in the entire temperature range and even below 0 ⁇ 1.5 ppb/K 2 in an interval of at least 30 K width.
  • FIG. 42 shows the gradient of a CTE-T curve in the temperature range from 0° C. to 45° C. of an advantageous EUVL precision component or glass ceramic based on the composition of example 6b from table 1b.
  • the CTE slope is below 0 ⁇ 1 ppb/K 2 in the entire temperature range and even below 0 ⁇ 0.5 ppb/K 2 in an interval of at least 30 K width (from approx. 12°C).
  • Glass ceramics and precision components with such an expansion behavior are particularly well suited for EUV lithography applications (e.g. as mirrors or substrates for mirrors or masks or mask blanks or as photomask carriers or wafer carriers), since in this area the requirements for the Materials and precision components used in optical components are becoming more and more demanding in terms of extremely low thermal expansion, zero crossing of the CTE-T curve close to the application temperature and, in particular, low slope of the CTE-T curve.
  • advantageous embodiments of an EUVL precision component or glass ceramic have a very flat CTE curve, with the curve showing both a zero crossing and a very low CTE gradient and possibly a very flat plateau.
  • FIGS. 24 and 25 show how the CTE curve can be adapted to different application temperatures by varying the ceramization temperature and/or ceramization time.
  • the zero crossing of the CTE-T curve can be shifted from, for example, 12° C. to a value of 22° C. by raising the ceramization temperature by 10 K.
  • the ceramization time can also be extended accordingly.
  • FIG. 25 demonstrates by way of example that the very flat profile of the CTE-T curve can be raised by 5 or 10 K, for example, by raising the ceramization temperature.
  • the ceramization time can also be extended accordingly.
  • FIGS. 44 and 45 show how the expansion curve can be adapted to different application temperatures by varying the ceramization temperature and/or ceramization time.
  • FIG. 44 shows that the resulting expansion curves of the precision component or glass ceramic can be specifically influenced by the selection of the maximum ceramization temperature at which the starting green glass is treated.
  • the dotted curve shows the expansion curve of a glass ceramic whose underlying green glass was ceramized at a maximum of 810°C for 2.5 days
  • the dash-dotted curve shows the expansion curve of a glass ceramic whose underlying green glass was ceramized at a maximum of 820°C for 2.5 days days was ceramized.
  • FIG. 44 shows that the resulting expansion curves of the precision component or glass ceramic can be specifically influenced by the selection of the maximum ceramization temperature at which the starting green glass is treated.
  • the dotted curve shows the expansion curve of a glass ceramic whose underlying green glass was ceramized at a maximum of 810°C for 2.5 days
  • the dash-dotted curve shows the expansion curve of a glass ceramic whose underlying green glass was ceramized at a maximum of 820°C for 2.5 days days was ceramized.
  • the glass ceramics according to the invention can be re-ceramized, which means that a targeted fine adjustment of the expansion curve of the glass ceramic is possible by subjecting material that has already been ceramized to a new temperature treatment.
  • material of the glass ceramic that was ceramified at a maximum of 810° C. for 2.5 days was post-ceramified again at 810° C. for 1.25 days, ie with a shortened holding time.
  • the effect of this post-ceramization is shown in the form of the dashed expansion curve. Comparing the expansion curves, it can be seen that the expansion curves and thus the average CTE (0:50) are different before and after post-ceramization.
  • FIG. 45 shows how the expansion curve can be set over different maximum ceramization temperatures during the ceramization of the same starting green glass. Shown in dashed lines: ceramization at a maximum of 830°C for 3 days; shown in dots: ceramization at a maximum of 825°C for 3 days.
  • the ceramization time can also be extended accordingly.
  • Advantageous EUVL precision components and glass ceramics also have good internal quality. Preferably they have at most 5 inclusions per 100 cm 3 , more preferably at most 3 inclusions per 100 cm 3 , most preferably at most 1 inclusion per 100 cm 3 . According to the invention, inclusions are understood to mean both bubbles and crystallites which have a diameter of more than 0.3 mm.
  • EUVL precision components for example photomask substrates, photomask carriers, EUVL mirrors and/or wafer tables, are provided which have a maximum diameter or edge length of 800 mm and a maximum thickness of 250 or 100 mm and which have a maximum 5, preferably at most 3, more preferably at most 1 inclusions each per 100 cm 3 with a diameter of a size greater than 0.03 mm.
  • the maximum diameter of the detected inclusions also serves as a measure of the internal quality.
  • the maximum diameter of individual inclusions in the total volume of a precision component with a diameter of less than 500 mm or edge lengths of less than 500 mm is preferably no more than 0.6 mm, preferably for use in a critical volume, for example near the surface at most 0.4 mm.
  • the maximum diameter of individual inclusions in glass ceramic components with a diameter of 500 mm to less than 2 m or edge lengths of 500 mm to less than 2 m is preferably at most 3 mm, preferably in the volume critical for the application, for example near the surface at most 1 mm. This can be advantageous in order to achieve the surface finish required for the application.
  • One embodiment relates to EUVL precision components with smaller dimensions, in particular for (rectangular shapes with edge lengths (width and/or depth) or in the case of round surfaces with a diameter of at least 50 mm, preferably at least 100 mm and/or at most 1500 mm, preferably at most 1000 mm and/or a thickness of less than 50 mm, preferably less than 10 mm and/or at least 1 mm, more preferably at least 2 mm.
  • precision components can be used, for example, in microlithography and EUV lithography, for example as a photomask substrate and/or reticle stage and/or spacers and/or holders for measurement technology/sensors and/or grid substrates and/or covers.
  • Another embodiment relates to precision components with very small dimensions, in particular with edge lengths (width and/or depth) or diameters and/or thicknesses of a few mm (e.g. at most 20 mm or at most 10 mm or at most 5 mm or at most 2 mm or at most 1 mm).
  • Such precision components can be used, for example, in microlithography and EUV lithography as a cover for lightweight structures.
  • One embodiment of the invention thus relates to large volume components.
  • this should include a component with a mass of at least 300 kg, preferably at least 400 kg, preferably at least 500 kg, preferably at least 1 t, more preferably at least 2 t, according to one variant of the invention at least 5 t, or with edge lengths (width and/or depth) for (rectangular) angular shapes of at least 0.5 m, more preferably at least 1 m or at most 2 m, preferably at most 1.5 m, and/or a thickness (height) of at least 50 mm, preferably at least 100 mm, preferably at least 200 mm, more preferably at least 250 mm, or in the case of round shapes with a diameter of at least 0.5 m, more preferably at least 1 m, more preferably at least 1.5 m and/or with a thickness (height) of at least 50 mm, preferably at least 100 mm, preferably at least 200
  • EUVL precision components can be produced in the sizes described above.
  • the invention can also be even larger components with, for example, a diameter of at least 1 m or at least 2 m or larger and/or a thickness of 50 mm to 400 mm, preferably 100 mm to 300 mm.
  • the invention also relates to rectangular components, preferably at least one surface having an area of at least 1 m 2 , preferably at least 1.2 m 2 , more preferably at least 1.4 m 2 , further preferably at least 3 m 2 or at least 4 m 2 and/or a thickness of 50 mm to 400 mm, preferably 100 mm to 300 mm.
  • large-volume components are manufactured that have a significantly larger base area than height. However, they can also be large-volume components which have a shape approximated to a cube or a sphere.
  • this comprises at least one inorganic material selected from the group consisting of doped quartz glass, glass ceramic and ceramic, preferably Ti-doped quartz glass, LAS glass ceramic and cordierite.
  • the invention also relates to an EUVL precision component which has a mean thermal expansion coefficient CTE in the range from 0 to 50° C. of at most 0 ⁇ 0.1 ⁇ 10 6 /K and a thermal hysteresis of ⁇ 0.1 ppm at least in the temperature range from 19 to 25° C., preferably at least in the temperature range from 10° C. to 25° C., particularly preferably at least in the temperature range from 10° C.
  • F TCL (0; 50°C) /
  • the invention also relates to an EUVL precision component which has a mean thermal expansion coefficient CTE in the range from 0 to 50° C. of at most 0 ⁇ 0.1 ⁇ 10 6 /K and a thermal hysteresis of ⁇ 0.1 ppm at least in the temperature range from 19 to 25°C, preferably at least in the temperature range from 10°C to 25°C, particularly preferably at least in the temperature range from 10°C to 35°C and an alternative parameter f T .i.
  • the inorganic material is a hysteresis-free, zero-expansion LAS glass ceramic. It is advantageous if the LAS glass ceramic contains less than 0.6 mol % of MgO and/or ZnO.
  • An advantageous variant of the precision component comprises an LAS glass ceramic according to the invention, the features and advantageous developments of which are described in detail below according to the invention.
  • the statements below regarding the LAS glass ceramic and its advantageous developments apply accordingly to the precision component that includes such a LAS glass ceramic, so that reference is made to the statements below with regard to the advantageous composition and advantageous features of the material.
  • the invention also relates to an EUVL precision component according to the invention, selected from the group consisting of photomasks or reticles, photomask substrates or reticle mask blanks or maskblanks, photomask carriers or reticle stages, mirrors, mirror carriers and wafer carriers or wafer stages, in particular a photomask or reticle, and/or a photomask substrate or reticle mask blank or mask blank and/or a photomask carrier or reticle stage.
  • an EUVL precision component selected from the group consisting of photomasks or reticles, photomask substrates or reticle mask blanks or maskblanks, photomask carriers or reticle stages, mirrors, mirror carriers and wafer carriers or wafer stages, in particular a photomask or reticle, and/or a photomask substrate or reticle mask blank or mask blank and/or a photomask carrier or reticle stage.
  • the invention also relates to the use of the EUVL precision component according to the invention.
  • the EUVL precision component according to the invention can thus advantageously be used in EUV lithography.
  • EUV lithography within the meaning of the present invention also includes EUV microlithography
  • the invention therefore also relates to the use of an EUVL precision component according to the invention, advantageously in EUVL lithography, in particular as a photo mask or reticle, photo mask substrate or reticle mask blank or mask blank, photo mask carrier or reticle stage, mirror, mirror carrier and/or wafer carrier or wafer stage.
  • EUVL precision components can, for example, optical components, namely a so-called normal incidence mirror, ie a mirror which is operated close to the vertical incidence of radiation, or a so-called grazing incidence mirror, ie a mirror operated in grazing incidence.
  • a mirror comprises a coating that reflects the incident radiation.
  • the reflective coating is, for example, a multilayer system or multilayer with a large number of layers with high reflectivity in the X-ray range at non-grazing incidence.
  • Such a multilayer system of a normal incidence mirror preferably comprises 40 to 200 pairs of layers, consisting of alternating layers, for example one of the material pairs Mo/Si, Mo/Bi, Ru/Si and/or MoRu/Be.
  • the optical elements according to the invention can be X-ray optical elements, i. H. optical elements which are used in connection with X-ray radiation, in particular soft X-ray radiation or EUV radiation, in particular reticle masks or photomasks operated in reflection, in particular for EUV (micro)lithography. It can advantageously be mask blanks.
  • the precision component can also advantageously be used as a mirror or as a substrate for a mirror for EUV lithography.
  • advantageous embodiments of the EUVL precision component or glass ceramic according to the invention have a flat CTE curve over a wide temperature range. These embodiments are therefore advantageous when used in EUVL applications in which temperatures below and/or above the typical application temperature can prevail, for example because the photomask and/or the photomask carrier are actively cooled and/or through the use of EUV radiation sources with higher power and/or the use of smaller photo masks and carriers, which can lead to a local increase in temperature in the photo mask or the photo mask carrier.
  • EUVL precision components with the described flat CTE curve over a wide temperature range are advantageous with regard to the adhesion and/or durability of the reflective multilayer system applied to the photomask substrate, since there is reduced tensile stress during temperature changes during production and the Use of the photomask can occur.
  • the EUVL precision components according to the invention made from advantageous glass ceramics can be used in so-called high-NA EUVL systems or in other EUVL systems with increased wafer throughput. Due to the higher modulus of elasticity of LAS glass-ceramics compared to other materials, such as Ti-doped quartz glass, the dynamic positioning accuracy of the photomask can be increased here, among other things.
  • the EUVL precision component according to the invention in particular in the case of a photomask carrier and/or wafer carrier, can be a lightweight structure.
  • the component of the present invention may further include a lightweight structure. This means that voids are provided in some areas of the component to reduce weight.
  • lightweight machining reduces the weight of a component by at least 80%, more preferably at least 90%, compared to the unmachined component.
  • the invention also includes a LAS glass ceramic, in particular for an EUVL precision component according to the invention, the glass ceramic having an average coefficient of thermal expansion CTE in the range from 0 to 50° C. of at most 0 ⁇ 0.1 ⁇ 10 6 /K and a thermal hysteresis at least in the temperature range from 19 to 25 °C, preferably at least in the temperature range from 10 °C to 25 °C, particularly preferably at least in the temperature range from 10 °C - 35 °C of ⁇ 0.1 ppm and comprises the following components ( in mol% based on oxide):
  • MgO+ZnO 0 - ⁇ 0.6 at least one component selected from the group consisting of P 2 Os, R 2 0, where R 2 0 is Na 2 0 and/or K 2 0 and/or Cs 2 0 and/or Rb 2 can be 0, and RO, where RO can be CaO and/or BaO and/or SrO, Nucleating agent with a content of 1.5 to 6 mol%, wherein the nucleating agent is at least one component selected from the group consisting of T1O2 , Zr0 2, Ta 2 Os, Nb 2 05, Sn0 2 , M0O 3 , WO 3 .
  • the EUVL precision component can include a substrate that has the glass ceramic according to the invention. In a further advantageous embodiment, the EUVL precision component can include or consist of the glass ceramic according to the invention.
  • a zero-stretching glass ceramic is provided for the first time, which has an extremely low thermal hysteresis at least in the temperature range from 19 to 25 °C, preferably at least in the temperature range from 10 °C to 25 °C, particularly preferably at least in the temperature range of 10 °C up to 35°C of ⁇ 0.1 ppm.
  • a material with such a low hysteresis effect of ⁇ 0.1 ppm in the stated temperature ranges is referred to below as “hysteresis-free”.
  • the statements on the hysteresis relate within the scope of the invention to a heating/cooling rate of 36 K/h, i.e. 0.6 K/min .
  • the LAS glass ceramic can be at least in the temperature range from 5° C. to 35° C. or at least from 5° C. to 40° C., advantageously at least in the temperature range from >0° C. to 45° C., preferably at least in the temperature range from -5°C to 50°C must be free of hysteresis.
  • a glass ceramic is understood to mean inorganic, non-porous materials with a crystalline phase and a glassy phase, with the matrix, ie the continuous phase, generally being a glass phase.
  • the components of the glass ceramic are first mixed, melted and clarified, and a so-called green glass is cast. After cooling, the green glass is crystallized in a controlled manner by reheating (so-called “controlled volume crystallization”).
  • controlled volume crystallization The chemical composition (analysis) of the green glass and the glass ceramic made from it are the same; the ceramization only changes the inner structure of the material. If therefore in the following from the composition of the glass-ceramic, what has been said applies in the same way to the precursor object of the glass-ceramic, ie the green glass.
  • LAS glass ceramics contain a negatively expanding crystal phase, which within the scope of the invention advantageously includes or consists of high quartz mixed crystal, also known as ⁇ -eucryptite, and a positively expanding glass phase.
  • U 2 O is a main component of the mixed crystal.
  • ZnO and/or MgO are also incorporated into the mixed crystal phase and, together with U 2 O, influence the expansion behavior of the crystal phase. This means that the above-mentioned specifications according to the invention (reduction, preferably exclusion of MgO and ZnO) have a significant influence on the type and properties of the mixed crystal formed in the course of ceramization.
  • At least one component is selected from the group consisting of P 2 O 5 , R 2 O, where R 2 O can be Na 2 Ü and/or K 2 O and/or Rb 2 Ü and/or CS 2 O, and RO, where RO CaO and/or BaO and/or SrO can be used.
  • R 2 O can be Na 2 Ü and/or K 2 O and/or Rb 2 Ü and/or CS 2 O
  • RO RO CaO and/or BaO and/or SrO can be used.
  • the above-mentioned alkaline earth metal oxides and alkali metal oxides if present, remain in the glass phase and are not incorporated into the high-quartz solid solution.
  • the glass-ceramic can include the following components individually or in any combination in mol %:
  • the glass-ceramic can include the following components individually or in any combination in mol %:
  • the following components can preferably be contained in the glass ceramic within the above limits for the sums of R2O, RO and Ti0 2 +Zr0 2 individually or in any combination in mol %:
  • the LAS glass-ceramic comprises (in mol % based on oxide):
  • the LAS glass-ceramic comprises (in mol % based on oxide):
  • the LAS glass-ceramic comprises (in mol % based on oxide):
  • nucleating agent 2.5 to 5 wherein the nucleating agent is preferably Ti0 2 and/or Zr0 2 .
  • the glass ceramic contains a proportion of silicon dioxide (Si0 2 ) of at least 60 mol%, more preferably at least 60.5 mol%, also preferably at least 61 mol%, also be preferably at least 61.5 mol%, more preferably at least 62.0 mol%.
  • the proportion of Si0 2 is at most 71 mol% or less than 71 mol%, more preferably at most 70 mol% or less than 70 mol%, more preferably at most 69 mol%, also preferably at most 68, 5 mol%. With larger proportions of Si0 2 , the mixture is more difficult to melt and the viscosity of the melt is higher, which can lead to problems with the homogenization of the melts in large-scale production plants.
  • the proportion of Al 2 Ü3 is advantageously at least 10 mol%, preferably at least 11 mol%, preferably at least 12 mol%, more preferably at least 13 mol%, also be preferably at least 14 mol%, also preferably at least 14, 5 mol%, more preferably at least 15 mol%. If the content is too low, no or too little low-expansion mixed crystal is formed.
  • the proportion of Al 2 Ü3 is advantageously at most 22 mol %, preferably at most 21 mol %, preferably at most 20 mol %, further preferably at most 19.0 mol %, more preferably at most 18.5 mol %. Too high an Al 2 0 3 content leads to increased viscosity and promotes the uncontrolled devitrification of the material.
  • the glass ceramic according to the invention can contain 0 to 6 mol% P 2 O 5 , in some advantageous embodiments 0.1 to 6 mol%.
  • the phosphate content P2O5 of the glass ceramic can advantageously be at least 0.1 mol %, preferably at least 0.3 mol %, preferably at least 0.5 mol %, also preferably at least 0.6 mol %, more preferably at least 0.7 mole %, more preferably at least 0.8 mole %.
  • P2O5 is mainly built into the crystal phase of the glass ceramic and has a positive influence on the expansion behavior of the crystal phase and thus of the glass ceramic. In addition, the melting of the components and the refining behavior of the melt are improved.
  • the glass-ceramics can be free of P2O5.
  • certain sums and ratios of the components S1O 2 , Al 2 O 3 and/or P2O5, ie the components that form the high-quartz mixed crystal, can be beneficial for the formation of a glass ceramic according to the invention.
  • the total proportion in mole % of the basic components of the LAS glass ceramic S1O 2 and Al 2 O 3 is advantageously at least 75 mole %, preferably at least 78 mole %, preferably at least 79 mole %, more preferably at least 80 mole % and/or or preferably at most 90 mol%, preferably at most 87 mol%, preferably at most 86 mol%, more preferably at most 85 mol%. If this sum is too high, the viscosity curve of the melt is shifted to higher temperatures, which is disadvantageous, as already explained above in connection with component S1O 2 . If the total is too low, too little solid solution is formed.
  • the total proportion in mole % of the basic components of the LAS glass ceramic S1O 2 , Al 2 O 3 and P2O5 is preferably at least 77 mole %, advantageously at least 81 mole %, advantageously at least 83 mole %, more preferably at least 84 mole % and/or preferably at most 91 mol%, advantageously at most 89 mol%, more preferably at most 87 mol%, according to a variant at most 86 mol%.
  • the mol % ratio of P2O5 to S1O2 is preferably at least 0.005, advantageously at least 0.01, preferably at least 0.012 and/or preferably at most 0.1, more preferably at most 0.08, according to one variant at most 0.07.
  • the glass ceramic contains lithium oxide (U2O) in a proportion of at least 7 mol %, advantageously at least 7.5 mol %, preferably at least 8 mol %, particularly preferably at least 8.25 mol %.
  • the proportion of U2O is limited to at most 9.4 mol%, more preferably at most 9.35 mol%, further preferably at most or less than 9.3 mol%.
  • U2O is part of the mixed crystal phase and contributes significantly to the thermal expansion of the glass ceramic.
  • the stated upper limit of 9.4 mol % should not be exceeded, since otherwise glass ceramics with a negative thermal expansion coefficient CTE (0:50) result. If the U2O content is less than 7 mol %, too little solid solution is formed and the CTE of the glass-ceramic remains positive.
  • the glass ceramic can contain at least one alkaline earth metal oxide selected from the group consisting of CaO, BaO, SrO, this group being collectively referred to as “RO”.
  • the components from the group RO essentially remain in the amorphous glass phase of the glass-ceramic and can be important for maintaining the zero expansion of the ceramized material. If the sum of CaO+BaO+SrO is too high, the CTE (0:50) aimed at according to the invention will not be achieved.
  • the proportion of RO is therefore advantageously at most 6 mol % or at most 5.5 mol %, preferably at most 5 mol %, advantageously at most 4.5 mol %, preferably at most 4 mol %, preferably at most 3 8 mol%, further preferably at most 3.5 mol%, also preferably at most 3.2 mol%.
  • an advantageous lower limit can be at least 0.1 mol %, advantageously at least 0.2 mol %, preferably at least 0.3 mol %, also preferably at least 0.4 mol %.
  • the glass ceramic can be free of RO.
  • the proportion of CaO can preferably be at most 5 mol%, advantageously at most 4 mol%, advantageously at most 3.5 mol%, advantageously at most 3 mol%, more preferably at most 2.8 mol%, more preferably at most 2, 6 mol%.
  • the glass ceramic can advantageously contain at least 0.1 mole %, advantageously at least 0.2 mole %, preferably at least 0.4 mole %, preferably at least 0.5 mole % CaO.
  • the glass ceramic can advantageously contain the BaO component, which is a good glass former, in a proportion of at least 0.1 mol %, preferably at least 0.2 mol % and/or at most 4 mol % at most 3 mol %, advantageously at most 2.5 mol %, preferably at most 2 mol %, preferably at most 1.5 mol %, also preferably at most 1.4 mol %.
  • the BaO component which is a good glass former
  • the glass ceramic can contain SrO in a proportion of at most 3 mol %, advantageously at most 2 mol %, preferably at most 1.5 mol %, preferably at most 1.3 mol %, preferably at most 1.1 mol %, more preferably at most 1 mol%, also preferably at most 0.9 mol% and/or preferably at least 0.1 mol%.
  • the glass ceramics are free from CaO and/or BaO and/or SrO.
  • Na 2 0 and/or potassium oxide (K2O) and/or cesium oxide (CS2O) and/or rubidium oxide (Rb2Ü) are optionally contained in the glass ceramic, ie Na 2 0-free and/or K2Ü-free and/or CS 2 0-free and/or Rb 2 0-free variants are possible.
  • the proportion of Na2Ü can advantageously be at most 3 mol %, preferably at most 2 mol %, preferably at most 1.7 mol %, preferably at most 1.5 mol %, preferably at most 1.3 mol %, preferably at most 1 .1 mol%.
  • the proportion of K2O can advantageously be at most 3 mol %, preferably at most 2.5 mol %, preferably at most 2 mol %, preferably at most 1.8 mol %, preferably at most 1.7 mol %.
  • the proportion of CS2O can advantageously be at most 2 mol %, preferably at most 1.5 mol %, preferably at most 1 mol %, preferably at most 0.6 mol %.
  • the proportion of Rb 2 O can advantageously be at most 2 mol %, preferably at most 1.5 mol %, preferably at most 1 mol %, preferably at most 0.6 mol %.
  • the glass ceramics are free from Na 2 O and/or K 2 O and/or Cs 2 O and/or Rb 2 O.
  • Na 2 0, K 2 O, CS 2 O, Rb 2 0 can each and independently in a proportion of at least 0.1 mol %, preferably at least 0.2 mol %, more preferably at least 0.5 mol % in the glass ceramic be included.
  • the components Na 2 O, K2O, CS2O and Rb 2 O essentially remain in the amorphous glass phase of the glass-ceramic and can be important for maintaining the zero expansion of the ceramized material.
  • the sum R2O of the contents of Na 2 0, K2O, CS2O and Rb 2 0 can advantageously be at least 0.1 mol%, preferably at least 0.2 mol%, advantageously at least 0.3 mol%, preferably at least 0 .4 mol%.
  • a low R 2 0 content of advantageously at least 0.2 mol % can contribute to enlarging the temperature range in which the expansion curve of the glass ceramic shows a flat profile.
  • the sum R2O of the contents of Na 2 0, K2O, CS2O and Rb 2 0 can advantageously be at most 6 mol%, preferably at most 5 mol%, preferably at most 4 mol%, preferably at most 3 mol%, preferably at most 2 .5 mol%. If the sum of Na 2 0+K 2 0+Cs 2 0+Rb 2 0 is too low or too high, it is possible that the CTE (0;50) targeted according to the invention will not be achieved. According to individual embodiments, the glass ceramic can be free from R 2 O.
  • the glass-ceramic can contain a maximum of 0.35 mol% of magnesium oxide (MgO).
  • MgO magnesium oxide
  • a further advantageous upper limit can be a maximum of 0.3 mol%, a maximum of 0.25 mol%, a maximum of 0.2 mol%, a maximum of 0.15 mol%, a maximum of 0.1 mol% or a maximum of 0.05 mol -% be.
  • the glass ceramics according to the invention are particularly preferably free of MgO.
  • the MgO component in the glass ceramic causes a thermal hysteresis in the temperature range from 0°C to 50°C. The less MgO the glass-ceramic contains, the smaller the hysteresis in the specified temperature range.
  • the glass-ceramic can contain a maximum of 0.5 mol% zinc oxide (ZnO).
  • ZnO zinc oxide
  • a further advantageous upper limit can be a maximum of 0.45 mol%, a maximum of 0.4 mol%, a maximum of 0.35 mol%, a maximum of 0.3 mol%, a maximum of 0.25 mol%, a maximum of 0.2 mol -%, maximum 0.15 mol%, maximum 0.1 mol% or maximum 0.05 mol%.
  • the glass ceramics according to the invention are particularly preferably free from ZnO.
  • the ZnO component in the glass ceramic causes a thermal hysteresis in the temperature range from 0°C to 50°C. The less ZnO is contained in the glass ceramic, the smaller the hysteresis in the specified temperature range.
  • a further advantageous upper limit for the sum of MgO+ZnO can be a maximum of 0.55 mol%, a maximum of 0.5 mol% or less than 0.5 mol%, a maximum of 0.45 mol%, a maximum of 0.4 mol% %, 0.35 mol% maximum, 0.3 mol% maximum, 0.25 mol% maximum, 0.2 mol% maximum, 0.15 mol% maximum, 0.1 mol% maximum, or at most 0.05 mol%.
  • the glass ceramic also contains at least one crystal nucleating agent selected from the group consisting of Ti0 2, Zr0 2 Ta 2 0 5 , Nb 2 0s, Sn0 2 , M0O 3 , WO 3 .
  • Nucleating agent can be a combination of two or more of the components mentioned.
  • Another advantageous nucleating agent can be Hf0 2 . Therefore, in an advantageous embodiment, the glass ceramic comprises Hf0 2 and at least one crystal nucleating agent selected from the group consisting of T1O2, Zr0 2 Ta 2 O5, Nb20s, Sn0 2 , M0O3, WO3.
  • the sum of the proportions of the nucleating agents is preferably at least 1.5 mol%, preferably at least 2 mol% or more than 2 mole %, more preferably at least 2.5 mole %, according to certain variants at least 3 mole %.
  • An upper limit can be at most 6 mol%, preferably at most 5 mol%, preferably at most 4.5 mol% or at most 4 mol%. In particularly advantageous variants, the upper and lower limits mentioned apply to the sum of PO2 and ZrÜ2.
  • the glass ceramic can contain titanium oxide (T1O2), preferably in a proportion of at least 0.1 mol %, advantageously at least 0.5 mol %, preferably at least 1.0 mol %, preferably at least 1.5 mol % at least 1.8 mol% and/or preferably at most 5 mol%, advantageously at most 4 mol%, more preferably at most 3 mol%, further preferably at most 2.5 mol%, preferably 2.3 mol%.
  • TiC>2-free variants of the glass ceramic according to the invention are possible.
  • the glass ceramic can advantageously also contain zirconium oxide (Zr0 2 ) in a proportion of at most 3 mol%, preferably at most 2.5 mol%, more preferably at most 2 mol%, preferably at most 1.5 mol% or 1.2 Mol% included.
  • ZrO2 may be contained in a proportion of at least 0.1 mole %, more preferably at least 0.5 mole %, at least 0.8 mole % or at least 1.0 mole %.
  • ZrÜ2-free variants of the glass ceramic according to the invention are possible.
  • the glass ceramic can contain individually or in total 0 to 5 mol % of Ta 2 O 5 and/or Nb 2 Os and/or SnO 2 and/or MOO 3 and/or WO 3 and, for example, as an alternative or additional Nucleating agents or to modulate the optical properties, such as refractive index, are used.
  • Hf0 2 can also be old native or additional nucleating agent.
  • Gd2Ü3, Y2O3, Hf0 2 , B12O3 and/or GeÜ2, for example can be contained in some advantageous variants.
  • the glass ceramic can also contain one or more conventional refining agents selected from the group consisting of AS2O3, Sb 2 0 3 , Sn0 2 , SO4 2 ' , F _ , CI-, Br, or a mixture thereof, in a proportion of more than 0 .05 mol% or at least 0.1 mol% and/or at most 1 mol%.
  • the fining agent fluorine can reduce the transparency of the glass ceramic, so that this component, if present, is advantageously reduced to a maximum of 0.5 mole %, preferably a maximum of 0.3 mole %, preferably a maximum of 0.1 mole %. is limited.
  • the glass ceramic is preferably free of fluorine.
  • An advantageous embodiment of the invention is a LAS glass ceramic, in particular for an EUVL precision component or an EUVL precision component, the glass ceramic having AS2O3 as the refining agent.
  • the LAS glass ceramic contains a maximum of 0.05 mol % AS2O3 as a refining agent.
  • the As2O3 content in the glass ceramic is advantageously ⁇ 0.04 mol %, preferably ⁇ 0.03 mol %, preferably ⁇ 0.025 mol %, preferably ⁇ 0.02 mol %, preferably ⁇ 0.015 mol %. It is advantageous if the glass ceramic contains as little AS2O3 as possible.
  • the glass ceramic are essentially As2O3-free, “essentially As2O3-free or As-free” meaning that the component AS2O3 is not intentionally added to the composition as a component, but is at most contained as an impurity , where for As2O3-free glass ceramics, an impurity limit for AS2O3 is ⁇ 0.01 mol %, preferably ⁇ 0.005 mol %. According to a special embodiment, the glass ceramic is free from AS2O3.
  • At least one chemical refining agent is used in an advantageous embodiment.
  • the glass ceramic can have at least one alternative redox fining agent and/or at least one evaporation fining agent and/or at least one decomposition fining agent as a chemical fining agent instead of AS2O3 or in addition to the small proportion of AS2O3 (maximum 0.05 mol %).
  • AS2O3 is also a redox refining agent
  • redox refining agents that are used as an alternative or in addition to AS2O3 are referred to as “alternative redox refining agents”.
  • the total content of the chemical refining agents detectable in the glass ceramic can be in the range from 0 mole % to 1 mole %.
  • the total content of the fining agents detectable in the glass ceramic (without AS2O3) is more than 0.01 mole %, preferably at least 0.05 mole %, preferably at least 0.1 mole %, preferably at least 0.15 mole %, advantageously at least 0.2 mole % and/or at most 1 mole %, preferably at most 0.7 mole %, preferably at most 0.5 mole %, preferably at most 0.4 mole %.
  • Some advantageous variants can also contain at most 0.3 mol %, preferably at most 0.25 mol % or at most 0.2 mol % of refining agent.
  • the proportions of the respective components can be detected by analyzing the glass ceramic. This applies in particular to all the refining agents mentioned below, with the exception of the sulfate component described.
  • Redox refining agents contain multivalent or polyvalent ions that can occur in at least two oxidation states, which are in a temperature-dependent equilibrium with one another, with a gas, usually oxygen, being released at high temperatures. Certain multivalent metal oxides can therefore be used as redox refiners.
  • the alternative redox refining agent can be at least one component selected from the group consisting of Sb 2 O 3 , SnO 2 , CeO 2 , MnO 2 , Fe 2 O 3 .
  • other redox compounds are also suitable if they release their refining gas in the temperature range relevant for refining and convert either to an oxide with a different valence level of the metal ion or to a metallic form.
  • An alternative redox fining agent which emits fining gas, in particular oxygen, at a temperature of less than 1700° C., such as Sb 2 O 3 , SnO 2 , CeO 2 .
  • the content of AS2O3 and/or the content of at least one alternative redox refining agent can be determined by analyzing the glass ceramic, from which experts can draw conclusions about the type and amount of refining agent used.
  • the alternative redox refining agents can be added to the batch, e.g. as oxides.
  • the total content of the alternative redox fining agents can be in the range from 0 mole % to 1 mole %.
  • the total content of the alternative redox refining agents detectable in the glass ceramic is more than 0.01 mole %, preferably at least 0.05 mole %, preferably at least 0.1 mole %, preferably at least 0.15 mole %, advantageously at least 0.2 mole % and/or at most 1 mole %, preferably at most 0.7 mol%, preferably at most 0.5 mol%, preferably at most 0.4 mol%.
  • Some advantageous variants can also contain at most 0.3 mol %, preferably at most 0.25 mol % or at most 0.2 mol % of alternative redox fining agent.
  • the glass ceramic can contain 0 mole % to 1 mole % antimony oxide (Sb 2 O 3 ) as an alternative redox refining agent.
  • the glass ceramic contains Sb 2 0 3 with a proportion of more than 0.01 mole %, preferably at least 0.05 mole %, advantageously at least 0.1 mole %, advantageously at least 0.15 mole %. %, preferably at least 0.2 mol% and/or preferably at most 1 mol%, advantageously at most 0.7 mol%, more preferably at most 0.5 mol%, further preferably at most 0.4 mol% at most 0.3 mol%.
  • a preferred embodiment of the glass-ceramic is essentially Sb 2 0 3 -free or Sb-free, "essentially Sb 2 0 3 -free" meaning that Sb 2 0 3 is not intentionally added to the composition as a raw material component but is at most contained as an impurity, with Sb 2 O 3 -free glass ceramics having an impurity limit of at most 0.01 mole %, preferably at most 0.005 mole %. According to special embodiments, the glass ceramic is Sb 2 O 3 -free.
  • the glass-ceramic can contain 0 mol% to 1 mol% of tin oxide (Sn0 2 ) as an alternative redox refining agent.
  • the glass ceramic contains SnO 2 in a proportion of more than 0.01 mole %, preferably at least 0.05 mole %, advantageously at least 0.1 mole %, advantageously at least 0.15 mole %. , preferably at least 0.2 mol%, preferably at least 0.3 mol% and/or preferably at most 1 mol%, advantageously at most 0.7 mol%, more preferably at most 0.6 mol%.
  • an upper limit of at most 0.5 mole %, more preferably at most 0.4 mole %, preferably at most 0.3 mole %, can be advantageous. If the content of Sn0 2 is too high, it may be possible that the ceramization process of the green glass is more difficult to control, since Sn0 2 not only acts as a refining agent but also as a crystal nucleating agent at higher levels.
  • Sn0 2 -free or Sn-free variants of the glass ceramic according to the invention are possible and advantageous, ie no Sn-containing raw material was added to the mixture for the refinement of the underlying green glass, with a limit for contamination introduced by raw materials or the process of Sn0 2 is at most 0.01 mol%, preferably at most 0.005 mol%.
  • the glass ceramic can contain 0 mol % to 1 mol % CeC>2 and/or MnO 2 and/or Fe 2 C>3.
  • These components can each and independently preferably in a proportion of more than 0.01 mole %, preferably at least 0.05 mole %, advantageously at least 0.1 mole %, advantageously at least 0.15 mole %, preferably at least 0.2 mol% and/or preferably at most 1 mol%, advantageously at most 0.7 mol%, more preferably at most 0.5 mol%, further preferably at most 0.4 mol%, preferably at most 0, 3 mol% be included.
  • Preferred variants of the glass ceramic are free from CeÜ2 and/or MnÜ2 and/or Fe 2 O 3 , ie no Ce-containing raw material and/or Mn-containing raw material and/or Fe-containing raw material was added to the mixture for the refining of the underlying green glass , a limit for contamination of CeÜ2 and/or MnÜ2 and/or Fe 2 O 3 introduced by raw materials or the process being at most 0.01 mol %, preferably at most 0.005 mol %.
  • Evaporation refining agents are components that are volatile at high temperatures due to their vapor pressure, so that the gas formed in the melt develops a refining effect.
  • the evaporation refining agent can have a halogen component.
  • the evaporation fining agent can comprise at least one halogen with a fining effect, in particular selected from the group consisting of chlorine (Cl), bromine (Br) and iodine (I).
  • the preferred halogen with a purifying effect is chlorine.
  • Fluorine is not a halogen with a refining effect, since it is already volatile at temperatures that are too low.
  • the glass-ceramic can still contain fluorine. However, the fluorine can reduce the transparency of the glass ceramic, so that this component, if present, is preferably limited to a maximum of 0.5 mol%, preferably a maximum of 0.3 mol%, preferably a maximum of 0.1 mol% .
  • the glass ceramic is preferably free of fluorine.
  • the halogen with a refining effect can be added in various forms. In one embodiment, it is added to the batch as a salt with an alkali metal cation or alkaline earth metal cation or as an aluminum halogen. In one embodiment, the halogen is used as a salt and the cation in the salt corresponds to a cation present as an oxide in the glass-ceramic.
  • the halogen with a refining effect can be in the form of Ner halogen compound, in particular a halide compound, are used.
  • Ge suitable halide compounds are, in particular, salts of chlorine anions, bromine anions and/or iodine anions with alkali metal cations or alkaline earth metal cations or aluminum cations.
  • chlorides such as LiCl, NaCl, KCl, CaC , BaC , SrCl2, AlCl3 and combinations thereof.
  • bromides and iodides such as LiBr, LiI, NaBr, Nal, KBr, KI, CaH, CaBr2 and combinations thereof are also possible.
  • Other examples are BaBr2, Bah, SrBr2, Srl2, and combinations thereof.
  • the total content of halogen with a fining effect can be in the range from 0 mole % to 1 mole %.
  • the total content of halogen with fining effect which is detectable in the glass ceramic mik, more than 0.03 mol%, preferably at least 0.04 mol%, preferably at least 0.06 mol%, preferably at least 0.08 mole %, preferably at least 0.1 mole %, preferably at least 0.15 mole %, advantageously at least 0.2 mole % and/or at most 1 mole %, preferably at most 0.7 mole -%, preferably at most 0.5 mol%, preferably at most 0.4 mol%.
  • Some advantageous variants can also contain at most 0.3 mol %, preferably at most 0.25 mol % or at most 0.2 mol % of halogen with a fining effect.
  • the stated contents relate to the amounts of halogen that can be detected in the glass ceramic. Those skilled in the art are familiar with using this information to calculate the amount of halogen or halide compound required for purification.
  • the glass-ceramic can contain 0 mole % to 1 mole % chlorine (determined atomically and given as CI).
  • the glass ceramic contains CI in a proportion of more than 0.03 mol %, advantageously at least 0.04 mol %, advantageously at least 0.05 mol %, advantageously at least 0.1 mol %, advantageously at least 0.15 mol%, preferably at least 0.2 mol% and/or preferably at most 1 mol%, advantageously at most 0.7 mol%, more preferably at most 0.5 mol%, more preferably at most 0, 4 mol%, preferably at most 0.3 mol%.
  • Some advantageous glass-ceramics can be Cl-free, i.e. no raw material containing Cl was added to the batch to refine the underlying green glass.
  • CI is at most present as an impurity, with the limit for a Cl impurity being a maximum of 0.03 mol%.
  • the chemical refining agent can contain at least one decomposition refining agent.
  • a decomposition refining agent is an inorganic compound which decomposes at high temperatures with the release of refining gas and the decomposition product has a sufficiently high gas pressure, in particular greater than 10 5 Pa.
  • the decomposition refining agent can preferably be a salt which contains an oxo anion, in particular a sulfate component.
  • the decomposition refining agent includes a sulfate component. Decomposition of the component added as sulphate releases SO2 and O2 gas at high temperatures, which contribute to the purification of the melt.
  • a sulfate component can be added in different forms. In one embodiment, it is added to the batch as a salt with an alkali metal or alkaline earth metal cation. In one embodiment, the sulfate is used as a salt and the cation in the salt corresponds to a cation present as an oxide in the glass ceramic.
  • the following components can advantageously be used as the sulfate source: Li 2 SO 4 , Na 2 SO 4 , K 2 SO 4 , CaSO 4 , BaSO 4 , SrSO 4 .
  • sulfate is determined as SO 3 in material analysis.
  • the sulphate component (ie SO 3 ) in the melted product can no longer be detected using standard X-ray fluorescence analysis after the melt. Therefore, in the case of sulfate-refined exemplary embodiments (see below), it is stated how many mole % SO 4 2 or mole % SO 3 were used, based on the synthesis of the glass melt.
  • the fact that a sulphate component was used as a refining agent can be determined, for example, by analyzing the residual gas content (SO 2 ) in the glass ceramic.
  • An advantageous glass ceramic which is refined with a sulfate component, has more than 0.01 mole %, preferably at least 0.05 mole %, advantageously at least 0.1 mole %, advantageously at least 0.15 mole %, preferably at least 0.2 mol% and/or preferably at most 1 mol%, advantageously at most 0.7 mol%, more preferably at most 0.5 mol%, more preferably at most 0.4 mol%, preferably at most 0.3 mol% SO 3 added via at least one corresponding sulfate compound in the synthesis.
  • Sulfate-free (ie SCh-free or S0 4 2_ free) refined glass ceramics are possible and advantageous.
  • the proportion of sulfate with a refining effect added in the synthesis of a glass ceramic can thus be in the range from 0 mol % to 1 mol % SO 3 .
  • the glass ceramic or the glass on which it is based can be refined using a suitable metal sulfide as a decomposition refining agent, as is described in US 2011/0098171 A, for example.
  • the cation in the sulfide corresponds to a cation present as an oxide in the glass-ceramic.
  • suitable metal sulfides are alkali metal sulfide, alkaline earth metal sulfide and/or aluminum sulfide, which release SO 3 in the melt under oxidizing conditions. So that a metal sulfide can fulfill its role as a refining agent, it is advantageously used in combination with an oxidizing agent, preferably a nitrate, and/or sulfate.
  • Advantageous glass ceramics with a reduced As 2 O 3 content or advantageous As 2 O 3 -free glass ceramics can have a combination of chemical refining agents.
  • the following combinations can be advantageous here, with the respective glass ceramic having the specified refining agents preferably within the above-mentioned limits for the individual components and/or the totals.
  • Advantageous embodiments include:
  • glass ceramics refined with only one refining agent can also be advantageous, for example glass ceramics which contain only Sb 2 O 3 or only SnO 2 as refining agent.
  • the mixture can contain nitrates (NO 3 ), which act as oxidizing agents in the melting and fining process and ensure that oxidizing conditions are present in the melt in order to reduce the effectiveness of the Refining agents, in particular alternative redox fining agents, to increase.
  • the nitrate is used as a salt and the cation in the salt corresponds to a cation present as an oxide in the glass ceramic. Examples of this can be: aluminum nitrate, alkali metal nitrate, alkaline earth metal nitrate, zirconium nitrate, but ammonium nitrate can also advantageously serve as a nitrate source.
  • a nitrate compound or a mixture of several nitrate compounds can be used. If a nitrate compound or a mixture of nitrate compounds is/are included in the batch to support the lautering process, the sum of NO3 is preferably at least 0.4 mol%, preferably at least 0.5 mol%, preferably at least 0.8 Mole %, preferably at least 1 mole % and/or advantageously at most 5 mole %, preferably at most 4 mole %. In some advantageous variants, a maximum of 3 mol % of nitrate can also be used. Nitrate can no longer be detected in the glass or in the glass ceramic due to its volatility.
  • the above glass compositions may optionally contain additions of coloring oxides, such as Nd 2 0 3 , Fe 2 0 3 , CoO, NiO, V 2 Os, Mn0 2 , CuO, Ce0 2 , Cr 2 0 3 , rare earth oxides in contents of each individually or in total 0 - 3 mol%.
  • coloring oxides such as Nd 2 0 3 , Fe 2 0 3 , CoO, NiO, V 2 Os, Mn0 2 , CuO, Ce0 2 , Cr 2 0 3 , rare earth oxides in contents of each individually or in total 0 - 3 mol%.
  • Preferred variants are free from coloring oxides.
  • B 2 0 3 can have a negative effect on the transparency of the glass ceramic. Therefore, in an advantageous variant, the content of this component is limited to ⁇ 0.2 mol %, preferably at most 0.1 mol %. Preferred variants are free from B 2 03.
  • the composition is free of components which are not mentioned above.
  • the glass ceramic according to the invention or the green glass preferably consists of at least 90 mol %, more preferably at least 95 mol %, most preferably at least 99 mol % of the components mentioned above or preferably from the components Si0 2 , Al 2 0 3 , Li 2 0, R 2 O d , R2O, RO and nucleating agents.
  • the glass ceramic it is essentially free of one glass component or several glass components selected from the group consisting of MgO, ZnO, PbO, B 2 O 3 , CrO 3 , F, and Cd compounds.
  • the expression “X-free” or “free of a component X” means that the glass ceramic essentially does not contain this component X, ie such a component is present at most as an impurity in the glass, but is not added to the composition as an individual component becomes.
  • a limit of 0.03 mol %, preferably 0.01 mol %, should not be exceeded in MgO-free and/or ZnO-free variants, based on each case a single component.
  • higher impurity contents of up to a maximum of 0.1 mole %, preferably a maximum of 0.05 mole %, advantageously a maximum of 0.01 mole %, advantageously a maximum of 0.005 mole %, for some components advantageously a maximum of 0.003 mole % each related to one component, be possible.
  • X stands for any component, such as PbO.
  • the glass-ceramics according to the invention have high-quartz mixed crystal as the main crystal phase.
  • Main crystal phase is the crystalline phase that has the largest vol% fraction in the crystal phase.
  • High quartz mixed crystal is a metastable phase that changes its composition and/or structure or transforms into a different crystal phase depending on the crystallization conditions.
  • the mixed crystals containing high quartz have a very low thermal expansion, or one that even decreases with increasing temperature.
  • the crystal phase contains no ß-spodumene and no keatite.
  • Advantageous versions of the LAS glass ceramic have a crystal phase proportion of less than 70% by volume and/or advantageously more than 45% by volume.
  • the crystal phase consists of high quartz mixed crystal, which is also called ß-eucryptite mixed crystal.
  • the average crystallite size of the high quartz mixed crystal is advantageously ⁇ 100 nm, preferably ⁇ 80 nm, preferably ⁇ 70 nm.
  • the small crystallite size means that the glass ceramic is transparent and can also be polished better.
  • the average crystallite size of the high quartz mixed crystal can be ⁇ 60 nm, preferably ⁇ 50 nm.
  • the crystal phase, its proportion and the average Liche crystallite size are determined in a known manner by means of X-ray diffraction analysis.
  • a transparent glass ceramic is produced. Due to the transparency, many properties of such a glass ceramic mik, in particular, of course, whose inner quality can be judged better.
  • the glass ceramics according to the invention are transparent, ie they have an internal transmission of at least 70% in the wavelength range from 350 to 650 nm. B2O3 and/or higher levels of fluorine can reduce transparency. Therefore, advantageous variants do not contain one or both of the components mentioned.
  • the glass ceramics produced within the scope of the inventions are non-porous and free of cracks. In the context of the invention, “non-porous” means a porosity of less than 1%, preferably less than 0.5%, more preferably less than 0.1%.
  • a crack is a gap, ie discontinuity, in an otherwise continuous structure.
  • the processing temperature Va of the green glass on which the glass ceramic is based is advantageously a maximum of 1330° C., preferably a maximum of 1320° C.
  • Some advantageous variants can have a processing temperature of at most 1310°C or at most 1300°C or less than 1300°C.
  • the processing temperature Va is the temperature at which the melt has a viscosity of 10 4 dPas.
  • homogeneity refers to the homogeneity of the CTE of the glass-ceramic over a large volume and a small number, preferably freedom, of inclusions such as bubbles and particles. This is a quality feature of the glass-ceramic and a prerequisite for use in EUVL precision components, particularly in very large EUVL precision components.
  • the processing temperature is determined by the composition of the glass ceramic. Since the glass network-forming component S1O2 in particular is to be regarded as the decisive component for increasing the viscosity and thus the processing temperature, the maximum Si0 2 content must be selected in accordance with the specifications mentioned above.
  • the glass ceramics according to the invention are zero-stretching (see Tables 1a and 1b), ie they have an average thermal expansion coefficient CTE in the range from 0 to 50° C. of at most 0 ⁇ 0.1 ⁇ 10 ⁇ 6 /K. Some advantageous variants even have an average CTE in the range from 0 to 50°C of at most 0 ⁇ 0.05 ⁇ 10 -6 /K. For certain applications it can be advantageous if the average CTE is at most 0 ⁇ 0 in a larger temperature range, for example in the range from -30°C to +70°C, preferably in the range from -40°C to +80°C. is 1 x 10 _6 /K. Further details on the average and differential CTE have already been given above in connection with the inventive EUVL precision component described. This disclosure content is included in its entirety in the description of the glass ceramic.
  • the glass ceramic has a thermal hysteresis of ⁇ 0 at least in the temperature range from 19 to 25° C., preferably at least in the temperature range from 10° C. to 25° C., particularly preferably at least in the temperature range from 10° C. to 35° C .1 ppm and is therefore free of hysteresis (see FIGS. 10 and 11 and FIGS. 31 to 33).
  • this freedom from hysteresis is at least in a temperature range from 5 to 35° C., preferably at least in the temperature range from 5 to 45° C., preferably at least in the temperature range > 0° C.
  • the temperature range of freedom from hysteresis is particularly preferably even wider, so that the material or the component is also suitable for applications at temperatures up to at least 100° C. and advantageously also above.
  • FIGS. 2 to 9 show the thermal expansion curves of known LAS glass ceramics, the curves all being created using the same method as the LAS glass ceramics according to the invention (FIGS. 10 and 11 and FIGS. 31 to 33).
  • the cooling curves (dashed) and heating curves (dotted) are in each case clearly spaced apart from one another precisely at lower temperatures.
  • the difference is more than 0.1 ppm, in some comparative examples it is up to approx. 1 ppm. That is, the materials show considerable thermal hysteresis in the relevant temperature range of at least 10°C to 35°C.
  • FIGS. 2 to 5 The examined LAS glass-ceramics, which are shown in FIGS. 2 to 5 (comparative examples 7, 9 and 10 in Table 2), all contain MgO and ZnO and exhibit a thermal hysteresis up.
  • FIGS. 6 and 7 show the hysteresis curves of LAS glass-ceramics (comparative examples 8 and 14 in Table 2) which are MgO-free but contain ZnO. Both materials show a rapidly increasing thermal hysteresis below 15°C.
  • FIG. 8 shows the hysteresis curve of a LAS glass-ceramic (comparative example 15 in Table 2), the ZnO are free but contain MgO.
  • This material also shows a strongly increasing thermal hysteresis below 15°C.
  • this known material (comparative example 1 in Table 2) has no thermal hysteresis, but the steep curve shows that it is not a zero-stretching material.
  • the average CTE here is -0.24 ppm/K.
  • LAS glass ceramics according to the invention have a very low content of MgO and/or ZnO or are preferably free of MgO and ZnO.
  • the heating curves and the cooling curves are superimposed at least in the temperature range of 10° C. to 35° C.
  • the materials are not only free of hysteresis in the range from 10°C to 35°C, but also at least in the range from 5 to 35°C, preferably at least in the temperature range from 5 to 45°C, preferably at least in the range >0°C to 45 °C
  • Example 7 from FIG. 11 is also free of hysteresis at least in the temperature range from ⁇ 5° C. to 50° C., preferably also at even higher and even lower temperatures.
  • the expansion curve of the LAS glass ceramic is flat in the temperature range from 0°C to 50°C.
  • a flat expansion curve can also be used for a different temperature interval (Ti), preferably in the temperature range (20;40), (20;70) and/or (-10; 30 ) may be desirable.
  • the glass ceramic has an alternative parameter f ( 2o ; 40 ) ⁇ 0.024 ppm/K and/or an alternative parameter f ( 2o ; 70 ) ⁇ 0.039 ppm/K and/or an alternative parameter f ( -io ; 30 ) ⁇ 0.015 ppm/K, which can be seen in FIGS. 27 to 30, 35 and 36.
  • FIGS. 20 and 21 as well as 37 to 41 show that advantageous versions of the LAS glass ceramic have a CTE plateau.
  • a glass-ceramic with a plateau ie with an optimized zero expansion over a wide temperature range, offers the same advantages that have already been mentioned above in connection with the flat course of the expansion curves and the parameter F and the alternative parameter fn . have been described.
  • the differential CTE has a plateau close to 0 ppm/K, ie the differential CTE in a temperature interval T P with a width of at least 40 K, preferably at least 50 K, is less than 0 ⁇ 0.025 ppm/K.
  • the temperature interval of the CTE plateau is denoted by T P .
  • the differential CTE can advantageously be less than 0 ⁇ 0.015 ppm/K in a temperature interval T P with a width of at least 40 K.
  • FIGS. 22, 23 and 26 as well as FIGS. 42 and 43, which have already been described above in connection with the EUVL precision component, show that advantageous versions of the LAS glass ceramic have CTE curves whose slope is very advantageous over wide temperature ranges is low. It is advantageous if the CTE-T curve in a temperature interval with a width of at least 30 K has a slope of ⁇ 0 ⁇ 2.5 ppb/K 2 , preferably ⁇ 0 ⁇ 2 ppb/K 2 , preferably ⁇ 0 ⁇ 1.5 ppb/K 2 , particularly preferably ⁇ 0 ⁇ 1 ppb/K 2 , according to some variants ⁇ 0 ⁇ 0.8 ppb/K 2 , according to special variants even ⁇ 0 ⁇ 0.5 ppb/K 2 .
  • the low slope feature may be present with or without the formation of an advantageous CTE plateau.
  • the glass ceramic according to the invention or advantageous EUVL precision component made from the glass ceramic according to the invention preferably has a modulus of elasticity, determined according to ASTM C 1259 (2021), of 75 GPa to 100 GPa, preferably of 80 GPa to 95 GPa.
  • a modulus of elasticity determined according to ASTM C 1259 (2021)
  • the use of such advantageous EUVL precision components in so-called high-NA EUVL systems or in other EUVL systems with increased wafer throughput is advantageous since the higher modulus of elasticity can, among other things, increase the dynamic positioning accuracy of the photomask.
  • Tables 1a, 1b and 2 show compositions of examples of glass ceramics according to the invention, in particular for EUVL precision components and compositions of comparative examples, and their properties.
  • compositions listed in Table 1a were melted from commercial raw materials such as oxides, carbonates and nitrates using conventional manufacturing processes.
  • the green glasses produced according to Table 1a were first ceramicized at the maximum temperature specified in each case for the duration specified.
  • Table 1a shows 23 examples (Ex.) of the invention, which are hysteresis-free at least in a temperature range from 10°C to 35°C and are zero-stretching.
  • Examples 6, 18, 19 and 20 only show the onset of thermal hysteresis from around 0°C, examples 11, 17 and 23 only from -5°C.
  • Examples 7, 12, 14, 15 and 22 are over the entire temperature range from -5°C to 45°C without hysteresis.
  • the parameter F ⁇ 1.2 ie the course of the expansion curve in the temperature range from 0° C. to 50° C., is advantageously flat in all examples.
  • the examples have a processing temperature of ⁇ 1330° C., so that the glass ceramics can be produced with high homogeneity in large-scale production plants.
  • the processing temperatures as specified in Tables 1a, 1b and 2 were determined in accordance with DIN ISO 7884-1 (2014 - source: Schott Techn. Glas catalogue).
  • example 7 the mean CTE was determined for the temperature range 19°C to 25°C with the result that example 7 has a CTE (19;25) of -1.7 ppb/K.
  • compositions mentioned in Table 1b were melted from commercial raw materials such as oxides, carbonates and nitrates in conventional production processes, where different fining agents or fining agent combinations were used.
  • AS2O3 was significantly reduced as a refining agent, or refining agents without AS2O3 were used.
  • 0.19 mol % SO3 was added as Na 2 SO4 to the synthesis, which corresponds to 0.22 mol % SO4 2 .
  • the SO 3 content was below the detection limit of ⁇ 0.02% by weight.
  • the green glasses produced according to Table 1b were first ceramized at the maximum temperature specified in each case for the duration specified. Samples were also prepared for examples 6b and 7b, which were ceramized with other ceramization parameters (in particular different maximum temperatures), as already explained above in connection with the figures.
  • Table 1b shows 15 examples (Ex.) of the invention which are hysteresis-free at least in a temperature range of 10°C to 35°C and are zero-stretching.
  • Examples 1b, 8b and 13b only show an incipient thermal hysteresis from approx. 5°C
  • examples 2b and 9b only from approx. -5°C.
  • Examples 3b, 5b, 6b and 7b are over the entire temperature range of -5°C up to 45°C hysteresis-free.
  • the parameter F ⁇ 1.2 ie the course of the expansion curve in the temperature range from 0° C. to 50° C., is advantageously flat in all examples.
  • the examples have a processing temperature of ⁇ 1330° C., so that the glass ceramics can be produced with high homogeneity in large-scale production plants.
  • the processing temperatures as specified in Tables 1a, 1b and 2 were determined in accordance with DIN ISO 7884-1 (2014 - source: Schott Techn. Glas-Katalog).
  • the average CTE for the temperature range 19°C to 25°C was determined for examples 6b and 7b, with example 6b having a CTE (19;25) of 0.77 ppb/K and example 7b having a CTE (19;25) of 0.37ppb/K.
  • Example 10b was refined with SnÜ2.
  • nitrate was contained as an oxidizing agent, namely the components BaO and Na2Ü were each used as nitrate raw materials in order to make the melt oxidizing.
  • Example 15b was refined with SnÜ2. SnÜ2 also served as a nucleating agent. Another nucleating agent was Zr0 2 .
  • Comparative examples 1 and 2 show Comparative Examples (Comp. Ex.). Comparative examples 1, 2, 5 and 6 have neither MgO nor ZnO, but the mean CTE(0;50) is greater than 0 ⁇ 0.1 ⁇ 10 6 /K, ie these comparative examples are not zero-stretching. Furthermore, comparative examples 1 and 2 have a processing temperature >1330°C. These materials are very viscous, so that components with a high level of homogeneity cannot be manufactured from them in large-scale production plants.
  • Comparative Examples 7 to 13 and 15 all contain MgO and/or ZnO, and most of them are zero elongation. However, these comparative examples show a thermal hysteresis of significantly more than 0.1 ppm at least in the temperature range from 10°C to 35°C. At room temperature, ie 22°C, this group of comparative examples has a thermal hysteresis except for Comparative Example 14. Comparative Example 9 also has an unfavorably steep expansion curve in the temperature range from 0° C. to 50° C., which can be seen from the high value of the parameter F, although it is zero-stretching.
  • Table 3a shows for some advantageous examples of the invention from Table 1a and a comparative example the calculated alternative parameter ffn .) for different temperature intervals, which shows that the expansion curves of the examples in the designated temperature ranges each have a flatter profile than the comparative example game.
  • Table 3b shows some advantageous examples of the invention from table 1b and a comparative example, the calculated alternative parameter ffn .) for different temperature intervals, which shows that the expansion curves of the examples in the designated temperature ranges each have a flatter profile than the comparative example.
  • Table 4a shows the CTE homogeneity for different component sizes for advantageous components with a composition according to Example 7 of the invention from Table 1a, which shows that the tested components advantageously high CTE homogeneities both in the temperature range 0 ° C to 50 ° C, as also in the temperature range of 19 to 25°C.
  • the modulus of elasticity also known as E-modulus, determined according to ASTM C 1259 (2021), is also given.
  • Table 4b shows the CTE homogeneity for different component sizes for advantageous components with a composition according to Example 6b of the invention from Table 1b, which shows that the tested components advantageously high CTE homogeneities both in the temperature range 0 ° C to 50 ° C, as also in the temperature range of 19 to 25°C.
  • the modulus of elasticity also known as E-modulus, determined according to ASTM C 1259 (2021), is also given.
  • Table 1a Compositions, ceramification and properties (mol %) Table 1a (continued): Compositions, ceramification and properties (mol %) Table 1a (continued): Compositions, ceramification and properties (mol %) Table 1a (continued): Compositions, ceramification and properties (mol %) Table 1b: Compositions, ceramification and properties (mol %) Table 1b (continued): Compositions, ceramification and properties (mol %) Table 1b (continued): Compositions, ceramification and properties (mol %) Table 1b (continued): Compositions, ceramification and properties (mol %) Table 2: Compositions, ceramification and properties (mol %) Table 2 (continued): Compositions, ceramification and properties (mol %) Table 2 (continued): Compositions, ceramification and properties (mol %) Table 3a: Alternative parameter f T i . for selected examples from Table 1a and Comp. Ex.
  • Table 3b Alternative parameter fr . ,. for selected examples from Table 1b and Comp. Ex.
  • the green glasses were first melted in a melting tank with 28 m 3 over a period of several days, with the temperature being kept at around 1600°C.
  • the decomposition of AS 2 O 3 or Sb 2 O 3 results in refining gases that take small gaseous inclusions with them and homogenize the melt.
  • the glass melt is further homogenized during the fining phase and during a subsequent cooling phase.
  • convection of the melt is induced in order to promote homogenization.
  • the temperature of the glass melt is reduced to approximately 1400° C. and then poured into molds with an edge length of 1.7 m and a height of 500 mm.
  • the ceramization took place under the following conditions:
  • the respective green glass block (or blank) was heated to a temperature between 630 and 680°C at a heating rate of 0.5°C/h. The heating rate was then reduced to 0.01 °C/h and continued until a temperature of between 770 and 830 °C was reached. This temperature was maintained for about 60 hours. Thereafter, the blanks were cooled to room temperature at a cooling rate of ⁇ 1° C./h.
  • the CTE homogeneity of the ceramized blocks obtained was determined as described below.
  • the CTE(0;50) was determined for each of the 64 samples of a component and the CTE(19;25) for a further 64 samples.
  • the determination of the thermal expansion of a sample taken was carried out using a static method in which the length of the respective sample at the beginning and at the end of the specific temperature interval, i.e. from 0°C to 50°C and from 19°C to 25 °C, was determined and the average expansion coefficient a or CTE was calculated from the difference in length.
  • the CTE is then given as an average for this temperature interval, e.g.

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Abstract

La présente invention concerne un composant de précision EUVL ayant un comportement d'expansion thermique amélioré.
EP22715032.3A 2021-03-16 2022-03-15 Composant de précision euvl ayant un comportement de dilatation thermique spécifique Pending EP4308512A1 (fr)

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US20240077798A1 (en) 2024-03-07
TW202306923A (zh) 2023-02-16
TW202300471A (zh) 2023-01-01
JP2024511363A (ja) 2024-03-13
US20240002281A1 (en) 2024-01-04
WO2022194840A1 (fr) 2022-09-22
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