US20210163766A1 - Chalcogenide glass based inks obtained by dissolution or nanoparticles milling - Google Patents
Chalcogenide glass based inks obtained by dissolution or nanoparticles milling Download PDFInfo
- Publication number
- US20210163766A1 US20210163766A1 US17/111,316 US202017111316A US2021163766A1 US 20210163766 A1 US20210163766 A1 US 20210163766A1 US 202017111316 A US202017111316 A US 202017111316A US 2021163766 A1 US2021163766 A1 US 2021163766A1
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- United States
- Prior art keywords
- chalcogenide glass
- fluid medium
- mixture
- chalcogenide
- ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000005387 chalcogenide glass Substances 0.000 title claims abstract description 174
- 238000004090 dissolution Methods 0.000 title claims description 15
- 239000000976 ink Substances 0.000 title description 60
- 239000002105 nanoparticle Substances 0.000 title description 16
- 238000003801 milling Methods 0.000 title description 15
- 238000000034 method Methods 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 239000012530 fluid Substances 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 49
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 238000012545 processing Methods 0.000 claims abstract description 9
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 15
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 14
- 239000001856 Ethyl cellulose Substances 0.000 claims description 11
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 11
- 229920001249 ethyl cellulose Polymers 0.000 claims description 11
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- QIHHYQWNYKOHEV-UHFFFAOYSA-N 4-tert-butyl-3-nitrobenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1[N+]([O-])=O QIHHYQWNYKOHEV-UHFFFAOYSA-N 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000007578 melt-quenching technique Methods 0.000 claims description 6
- 229940116411 terpineol Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- MBZCRQUAUUFQSA-UHFFFAOYSA-N [Ge][Sn][Se] Chemical compound [Ge][Sn][Se] MBZCRQUAUUFQSA-UHFFFAOYSA-N 0.000 claims description 3
- KRTIAPDUMFJDBE-UHFFFAOYSA-N [Pb].[S].[Ge] Chemical compound [Pb].[S].[Ge] KRTIAPDUMFJDBE-UHFFFAOYSA-N 0.000 claims description 3
- WLLYEMCJTFAFKV-UHFFFAOYSA-N [Sn].[S].[Ge] Chemical compound [Sn].[S].[Ge] WLLYEMCJTFAFKV-UHFFFAOYSA-N 0.000 claims description 3
- VDNSGQQAZRMTCI-UHFFFAOYSA-N sulfanylidenegermanium Chemical compound [Ge]=S VDNSGQQAZRMTCI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000618 GeSbTe Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000002203 sulfidic glass Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 18
- 238000007639 printing Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 8
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 239000003708 ampul Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
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- 229910052711 selenium Inorganic materials 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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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
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
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- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
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- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
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- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
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- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
- C03B5/2252—Refining under reduced pressure, e.g. with vacuum refiners
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- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
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- C—CHEMISTRY; METALLURGY
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- 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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/005—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to introduce in the glass such metals or metallic ions as Ag, Cu
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- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
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- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
- G11C13/0009—RRAM elements whose operation depends upon chemical change
- G11C13/0011—RRAM elements whose operation depends upon chemical change comprising conductive bridging RAM [CBRAM] or programming metallization cells [PMCs]
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- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y40/00—Manufacture or treatment of nanostructures
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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
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- C—CHEMISTRY; METALLURGY
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- 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
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Definitions
- This disclosure is generally related to the field of additive manufacturing and, in particular, to chalcogenide glass nanoparticle-based ink for additive manufacturing and chalcogenide glass ink obtained by dissolution.
- Chalcogenide glasses and electrical systems made with chalcogenide glasses may be beneficial for several reasons.
- chalcogenide glasses may include up to 5% impurities without affecting their electrical performance. They may also be radiation hard. They can further have various optical properties for use in sensing and communication systems. Based on these properties, chalcogenide glasses offer a wide range of applications including phase change memory, temperature sensing, infrared laser power delivery, high-speed communications, and ultra-fast switching.
- Chalcogenide glass layers may typically be formed through conventional deposition methods, such as evaporative deposition techniques. These techniques may be costly and may not be suitable from some applications. Additive manufacturing technologies may help reduce the cost of manufacturing in general, however, typical additive manufacturing techniques rely on inks that include the desired material. Traditional additive manufacturing inks may not be compatible with the properties of chalcogenide glasses. Other disadvantages may exist.
- an additive manufacturing ink composition may include a fluid medium and a chalcogenide glass suspended within the fluid medium to form a chalcogenide glass mixture solution.
- solution may refer to a solute dissolved in a solvent, or a suspension of nanoparticles in a fluid medium, which may not be dissolved.
- the additive manufacturing ink composition may further include a surfactant.
- the fluid medium includes terpineol or cyclohexanone.
- the chalcogenide glass includes a variety of glass compositions, such as Ge—Se, Ge—S, Ge—Sn—Se. Ge—Sn—S Ge—Sb—Te, Ge—Pb—S, and other chalcogenide glass systems.
- the surfactant includes ethyl cellulose.
- the chalcogenide glass mixture includes between 0.15 grams of chalcogenide glass per milliliter of the fluid medium and 0.3 grams of chalcogenide glass per milliliter of the fluid medium. In some embodiments, the chalcogenide glass mixture includes 0.12 grams of the surfactant per milliliter of the fluid medium.
- a method for forming an additive manufacturing ink includes wet milling a chalcogenide glass in a fluid medium and a surfactant to produce a chalcogenide glass mixture. The method further includes, after wet milling the chalcogenide glass, processing the chalcogenide glass mixture to reduce an average particle size of the chalcogenide glass.
- the method includes synthesizing the chalcogenide glass from bulk materials having 5N purity using a melt quenching process.
- the fluid medium is free of amines.
- the fluid medium includes cyclohexanone.
- the surfactant includes ethyl cellulose.
- processing the chalcogenide glass mixture includes ultrasonicating the chalcogenide glass mixture and centrifuging the chalcogenide glass mixture.
- the method includes adjusting a viscosity of the chalcogenide glass mixture by adding additional fluid medium to the chalcogenide glass mixture.
- the chalcogenide glass mixture after adjusting the viscosity of the chalcogenide glass mixture, includes between 0.15 grams of chalcogenide glass per milliliter of the fluid medium and 0.3 grams of chalcogenide glass per milliliter of the fluid medium. In some embodiments, after adjusting the viscosity of the chalcogenide glass mixture, the chalcogenide glass mixture includes 0.12 grams of the surfactant per milliliter of the fluid medium. In an embodiment, during the processing of the chalcogenide glass mixture, the average particle size of the chalcogenide glass is reduced to less than or equal to 100 nm.
- a method for forming a dissolution based chalcogenide glass ink includes dissolving a chalcogenide glass into an amine-based solvent to form a chalcogenide glass solution. The method further includes filtering the chalcogenide glass solution.
- the solvent includes ethylenediamine or propylamine.
- dissolving the chalcogenide glass into the amine-based solvent includes stirring the chalcogenide glass and the solvent using a magnetic stirrer at the rate of 700 rpm for at least 72 hours.
- the method includes synthesizing the chalcogenide glass from bulk materials having 5N purity using a melt quenching process.
- the method includes filtering the chalcogenide glass solution through a filter.
- the method includes adding terpineol to the chalcogenide glass solution to increase its viscosity.
- particles of chalcogenide glass from the chalcogenide glass solution are configured to agglomerate into a solid film upon application of a two-part sintering process.
- the two-part sintering process includes heating the chalcogenide glass solution in a vacuum furnace to 100° C. for at least 24 hours and heating the chalcogenide glass solution to 130° C. for at least 24 hours.
- FIG. 1 depicts an embodiment of an additive manufacturing ink obtained by dissolution or milling to nanoparticle size with added solvent.
- FIG. 2 depicts an embodiment of a method for forming an additive manufacturing ink.
- FIG. 3 depicts a transformation of bulk elements to bulk chalcogenide glass particles.
- FIG. 4 depicts an embodiment of a chalcogenide glass paste.
- FIG. 5 depicts the formation of a chalcogenide glass nanoparticle ink with a predetermined viscosity.
- FIG. 6 depicts an embodiment of a method for making a dissolution based chalcogenide glass ink.
- FIG. 7 depicts a chalcogenide glass ink including glass particles dissolved in a solvent.
- FIG. 8 depicts a chalcogenide glass ink after evaporation has occurred.
- FIG. 9 depicts a dissolution based chalcogenide ink after a second sintering phase has occurred.
- the additive manufacturing ink may be a chalcogenide glass nanoparticle ink 100 .
- the depictions of FIG. 1 are for clarity and may accurately depict the shape and proportions of the components of the chalcogenide glass nanoparticle ink 100 .
- the chalcogenide glass nanoparticle ink 100 may include a fluid medium 102 , a chalcogenide glass 104 , and a surfactant 106 .
- the fluid medium 102 may include cyclohexanone (C6H100), which may have a boiling point of 156° C. and a viscosity 2.02 cP at 25° C. This high boiling point may prevent the fluid medium 102 from evaporating while flowing through a nozzle of a printer or of other piece of additive manufacturing equipment. Further, cyclohexanone may not react with the chalcogenide glass 104 . Other compositions may also be used as the fluid medium 102 . In order to reduce the risk of reaction with printer parts and nozzles, the fluid medium 102 may be free of amines. Amines may be more reactive with types of plastic that may be used in additive manufacturing.
- the surfactant 106 may include ethyl cellulose (n-CH2CH3).
- the ethyl cellulose may include long chain polymers that can connect themselves to the chalcogenide glass 104 and prevent agglomeration. Thus, a texture and viscosity of the chalcogenide glass nanoparticle ink 100 may be maintained.
- the chalcogenide glass 104 may include multiple compositions, such as a germanium-sulfide (Ge—S), a germanium-selenide (Ge—Se), a germanium-tin-sulfide (Ge—Sn—S), a germanium-tin-selenide (Ge—Sn—Se), a germanium-antimony-telleride (Ge—Sb—Te), or a germanium-lead-sulfide (Ge—Pb—S).
- germanium-sulfide Ge—S
- Ge—S germanium-selenide
- Ge—Sn—S germanium-tin-sulfide
- Ge—Sb—Te germanium-antimony-telleride
- Ge—Pb—S germanium-lead-sulfide
- the chalcogenide glass 104 may be mixed with the fluid medium 102 at a concentration of between 0.15 grams of chalcogenide glass per milliliter of the fluid medium 102 and 0.3 grams of chalcogenide glass per milliliter of the fluid medium 102 .
- the surfactant 106 may be mixed with the fluid medium 102 at a concentration of 0.12 grams of the surfactant 106 per milliliter of the fluid medium 102 .
- An average particle size of the chalcogenide glass 104 may be less than or equal to 100 nm. Hence, the chalcogenide glass 104 may be referred to as nanoparticles.
- a benefit of the chalcogenide glass nanoparticle ink 100 is that it may be used with printing processes and other additive manufacturing processing to form chalcogenide glass layers. Using printing processes may be less expensive than typical vapor deposition processes. Further, the chalcogenide glass nanoparticle ink 100 may include components that do not harm typical printers. Other benefits may exist.
- the method 200 may include synthesizing a chalcogenide glass, at 202 .
- Some of the options for the chalcogenide glass include germanium-sulfide (Ge—S), germanium-selenide (Ge—Se), germanium-tin-sulfide (Ge—Sn—S), germanium-tin-selenide (Ge—Sn—Se), germanium-antimony-telluride (Ge—Sb—Te), and germanium-lead-sulfide (Ge—Pb—S) because they are thermally stable, have wide glass forming regions, and may be less toxic as compared to other chalcogenides, for example those containing Amines.
- ternaries such as Pb2Ge8S15 and Sn2Ge8S15 may belong to a family of chalcogenide glasses where the members have more than one crystallization temperature. These chalcogenide glasses could be beneficial for increasing temperature sensing resolutions and could also make sensing devices more compact.
- Ge20Se80, Ge30Se70, Ge33Se67, Ge40Se60, Sn2Ge8S15, Ge2Sb2Te5, and Pb2Ge8S15 bulk glasses may be synthesized through melt quenching technique.
- Pure 5N elements may be weighed and loaded into quartz ampules, which are sealed under a vacuum at about 10 ⁇ 4 mbar.
- the glass synthesis may be carried out in a programmable tube furnace for 168 hours with a peak temperature of 750° C. The furnace may be programmed at different rates, depending on the composition, to reach 750° C. within the first 24 hours of synthesis with some holdings at characteristic temperatures.
- the quartz ampules may be kept at the highest temperature for 168 hours (about one week). This may result in a good homogenization of the melt.
- the resulting glass may be quenched in water from a temperature of 20° C. above the melting temperature for the synthesized composition as can be derived from phase diagrams.
- the method 200 may further include crushing the chalcogenide glass into a chalcogenide glass powder, at 204 .
- a chalcogenide glass may include an uneven distribution of chunks and shards. In order to further process it, it may be beneficial to crush the chalcogenide glass into substantially more uniform particles.
- the method 200 may also include wet milling the chalcogenide glass powder, at 206 .
- wet milling the chalcogenide glass powder For milling 2 mm stainless steel milling balls may be used. The starting particle size of the chalcogenide glass may be smaller than the milling balls.
- An agate mortar and pestle may be used to ensure that particles within the chalcogenide glass powder less than about 2 mm.
- ball milling can be done either dry or wet. In this case, wet milling may help prevent particle agglomeration. Further, the use of a surfactant during milling may produce finer particles and also reduce wastage of material by preventing particle adhesion to a milling jar and to the milling balls.
- the chalcogenide glass e.g., germanium-selenide
- the surfactant e.g., ethyl cellulose
- the fluid medium e.g., cyclohexanone
- Ethyl cellulose may takes some time to dissolve in cyclohexanone. However, un-dissolved ethyl cellulose may not have a significant impact the milling and may be dissolved during the process instead of before the process begins.
- the fluid medium may be selected to prevent chemical reaction with either the chalcogenide glass particles or the surfactant.
- a ball mill may not be designed for continuous production. In these cases, it may be set to mill for 30 minutes, pause for 30 minutes, and then repeat the process until the milling time has been completed. During milling, the temperature may be kept below 50° C. to prevent undesired crystallization of the chalcogenide glass particles. Milling may be continued until a particle size of the chalcogenide glass becomes saturated.
- the method 200 may include determining whether a particle size of the chalcogenide glass is about 250 nm, at 208 . If the target particle size has not been reached, the method 200 may include continuing to wet mill the chalcogenide glass power, at 206 .
- a dynamic Light Scattering (DLS) system may be used to measure the particle size every 24 hours. DLS utilizes light scattering to measure particle size. Pure cyclohexanone may be poured in a vendor recommended glass cuvette. A drop of ink may be mixed with the cyclohexanone. Individual particle sizes may then be determined using DLS.
- DLS Dynamic Light Scattering
- the method 200 may include mixing the resulting paste with additional fluid medium, at 210 . Milling alone may not result in a desired viscosity. After ball milling the chalcogenide glass mixture may come out as a paste. A viscosity between 8 cP and 24 cP may be desirable for an additive manufacturing process. For final adjustment of the ink viscosity, cyclohexanone and ethyl cellulose may be added. For example, another 50 ml of cyclohexanone may be added to the paste to prepare a less viscous solution.
- a good concentration was found to be between 0.15 g/ml and 0.3 g/ml of chalcogenide glass in cyclohexanone and about 0.12 g/ml of ethyl cellulose in cyclohexanone. Further, a particle size between 100 nm and 270 nm showed good results in terms of processing and device performance. In some embodiments, this mixing of the paste with additional fluid medium may be performed after the following steps of ultrasonicating and centrifuging.
- the method 200 may further include ultrasonicating the mixture, at 212 .
- an ultrasonicator may utilize a probe to transfer vibrational energy to the mixture.
- the diameter of the probe may be selected based on the volume of the mixture. For example, a 2 mm diameter probe may be used for a 30 ml mixture. Other possibilities may exist based on experimentation.
- the mixture may be sonicated for about 21 ⁇ 2 hours.
- a diameter of the particles after ultrasonication may be as low as 145 nm. However, the average size may be much higher due to a wide variability in particle size.
- Further ultrasonication can be used to both disperse and reduce particle size. For example, in 10 to 12 hours ultrasonication can reduce the average particle size from its bulk size to less than 250 nm.
- the method 200 may also include centrifuging the mixture, at 214 . Centrifuging the mixture at 4500 rpm for about 1.5 hours may help create a uniform particle size within the mixture.
- the resulting mixture may have chalcogenide glass nanoparticles having a diameter of less than 100 nm, which may be sufficient for sintering or melting the particles at a temperature below 427° C., which may be lower than the lowest crystallization temperature of the materials used in the mixture.
- the method 200 may include determining whether a particle size of the chalcogenide glass less than 100 nm, at 216 . If the target particle size has not been reached, the method 200 may include repeatedly ultrasonicating the mixture, at 212 , and centrifuging the mixture, at 214 . If the target particle size has been reached, then the resulting ink may be ready for printing, at 218 .
- a benefit of the method 200 is that it may be used to form a chalcogenide glass nanoparticle ink for printing in conventional additive printers. Using printers may be less expensive than typical vapor deposition processes for chalcogenide glass layers. Further, the chalcogenide glass nanoparticle ink may include components that do not harm typical printers. Other benefits may exist.
- a transformation 300 of bulk elements to bulk chalcogenide glass particles 306 is depicted.
- bulk germanium 302 and bulk selenium 304 may be synthesized into chalcogenide glass and then crushed into a powder that includes the chalcogenide glass particles 306 .
- the chalcogenide glass particles 306 may correspond to a state after the step 204 of the method 200 .
- the germanium-selenide composition depicted in FIG. 3 is only for example, purposes. Other compositions may exist as described herein.
- the bulk chalcogenide glass powder may have an average diameter 308 that may be less than about 2 mm after the transformation 300 .
- the paste 400 may correspond to a state after the step 208 of the method 200 .
- the paste 400 may be the result of wet milling as described herein.
- the paste 400 may include a fluid medium 402 , chalcogenide glass particles 404 , and a surfactant 406 .
- the chalcogenide glass particles 404 may have a diameter 408 of about 250 nm.
- the formation of a chalcogenide glass nanoparticle ink 510 with a desired viscosity is depicted.
- the paste 400 may be mixed with additional fluid medium 502 to reduce a concentration of the chalcogenide glass particles 404 and the surfactant 406 within the combined fluid medium 512 .
- the addition of the additional fluid medium 502 may be performed after the step 208 of method 200 , as shown in FIG. 2 .
- the additional fluid medium 502 may be added after the ultrasonication step 212 and the centrifuge step 214 .
- Amines, as described herein, may be used to make dissolution-based chalcogenide glass inks.
- the amines described herein may be reactive with various parts of printers.
- the chalcogenide glass mixtures used may include corrosive fluid mediums or solvents, such as amine-based mediums. These mixtures may not be suitable for many printing applications because they can damage printers and printer components if made from plastic polymers. However, these inks may be appropriate for other additive manufacturing processes, such as screen printing, nScrypt printer, and spin coating.
- the method 600 may include synthesizing a chalcogenide glass, at 602 .
- the process of synthesizing the chalcogenide glass may be the same process as described with reference to the method 200 .
- Ge20Se80, Ge30Se70, Ge33Se67, Ge40Se60, Sn2Ge8S15, Ge2Sb2Te5, and Pb2Ge8S15 bulk glasses may be synthesized through melt quenching technique using pure 5N elements.
- the method 600 may further include crushing the chalcogenide glass into a chalcogenide glass powder, at 604 .
- the crushing may be performed using an agate mortar and pestle. Other techniques are possible.
- the method 600 may also include dissolving the chalcogenide glass powder into a solvent, at 606 .
- Amine solvents may be capable of dissolving the chalcogenide glass powder. Examples of amines that may be used are ethylenediamine (EDA) and propylamine (PA). Other solvents are possible.
- EDA ethylenediamine
- PA propylamine
- a volumetric flask may be used to perform the mixing.
- the dissolution rate of Ge—Se based chalcogenide glass, for example, into an amine-based solvent may be about 0.08 g per 20 ml.
- the solution may be stirred by using a magnetic stirrer at a rate of 700 rpm for 72 hours.
- a lid of the volumetric flask may be kept closed by para-film to prevent evaporation.
- the method 600 may include increasing a viscosity of the solution, at 608 .
- terpineol may be added to the solution to increase its viscosity.
- the terpineol and the increased viscosity may improve a resolution of a resulting printed film. In some applications 5% to 10% of terpineol is sufficient to achieve a good resolution for screen-printed patterns.
- the method 600 may further include performing vacuum filtration of the solution, at 610 .
- the solution may be filtered through a 0.025 ⁇ m nylon filter using a vacuum filtration technique.
- the filtration may remove larger particles of chalcogenide glass that have not been dissolved in the solvent.
- the step 608 of increasing the viscosity of the solution may be performed after the step 610 of filtering the solution.
- the resulting ink may be ready for printing, at 612 .
- the dissolution based ink may be characterized using a tensiometer.
- a contact angle of the ink when applied to a substrate may provide information about how well the ink will spread over the substrate. It may be an important indicator of proper ink viscosity and the quality of the ink formulation process.
- the tensiometer may be used to measure the contact angle by applying a droplet of ink to a stage and then analyzing image data of the droplet.
- the stage may be flattened to ensure that the droplet of ink does not move during deposition.
- an image may be recorded by a camera. The image may be analyzed using software to determine the contact angle.
- the prepared ink can be applied for printing on a substrate using a screen printer or a 3D printer or by spin coating the ink on the substrate.
- screen printing a monofilament polyester fabric may be stretched extremely tightly on a metal frame.
- a photosensitive emulsion may be coated over the fabric to form a stencil.
- the combination of the stencil and the metal frame may form a screen.
- the desired printing design may be transferred to the screen.
- a desired print design transparent sheet may be laid onto an emulsion coated screen.
- the screen may be exposed to UV light and the exposed area may be hardened.
- the unexposed area may be washed away using water.
- the screen may be placed on a printing press.
- the substrate may be placed on a flat printing board underneath the screen and the screen may be lowered onto the printing board.
- the chalcogenide glass dissolution based ink may be added to a top of the screen and a squeegee may be used to pull the ink along the full length of the screen.
- the ink may then transfer through the open areas of the stencil design.
- the desired design may be imprinted on the substrate.
- a thickness of the printed film can be varied by changing an emulsion thickness of the screen.
- a chalcogenide glass ink 700 may include chalcogenide glass particles 702 dissolved in a solvent 704 .
- the solvent 704 may obstruct electrical conduction within the chalcogenide glass ink 700 .
- Sintering may combine particles of chalcogenide glass to create a solid film. This may form a conductive printed pattern.
- the sintering process may depend on factors, such as the composition of the solution, the particle size of the chalcogenide glass, a heat rate, a sintering temperature, a sintering time, liquid phase formation properties, and so on.
- the sintering process may also help the printed pattern or film to have better adhesion to the substrate.
- the basic sintering process may expose the printed film to heat, intense light, microwave radiation, plasma, or an electric field, which may trigger the formation of continuous films.
- the main challenge may be to remove the solvent from the surface of the printed pattern and to break down polymer backbones of the solution. Since the chalcogenide glass may be a photosensitive material, a thermal sintering process may be more appropriate.
- a chalcogenide ink 800 which may correspond to the chalcogenide ink 700 , is depicted after evaporation has occurred.
- FDA or PA may be used as the solvent 704 .
- the boiling point of EDA may be 116° C.
- the boiling point of PA may be 51° C.
- the printed film may be placed into a vacuum furnace at 100° C. for 24 hours. In this phase, the solvent 704 of the dissolution based ink may be evaporated from a surface of the printed film, placing the chalcogenide glass particles 704 in close contact.
- a dissolution based chalcogenide ink 900 which may correspond to the chalcogenide ink 700 and to the chalcogenide glass ink 800 , is depicted after a second sintering phase has occurred.
- the second sintering phase may include heating the chalcogenide glass ink 900 to 130° C. for 24 hours.
- the particles 702 of the printed film may agglomerate and create a solid film.
- a vacuum furnace window may be covered with Aluminum to avoid light and assist with the occurrence of photoinduced processes in the sintering films, due to the photosensitivity properties of the chalcogenide glass.
- the temperature may be increased in increments of 20° C. with a hold of 15 minutes between them starting at room temperature and reaching 100° C. slowly during the first phase of the sintering process to avoid cracks formation on the printed films.
- an EDA based Ge30Se70 ink printed into a film composition had about 1% variance from the bulk materials used to formulate the ink.
- a PA-based Ge30Se70 printed film may vary by about 5% to 6% as compared to the bulk material.
Abstract
Description
- This application claims priority to, and the benefit of, U.S. Provisional Patent Application No. 62/943,031, filed on Dec. 3, 2019, and entitled “Materials Characterization of Thin Films Printed with Ge20Se80 Ink,” and U.S. Provisional Patent Application No. 62/943,044, filed on Dec. 3, 2019, and entitled “Studies and Analysis of GexSe100-x Based Spin Coated Chalcogenide Thin Films,” the contents of each of which are incorporated by reference herein in their entirety.
- This invention was made with Government support under contract number FPK809-SB-001 awarded by NASA. The Government has certain rights in the invention.
- This disclosure is generally related to the field of additive manufacturing and, in particular, to chalcogenide glass nanoparticle-based ink for additive manufacturing and chalcogenide glass ink obtained by dissolution.
- Chalcogenide glasses and electrical systems made with chalcogenide glasses may be beneficial for several reasons. For example, chalcogenide glasses may include up to 5% impurities without affecting their electrical performance. They may also be radiation hard. They can further have various optical properties for use in sensing and communication systems. Based on these properties, chalcogenide glasses offer a wide range of applications including phase change memory, temperature sensing, infrared laser power delivery, high-speed communications, and ultra-fast switching.
- Chalcogenide glass layers may typically be formed through conventional deposition methods, such as evaporative deposition techniques. These techniques may be costly and may not be suitable from some applications. Additive manufacturing technologies may help reduce the cost of manufacturing in general, however, typical additive manufacturing techniques rely on inks that include the desired material. Traditional additive manufacturing inks may not be compatible with the properties of chalcogenide glasses. Other disadvantages may exist.
- In an embodiment, an additive manufacturing ink composition may include a fluid medium and a chalcogenide glass suspended within the fluid medium to form a chalcogenide glass mixture solution. It should be noted that, as used herein, the term “solution” may refer to a solute dissolved in a solvent, or a suspension of nanoparticles in a fluid medium, which may not be dissolved. The additive manufacturing ink composition may further include a surfactant.
- In some embodiments, the fluid medium includes terpineol or cyclohexanone. In some embodiments, the chalcogenide glass includes a variety of glass compositions, such as Ge—Se, Ge—S, Ge—Sn—Se. Ge—Sn—S Ge—Sb—Te, Ge—Pb—S, and other chalcogenide glass systems. In some embodiments, the surfactant includes ethyl cellulose. In some embodiments, the chalcogenide glass mixture includes between 0.15 grams of chalcogenide glass per milliliter of the fluid medium and 0.3 grams of chalcogenide glass per milliliter of the fluid medium. In some embodiments, the chalcogenide glass mixture includes 0.12 grams of the surfactant per milliliter of the fluid medium.
- In an embodiment, a method for forming an additive manufacturing ink includes wet milling a chalcogenide glass in a fluid medium and a surfactant to produce a chalcogenide glass mixture. The method further includes, after wet milling the chalcogenide glass, processing the chalcogenide glass mixture to reduce an average particle size of the chalcogenide glass.
- In some embodiments, the method includes synthesizing the chalcogenide glass from bulk materials having 5N purity using a melt quenching process. In some embodiments, the fluid medium is free of amines. In some embodiments, the fluid medium includes cyclohexanone. In some embodiments, the surfactant includes ethyl cellulose. In some embodiments, processing the chalcogenide glass mixture includes ultrasonicating the chalcogenide glass mixture and centrifuging the chalcogenide glass mixture. In some embodiments, the method includes adjusting a viscosity of the chalcogenide glass mixture by adding additional fluid medium to the chalcogenide glass mixture. In some embodiments, after adjusting the viscosity of the chalcogenide glass mixture, the chalcogenide glass mixture includes between 0.15 grams of chalcogenide glass per milliliter of the fluid medium and 0.3 grams of chalcogenide glass per milliliter of the fluid medium. In some embodiments, after adjusting the viscosity of the chalcogenide glass mixture, the chalcogenide glass mixture includes 0.12 grams of the surfactant per milliliter of the fluid medium. In an embodiment, during the processing of the chalcogenide glass mixture, the average particle size of the chalcogenide glass is reduced to less than or equal to 100 nm.
- In an embodiment, a method for forming a dissolution based chalcogenide glass ink includes dissolving a chalcogenide glass into an amine-based solvent to form a chalcogenide glass solution. The method further includes filtering the chalcogenide glass solution.
- In some embodiments, the solvent includes ethylenediamine or propylamine. In some embodiments, dissolving the chalcogenide glass into the amine-based solvent includes stirring the chalcogenide glass and the solvent using a magnetic stirrer at the rate of 700 rpm for at least 72 hours. In some embodiments, the method includes synthesizing the chalcogenide glass from bulk materials having 5N purity using a melt quenching process. In some embodiments, the method includes filtering the chalcogenide glass solution through a filter. In some embodiments, the method includes adding terpineol to the chalcogenide glass solution to increase its viscosity. In some embodiments, particles of chalcogenide glass from the chalcogenide glass solution are configured to agglomerate into a solid film upon application of a two-part sintering process. In some embodiments, the two-part sintering process includes heating the chalcogenide glass solution in a vacuum furnace to 100° C. for at least 24 hours and heating the chalcogenide glass solution to 130° C. for at least 24 hours.
-
FIG. 1 depicts an embodiment of an additive manufacturing ink obtained by dissolution or milling to nanoparticle size with added solvent. -
FIG. 2 depicts an embodiment of a method for forming an additive manufacturing ink. -
FIG. 3 depicts a transformation of bulk elements to bulk chalcogenide glass particles. -
FIG. 4 depicts an embodiment of a chalcogenide glass paste. -
FIG. 5 depicts the formation of a chalcogenide glass nanoparticle ink with a predetermined viscosity. -
FIG. 6 depicts an embodiment of a method for making a dissolution based chalcogenide glass ink. -
FIG. 7 depicts a chalcogenide glass ink including glass particles dissolved in a solvent. -
FIG. 8 depicts a chalcogenide glass ink after evaporation has occurred. -
FIG. 9 depicts a dissolution based chalcogenide ink after a second sintering phase has occurred. - While the disclosure is susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and will be described in detail herein. However, it should be understood that the disclosure is not intended to be limited to the particular forms disclosed. Rather, the intention is to cover all modifications, equivalents and alternatives falling within the scope of the disclosure.
- Referring to
FIG. 1 , an embodiment of an additive manufacturing ink is depicted. In the case ofFIG. 1 , the additive manufacturing ink may be a chalcogenideglass nanoparticle ink 100. The depictions ofFIG. 1 are for clarity and may accurately depict the shape and proportions of the components of the chalcogenideglass nanoparticle ink 100. The chalcogenideglass nanoparticle ink 100 may include afluid medium 102, achalcogenide glass 104, and asurfactant 106. - The
fluid medium 102 may include cyclohexanone (C6H100), which may have a boiling point of 156° C. and a viscosity 2.02 cP at 25° C. This high boiling point may prevent the fluid medium 102 from evaporating while flowing through a nozzle of a printer or of other piece of additive manufacturing equipment. Further, cyclohexanone may not react with thechalcogenide glass 104. Other compositions may also be used as thefluid medium 102. In order to reduce the risk of reaction with printer parts and nozzles, thefluid medium 102 may be free of amines. Amines may be more reactive with types of plastic that may be used in additive manufacturing. - The
surfactant 106 may include ethyl cellulose (n-CH2CH3). As thesurfactant 106, the ethyl cellulose may include long chain polymers that can connect themselves to thechalcogenide glass 104 and prevent agglomeration. Thus, a texture and viscosity of the chalcogenideglass nanoparticle ink 100 may be maintained. - The
chalcogenide glass 104 may include multiple compositions, such as a germanium-sulfide (Ge—S), a germanium-selenide (Ge—Se), a germanium-tin-sulfide (Ge—Sn—S), a germanium-tin-selenide (Ge—Sn—Se), a germanium-antimony-telleride (Ge—Sb—Te), or a germanium-lead-sulfide (Ge—Pb—S). Other possibilities may also exist. Thechalcogenide glass 104 may be mixed with thefluid medium 102 at a concentration of between 0.15 grams of chalcogenide glass per milliliter of thefluid medium 102 and 0.3 grams of chalcogenide glass per milliliter of thefluid medium 102. Thesurfactant 106 may be mixed with thefluid medium 102 at a concentration of 0.12 grams of thesurfactant 106 per milliliter of thefluid medium 102. An average particle size of thechalcogenide glass 104 may be less than or equal to 100 nm. Hence, thechalcogenide glass 104 may be referred to as nanoparticles. - A benefit of the chalcogenide
glass nanoparticle ink 100 is that it may be used with printing processes and other additive manufacturing processing to form chalcogenide glass layers. Using printing processes may be less expensive than typical vapor deposition processes. Further, the chalcogenideglass nanoparticle ink 100 may include components that do not harm typical printers. Other benefits may exist. - Referring to
FIG. 2 , an embodiment of amethod 200 for forming an additive manufacturing ink is depicted. Themethod 200 may include synthesizing a chalcogenide glass, at 202. Some of the options for the chalcogenide glass include germanium-sulfide (Ge—S), germanium-selenide (Ge—Se), germanium-tin-sulfide (Ge—Sn—S), germanium-tin-selenide (Ge—Sn—Se), germanium-antimony-telluride (Ge—Sb—Te), and germanium-lead-sulfide (Ge—Pb—S) because they are thermally stable, have wide glass forming regions, and may be less toxic as compared to other chalcogenides, for example those containing Amines. Further, ternaries such as Pb2Ge8S15 and Sn2Ge8S15 may belong to a family of chalcogenide glasses where the members have more than one crystallization temperature. These chalcogenide glasses could be beneficial for increasing temperature sensing resolutions and could also make sensing devices more compact. - Ge20Se80, Ge30Se70, Ge33Se67, Ge40Se60, Sn2Ge8S15, Ge2Sb2Te5, and Pb2Ge8S15 bulk glasses may be synthesized through melt quenching technique. Pure 5N elements may be weighed and loaded into quartz ampules, which are sealed under a vacuum at about 10−4 mbar. The glass synthesis may be carried out in a programmable tube furnace for 168 hours with a peak temperature of 750° C. The furnace may be programmed at different rates, depending on the composition, to reach 750° C. within the first 24 hours of synthesis with some holdings at characteristic temperatures. The quartz ampules may be kept at the highest temperature for 168 hours (about one week). This may result in a good homogenization of the melt. The resulting glass may be quenched in water from a temperature of 20° C. above the melting temperature for the synthesized composition as can be derived from phase diagrams.
- The
method 200 may further include crushing the chalcogenide glass into a chalcogenide glass powder, at 204. For example, after synthesis, a chalcogenide glass may include an uneven distribution of chunks and shards. In order to further process it, it may be beneficial to crush the chalcogenide glass into substantially more uniform particles. - The
method 200 may also include wet milling the chalcogenide glass powder, at 206. For milling 2 mm stainless steel milling balls may be used. The starting particle size of the chalcogenide glass may be smaller than the milling balls. An agate mortar and pestle may be used to ensure that particles within the chalcogenide glass powder less than about 2 mm. In general, ball milling can be done either dry or wet. In this case, wet milling may help prevent particle agglomeration. Further, the use of a surfactant during milling may produce finer particles and also reduce wastage of material by preventing particle adhesion to a milling jar and to the milling balls. The chalcogenide glass (e.g., germanium-selenide), the surfactant (e.g., ethyl cellulose) and the fluid medium (e.g., cyclohexanone) may be mixed and introduced into a milling jar with the milling balls. - Ethyl cellulose may takes some time to dissolve in cyclohexanone. However, un-dissolved ethyl cellulose may not have a significant impact the milling and may be dissolved during the process instead of before the process begins. The fluid medium may be selected to prevent chemical reaction with either the chalcogenide glass particles or the surfactant.
- In some cases, a ball mill may not be designed for continuous production. In these cases, it may be set to mill for 30 minutes, pause for 30 minutes, and then repeat the process until the milling time has been completed. During milling, the temperature may be kept below 50° C. to prevent undesired crystallization of the chalcogenide glass particles. Milling may be continued until a particle size of the chalcogenide glass becomes saturated.
- The
method 200 may include determining whether a particle size of the chalcogenide glass is about 250 nm, at 208. If the target particle size has not been reached, themethod 200 may include continuing to wet mill the chalcogenide glass power, at 206. A dynamic Light Scattering (DLS) system may be used to measure the particle size every 24 hours. DLS utilizes light scattering to measure particle size. Pure cyclohexanone may be poured in a vendor recommended glass cuvette. A drop of ink may be mixed with the cyclohexanone. Individual particle sizes may then be determined using DLS. - If the target particle size has been reached, then the
method 200 may include mixing the resulting paste with additional fluid medium, at 210. Milling alone may not result in a desired viscosity. After ball milling the chalcogenide glass mixture may come out as a paste. A viscosity between 8 cP and 24 cP may be desirable for an additive manufacturing process. For final adjustment of the ink viscosity, cyclohexanone and ethyl cellulose may be added. For example, another 50 ml of cyclohexanone may be added to the paste to prepare a less viscous solution. In an example preparation, a good concentration was found to be between 0.15 g/ml and 0.3 g/ml of chalcogenide glass in cyclohexanone and about 0.12 g/ml of ethyl cellulose in cyclohexanone. Further, a particle size between 100 nm and 270 nm showed good results in terms of processing and device performance. In some embodiments, this mixing of the paste with additional fluid medium may be performed after the following steps of ultrasonicating and centrifuging. - The
method 200 may further include ultrasonicating the mixture, at 212. For example, an ultrasonicator may utilize a probe to transfer vibrational energy to the mixture. The diameter of the probe may be selected based on the volume of the mixture. For example, a 2 mm diameter probe may be used for a 30 ml mixture. Other possibilities may exist based on experimentation. To reduce the size of the particles, the mixture may be sonicated for about 2½ hours. A diameter of the particles after ultrasonication may be as low as 145 nm. However, the average size may be much higher due to a wide variability in particle size. Further ultrasonication can be used to both disperse and reduce particle size. For example, in 10 to 12 hours ultrasonication can reduce the average particle size from its bulk size to less than 250 nm. - The
method 200 may also include centrifuging the mixture, at 214. Centrifuging the mixture at 4500 rpm for about 1.5 hours may help create a uniform particle size within the mixture. The resulting mixture may have chalcogenide glass nanoparticles having a diameter of less than 100 nm, which may be sufficient for sintering or melting the particles at a temperature below 427° C., which may be lower than the lowest crystallization temperature of the materials used in the mixture. - The
method 200 may include determining whether a particle size of the chalcogenide glass less than 100 nm, at 216. If the target particle size has not been reached, themethod 200 may include repeatedly ultrasonicating the mixture, at 212, and centrifuging the mixture, at 214. If the target particle size has been reached, then the resulting ink may be ready for printing, at 218. - A benefit of the
method 200 is that it may be used to form a chalcogenide glass nanoparticle ink for printing in conventional additive printers. Using printers may be less expensive than typical vapor deposition processes for chalcogenide glass layers. Further, the chalcogenide glass nanoparticle ink may include components that do not harm typical printers. Other benefits may exist. - Referring to
FIG. 3 , atransformation 300 of bulk elements to bulkchalcogenide glass particles 306 is depicted. For example,bulk germanium 302 andbulk selenium 304 may be synthesized into chalcogenide glass and then crushed into a powder that includes thechalcogenide glass particles 306. Thechalcogenide glass particles 306 may correspond to a state after thestep 204 of themethod 200. It should be noted that the germanium-selenide composition depicted inFIG. 3 is only for example, purposes. Other compositions may exist as described herein. The bulk chalcogenide glass powder may have anaverage diameter 308 that may be less than about 2 mm after thetransformation 300. - Referring to
FIG. 4 , an embodiment of achalcogenide glass paste 400 is depicted. Thepaste 400 may correspond to a state after thestep 208 of themethod 200. For example, thepaste 400 may be the result of wet milling as described herein. Thepaste 400 may include afluid medium 402,chalcogenide glass particles 404, and asurfactant 406. Thechalcogenide glass particles 404 may have adiameter 408 of about 250 nm. - Referring to
FIG. 5 , the formation of a chalcogenideglass nanoparticle ink 510 with a desired viscosity is depicted. For example, thepaste 400 may be mixed with additional fluid medium 502 to reduce a concentration of thechalcogenide glass particles 404 and thesurfactant 406 within the combinedfluid medium 512. In some cases, the addition of theadditional fluid medium 502 may be performed after thestep 208 ofmethod 200, as shown inFIG. 2 . In other cases, theadditional fluid medium 502 may be added after theultrasonication step 212 and thecentrifuge step 214. - Amines, as described herein, may be used to make dissolution-based chalcogenide glass inks. In some cases, the amines described herein may be reactive with various parts of printers. For example, the chalcogenide glass mixtures used may include corrosive fluid mediums or solvents, such as amine-based mediums. These mixtures may not be suitable for many printing applications because they can damage printers and printer components if made from plastic polymers. However, these inks may be appropriate for other additive manufacturing processes, such as screen printing, nScrypt printer, and spin coating.
- Referring to
FIG. 6 , an embodiment of amethod 600 for making a dissolution based chalcogenide glass ink is depicted. Themethod 600 may include synthesizing a chalcogenide glass, at 602. The process of synthesizing the chalcogenide glass may be the same process as described with reference to themethod 200. In particular, Ge20Se80, Ge30Se70, Ge33Se67, Ge40Se60, Sn2Ge8S15, Ge2Sb2Te5, and Pb2Ge8S15 bulk glasses may be synthesized through melt quenching technique using pure 5N elements. - The
method 600 may further include crushing the chalcogenide glass into a chalcogenide glass powder, at 604. The crushing may be performed using an agate mortar and pestle. Other techniques are possible. - The
method 600 may also include dissolving the chalcogenide glass powder into a solvent, at 606. Amine solvents may be capable of dissolving the chalcogenide glass powder. Examples of amines that may be used are ethylenediamine (EDA) and propylamine (PA). Other solvents are possible. A volumetric flask may be used to perform the mixing. The dissolution rate of Ge—Se based chalcogenide glass, for example, into an amine-based solvent may be about 0.08 g per 20 ml. To speed up the dissolution process, the solution may be stirred by using a magnetic stirrer at a rate of 700 rpm for 72 hours. During the process, a lid of the volumetric flask may be kept closed by para-film to prevent evaporation. - The
method 600 may include increasing a viscosity of the solution, at 608. For example, terpineol may be added to the solution to increase its viscosity. The terpineol and the increased viscosity may improve a resolution of a resulting printed film. In some applications 5% to 10% of terpineol is sufficient to achieve a good resolution for screen-printed patterns. - The
method 600 may further include performing vacuum filtration of the solution, at 610. For example, the solution may be filtered through a 0.025 μm nylon filter using a vacuum filtration technique. The filtration may remove larger particles of chalcogenide glass that have not been dissolved in the solvent. In some embodiments, thestep 608 of increasing the viscosity of the solution may be performed after thestep 610 of filtering the solution. - The resulting ink may be ready for printing, at 612. Before the printing process, the dissolution based ink may be characterized using a tensiometer. A contact angle of the ink when applied to a substrate may provide information about how well the ink will spread over the substrate. It may be an important indicator of proper ink viscosity and the quality of the ink formulation process.
- The tensiometer may be used to measure the contact angle by applying a droplet of ink to a stage and then analyzing image data of the droplet. First, the stage may be flattened to ensure that the droplet of ink does not move during deposition. After the droplet is deposited on the stage, an image may be recorded by a camera. The image may be analyzed using software to determine the contact angle.
- The prepared ink can be applied for printing on a substrate using a screen printer or a 3D printer or by spin coating the ink on the substrate. In the case of screen printing, a monofilament polyester fabric may be stretched extremely tightly on a metal frame. A photosensitive emulsion may be coated over the fabric to form a stencil. The combination of the stencil and the metal frame may form a screen. After drying the photosensitive emulsion, the desired printing design may be transferred to the screen. In some screen printing processes, a desired print design transparent sheet may be laid onto an emulsion coated screen. The screen may be exposed to UV light and the exposed area may be hardened. The unexposed area may be washed away using water.
- The screen may be placed on a printing press. The substrate may be placed on a flat printing board underneath the screen and the screen may be lowered onto the printing board. The chalcogenide glass dissolution based ink may be added to a top of the screen and a squeegee may be used to pull the ink along the full length of the screen. The ink may then transfer through the open areas of the stencil design. As a result, the desired design may be imprinted on the substrate. A thickness of the printed film can be varied by changing an emulsion thickness of the screen.
- After the printing process, a sintering process may be applied to the printed ink. The printed and dried film patterns may be highly resistive due to the inconsistencies in the films, which may not be sufficient for some applications. For example, referring to
FIG. 7 , achalcogenide glass ink 700 may includechalcogenide glass particles 702 dissolved in a solvent 704. The solvent 704 may obstruct electrical conduction within thechalcogenide glass ink 700. Sintering may combine particles of chalcogenide glass to create a solid film. This may form a conductive printed pattern. The sintering process may depend on factors, such as the composition of the solution, the particle size of the chalcogenide glass, a heat rate, a sintering temperature, a sintering time, liquid phase formation properties, and so on. The sintering process may also help the printed pattern or film to have better adhesion to the substrate. The basic sintering process may expose the printed film to heat, intense light, microwave radiation, plasma, or an electric field, which may trigger the formation of continuous films. The main challenge may be to remove the solvent from the surface of the printed pattern and to break down polymer backbones of the solution. Since the chalcogenide glass may be a photosensitive material, a thermal sintering process may be more appropriate. - Referring to
FIG. 8 , achalcogenide ink 800, which may correspond to thechalcogenide ink 700, is depicted after evaporation has occurred. As mentioned before, FDA or PA may be used as the solvent 704. The boiling point of EDA may be 116° C., and the boiling point of PA may be 51° C. The printed film may be placed into a vacuum furnace at 100° C. for 24 hours. In this phase, the solvent 704 of the dissolution based ink may be evaporated from a surface of the printed film, placing thechalcogenide glass particles 704 in close contact. - Referring to
FIG. 9 , a dissolution basedchalcogenide ink 900, which may correspond to thechalcogenide ink 700 and to thechalcogenide glass ink 800, is depicted after a second sintering phase has occurred. The second sintering phase may include heating thechalcogenide glass ink 900 to 130° C. for 24 hours. In this phase, theparticles 702 of the printed film may agglomerate and create a solid film. A vacuum furnace window may be covered with Aluminum to avoid light and assist with the occurrence of photoinduced processes in the sintering films, due to the photosensitivity properties of the chalcogenide glass. The temperature may be increased in increments of 20° C. with a hold of 15 minutes between them starting at room temperature and reaching 100° C. slowly during the first phase of the sintering process to avoid cracks formation on the printed films. - In an example, an EDA based Ge30Se70 ink printed into a film composition had about 1% variance from the bulk materials used to formulate the ink. As another example, a PA-based Ge30Se70 printed film may vary by about 5% to 6% as compared to the bulk material.
- Although various embodiments have been shown and described, the present disclosure is not so limited and will be understood to include all such modifications and variations as would be apparent to one skilled in the art.
Claims (25)
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US201962943044P | 2019-12-03 | 2019-12-03 | |
US17/111,316 US20210163766A1 (en) | 2019-12-03 | 2020-12-03 | Chalcogenide glass based inks obtained by dissolution or nanoparticles milling |
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US17/111,353 Active 2041-10-29 US11845870B2 (en) | 2019-12-03 | 2020-12-03 | Thin films printed with chalcogenide glass inks |
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