US20190047898A1 - Alkali-free boroalumino silicate glasses - Google Patents

Alkali-free boroalumino silicate glasses Download PDF

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US20190047898A1
US20190047898A1 US16/078,425 US201716078425A US2019047898A1 US 20190047898 A1 US20190047898 A1 US 20190047898A1 US 201716078425 A US201716078425 A US 201716078425A US 2019047898 A1 US2019047898 A1 US 2019047898A1
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glass
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temperature
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Adam James Ellison
Sinue Gomez
Yoshiaki Kato
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Corning Inc
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Corning Inc
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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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/06—Forming glass sheets
    • C03B17/064—Forming glass sheets by the overflow downdraw fusion process; Isopipes therefor
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • 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
    • C03C2203/10—Melting processes

Definitions

  • Embodiments of the present disclosure relate to display glass for liquid crystal and other suitable displays.
  • AMLCDs active matrix liquid crystal display devices
  • AMOLEDs active matrix organic light emitting diode displays
  • TFTs thin film transistors
  • panel makers have produced either large, low resolution displays utilizing amorphous-silicon (a-Si) based transistors, or small, high resolution displays utilizing poly-crystalline (p-Si) based and oxide thin film (Ox) based transistors.
  • a-Si TFTs would be replaced by p-Si TFTs
  • consumer demand for low cost, large, high resolution displays, and the cost of manufacturing such large scale displays with p-Si TFTs is driving AMLCD manufacturers to extend their use of a-Si TFTs to higher and higher resolution.
  • Glass that is cooled quickly from a high temperature is said to have a higher fictive temperature because of the “frozen in” higher temperature structure.
  • Glass that is cooled more slowly, or that is annealed by holding for a time near its annealing point, is said to have a lower fictive temperature.
  • the magnitude of compaction depends both on the process by which a glass is made and the viscoelastic properties of the glass.
  • the glass sheet In the float process for producing sheet products from glass, the glass sheet is cooled relatively slowly from the melt and, thus, “freezes in” a comparatively low temperature structure into the glass.
  • the fusion process results in very rapid quenching of the glass sheet from the melt, and freezes in a comparatively high temperature structure.
  • a glass produced by the float process may undergo less compaction when compared to glass produced by the fusion process, since the driving force for compaction is the difference between the fictive temperature and the process temperature experienced by the glass during compaction.
  • Another approach is to slow the rate of strain at the process temperature by increasing the viscosity of the glass. This can be accomplished by raising the annealing point of the glass.
  • the annealing point represents the temperature corresponding to a fixed viscosity for a glass, and thus an increase in annealing point equates to an increase in viscosity at fixed temperature.
  • the challenge with this approach is the production of high annealing point glass that is cost effective. The main factors impacting cost include defects and asset lifetime.
  • a modern continuous unit (CU) melter comprising a refractory premelt, a precious metal finer and a precious metal glass delivery stem—coupled to a fusion draw machine
  • four types of defects are commonly encountered: (1) gaseous inclusions (bubbles or blisters); (2) solid inclusions from refractories or from failure to properly melt the batch; (3) metallic defects consisting largely of platinum; and (4) devitrification products resulting from low liquidus viscosity or excessive devitrification at either end of the forming device, mandrel or isopipe.
  • Glass composition has a disproportionate impact on the rate of melting, and hence on the tendency of a glass to form gaseous or solid defects and the oxidation state of the glass impacts the tendency to incorporate platinum defects. Devitrification of the glass on the forming mandrel, or isopipe, is best managed by selecting compositions with high liquidus viscosities.
  • Some embodiments pertain to compounds, compositions, articles, devices, and methods for the manufacture of alkali-free, boroalumino silicate glasses exhibiting desirable physical and chemical properties.
  • the glasses are suitable for use as substrates in flat panel display devices, such as, active matrix liquid crystal displays (AMLCDs) and active matrix organic light emitting diode displays (AMOLEDs).
  • AMLCDs active matrix liquid crystal displays
  • AMOLEDs active matrix organic light emitting diode displays
  • glasses are provided that possess densities less than 2.55 g/cm 3 and good dimensional stability (i.e., low compaction).
  • one or more embodiments of the disclosed compositions have strain points in excess of 680° C. which, when subjected to the thermal history of the fusion process, have acceptable thermal stability for a-Si thin film transistor processes.
  • glasses that are substantially free of alkalis that possess high annealing points and high Young's modulus, thus, good dimensional stability (i.e., low compaction, elastic strain and stress relaxation) for use as TFT backplane substrates in amorphous silicon and oxide TFT processes.
  • a high annealing point glass can prevent panel distortion due to compaction/shrinkage or stress relaxation during thermal processing subsequent to manufacturing of the glass.
  • Embodiments of the inventive glasses also possess a high elastic modulus and relatively low density, thereby increasing the specific modulus of the glass and greatly reducing the risk of elastic sag in the glass sheet.
  • inventive glasses possess unusually high liquidus viscosity, and thus a significantly reduced risk to devitrification at cold places in the forming apparatus. It is to be understood that while low alkali concentrations are generally desirable, in practice it may be difficult or impossible to economically manufacture glasses that are entirely free of alkalis. The alkalis in question arise as contaminants in raw materials, as minor components in refractories, etc., and can be very difficult to eliminate entirely. Therefore, the inventive glasses are considered substantially free of alkalis if the total concentration of the alkali elements Li 2 O, Na 2 O, and K 2 O is less than about 0.1 mole percent (mol %).
  • a glass comprising in mole percent on an oxide basis in the ranges: SiO 2 65-72, Al 2 O 3 10-14, B 2 O 3 3-8, MgO 2-6, CaO 3-9, SrO 0-6, and BaO 0- ⁇ 1, wherein the glass exhibits a strain point >650° C., an annealing point greater than or equal to about 730° C., a Young's modulus >78 GPa, T 35kP ⁇ T liq >30° C., a density ⁇ about 2.55 g/cm 3 , a CTE less than about 39 ⁇ 10 ⁇ 7 /° C.
  • a glass comprising, in mole percent on an oxide basis in the ranges: SiO 2 67-70, Al 2 O 3 11-13, B 2 O 3 4-6, MgO 3-5.5, CaO 5.5-7, SrO 3-5, and BaO 0- ⁇ 1, wherein the glass exhibits a strain point >700° C., an annealing point greater than or equal to about 750° C., a Young's modulus >79 GPa, T 35kP ⁇ T liq >65° C., a density ⁇ about 2.55 g/cm 3 , a CTE less than about 36 ⁇ 10 ⁇ 7 /° C.
  • a glass comprising in mole percent on an oxide basis in the ranges: SiO 2 >60, Al 2 O 3 >10, B 2 O 3 >0.1, (MgO+CaO+SrO+BaO)/Al 2 O 3 >1.0, wherein the glass exhibits an annealing point greater than or equal to about 730° C., a strain point greater than or equal to about 650° C., a softening point greater than or equal to about 950° C., a T 200P less than about 1650° C., a T 35kP less than about 1300° C., a T 35kP ⁇ T liq >30° C., a specific modulus greater than 31, and a Young's Modulus greater than or equal to 78 GPa.
  • FIG. 1 is a schematic representation of an isopipe, the forming mandrel used to make precision sheet in the fusion draw process
  • FIG. 2 is a cross section of the isopipe of FIG. 1 at section line 6 .
  • Described herein are glasses that are substantially free of alkalis that possess densities less than 2.55 g/cm 3 and good dimensional stability (i.e., low compaction, reduced stress relaxation and elastic strain). Additionally, one or more embodiments of the disclosed compositions have strain points in excess of 680° C. which, when subjected to the thermal history of the fusion process, have acceptable thermal stability for a-Si thin film transistor processes. Embodiments of the present subject matter also provide glasses with high annealing points. A high annealing point glass can prevent panel distortion due to compaction/shrinkage and stress relaxation during thermal processing subsequent to manufacturing of the glass.
  • the disclosed glasses are considered substantially free of alkalis if the total concentration of the alkali elements Li 2 O, Na 2 O, and K 2 O is less than about 0.1 weight percent (mol %).
  • the substantially alkali-free glasses have annealing points greater than about 730° C., greater than 735° C., greater than 740° C., or greater than 750° C. In further embodiments, the substantially alkali-free glasses have strain points greater than about 650° C., greater than 680° C., greater than 690° C., or greater than 700 OC. In yet additional embodiments, the substantially alkali-free glasses have softening points greater than about 950° C., greater than 970° C., greater than 980° C., or greater than 990° C.
  • the temperature of the disclosed glasses at a viscosity of about 200 poise is less than about 1650° C., less than about 1625° C., or less than about 1610° C.
  • the temperature of the disclosed glasses at a viscosity of about 35,000 poise is less than about 1300° C., less than about 1260° C., or less than about 1250° C.
  • the liquidus temperature of a glass (T liq ) is the highest temperature above which no crystalline phases can coexist in equilibrium with the glass.
  • the float process delivers glass at a viscosity between 3000 and 10,000 poise. If the glass devitrifies anywhere near the temperature corresponding to this viscosity, then devitrification products would show up in the finished product.
  • the glasses exhibit a specific modulus greater than 31, greater than 31.5, or greater than 32.
  • the specific modulus of the glass defined as E/ ⁇ , (elastic or Young's modulus in GPa divided by density in g/cm 3 ) is indicative of the magnitude of elastic sag which a glass sheet will experience during processing. For this reason glass compositions with a specific modulus of 31 or greater are desirable.
  • the disclosed glasses can exhibit one or more of the disclosed properties provided above.
  • the disclosed glasses may exhibit one of the above disclosed properties, two of the above disclosed properties, three of the disclosed properties, four of the disclosed properties, five of the disclosed properties, six of the disclosed properties and/or seven of the disclosed properties, in any combination of the disclosed properties.
  • exemplary substantially alkali-free glass comprises in mole percent on an oxide basis in the following ranges:
  • exemplary substantially alkali-free glass comprises in mole percent on an oxide basis in the following ranges:
  • any of the aforementioned embodiments can include one or more of the following properties: (MgO+CaO+SrO+BaO)/Al 2 O 3 ⁇ 1.05, ⁇ 1.08, ⁇ 1.10, an annealing point greater than or equal to about 730° C., 735° C., 740° C., or 750° C., a strain point greater than or equal to about 650° C., 680° C., 690° C., or 700° C., and/or a softening point greater than or equal to about 950° C., 970° C., 980° C., or 990° C.
  • any of these embodiments may also include one or more of the following properties: a T 200P less than about 1650° C., 1625° C., or 1610° C., a T 35kP less than about 1300° C., 1260° C., or 1250° C., a T 35kP ⁇ T liq >40° C., >30° C., >50° C., >60° C., >65° C., or >70° C., and/or a specific modulus greater than 31, 31.5, or 32.
  • any of these embodiments may further include one or more of the following properties: a density less than or equal to 2.55 g/cm 3 , a CTE less than about 39 ⁇ 10 ⁇ 7 /° C., less than about 38 ⁇ 10 ⁇ 7 /° C., or less than about 36 ⁇ 10 ⁇ 7 /° C., a Young's Modulus greater than or equal to 78 GPa, 79 GPa, 80 GPa, or 81 GPa.
  • the disclosed glass includes a chemical fining agent.
  • Such fining agents include, but are not limited to, SnO 2 , As 2 O 3 , Sb 2 O 3 , F, Cl and Br, and in which the concentrations of the chemical fining agents are kept at a level of 0.5 mol % or less.
  • Chemical fining agents may also include CeO 2 , Fe 2 O 3 , and other oxides of transition metals, such as MnO 2 . These oxides may introduce color to the glass via visible absorptions in their final valence state(s) in the glass, and thus their concentration is specifically kept at a level of 0.2 mol % or less.
  • the disclosed glasses are manufactured into sheets via the fusion process.
  • the fusion draw process results in a pristine, fire-polished glass surface that reduces surface-mediated distortion to high resolution TFT backplanes and color filters.
  • FIG. 1 is a schematic drawing of the fusion draw process at the position of the forming mandrel, or isopipe, so called because its gradient trough design produces the same (hence “iso”) flow at all points along the length of the isopipe (from left to right).
  • FIG. 2 is a schematic cross-section of the isopipe near position 6 in FIG. 1 . Glass is introduced from the inlet 1 , flows along the bottom of the trough 2 formed by the weir walls 3 to the compression end 4 .
  • Edge directors 7 at either end of the isopipe serve to cool the glass and create a thicker strip at the edge called a bead.
  • the bead is pulled down by pulling rolls, hence enabling sheet formation at high viscosity.
  • glass substrates made from the fusion process do not require polishing.
  • Current glass substrate polishing is capable of producing glass substrates having an average surface roughness greater than about 0.5 nm (Ra), as measured by atomic force microscopy.
  • the glass substrates produced by the fusion process have an average surface roughness as measured by atomic force microscopy of less than 0.5 nm.
  • the substrates also have an average internal stress as measured by optical retardation which is less than or equal to 150 psi.
  • the disclosed glasses are manufactured into sheet form using the fusion process. While the disclosed glasses are compatible with the fusion process, they may also be manufactured into sheets or other ware through less demanding manufacturing processes. Such processes include but are not limited to slot draw, float, rolling, and other sheet-forming processes known to those skilled in the art.
  • the fusion process as discussed above is capable of creating very thin, very flat, very uniform sheets with a pristine surface.
  • Slot draw also can result in a pristine surface, but due to change in orifice shape over time, accumulation of volatile debris at the orifice-glass interface, and the challenge of creating an orifice to deliver truly flat glass, the dimensional uniformity and surface quality of slot-drawn glass are generally inferior to fusion-drawn glass.
  • the float process is capable of delivering very large, uniform sheets, but the surface is substantially compromised by contact with the float bath on one side, and by exposure to condensation products from the float bath on the other side. This means that float glass must be polished for use in high performance display applications.
  • the fusion process results in rapid cooling of the glass from high temperature.
  • This rapid cooling results in a high fictive temperature T f .
  • the fictive temperature can be thought of as representing the discrepancy between the structural state of the glass and the state it would assume if fully relaxed at the temperature of interest.
  • the rate of this relaxation scales inversely with the effective viscosity of the glass at T p , such that high viscosity results in a slow rate of relaxation, and a low viscosity results in a fast rate of relaxation.
  • the effective viscosity varies inversely with the fictive temperature of the glass, such that a low fictive temperature results in a high viscosity, and a high fictive temperature results in a comparatively low viscosity. Therefore, the rate of relaxation at T p scales directly with the fictive temperature of the glass. A process that introduces a high fictive temperature results in a comparatively high rate of relaxation when the glass is reheated at T p .
  • the annealing point of a glass represents the temperature at which the glass has a viscosity of 10 13.2 poise. As temperature decreases below the annealing point, the viscosity of the supercooled melt increases. At a fixed temperature below T g , a glass with a higher annealing point has a higher viscosity than a glass with a lower annealing point. Therefore, to increase the viscosity of a substrate glass at T p , one might choose to increase its annealing point. Unfortunately, it is generally the case that the composition changes necessary to increase the annealing point also increase viscosity at all other temperatures.
  • the fictive temperature of a glass made by the fusion process corresponds to a viscosity of about 10 11 -10 12 poise, so an increase in annealing point for a fusion-compatible glass generally increases its fictive temperature as well.
  • higher fictive temperature results in lower viscosity at temperature below T g , and thus increasing fictive temperature works against the viscosity increase that would otherwise be obtained by increasing the annealing point.
  • T p To see a substantial change in the rate of relaxation at T p , it is generally necessary to make relatively large changes in annealing point.
  • An aspect of the disclosed glass is that it has an annealing point greater than or equal to about 730° C., 735° C., 740° C., or 750° C. Without being bound by any particular theory of operation, it is believed that such high annealing points result in acceptably low rates of thermal relaxation during low-temperature TFT processing, e.g., typical low-temperature polysilicon rapid thermal anneal cycles.
  • annealing point In addition to its impact on fictive temperature, increasing annealing point also increases temperatures throughout the melting and forming system, particularly the temperatures on the isopipe.
  • Eagle XG® glass and LotusTM glass have annealing points that differ by about 50° C., and the temperature at which they are delivered to the isopipe also differ by about 50° C.
  • zircon refractory forming the isopipe shows thermal creep, which can be accelerated by the weight of the isopipe itself plus the weight of the glass on the isopipe.
  • a second aspect of exemplary glasses is that their delivery temperatures are less than or equal to about 1350° C., or 1345° C., or 1340° C., or 1335° C., or 1330° C., or 1325° C., or 1320° C., or 1315° C. or 1310° C. Such delivery temperatures may permit extended manufacturing campaigns without a need to replace the isopipe or extend the time between isopipe replacements.
  • the glass showed a greater tendency toward devitrification on the root of the isopipe and—especially—the edge directors relative to glasses with lower annealing points.
  • Careful measurement of the temperature profile on the isoipe showed that the edge director temperatures were much lower relative to the center root temperature than had been anticipated and is believed to be due to radiative heat loss.
  • the edge directors typically are maintained at a temperature below the center root temperature to ensure that the glass is viscous enough as it leaves the root to put the sheet in between the edge directors under tension, thus maintaining a flat shape.
  • edge directors are located at either end of the isopipe, the edge directors are difficult to heat, and thus the temperature difference between the center of the root and the edge directors may differ by 50° C. or more.
  • the liquidus temperature of a glass is defined as the highest temperature at which a crystalline phase would appear if a glass were held indefinitely at that temperature.
  • the liquidus viscosity is the viscosity of a glass at the liquidus temperature. To completely avoid devitrification on an isopipe, it may be helpful for the liquidus viscosity to be high enough to ensure that glass is no longer on the isopipe refractory or edge director material at or near the liquidus temperature.
  • T 35kP ⁇ T liq For a particular delivery temperature, it may be useful to make T 35kP ⁇ T liq as large possible, but for an amorphous silicon substrate such as Eagle XG® glass, it is found that extended manufacturing campaigns can be conducted if T 35kP ⁇ T liq is about 80° C. or more. As temperature increases, T 35kP ⁇ T liq must increase as well, such that for T 35k near 1300° C., it may be helpful to have T 35kP ⁇ T liq equal to or greater than about 100° C.
  • the minimum useful value for T 35kP ⁇ T liq varies approximately linearly with temperature from about 1200° C. to about 1320° C., and can be expressed according the relationship below:
  • one or more embodiments of exemplary glasses has a T 35kP ⁇ T liq >30° C., T 35kP ⁇ T liq >40° C., T 35kP ⁇ T liq >50° C., T 35kP ⁇ T liq >60° C., T 35kP ⁇ T liq >65° C., or T 35kP ⁇ T liq >70° C.
  • the forming process may require glass with a high liquidus viscosity. This is necessary so as to avoid devitrification products at interfaces with glass and to minimize visible devitrification products in the final glass.
  • adjusting the process so as to manufacture wider sheet or thicker sheet generally results in lower temperatures at either end of the isopipe.
  • Some embodiments have higher liquidus viscosities to provide greater flexibility for manufacturing via the fusion process. In some embodiments, the liquidus viscosity is greater than or equal to about 150 kP.
  • one or more embodiments of the glass compositions have a liquidus viscosity greater than or equal to about 150,000 poises, or 175,000 poises, or 200,000 poises.
  • a surprising result is that throughout the range of exemplary glasses, it is possible to obtain a liquidus temperature low enough, and a viscosity high enough, such that the liquidus viscosity of the glass is unusually high compared to other compositions.
  • SiO 2 serves as the basic glass former.
  • the concentration of SiO 2 can be greater than 60 mole percent to provide the glass with a density and chemical durability suitable for a flat panel display glass (e.g., an AMLCD or AMOLED glass), and a liquidus temperature (liquidus viscosity), which allows the glass to be formed by a downdraw process (e.g., a fusion process).
  • the SiO 2 concentration can be less than or equal to about 80 mole percent to allow batch materials to be melted using conventional, high volume, melting techniques, e.g., Joule melting in a refractory melter.
  • the SiO 2 concentration is adjusted so that the glass composition has a melting temperature less than or equal to 1,750° C.
  • the SiO 2 concentration is in the range of about 60.0 mol % to about 80.0 mol %, or in the range of about 62.0 mol % to about 78.0 mol %, or in the range of about 65.0 mol % to about 72 mol % or in the range of about 67 mol % and 70 mol %.
  • Al 2 O 3 is another glass former used to make the glasses described herein.
  • An Al 2 O 3 concentration greater than or equal to 10 mole percent provides the glass with a low liquidus temperature and high viscosity, resulting in a high liquidus viscosity.
  • the use of at least 10 mole percent Al 2 O 3 also improves the glass's annealing point and modulus.
  • the Al 2 O 3 concentration may be below about 15 mole percent.
  • the Al 2 O 3 concentration is in the range of about 10.0 to 14.0 mole percent, or in the range of about 11.0 to about 13.0 mol % while maintaining a ratio of (MgO+CaO+SrO+BaO)/Al 2 O 3 greater than or equal to about 1.0.
  • Some embodiments of the disclosure have a modulus greater than about 79 GPa, or 80 GPa, or 80.5 GPa, or 81 GPa, or 81.5 GPa, or 82 GPa, or 82.5 GPa, or 83 GPa, or 83.5 GPa, or 84 GPa, or 84.5 GPa or 85 GPa.
  • an aluminosilicate glass article has a Young's modulus in the range of about 81 GPa to about 88 GPa, or in the range of about 81.5 GPa to about 85 GPa, or in the range of about 82 GPa to about 84.5 GPa.
  • the density of some embodiments of aluminosilicate glass articles is less than about 2.7 g/cc, or 2.65 g/cc, or 2.61 g/cc, or 2.6 g/cc, or 2.55 g/cc. In various embodiments, the density is in the range of about 2.49 g/cc to about 2.53 g/cc, or in the range of about 2.50 g/cc to about 2.60 g/cc.
  • B 2 O 3 is both a glass former and a flux that aids melting and lowers the melting temperature. It has an impact on both liquidus temperature and viscosity. Increasing B 2 O 3 can be used to increase the liquidus viscosity of a glass. To achieve these effects, the glass compositions of one or more embodiments may have B 2 O 3 concentrations that are equal to or greater than 0.1 mole percent. As discussed above with regard to SiO 2 , glass durability is very important for flat panel display applications. Durability can be controlled somewhat by elevated concentrations of alkaline earth oxides, and significantly reduced by elevated B 2 O 3 content. Annealing point decreases as B 2 O 3 increases, so it may be helpful to keep B 2 O 3 content low relative to its typical concentration in amorphous silicon substrates.
  • the glass composition has B 2 O 3 concentrations that are in the range of about 3 to about 8.0 mole percent, or greater than 0 to about 10.0 mol %, or about 2.0 to about 9.0 mol %, or greater than 0 to about 9.0 mol %, or about 3 to about 7 mol %, or in the range of about 4.0 to about 6.0 mol %.
  • the Al 2 O 3 and B 2 O 3 concentrations can be selected as a pair to increase annealing point, increase modulus, improve durability, reduce density, and reduce the coefficient of thermal expansion (CTE), while maintaining the melting and forming properties of the glass.
  • CTE coefficient of thermal expansion
  • an increase in B 2 O 3 and a corresponding decrease in Al 2 O 3 can be helpful in obtaining a lower density and CTE
  • an increase in Al 2 O 3 and a corresponding decrease in B 2 O 3 can be helpful in increasing annealing point, modulus, and durability, provided that the increase in Al 2 O 3 does not reduce the (MgO+CaO+SrO+BaO)/Al 2 O 3 ratio below about 1.0.
  • the glass composition has (MgO+CaO+SrO+BaO)/Al 2 O 3 ⁇ 1.0 (or greater than or equal to about 1.0). In various embodiments, the glass has (MgO+CaO+SrO+BaO)/Al 2 O 3 ⁇ 1.05 (or greater than or equal to about 1.05), or in the range of about 1 to about 1.25.
  • glasses for use in flat panel display applications have coefficients of thermal expansion (CTEs) (22-300° C.) in the range of about 28 ⁇ 10 ⁇ 7 /° C. to about 42 ⁇ 10 ⁇ 7 /° C., or in the range of about 30 ⁇ 10 ⁇ 7 /° C. to about 40 ⁇ 10 ⁇ 7 /° C., or in the range of about 32 ⁇ 10 ⁇ 7 /° C. to about 38 ⁇ 10 ⁇ 7 /° C.
  • CTEs coefficients of thermal expansion
  • the glasses described herein also include alkaline earth oxides.
  • at least three alkaline earth oxides are part of the glass composition, e.g., MgO, CaO, and BaO, and, optionally, SrO.
  • the alkaline earth oxides provide the glass with various properties important to melting, fining, forming, and ultimate use. Accordingly, to improve glass performance in these regards, in one embodiment, the (MgO+CaO+SrO+BaO)/Al 2 O 3 ratio is greater than or equal to about 1.0.
  • ratio (MgO+CaO+SrO+BaO)/Al 2 O 3 is less than or equal to about 2.
  • the (MgO+CaO+SrO+BaO)/Al 2 O 3 ratio is in the range of about 1 to about 1.25, or in the range of about 1 to about 1.18, or in the range of about 1.1 to about 1.8.
  • the alkaline earth oxides may be treated as what is in effect a single compositional component. This is because their impact upon viscoelastic properties, liquidus temperatures and liquidus phase relationships are qualitatively more similar to one another than they are to the glass forming oxides SiO 2 , Al 2 O 3 and B 2 O 3 .
  • the alkaline earth oxides CaO, SrO and BaO can form feldspar minerals, notably anorthite (CaAl 2 Si 2 O 8 ) and celsian (BaAl 2 Si 2 O 8 ) and strontium-bearing solid solutions of same, but MgO does not participate in these crystals to a significant degree.
  • a superaddition of MgO may serves to stabilize the liquid relative to the crystal and thus lower the liquidus temperature.
  • the viscosity curve typically becomes steeper, reducing melting temperatures while having little or no impact on low-temperature viscosities.
  • the glass composition comprises MgO in an amount in the range of about 0.1 mol % to about 6 mol %, or in the range of about 1.0 mol % to about 6.0 mol %, or in the range of about 2.0 mol % to about 6.0 mol %, or in the range of about 3.0 mol % to about 5.5 mol %.
  • the inventors have surprisingly found that glasses with suitably high values of T 35kP ⁇ T liq , the ratio of MgO to the other alkaline earths, MgO/(MgO+CaO+SrO+BaO), falls within a relatively narrow range.
  • additions of MgO can destabilize feldspar minerals, and thus stabilize the liquid and lower liquidus temperature.
  • mullite, Al 6 Si 2 O 13 may be stabilized, thus increasing the liquidus temperature and reducing the liquidus viscosity.
  • MgO may be varied relative to the glass formers and the other alkaline earth oxides to maximize the value of T 35k ⁇ T liq consistent with obtaining other desired properties.
  • calcium oxide present in the glass composition can produce low liquidus temperatures (high liquidus viscosities), high annealing points and moduli, and CTE's in the most desired ranges for flat panel applications, specifically, AMLCD or AMOLED applications. It also contributes favorably to chemical durability, and compared to other alkaline earth oxides, it is relatively inexpensive as a batch material.
  • CaO increases the density and CTE.
  • CaO may stabilize anorthite, thus decreasing liquidus viscosity. Accordingly, in one or more embodiment, the CaO concentration can be greater than or equal to 2 mole percent.
  • the CaO concentration of the glass composition is in the range of about 2.0 mol % to about 10.0 mol %, or in the range of about 3 mol % to about 9.0 mol %, or in the range of about 4 mol % to about 8 mol %, or in the range of about 5 mol % to about 7 mol %, or in the range of about 5.5 mol % to about 7 mol %.
  • SrO and BaO can both contribute to low liquidus temperatures (high liquidus viscosities) and, thus, the glasses described herein will typically contain at least both of these oxides. However, the selection and concentration of these oxides are selected to avoid an increase in CTE and density and a decrease in modulus and annealing point. The relative proportions of SrO and BaO can be balanced so as to obtain a suitable combination of physical properties and liquidus viscosity such that the glass can be formed by a downdraw process.
  • the glass comprises SrO in the range of about 0 to about 6.0 mol %, or greater than 0 to about 6.0 mol %, or about 0 to about 5.5 mol %, or in the range of about 3 mol % to about 5 mol %. In one or more embodiments, the glass comprises BaO in the range of about 0 to less than about 1.0 mol %, or greater than 0 to about 0.5 mol %, or about 0 to about 0.09 mol %, or about 0 mol % to about 0.03 mol %.
  • SiO 2 is the basic glass former.
  • the CTE of the glass should be compatible with that of silicon.
  • exemplary glasses can control the RO content of the glass. For a given Al 2 O 3 content, controlling the RO content corresponds to controlling the RO/Al 2 O 3 ratio. In practice, glasses having suitable CTE's are produced if the RO/Al 2 O 3 ratio is below about 1.6.
  • the glasses are preferably formable by a downdraw process, e.g., a fusion process, which means that the glass' liquidus viscosity needs to be relatively high.
  • a downdraw process e.g., a fusion process
  • Individual alkaline earths play an important role in this regard since they can destabilize the crystalline phases that would otherwise form.
  • BaO and SrO are particularly effective in controlling the liquidus viscosity and are included in exemplary glasses for at least this purpose.
  • various combinations of the alkaline earths will produce glasses having high liquidus viscosities, with the total of the alkaline earths satisfying the RO/Al 2 O 3 ratio constraints needed to achieve low melting temperatures, high annealing points, and suitable CTE's.
  • the liquidus viscosity is greater than or equal to about 150 kP.
  • the glass compositions described herein can include various other oxides to adjust various physical, melting, fining, and forming attributes of the glasses.
  • examples of such other oxides include, but are not limited to, TiO 2 , MnO, Fe 2 O 3 , ZnO, Nb 2 O 5 , MoO 3 , Ta 2 O 5 , WO 3 , Y 2 O 3 , La 2 O 3 and CeO 2 as well as other rare earth oxides and phosphates.
  • the amount of each of these oxides can be less than or equal to 2.0 mole percent, and their total combined concentration can be less than or equal to 5.0 mole percent.
  • the glass composition comprises ZnO in an amount in the range of about 0 to about 1.5 mol %, or about 0 to about 1.0 mol %.
  • the glass compositions described herein can also include various contaminants associated with batch materials and/or introduced into the glass by the melting, fining, and/or forming equipment used to produce the glass, particularly Fe 2 O 3 and ZrO 2 .
  • the glasses can also contain SnO 2 either as a result of Joule melting using tin-oxide electrodes and/or through the batching of tin containing materials, e.g., SnO 2 , SnO, SnCO 3 , SnC 2 O 2 , etc.
  • the glass compositions are generally alkali free; however, the glasses can contain some alkali contaminants. In the case of AMLCD and AMOLED applications, it is desirable to keep the alkali levels below 0.1 mole percent to avoid having a negative impact on thin film transistor (TFT) performance through diffusion of alkali ions from the glass into the silicon of the TFT.
  • an “alkali-free glass” is a glass having a total alkali concentration which is less than or equal to 0.1 mole percent, where the total alkali concentration is the sum of the Na 2 O, K 2 O, and Li 2 O concentrations. In one embodiment, the total alkali concentration is less than or equal to 0.1 mole percent.
  • the glass compositions described herein can have one or more or all of the following compositional characteristics: (i) an As 2 O 3 concentration of at most 0.05 mole percent; (ii) an Sb 2 O 3 concentration of at most 0.05 mole percent; (iii) a SnO 2 concentration of at most 0.25 mole percent.
  • As 2 O 3 is an effective high temperature fining agent for AMLCD and AMOLED glasses, and in some embodiments described herein, As 2 O 3 is used for fining because of its superior fining properties. However, As 2 O 3 is poisonous and requires special handling during the glass manufacturing process. Accordingly, in certain embodiments, fining is performed without the use of substantial amounts of As 2 O 3 , i.e., the finished glass has at most 0.05 mole percent As 2 O 3 . In one embodiment, no As 2 O 3 is purposely used in the fining of the glass. In such cases, the finished glass will typically have at most 0.005 mole percent As 2 O 3 as a result of contaminants present in the batch materials and/or the equipment used to melt the batch materials.
  • Sb 2 O 3 is also poisonous and requires special handling.
  • Sb 2 O 3 raises the density, raises the CTE, and lowers the annealing point in comparison to glasses that use As 2 O 3 or SnO 2 as a fining agent.
  • fining is performed without the use of substantial amounts of Sb 2 O 3 , i.e., the finished glass has at most 0.05 mole percent Sb 2 O 3 .
  • no Sb 2 O 3 is purposely used in the fining of the glass. In such cases, the finished glass will typically have at most 0.005 mole percent Sb 2 O 3 as a result of contaminants present in the batch materials and/or the equipment used to melt the batch materials.
  • tin fining i.e., SnO 2 fining
  • SnO 2 fining is less effective, but SnO 2 is a ubiquitous material that has no known hazardous properties.
  • SnO 2 has been a component of AMLCD and AMOLED glasses through the use of tin oxide electrodes in the Joule melting of the batch materials for such glasses.
  • the presence of SnO 2 in AMLCD and AMOLED glasses has not resulted in any known adverse effects in the use of these glasses in the manufacture of liquid crystal displays.
  • high concentrations of SnO 2 are not preferred as this can result in the formation of crystalline defects in AMLCD and AMOLED glasses.
  • the concentration of SnO 2 in the finished glass is less than or equal to 0.25 mole percent.
  • Tin fining can be used alone or in combination with other fining techniques if desired.
  • tin fining can be combined with halide fining, e.g., bromine fining.
  • halide fining e.g., bromine fining.
  • Other possible combinations include, but are not limited to, tin fining plus sulfate, sulfide, cerium oxide, mechanical bubbling, and/or vacuum fining. It is contemplated that these other fining techniques can be used alone.
  • maintaining the (MgO+CaO+SrO+BaO)/Al 2 O 3 ratio and individual alkaline earth concentrations within the ranges discussed above makes the fining process easier to perform and more effective.
  • the glasses described herein can be manufactured using various techniques known in the art.
  • the glasses are made using a downdraw process such as, for example, a fusion downdraw process.
  • described herein is a method for producing an alkali-free glass sheet by a downdraw process comprising selecting, melting, and fining batch materials so that the glass making up the sheets comprises SiO 2 , Al 2 O 3 , B 2 O 3 , MgO, CaO and BaO, and, on an oxide basis, comprises: (i) a (MgO+CaO+SrO+BaO)/Al 2 O 3 ratio greater than or equal to 1.0; (ii) a MgO content greater than or equal to 3.0 mole percent; (iii) a CaO content greater than or equal to 4.0 mole percent; and (iv) a BaO content greater than or equal to 1.0 mole percent, wherein: (a) the fining is performed without the use of substantial amounts of arsenic (and, optionally,
  • a population of 50 sequential glass sheets produced by the downdraw process from the melted and fined batch materials has an average gaseous inclusion level of less than 0.05 gaseous inclusions/cubic centimeter, where each sheet in the population has a volume of at least 500 cubic centimeters
  • the glass properties set forth in Table 1 were determined in accordance with techniques conventional in the glass art.
  • CTE linear coefficient of thermal expansion
  • x 10 ⁇ 7 /° C. the linear coefficient of thermal expansion
  • annealing point is expressed in terms of ° C.
  • the density in terms of grams/cm 3 was measured via the Archimedes method (ASTM C693).
  • the melting temperature in terms of ° C. (defined as the temperature at which the glass melt demonstrates a viscosity of 200 poises) was calculated employing a Fulcher equation fit to high temperature viscosity data measured via rotating cylinders viscometry (ASTM C965-81).
  • the liquidus temperature of the glass in terms of OC was measured using the standard gradient boat liquidus method of ASTM C829-81. This involves placing crushed glass particles in a platinum boat, placing the boat in a furnace having a region of gradient temperatures, heating the boat in an appropriate temperature region for 24 hours, and determining by means of microscopic examination the highest temperature at which crystals appear in the interior of the glass. More particularly, the glass sample is removed from the Pt boat in one piece, and examined using polarized light microscopy to identify the location and nature of crystals which have formed against the Pt and air interfaces, and in the interior of the sample. Because the gradient of the furnace is very well known, temperature vs. location can be well estimated, within 5-10° C.
  • the temperature at which crystals are observed in the internal portion of the sample is taken to represent the liquidus of the glass (for the corresponding test period). Testing is sometimes carried out at longer times (e.g. 72 hours), to observe slower growing phases.
  • the temperature corresponding to 200 poise and the viscosity at the liquidus (in poises) were determined from fits to high viscosity data using the Vogel-Fulcher-Tammann equation,
  • T temperature and A, B and T o are fitting parameters.
  • T liquidus temperature
  • T o the liquidus temperature
  • Young's modulus values in terms of GPa were determined using a resonant ultrasonic spectroscopy technique of the general type set forth in ASTM E1875-00e1.
  • the exemplary glasses have density, CTE, annealing point and Young's modulus values that make the glasses suitable for display applications, such as AMLCD and AMOLED substrate applications, and more particularly for low-temperature polysilicon and oxide thin film transistor applications.
  • the glasses have durabilityities in acid and base media that are similar to those obtained from commercial AMLCD and AMOLED substrates, and thus are appropriate for AMLCD and AMOLED applications.
  • the exemplary glasses can be formed using downdraw techniques, and in particular are compatible with the fusion process, via the aforementioned criteria.
  • the exemplary glasses of Table 1 were prepared using a commercial sand as a silica source, milled such that 90% by weight passed through a standard U.S. 100 mesh sieve.
  • Alumina was the alumina source
  • periclase was the source for MgO
  • limestone the source for CaO
  • strontium carbonate strontium nitrate or a mix thereof was the source for SrO
  • barium carbonate was the source for BaO
  • tin (IV) oxide was the source for SnO 2 .
  • the raw materials were thoroughly mixed, loaded into a platinum vessel suspended in a furnace heated by silicon carbide glowbars, melted and stirred for several hours at temperatures in the range of 1600 and 1650° C.
  • the glasses of Table 1 can be prepared using standard methods well-known to those skilled in the art.
  • Such methods include a continuous melting process, such as would be performed in a continuous melting process, wherein the melter used in the continuous melting process is heated by gas, by electric power, or combinations thereof.
  • Raw materials appropriate for producing the disclosed glass include commercially available sands as sources for SiO 2 ; alumina, aluminum hydroxide, hydrated forms of alumina, and various aluminosilicates, nitrates and halides as sources for Al 2 O 3 ; boric acid, anhydrous boric acid and boric oxide as sources for B 2 O 3 ; periclase, dolomite (also a source of CaO), magnesia, magnesium carbonate, magnesium hydroxide, and various forms of magnesium silicates, aluminosilicates, nitrates and halides as sources for MgO; limestone, aragonite, dolomite (also a source of MgO), wolastonite, and various forms of calcium silicates, aluminosilicates, nitrates and halides as sources for CaO; and oxides, carbonates, nitrates and halides of strontium and barium.
  • tin can be added as SnO 2 , as a mixed oxide with another major glass component (e.g., CaSnO 3 ), or in oxidizing conditions as SnO, tin oxalate, tin halide, or other compounds of tin known to those skilled in the art.
  • another major glass component e.g., CaSnO 3
  • oxidizing conditions as SnO, tin oxalate, tin halide, or other compounds of tin known to those skilled in the art.
  • the glasses in Table 1 contain SnO 2 as a fining agent, but other chemical fining agents could also be employed to obtain glass of sufficient quality for TFT substrate applications.
  • the disclosed glasses could employ any one or combinations of As 2 O 3 , Sb 2 O 3 , CeO 2 , Fe 2 O 3 , and halides as deliberate additions to facilitate fining, and any of these could be used in conjunction with the SnO 2 chemical fining agent shown in the examples.
  • As 2 O 3 and Sb 2 O 3 are generally recognized as hazardous materials, subject to control in waste streams such as might be generated in the course of glass manufacture or in the processing of TFT panels. It is therefore desirable to limit the concentration of As 2 O 3 and Sb 2 O 3 individually or in combination to no more than 0.005 mol %.
  • zirconium may be introduced as a contaminant via interaction with zirconium-rich refractories.
  • platinum and rhodium may be introduced via interactions with precious metals.
  • iron may be introduced as a tramp in raw materials, or deliberately added to enhance control of gaseous inclusions.
  • manganese may be introduced to control color or to enhance control of gaseous inclusions.
  • alkalis may be present as a tramp component at levels up to about 0.1 mol % for the combined concentration of Li 2 O, Na 2 O and K 2 O.
  • Hydrogen is inevitably present in the form of the hydroxyl anion, OH ⁇ , and its presence can be ascertained via standard infrared spectroscopy techniques. Dissolved hydroxyl ions significantly and nonlinearly impact the annealing point of the disclosed glasses, and thus to obtain the desired annealing point it may be necessary to adjust the concentrations of major oxide components so as to compensate. Hydroxyl ion concentration can be controlled to some extent through choice of raw materials or choice of melting system. For example, boric acid is a major source of hydroxyls, and replacing boric acid with boric oxide can be a useful means to control hydroxyl concentration in the final glass.
  • hydroxyl ions can also be introduced through the combustion products from combustion of natural gas and related hydrocarbons, and thus it may be desirable to shift the energy used in melting from burners to electrodes to compensate.
  • Sulfur is often present in natural gas, and likewise is a tramp component in many carbonate, nitrate, halide, and oxide raw materials.
  • sulfur can be a troublesome source of gaseous inclusions.
  • the elevated barium concentrations of the disclosed glasses appear to increase sulfur retention in the glass in early stages of melting, but as noted above, barium is required to obtain low liquidus temperature, and hence high T 35k -T liq and high liquidus viscosity.
  • Deliberately controlling sulfur levels in raw materials to a low level is a useful means of reducing dissolved sulfur (presumably as sulfate) in the glass.
  • sulfur is specifically less than 200 ppm by weight in the batch materials, and more specifically less than 100 ppm by weight in the batch materials.
  • Reduced multivalents can also be used to control the tendency of the disclosed glasses to form SO 2 blisters. While not wishing to be bound to theory, these elements behave as potential electron donors that suppress the electromotive force for sulfate reduction. Sulfate reduction can be written in terms of a half reaction such as
  • brackets denote chemical activities. Ideally one would like to force the reaction so as to create sulfate from SO 2 , O 2 and 2e ⁇ . Adding nitrates, peroxides, or other oxygen-rich raw materials may help, but also may work against sulfate reduction in the early stages of melting, which may counteract the benefits of adding them in the first place. SO 2 has very low solubility in most glasses, and so is impractical to add to the glass melting process. Electrons may be “added” through reduced multivalents. For example, an appropriate electron-donating half reaction for ferrous iron (Fe 2+ ) is expressed as
  • Suitable reduced multivalents include, but are not limited to, Fe 2+ , Mn 2+ , Sn 2+ , Sb 3+ , As 3+ , V 3+ , Ti 3+ , and others familiar to those skilled in the art. In each case, it may be important to minimize the concentrations of such components so as to avoid deleterious impact on color of the glass, or in the case of As and Sb, to avoid adding such components at a high enough level so as to complication of waste management in an end-user's process.
  • halides may be present at various levels, either as contaminants introduced through the choice of raw materials, or as deliberate components used to eliminate gaseous inclusions in the glass.
  • halides may be incorporated at a level of about 0.4 mol % or less, though it is generally desirable to use lower amounts if possible to avoid corrosion of off-gas handling equipment.
  • the concentration of individual halide elements are below about 200 ppm by weight for each individual halide, or below about 800 ppm by weight for the sum of all halide elements.
  • Such oxides include, but are not limited to, TiO 2 , ZrO 2 , HfO 2 , Nb 2 O 5 , Ta 2 O 5 , MoO 3 , WO 3 , ZnO, In 2 O 3 , Ga 2 O 3 , Bi 2 O 3 , GeO 2 , PbO, SeO 3 , TeO 2 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , and others known to those skilled in the art.
  • such colorless oxides can be added to a level of up to about 2 mol % without unacceptable impact to annealing point, T 10k ⁇ T liq or liquidus viscosity.
  • a ring includes examples having two or more such rings unless the context clearly indicates otherwise.
  • a “plurality” or an “array” is intended to denote “more than one.”
  • a “plurality of droplets” includes two or more such droplets, such as three or more such droplets, etc.
  • an “array of rings” comprises two or more such droplets, such as three or more such rings, etc.
  • Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, examples include from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

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KR20180115749A (ko) 2018-10-23
EP4234504A2 (en) 2023-08-30
EP3419940B1 (en) 2023-10-11
TW202304826A (zh) 2023-02-01
EP3419940A1 (en) 2019-01-02
KR102623926B1 (ko) 2024-01-11
US11655180B2 (en) 2023-05-23
WO2017146926A1 (en) 2017-08-31
EP4234504A3 (en) 2023-09-13
US20200339468A1 (en) 2020-10-29
TW201733944A (zh) 2017-10-01
TWI774655B (zh) 2022-08-21
KR20240010577A (ko) 2024-01-23
JP2021120342A (ja) 2021-08-19

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