US20230192528A1 - Optical glass with high refractive index - Google Patents

Optical glass with high refractive index Download PDF

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US20230192528A1
US20230192528A1 US18/086,157 US202218086157A US2023192528A1 US 20230192528 A1 US20230192528 A1 US 20230192528A1 US 202218086157 A US202218086157 A US 202218086157A US 2023192528 A1 US2023192528 A1 US 2023192528A1
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glass
sio
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max
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Simone Monika Ritter
Sebastian Leukel
Benedikt Ziebarth
Stefanie Hansen
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Schott AG
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Schott AG
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Assigned to SCHOTT AG reassignment SCHOTT AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RITTER, SIMONE MONIKA, DR., HANSEN, STEFANIE, ZIEBARTH, BENEDIKT, DR., LEUKEL, SEBASTIAN, DR.
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/04—Fibre optics, e.g. core and clad fibre compositions
    • C03C13/045—Silica-containing oxide glass compositions
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0085—Compositions for glass with special properties for UV-transmitting glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear glass
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
    • 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 invention relates to an optical glass, to a glass article and to the use thereof.
  • the invention concerns glasses that can be used in the optics and lenses sectors and also in metaoptics and in “augmented reality” (AR).
  • AR augmented reality
  • the latter is understood as meaning the augmentation of reality, especially with visually presented, computer-generated information.
  • Augmented reality is realized with the aid of special AR eyeglasses.
  • an optical component comprising one to three planar waveguides made of glass.
  • the waveguides in turn have integrated gratings, in each case for a wavelength in the red, green or optionally blue region of the visible spectrum. Via these gratings, the imaginary image or information is incoupled/outcoupled in the waveguide to make it visible to the eye.
  • a high refractive index in the glass substrates serving as waveguides has the advantage that it is possible to achieve a wide field of view (FoV).
  • the FoV is here determined by the lowest refractive index in the system, i.e. by the refractive index of the glass in the red region of the spectrum. Preference is therefore given to glasses that in addition to a high refractive index n d at 587.6 nm also have a relatively high Abbe number and accordingly low dispersion.
  • Metaoptics are understood as meaning nanooptics on a structural scale considerably smaller—for example by a factor of 5 or a factor of 10—than the wavelength of light.
  • Heavy glass components i.e. components having a high molar mass, help increase the refractive index, also referred to as the refractive power, but at the same time increase the density of glasses, which is disadvantageous.
  • the density of such glasses here often increases disproportionately with increasing refractive index. This means that, even with a possibility of making glass substrates thinner for use in AR, the glass substrate would become heavier, making AR eyeglasses uncomfortable to wear for long periods.
  • headsets Given the trend for headsets to become more like standard spectacles in shape, which are then to be worn for longer or—like normal spectacles—at all times, there is a need for the eyeglasses to become lighter.
  • Such a reduction on weight is an advantage for other fields of use too, since camera optics in the DSLR sector are also very often either very bulky or very heavy, which also significantly increases the battery power requirement of the autofocus.
  • high-refractive-index glasses optionally have particularly good internal transmission ⁇ i in the visible wavelength range.
  • a particular problem in this context has proved to be the internal transmission in the lower visible wavelength range, for example in the blue region from 420 nm to 490 nm, inter alia at 420 nm, 450 nm or 460 nm.
  • a further problem with high-refractive-index glasses is that such glasses have a high liquidus temperature, i.e. the temperature at which melt and solid/crystal are in equilibrium. Below the liquidus temperature, crystals separate out from the melt. Since high-refractive-index glasses have a reduced content of glass formers and very low viscosity, going below the liquidus temperature of such glasses leads very quickly to the formation of crystals, since crystallization is subject to very little kinetic inhibition due to the “thickness” of the melt, or none at all. A high liquidus temperature is accordingly accompanied by high melting temperatures. A high liquidus temperature is moreover disadvantageous, since at high temperatures an interfering ingress of refractory material (particularly platinum in dissolved and particulate form) can occur.
  • niobium phosphate system or titanium phosphate system; they therefore comprise considerable proportions of P 2 O 5 and niobium and/or titanium.
  • These glasses, especially the niobium phosphate glasses have a refractive index of less than 2.1 and are in some cases very problematic in production, since loss of oxygen, for example due to excessively high melting and refining temperatures in a phosphate system that is in any case already reducing, can result in lower oxidation states. In the case of niobium, this is for example an oxidation state of less than V and, in the case of titanium, of less than IV.
  • the niobium phosphate family of glasses like the high-refractive-index heavy flint or lanthanum heavy flint family—has a tendency not just to interfacial crystallization, but also shows very rapid crystal growth, which makes post-cooling (tension cooling or setting the refractive index) critical for optionally preseeded glasses.
  • the glass is moreover known to be relatively brittle and therefore difficult to polish into very thin wafers.
  • DE 102006030867 A1 describes optical glasses having a refractive index n d of 2.000 and higher.
  • the glasses disclosed therein have high contents of barium oxide, which has an adverse effect on glass formation and on the refractive index.
  • US 20160194237 A1 describes optical glasses that comprise silicon, boron, lanthanum, titanium, niobium, and zirconium but which generally have a refractive index of less than 2.10.
  • EP 3845503A1 JP 2020 59629 A1 and WO 2021085271 A1 disclose only glasses having a refractive index of less than 2.10, in most cases lower even than 2.05.
  • What is needed in the art is a way to provide optical glasses that overcome the disadvantages of the prior art.
  • What is also needed in the art is a way to provide glasses that have a high refractive index n d alongside a liquidus temperature that is as low as possible and advantageously an internal transmission that is as high as possible and a relatively high Abbe number.
  • the glass would advantageously have a density that is as low as possible, readily undergo heat-forming, and be easy to work with.
  • an optical glass has a refractive index n d of more than 2.10 and includes at least TiO 2 , NbO 2.5 , LaO 1.5 , SiO 2 , and B 2 O 3 .
  • a glass article includes an optical glass.
  • the optical glass has a refractive index n d of more than 2.10 and includes at least TiO 2 , NbO 2.5 , LaO 1.5 , SiO 2 , and B 2 O 3 .
  • the glass article is in the form of a glass substrate, a wafer, a lens, a spherical lens, a prism, an asphere, an optical waveguide, a fibre, and/or a plate
  • FIG. 1 illustrates an internal transmission spectrum of exemplary glass 31 from Table 1;
  • FIG. 2 illustrates the relationship of the cation parameter K and Tmax for exemplary embodiments and comparative examples from Tables 1 to 9 and 14;
  • FIG. 3 shows the relationship of the cation parameter K and Tmax for exemplary embodiments and comparative examples from the tables.
  • the invention relates to an optical glass having a refractive index n d of more than 2.10 that comprises at least TiO 2 , NbO 2.5 and LaO 1.5 , the glass having the following features:
  • Exemplary embodiments provided according to the invention are based to a large extent on the correct setting of the molar fractions of cations of the glass components with respect to one another. It is therefore convenient to characterize the composition of the glass by specifying it in cat %.
  • the glass does also contain anions, in particular oxygen.
  • the properties of the glass provided according to the invention are determined less by the anions, consequently the core of the embodiments provided according to the invention lies more in the composition of the cations.
  • cation-percent (cat % for short) relates here to the relative molar fractions of the cations based on the total cation content of the glass.
  • the glass does also contain anions, the relative molar fractions of which are described in anion-percent (an %) based on the total anion content of the glass.
  • the cations are in each case specified in the highest oxidation state and shown charge-compensated with oxygen as anion. This does not mean that the cations are necessarily present in glass exclusively in the highest oxidation state.
  • niobium is also used in the description of the composition of the glass. This stands in this instance for “cations of niobium” and thus does not imply that niobium is present in elemental form in the glass.
  • the glass provided according to the invention also includes anions, which are optionally selected from the group consisting of O 2 ⁇ , F ⁇ , Br ⁇ and Cl ⁇ .
  • the molar fraction of O 2 ⁇ can optionally be at least 50% (an %), at least 70%, at least 90%, or at last 99%, based on the anion content.
  • the glass contains only O 2 ⁇ as anion and is free of other anions.
  • compositional features are better described in terms of the molar fraction of the oxidic glass component.
  • the individual glass component or the sum total of the glass components is given in mol %. Values in mol % can be calculated from the glass composition specified in cat %.
  • a glass system comprising SiO 2 that has a high TiO 2 content has been found that—unlike the glasses produced from the niobium phosphate system or titanium phosphate system that are described in the background—are more stable in respect of the internal transmission that can be achieved and have a higher refractive index but yet a relatively low density. As the refractive index increases, so does the tendency to devitrification.
  • An inventive glass has nevertheless been found that has n d >2.10 and is similarly stable in respect of devitrification to the known titanium-, niobium- and lanthanum-containing glasses.
  • An optical glass provided according to the invention has a defined ratio of the proportions (in cat %) of particular cations of the glass components, which is described as the cation parameter K and determined as follows:
  • This condition describes a composition range within which it is possible for the components that are advantageous for achievement of a high refractive index and high internal transmission to form an amorphous glass, i.e. without the formation of crystal phases.
  • the challenge in such a high-refractive-index glass system is to obtain a stable glassy region alongside a low liquidus temperature.
  • the condition according to the invention has allowed such a composition range to be found, which is described similarly to a miscibility gap in binary or ternary systems.
  • the glass here also has a temperature T max ⁇ 1330° C. and a n d of 2.10.
  • cations of the glass composition are classified—as published for example in: R. D. Shannon; Revised Effective Ionic Radii and Systematic Studies of Interatomic Distances in Halides and Chalcogenides; Acta Crystallographica. Section A 32, 751, 1976—into various groups according to their crystal ion radii:
  • the cation parameter K is according to the invention greater than 1.8 and max. 2.8. If the cation parameter is 1.8 or less, then T max will be too high, with the result that internal transmission decreases through the ingress of refractory material and heightened reduction of polyvalent oxides brought about by the higher process temperatures that are necessary. In addition, the refractive index tends to fall when K is smaller, since lanthanum equivalents raise the refractive index less strongly than titanium equivalents. However, the cation parameter must not be too high either.
  • a K value greater than 2.8 means that the glass contains too few lanthanum equivalents, which has an adverse effect on the tendency to crystallization and thus on T max .
  • An advantageous lower limit for the cation parameter may be at least or more than 1.9 or at least 2.0.
  • Some exemplary embodiments have a lower limit for the cation parameter of more than 2.0 or a lower limit of at least or more than 2.1 or at least or more than 2.2 or at least or more than 2.25 or at least or more than 2.3.
  • Some embodiments provided according to the invention may have an upper limit for the cation parameter K of at most or less than 2.75 or at most or less than 2.7 or, for some exemplary variants, of at most or less than 2.6.
  • the sum total of the glass components SiO 2 and B 2 O 3 is at least 8.0 mol % and not more than 20.0 mol %, the proportion of B 2 O 3 being >0 mol % and the proportion of SiO 2 >0 mol %.
  • the proportions of the glass components SiO 2 and B 2 O 3 in mol % based on oxide can in each case be calculated from the composition stated in cat %.
  • a glass provided according to the invention requires a sum total (SiO 2 +B 2 O 3 ) of at least 8.0 mol %, optionally of more than 8.0 mol %, of at least 9.0 mol % or at least 10.0 mol %, in order for it to be possible for a glassy composition to form in the melting process.
  • the sum total should not exceed an upper limit of 20.0 mol %, since otherwise the glass will contain too small a proportion of glass components that increase the refractive index and the resulting refractive index will thus be too low.
  • An advantageous upper limit for the sum total SiO 2 +B 2 O 3 may be ⁇ 20 mol %.
  • the upper limit of the sum total SiO 2 +B 2 O 3 may be max.
  • B 2 O 3 may optionally amount to at least 1.0 mol % or at least 1.5 mol % or at least 2.0 mol % and/or optionally not more than 19.0 mol % or not more than 17.0 mol % or not more than 15.0 mol % or not more than 13.0 mol % or not more than 12.0 mol %.
  • SiO 2 may optionally amount to at least 1.0 mol % or at least 2.0 mol % or at least 3.0 mol % and/or optionally not more than 19.0 mol % or not more than 18.0 mol % or not more than 16.0 mol % or not more than 15.0 mol %.
  • the glass provided according to the invention has a temperature T max of ⁇ 1330° C.
  • T max is a composition-dependent glass variable and indicates the temperature that is at least necessary in the melting process in order to generate a “blank” melt from the starting materials (for example raw materials, shards, etc.).
  • a “blank” melt is present here when there are no remnants from melting—for example incompletely melted raw materials—and no crystals present in the melt.
  • the melting and refining temperatures should be as low as possible in order to avoid ingress of refractory material into the glass and coloration of the glass by polyvalent ions in a low oxidation state. This allows high internal transmission to be achieved.
  • T max is thus the lowest temperature at which a blank, crystal-free melt can still be produced. This relationship makes T max a good measure for the liquidus temperature of the glass (see below).
  • the T max of a glass composition is determined systematically on a laboratory scale in test series by melting the same glass from the starting components in small crucibles having a volume of in each case 20 ml at different maximum temperatures, with temperature increments of 10° C. chosen. Starting with the lowest temperature up to the highest temperature, the melting result is then visually evaluated in respect of whether a blank melt has been obtained or whether there are still remnants and/or crystals present in the glass.
  • the T max value determined for a composition in this way is reproducible even with laboratory melts of larger volume (e.g. 1 litre). Moreover, further experiments have shown that the temperature T max is only slightly above the liquidus temperature of the glass. It was inferred that the temperature T max , which can be determined in an easily operated laboratory procedure, is a good measure for the liquidus temperature of the glass, which is not determined exactly here.
  • T max is less than 1330° C., for example not more than 1320° C., optionally not more than 1310° C., optionally not more than 1300° C. Some embodiments have a T max of not more than 1290° C. or not more than 1280° C.
  • a glass provided according to the invention has a refractive index n d of more than 2.10, which makes it possible for the system, for example a pair of AR eyeglasses, to achieve an advantageously greater FoV.
  • the refractive index n d is more than 2.100, optionally at least 2.110, optionally at least 2.115, optionally at least 2.120, optionally at least 2.125 or optionally at least 2.130 or at least 2.133.
  • An exemplary upper limit for n d may be 2.20 or 2.200 or 2.195 or 2.190 or 2.189.
  • the refractive index can thus be within a range of from 2.10 to 2.20.
  • the refractive index n d is known to those skilled in the art and refers in particular to the refractive index at a wavelength of about 587.6 nm (wavelength of the d line of helium). Those skilled in the art will know how the refractive index n d can be determined.
  • the refractive index is determined with a refractometer, in particular with a V-block refractometer.
  • samples having a square or approximately square base area for example having dimensions of about 20 mm ⁇ 20 mm ⁇ 5 mm
  • the samples are generally placed in a V-shaped block prism having a known refractive index.
  • the refraction of an incident light beam depends on the difference between the refractive index of the sample and the refractive index of the V-block prism, thereby allowing the refractive index of the sample to be determined.
  • the measurement is optionally carried out at a temperature of 22° C.
  • An exemplary embodiment provided according to the invention has an internal transmission of at least 75%, at least 79%, at least 82% or at least 85% or at least 87% or at least 88% or at least 90% or at least 92% or at least 93% or at least 94% or at least 95% or at least 97%, measured at a wavelength of 460 nm and a sample thickness of 10 mm.
  • the color impression is not distorted in the image that is generated in, for example, AR eyeglasses.
  • the internal transmission or degree of internal transmission can be measured using customary methods known to those skilled in the art, for example according to DIN 5036-1:1978.
  • stated values for the internal transmission refer to a wavelength of 460 nm and a sample thickness of 10 mm.
  • Stating a “sample thickness” does not mean that the glass has this thickness, but merely states the thickness to which the stated internal transmission refers.
  • the density of the glass is optionally ⁇ 5.3 g/cm 3 , optionally ⁇ 5.2 g/cm 3 or ⁇ 5.1 g/cm 3 or ⁇ 5.0 g/cm 3 .
  • the glasses have a low density in relation to a high refractive index, which allows weight savings to be made in optical components, for example in a pair of AR eyeglasses.
  • This can be advantageous when the numerical value for the ratio (n d ) 2 /density is more than 0.85, optionally more than 0.87, optionally more than 0.89, optionally more than 0.90 and/or optionally more than 0.99, optionally less than 0.98, optionally less than 0.97.
  • the glass has an Abbe number, i.e. dispersion ( ⁇ d ), of more than 18.5.
  • the dispersion is greater than 18.9, more optionally greater than 19.2 and/or more optionally greater than 19.5 and/or less than 30.0 or less than 25.0 or less than 24.0.
  • the glass has a glass transition temperature T g of 600° C. to 800° C.
  • T g may be more than 670° C., more than 700° C., optionally more than 720° C.
  • a higher T g can be advantageous in respect of stability to crystallization since this means that the difference in temperature from T max is lower and the glass achieves a stable glassy state more rapidly.
  • the glasses can however still readily undergo heat-forming and processing.
  • the average coefficient of thermal expansion (CTE) in the 20 to 300° C. temperature range should likewise not be too high, optionally in the range from 8.0 to 12.0 ppm/K, in the range from 8.3 to 11.5 ppm/K, optionally in the range from 8.5 to 11.0 ppm/K.
  • the CTE is determined in accordance with DIN ISO 7991:1987.
  • the glass provided according to the invention contains titanium, niobium and lanthanum.
  • Niobium-containing glasses are reputed to exhibit poorer internal transmission at the UV end of the visible range of the spectrum and, on account of the titanium content, to have a pronounced tendency to interfacial crystallization. These disadvantages to not occur with the lass described herein or occur only to a controllable degree.
  • the content of titanium (TiO 2 ) in the glass may be at least 32.0 cat %, optionally at least 34.0 cat % or at least 35.0 cat %. In some embodiments the content is even at least 37.0 cat % or at least 38.0 cat %. Some embodiments may even contain at least 39 cat % of TiO 2 .
  • the content of TiO 2 may optionally be limited to not more than 52.0 cat %, not more than 50.0 cat %, not more than 49.0 cat % or not more than 48.0 cat % or not more than 47.0 cat %.
  • the component TiO 2 takes on the role of glass formation and can therefore be described as an imperfect glass former. An excessively high TiO 2 content would cause a sharp reduction in the Abbe number.
  • the proportion of niobium (NbO 2.5 ) in the glass may be at least 3.0 cat %, optionally at least 4.0 cat %, optionally at least 4.5 cat %, optionally at least 5.0 cat % or at least 6.0 cat %.
  • the content of NbO 2.5 may optionally be limited to not more than 15.0 cat %, not more than 13.0 cat %, not more than 11.0 cat % or not more than 10.0 cat %. Some embodiments may even contain max. 9.0 cat %.
  • NbO 2.5 contributes to a high refractive index. However, excessively high NbO 2.5 contents are disadvantageous in this glass system and result in increased crystallization.
  • the proportion of zirconium (ZrO 2 ) in the glass may be 0 to 11.0 cat %. There may be present in the glass at least 1.0 cat % or at least 2.0 cat %, optionally at least 3.0 cat % or at least 4.0 cat %, of ZrO 2 . ZrO 2 can contribute to setting the cation parameter such that a glassy region with correspondingly low T max is achieved for the glass system.
  • the content of ZrO 2 may optionally be limited to not more than 11.0 cat %, not more than 10.0 cat %, not more than 9.0 cat % or not more than 8.0 cat %. Some embodiments may even contain max. 7.0 cat %.
  • ZrO 2 contributes to achieving the high refractive index, but at high amounts it also increases the tendency of the glass to crystallization, consequently its content is optionally limited. ZrO 2 -free variants are possible.
  • Tungsten is an optional component of the glass.
  • WO 3 may be present in the glass in a content of max. 5.0 cat %, optionally max. 3.0 cat %, optionally max. 2 cat % or max. 1.5 cat % or max. 1 cat % or max. 0.7 cat %.
  • a lower limit may be 0.1 cat %, optionally 0.3 cat %.
  • WO 3 -free variants are possible and advantageous.
  • Tantalum (TaO 2.5 ) is an optional component of the glass.
  • TaO 2.5 may be present in the glass in a content of max. 5.0 cat %, optionally max. 3.0 cat %, optionally max. 2.0 cat % or max. 1.0 cat % or max. 0.7 cat %. When this component is present, a lower limit may be 0.1 cat %, optionally 0.3 cat %. TaO 2.5 -free variants are also possible and may be advantageous.
  • Aluminum (AlO 1.5 ) is an optional component of the glass that can contribute to the chemical resistance, but also to the refractive index of the glass. Its content may be from 0 to 5.0 cat % or up to 3.0 cat % or up to 2.0 cat % or up to 1.0 cat %. When AlO 1.5 is present, it may be present in a proportion of at least 0.1 cat % or at least 0.5 cat %. Some embodiments are free of AlO 1.5 .
  • Antimony (SbO 2.5 ) and arsenic (AsO 2.5 ) are optional components and may be present in the glass in each case and independently of one another in a content of max. 0.5 cat %, optionally max. 0.3 cat % or max. 0.1 cat % or max. 0.05 cat %. When at least one of these components is present in the glass, 0.005 cat % may be a lower limit in each case. SbO 2.5 - and/or AsO 2.5 -free variants are possible. Since the melts of the glasses provided according to the invention have low thickness, the use of classical refining agents to reduce bubble formation can be dispensed with. Vacuum refining may optionally be employed.
  • SbO 2.5 and/or AsO 2.5 may however be added to the mixture in order to keep the glass melt in an oxidizing state at high melting and refining temperatures so that polyvalent ions, especially titanium and niobium ions, are not present in their respective lower oxidation states, with the result that the internal transmission of the glass produced is improved.
  • the total proportion of titanium equivalents (Ti-eq.) in the glass i.e. the sum total of TiO 2 +NbO 2.5 +ZrO 2 +WO 3 +AlO 1.5 +TaO 2.5 +AsO 2.5 +SbO 2.5 , is at least 43.0 cat % or at least 44.0 cat %.
  • the sum total may be at least 45.0 cat % or at least 46.0 cat %, optionally at least 47.0 cat %, optionally at least 49.0 cat % or at least 50.0 cat % and/or not more than 63.0 cat %, optionally not more than 61.0%, optionally not more than 59.0% or not more than 58.0%.
  • An excessively high amount of titanium equivalent can result in crystallization and a high T max . The same applies to an excessively low amount.
  • the feature titanium equivalent is formed from the sum total of the molar fractions of the cations of titanium (TiO 2 ), niobium (NbO 2.5 ), zirconium (ZrO 2 ), antimony (SbO 2.5 ) and arsenic (AsO 2.5 ), with the upper limits and/or lower limits stated above for the total proportion of titanium equivalents (Ti-eq.) accordingly applying. It is self-evident that the glasses in such embodiments are essentially free of WO 3 , AlO 1.5 and TaO 2.5 .
  • the feature titanium equivalent is formed from the sum total of the molar fractions of the cations of titanium (TiO 2 ), niobium (NbO 2.5 ) and zirconium (ZrO 2 ), with the upper limits and/or lower limits stated above for the total proportion of titanium equivalents (Ti-eq.) accordingly applying. It is self-evident that the glasses in such embodiments are essentially free of WO 3 , AlO 1.5 , TaO 2.5 , AsO 2.5 and SbO 2.5 .
  • the following condition is satisfied: content of TiO 2 (in cat %) >content of NbO 2.5 (in cat %)>content of ZrO 2 (in cat %).
  • the content of lanthanum (LaO 1.5 ) in the glass may be at least 13.0 cat %, optionally at least 15.0 cat % or at least 16.0 cat %. In some embodiments the content is even at least 17.0 cat % or at least 18.0 cat %. In some embodiments the content is even at least 19.0 cat % or at least 20 cat %.
  • the content of LaO 1.5 may optionally be limited to not more than 30.0 cat % or not more than 29.0 cat %. Some embodiments may have a LaO 1.5 content of not more than 28.0 cat %, not more than 26.0 cat %, not more than 25.0 cat % or not more than 24.0 cat % or not more than 23.0 cat %.
  • LaO 1.5 contributes to a high refractive index. Excessively high contents of LaO 1.5 contribute to increased devitrification and thus to an increase in T max .
  • the proportion of gadolinium (GdO 1.5 ) in the glass may be 0 to 10.0 cat %. When it is present, the proportion may be at least 1.0 cat %, optionally at least 2.0 cat % or at least 3.0 cat %.
  • the content of GdO 1.5 may optionally be limited to not more than 10.0 cat %, not more than 9.0 cat %, not more than 8.0 cat % or not more than 7.0 cat %. Some embodiments may also contain max. 6.0 cat % or max. 5.0 cat % of GdO 1.5 .
  • Yttrium is an optional component of the glass and may be present in the glass in a content of max. 5.0 cat %, optionally max. 3.0 cat %, optionally max. 2.0 cat % or max. 1.5 cat % or max. 1.0 cat %. When this component is present, a lower limit may be 0.1 cat %, optionally 0.3 cat %. YO 1.5 -free variants are possible.
  • Ytterbium is an optional component of the glass and may be present in the glass in a content of max. 5.0 cat %, optionally max. 3.0 cat %, optionally max. 2 cat % or max. 1.5 cat % or max. 1.0 cat %. When this component is present, a lower limit is advantageously 0.1 cat %, optionally 0.3 cat %. YO 1.5 -free variants are possible and may be advantageous.
  • the total proportion of lanthanum equivalents (La-eq.) in the glass i.e. the sum total LaO 1.5 +GdO 1.5 +YO 1.5 +YbO 1.5 in the glass is at least 21.0 cat %, optionally at least 22.0 cat %, optionally at least 23.0 cat % or at least 24.0 cat % and/or not more than 35.0 cat %, not more than 33.0 cat %, not more than 31.0 cat %.
  • Some embodiments may also contain not more than 30.0 cat %, optionally not more than 29.0 cat %, optionally not more than 28.0 cat % or, in some embodiments, not more than 27.0 cat %, of lanthanum equivalents.
  • An excessively high amount of lanthanum equivalent can result in crystallization and a high T max . The same applies to an excessively low amount.
  • the feature lanthanum equivalent is formed from the sum total of the molar fractions of the cations of lanthanum (LaO 1.5 ), gadolinium (GdO 1.5 ) and yttrium (YO 1.5 ), with the upper limits and/or lower limits stated above for the total proportion of lanthanum equivalents (La-eq.) accordingly applying. It is self-evident that the glasses in such embodiments are essentially free of YbO 1.5 .
  • the following condition is satisfied: content of LaO 1.5 (in cat %)>content of GdO 1.5 (in cat %)>content of YO 1.5 (in cat %).
  • the proportion of the components TiO 2 and LaO 1.5 in the glass is at least 53.0 cat %, optionally at least 55.0 cat %, optionally at least 57.0 cat %, optionally at least 59.0 cat % and/or not more than 70.0 cat %, optionally not more than 69.0 cat % or not more than 68 cat %.
  • the proportion of the components TiO 2 , LaO 1.5 and NbO 2.5 is at least 60.0 cat %, optionally at least 63.0 cat %, optionally at least 65.0 cat %, optionally at least 67.0 cat % and/or not more than 80.0 cat %, optionally not more than 77 cat % or not more than 75 cat %, optionally not more than 73.0 cat %.
  • the sum total (Ti-eq.+La-eq.) in the glass is at least 72.0 cat %, optionally at least 73.0 cat %, optionally at least 74.0 cat % and/or not more than 85.0 cat %, optionally not more than 84.0 cat %, optionally not more than 83.0 cat %.
  • Some embodiments also have a lower limit for the sum total (Ti-eq.+La-eq.) of at least 75.0 cat % or at least 76.0 cat %. The higher the sum total, the higher the refractive index of the glass. However, as the sum total increases, so it also becomes more difficult to provide a glass that is stable to crystallization and has a high T max and accordingly high internal transmission.
  • Silicon (SiO 2 ) is a glass former.
  • the component contributes to the chemical resistance. If it is used in very large amounts, the refractive index values of the invention cannot be achieved.
  • the glass contains SiO 2 in a proportion of >0 cat %.
  • the glass contains at least 1.0 cat %, at least 2.0 cat % or at least 3.0 cat %.
  • Some embodiments may also contain at least 4.0 cat % or at least 5.0 cat % of SiO 2 .
  • the SiO 2 content may be limited to less than 20.0 cat %, max. 18.0 cat % or max. 16.0 cat % or max. 14.0 cat % or max. 13.0 cat % or max. 12.0 cat %.
  • the glass contains BO 1.5 in a proportion of >0 cat %.
  • the glass contains at least 1.0 cat %, at least 2.0 cat % or at least 3.0 cat %.
  • Some embodiments may also contain at least 4.0 cat % or at least 5.0 cat % or at least 6.0 cat % of BO 1.5 .
  • the BO 1.5 content may be limited to less than 20.0 cat %, max. 19.0 cat % or max. 18.0 cat %.
  • Some embodiments contain BO 1.5 in a proportion of max. 17.0 cat % or max. 16.0 cat % or max. 14.0 cat % or max. 12.0 cat % or max. 11.0 cat %.
  • the glass may comprise barium (BaO).
  • BaO barium
  • the content of BaO is in some embodiments restricted to not more than 6.5 cat %, not more than 6.0 cat %, in some embodiments to not more than 5.5 cat %, since excessively high proportions result in undesired crystallization.
  • this component may amount to at least 0.1 cat %, at least 0.2 cat %, at least 0.5 cat %, or at least 1.0 cat %, at least 2.0 cat % or at least 3.0 cat %.
  • the presence of BaO in the glass can be helpful in ensuring the viscosity is higher and steeper in the high-viscosity range from approx. 10 6 dPas to 10 14 dPas. BaO-free variants are possible.
  • Zinc (ZnO), magnesium (MgO), calcium (CaO) and/or strontium (SrO) may optionally be used in the glass. They lower the melting temperature and stabilize the glass against crystallization without reducing its chemical resistance to the degree brought about by alkali metal oxides.
  • the content of ZnO may here be from 0 to 5.0 cat %, up to max. 4.0 cat % or up to max. 3.0 cat % or up to max. 2.0 cat % or up to max. 1.0 cat %. Some embodiments are free of ZnO.
  • the content of MgO may be from 0 to 2.0 cat % or up to max. 1.0 cat %. Some embodiments are free of MgO.
  • the content of CaO may be from 0 to 2.0 cat % or up to max. 1.0 cat %. Some embodiments are free of CaO.
  • the content of SrO may be from 0 to 2.0 cat % or up to max. 1.0 cat %. Some embodiments are free of SrO.
  • an exemplary lower limit may in each case be at least 0.1 cat % or at least 0.3 cat % or at least 0.5 cat %.
  • Alkali metal oxides such as LiO 0.5 , NaO 0.5 , KO 0.5 , RbO 0.5 , CsO 0.5 , may be present in the glass in a proportion for the individual components, in a proportion for the sum total thereof, of max. 2 cat %, max. 1 cat %, optionally max. 0.5 cat %. Small amounts of at least 0.1 cat % or at least 0.2 cat % (for the individual components or optionally for the sum total thereof) may be advantageous for the meltability of the glass. However, since these components lower the refractive index, there is an upper limit on the content thereof. Some embodiments are free of LiO 0.5 and/or NaO 0.5 and/or KO 0.5 and/or RbO 0.5 and/or CsO 0.5 , optionally free of alkali metal oxides.
  • Tin oxide shows only very low or no activity as a refining agent in the glass system provided according to the invention. It may however be present as a glass component in a proportion of max. 2 cat % or max. 1 cat % or max. 0.5 cat %. Optionally, the glass is SnO 2 -free.
  • Sulfate (SO 3 ) may be present in a small proportion in the glass in order to stabilize higher oxidation states in polyvalent ions. When it is present, the proportion is at least 0.01 cat %. Higher proportions of sulfate increase the risk of pronounced bubble formation in the glass and the risk of platinum getting into the glass.
  • the sulfate content may therefore be max. 0.5 cat %, optionally max. 0.1 cat %, optionally max. 0.05 cat %.
  • the glass is SO 3 -free.
  • the glass may contain small amounts of hafnium (HfO 2 ), optionally max. 0.1 cat % or max. 0.05 cat %. It is generally not actively added but gets into the glass with the component ZrO 2 via the raw material. If using very pure ZrO 2 raw material, the glass may be HfO 2 -free.
  • hafnium HfO 2
  • the glass may be HfO 2 -free.
  • the optical glass may comprise fluorine (F).
  • Embodiments may contain max. 1 cat %, optionally max. 0.5 cat %, optionally max. 0.1 cat %, of this component. Some embodiments are free of F.
  • the glass includes the following components in cat %:
  • the glass includes the following components in cat %:
  • the glass includes the following components in cat %:
  • the glass consists to an extent of at least 95.0 cat %, of at least 98.0 cat % or of at least 99.0 cat %, of the components described herein, especially of the components listed in the tables above. In some embodiments the glass essentially consists entirely of these components.
  • the glass may optionally include one or more of the following components having a refining effect in the stated proportions in cat %.
  • the glass is essentially free of cations of bismuth (BiG 1.5 ) and/or lead (PbO).
  • bismuth bismuth
  • PbO lead
  • niobium, titanium and lanthanum means that costly components such as tantalum and/or tungsten and/or ytterbium and/or germanium (GeO 2 ) are not necessary in the glass, or necessary only in small proportions, in order to obtain a glass having the desired high refractive index.
  • costly components such as tantalum and/or tungsten and/or ytterbium and/or germanium (GeO 2 ) are not necessary in the glass, or necessary only in small proportions, in order to obtain a glass having the desired high refractive index.
  • Lithium is known for its aggressiveness towards ceramic bath and crucible materials and is therefore also where possible not used, or used only in small amounts.
  • the glass is free of phosphate (PO 2.5 ), since this makes the melt significantly reducing and thus significantly increases the oxygen requirement of the melt, which in turn increases platinum consumption, resulting in coloration of the glass.
  • PO 2.5 phosphate
  • the glass is—based on the respective cations—essentially free of one or more constituents selected from magnesium, cadmium, gallium, germanium, coloring components—for example cobalt, vanadium, chromium, molybdenum, copper, nickel—and combinations thereof.
  • Components such as iron, manganese, selenium, tellurium and/or thallium may be present in small proportions in the glass, for example they may get into the glass as impurities.
  • Particularly iron, selenium and tellurium, but also manganese can act as redox partners. It may however be advantageous when these components too are not specifically added to the glass either individually or in combination
  • the glass is free of a component or does not contain a certain component, what this means is that said component may at most be present as an impurity in the glass. This means that it is not added in significant amounts. Not significant amounts are amounts according to the invention of less than 100 ppm, optionally less than 50 ppm or less than 10 ppm (m/m).
  • the invention relates to a glass article that includes or consists of the described glass.
  • the glass article can take different forms.
  • the article has the form
  • the invention relates to the use of a glass or glass article described herein in AR eyeglasses, metaoptics, wafer-level optics, optical wafer applications or classical optics.
  • the glass or glass article described herein may be used as a wafer, lens, spherical lens or optical waveguide.
  • the glasses provided according to the invention may be produced by melting commercial raw materials. For example, it is possible to melt the glasses in a device as described in the as yet unpublished DE 102020120168.
  • Tables 1 to 14 show exemplary embodiments provided according to the invention (examples 1 to 99) and Table 14 comparative examples (comparative examples A to G). In some of the glasses the internal transmission was determined. The internal transmission of example 31 is shown in FIG. 1 .
  • FIG. 1 shows an internal transmission spectrum of exemplary glass 31 from Table 1. It can be seen that this example exhibits at 460 nm an internal transmission T i of more than 88% at a sample thickness of 10 mm. In addition, the transmission curve shows the advantageously steep fall from the visible region of the spectrum to the adjoining UV region.
  • FIG. 2 shows the relationship of the cation parameter K and T max for exemplary embodiments and comparative examples from Tables 1 to 9 and 14. It can be seen that the glasses provided according to the invention from Tables 1 to 9 have a cation parameter in the range from above 2.0 and max. 2.8 and at the same time a T max of in this case less than 1330° C., i.e. they have a relatively low liquidus temperature. In addition, all examples have a refractive index n d of more than 2.10. Thus, what has been found in the context of the invention is a stable glassy range alongside a low liquidus temperature in a high-refractive-index glass system.
  • FIG. 3 shows the relationship of the cation parameter K and T max for exemplary embodiments and comparative examples from the tables.
  • the exemplary embodiments of Tables 10 to 12 are depicted. It can be seen that even examples having a cation parameter in the range from above 1.8 to 2.0 alongside a refractive index of more than 2.10 may at the same time have a T max here of less than 1330° C., i.e. they may have a relatively low liquidus temperature.
  • glasses having a cation parameter of more than 2.0 have a lower tendency to crystallization than glasses having a cation parameter of max. 2.0, which have a stronger tendency to crystallization.
  • a higher tendency to crystallization narrows the process window during production, making production more laborious for such glasses.
  • the temperature of the melt is above T max .
  • the chosen temperature cannot be too high.
  • a further consequence of an increased tendency to crystallization may be, for example, that it is possible to produce only smaller glass articles.

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090325779A1 (en) * 2008-06-27 2009-12-31 Tomoaki Negishi Optical glass
US20150045204A1 (en) * 2012-02-28 2015-02-12 Hoya Corporation Optical glass and use thereof
US20160194237A1 (en) * 2013-08-23 2016-07-07 Hoya Corporation Optical glass and use thereof

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4466955B2 (ja) 2005-07-15 2010-05-26 Ｈｏｙａ株式会社 光学ガラス、プレス成形用ガラスゴブおよび光学素子
US11932572B2 (en) * 2018-06-26 2024-03-19 Nippon Electric Glass Co., Ltd. Plate glass
DE112018007655T5 (de) * 2018-07-06 2021-05-12 Schott Glass Technologies (Suzhou) Co. Ltd. Nahinfrarot-Absorptionsfilterglas mit hohem Brechungsindex
CN116655238A (zh) 2018-08-31 2023-08-29 Ａｇｃ株式会社 光学玻璃和光学部件
JP7194551B6 (ja) 2018-10-11 2024-02-06 Ｈｏｙａ株式会社 光学ガラス、プレス成形用ガラス素材、光学素子ブランクおよび光学素子
WO2020090051A1 (ja) * 2018-10-31 2020-05-07 Ａｇｃ株式会社 導光板用光学材料及び導光板
EP3915952B1 (en) * 2019-08-26 2022-12-28 AGC Inc. Optical glass
EP4053087A4 (en) 2019-10-31 2023-12-06 Nippon Electric Glass Co., Ltd. OPTICAL GLASS PLATE
US20230083714A1 (en) * 2020-04-06 2023-03-16 Nippon Electric Glass Co., Ltd. Optical glass
DE102021110497A1 (de) * 2020-05-04 2021-11-04 Schott Ag Optisches Glas mit geringer Dichte
DE102020120168B4 (de) 2020-07-30 2026-01-15 Schott Ag Sicherheitsvorrichtung, Glasschmelzanlage und Glasartikel
DE102020120171A1 (de) * 2020-07-30 2022-02-03 Schott Ag Hochbrechendes Glas
US11802073B2 (en) * 2020-09-10 2023-10-31 Corning Incorporated Silicoborate and borosilicate glasses with high refractive index and low density
CN113735436B (zh) * 2021-09-07 2022-12-13 成都光明光电股份有限公司 光学玻璃、玻璃预制件、光学元件和光学仪器

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090325779A1 (en) * 2008-06-27 2009-12-31 Tomoaki Negishi Optical glass
US20150045204A1 (en) * 2012-02-28 2015-02-12 Hoya Corporation Optical glass and use thereof
US20160194237A1 (en) * 2013-08-23 2016-07-07 Hoya Corporation Optical glass and use thereof

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