# US 10,483,093 B2 · Plasma source and methods for depositing thin film coatings using plasma enhanced chemical vapor deposition > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,483,093 B2 - Document ID: US10483093B2 - Status: Granted - Kind: B2 - Application number: 14/148,606 - Filed: 2014-01-06 - Published: 2014-08-07 - Granted: 2019-11-19 - Earliest claimed: 2008-08-04 - Assignees: Agc Flat Glass North America, Inc.; Asahi Glass Company, Limited; Agc Glass Europe - Applicants: AGC Flat Glass North America, Inc.; Asahi Glass Co., Ltd.; AGC Glass Europe S.A. - Inventors: Peter Maschwitz - Web page: https://patentgrep.com/patent/US10483093B2 ## CPC - H01J 37/32596: {Hollow cathodes} - C03C 17/245: by deposition from the vapour phase - C03C 17/2456: {Coating containing TiO2} - C23C 16/402: {Silicon dioxide} - C23C 16/45517: {Confinement of gases to vicinity of substrate} - C23C 16/503: using DC or AC discharges - C23C 16/513: using plasma jets - H01J 37/32036: {AC powered} - H01J 37/3266: {Magnetic control means} - H01J 37/32568: {Relative arrangement or disposition of electrodes; moving means} - H01J 37/32724: {Temperature} - H05H 1/24: Generating plasma {(nuclear fusion reactors G21B1/00; gas-filled discharge reactors H01J37/32)} - H05H 1/42: with provisions for introducing materials into the plasma, e.g. powder or liquid {(arc stabilising or constricting arrangements H05H1/3405; coaxial protecting fluids H05H1/341)} - H05H 1/46: using applied electromagnetic fields, e.g. high frequency or microwave energy (H05H1/26 takes precedence) - C03C 2217/213: SiO2 - C03C 2218/153: by plasma-enhanced cvd - H01J 2237/3321: CVD [Chemical Vapor Deposition] - H01J 2237/3328: adhesion, stress, lift-off of deposited films - H05H 2001/466 - H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H) - 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 - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) - H05H: PLASMA TECHNIQUE (apparatus or processes specially adapted for producing X-rays H05G2/00); PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS ## Abstract The present invention provides novel plasma sources useful in the thin film coating arts and methods of using the same. More specifically, the present invention provides novel linear and two dimensional plasma sources that produce linear and two dimensional plasmas, respectively, that are useful for plasma-enhanced chemical vapor deposition. The present invention also provides methods of making thin film coatings and methods of increasing the coating efficiencies of such methods. ## Claims ### Claim 1 A plasma source forming a coating using plasma enhanced chemical vapor deposition (PECVD) comprising: i) a first electron emitting surface and a second electron emitting surface separated by a gas containing space, wherein a first restricted opening is disposed in the first electron emitting surface and a second restricted opening is disposed in the second electron emitting surface, wherein the first and second restricted openings are configured to face the substrate to be coated, wherein the first electron emitting surface and the second electron emitting surface are positioned so that a current comprising secondary electrons flows from the first electron emitting surface through the first restricted opening, through the gas containing space, and through the second restricted opening to the second electron emitting surface; ii) at least one precursor gas manifold supplying precursor gas; iii) at least one reactant gas manifold supplying reactant gas; iv) a power source to which the electron emitting surfaces are electrically connected supplying a voltage that alternates between positive and negative to cause the voltage supplied to the first electron emitting surface to be out of phase with the voltage supplied to the second electron emitting surface and creating a current comprising electrons that flows between the electron emitting surfaces; and v) one or more walls for pressure control, wherein the operating gas pressure between the first electron emitting surface and the second electron emitting surface is 1 millibar to 10−3 millibar; wherein the current creates a plasma between the electron emitting surfaces that is substantially uniform over its length in the substantial absence of Hall current; wherein the at least one reactant gas manifold is positioned so that reactant gas flows along the electron emitting surfaces; wherein the at least one precursor gas manifold is positioned so that the precursor gas flows into the gas containing space separating the electron emitting surfaces; and wherein the plasma energizes, partially decomposes, or fully decomposes the precursor gas proximate to the substrate to be coated, and wherein the plasma source is able to produce a coating at a rate of deposition of at least 0.2 μm/second. ### Claim 2 (depends on 1) The plasma source of claim 1, wherein the first electron emitting surface and the second electron emitting surface are hollow cathodes. ### Claim 3 (depends on 1) The plasma source of claim 1, wherein the first electron emitting surface and the second electron emitting surface are comprised of a porous material. ### Claim 4 (depends on 1) The plasma source of claim 1, wherein the electron emitting surfaces are at a temperature of at least 600° C. to 2000° C. ### Claim 5 (depends on 4) The plasma source of claim 4, wherein the electron emitting surfaces are at a temperature of at least 800° C. to 1200° C. ### Claim 6 (depends on 1) The plasma source of claim 1, further comprising electrical insulators that electrically isolate conductive regions other than electron emitting surfaces or ion accelerating electrodes. ### Claim 7 (depends on 1) The plasma source of claim 1, further comprising a secondary electrode that generates a secondary electric field, wherein the secondary electric field is projected into the gas containing space through which the current passes. ### Claim 8 (depends on 7) The plasma source of claim 7, wherein the secondary electric field accelerates electron and ion movement in the gas containing space through which the current passes. ### Claim 9 (depends on 1) The plasma source of claim 1, further comprising a magnetic field source proximate to the gas containing space, wherein the magnetic field source projects a magnetic field into the gas containing space such that the plasma formed is densified by the magnetic field in the gas containing space. ### Claim 10 (depends on 1) The plasma source of claim 1, wherein the power source is a bipolar power source. ### Claim 11 (depends on 10) The plasma source of claim 10, wherein the bipolar power source supplies an alternating voltage. ### Claim 12 (depends on 10) The plasma source of claim 10, wherein the bipolar power source supplies a pulsed voltage. ### Claim 13 (depends on 1) The plasma source of claim 1, wherein the plasma created by the plasma source is at least 0.5 meters in length. ### Claim 14 (depends on 1) The plasma source of claim 1, wherein the plasma created by the plasma source is at least one meter in length. ### Claim 15 (depends on 1) The plasma source of claim 1, wherein the plasma created by the plasma source is linear. ### Claim 16 (depends on 1) The plasma source of claim 1, wherein the plasma created by the plasma source is two-dimensional. ### Claim 17 (depends on 1) The plasma source of claim 1, wherein the gas containing space contains at least one of a precursor gas and a reactant gas. ### Claim 18 (depends on 1) The plasma source of claim 1, wherein the precursor gas comprises one of metals, transition metals, boron, carbon, silicon, germanium, selenium, and combinations thereof. ### Claim 19 (depends on 1) The plasma source of claim 1, wherein the reactant gas comprises one of oxygen, nitrogen, halogens, hydrogen, and combinations thereof. ### Claim 20 (depends on 1) The plasma source of claim 1, wherein the plasma source is able to produce a coating at a rate of deposition of at least 0.3 μm/second. ### Claim 21 (depends on 1) The plasma source of claim 1, wherein the plasma source is able to produce a coating at a rate of deposition of at least 0.5 μm/second. ### Claim 22 A plasma source forming a coating using plasma enhanced chemical vapor deposition (PECVD) comprising: i) a first hollow cathode and a second hollow cathode comprising a first restricted opening disposed in the first hollow cathode and a second restricted opening disposed in the second hollow cathode, wherein the first and second restricted openings are configured to face the substrate to be coated, wherein the first hollow cathode and second hollow cathode are positioned so that a current comprising secondary electrons flows from the first hollow cathode through the first restricted opening, through the gas containing space, and through the second restricted opening to the second hollow cathode separated by a gas containing space, and wherein each hollow cathode comprises facing cathodic surfaces; ii) at least one precursor gas manifold supplying precursor gas; iii) at least one reactant gas manifold supplying reactant gas; iv) a power source to which the hollow cathodes are electrically connected supplying a voltage that alternates between positive and negative to cause the voltage supplied to the first hollow cathode to be out of phase with the voltage supplied to the second hollow cathode and creating a current comprising electrons that flows between the hollow cathodes; and v) one or more walls for pressure control, wherein the operating gas pressure between the first hollow cathode and the second hollow cathode is 1 millibar to 10−3 millibar; wherein the current creates a plasma between the hollow cathodes that is substantially uniform over its length in the substantial absence of Hall current; wherein the at least one reactant gas manifold is positioned so that reactant gas flows between the two facing cathodic surfaces of each hollow cathode; wherein the at least one precursor gas manifold is positioned so that the precursor gas flows into the gas containing space separating the hollow cathodes; and wherein the plasma energizes, partially decomposes, or fully decomposes the precursor gas proximate to the substrate to be coated, and wherein the plasma source is able to produce a coating at a rate of deposition of at least 0.2 μm/second. ### Claim 23 (depends on 22) The plasma source of claim 22, wherein the first hollow cathode and the second hollow cathode are comprised of a porous material. ### Claim 24 (depends on 22) The plasma source of claim 22, wherein the hollow cathodes are at a temperature of at least 600° C. to 2000° C. ### Claim 25 (depends on 22) The plasma source of claim 22, wherein the hollow cathodes are at a temperature of at least 800° C. to 1200° C. ### Claim 26 (depends on 22) The plasma source of claim 22, further comprising electrical insulators that electrically isolate conductive regions other than the hollow cathodes. ### Claim 27 (depends on 22) The plasma source of claim 22, further comprising a secondary electrode that generates a secondary electric field, wherein the secondary electric field is projected into the gas containing space through which the current passes. ### Claim 28 (depends on 27) The plasma source of claim 27, wherein the secondary electric field accelerates electron and ion movement in the gas containing space through which the current passes. ### Claim 29 (depends on 22) The plasma source of claim 22, further comprising a magnetic field source proximate to the gas containing space, wherein the magnetic field source projects a magnetic field into the gas containing space such that the plasma formed is densified by the magnetic field in the gas containing space. ### Claim 30 (depends on 22) The plasma source of claim 22, wherein the power source is a bipolar power source. ### Claim 31 (depends on 30) The plasma source of claim 30, wherein the bipolar power source supplies an alternating voltage. ### Claim 32 (depends on 30) The plasma source of claim 30, wherein the bipolar power source supplies a pulsed voltage. ### Claim 33 (depends on 22) The plasma source of claim 22, wherein the plasma created by the plasma source is at least 0.5 meters in length. ### Claim 34 (depends on 22) The plasma source of claim 22, wherein the plasma created by the plasma source is at least one meter in length. ### Claim 35 (depends on 22) The plasma source of claim 22, wherein the plasma created by the plasma source is linear. ### Claim 36 (depends on 22) The plasma source of claim 22, wherein the plasma created by the plasma source is two-dimensional. ### Claim 37 (depends on 22) The plasma source of claim 22, wherein the gas containing space contains at least one of a precursor gas and a reactant gas. ### Claim 38 (depends on 22) The plasma source of claim 22, wherein the precursor gas comprises one of metals, transition metals, boron, carbon, silicon, germanium, selenium, and combinations thereof. ### Claim 39 (depends on 22) The plasma source of claim 22, wherein the reactant gas comprises one of oxygen, nitrogen, halogens, hydrogen, and combinations thereof. ### Claim 40 (depends on 22) The plasma source of claim 22, wherein the plasma source is able to produce the coating at a rate of deposition of at least 0.3 μm/second. ### Claim 41 (depends on 22) The plasma source of claim 22, wherein the plasma source is able to produce the coating at a rate of deposition of at least 0.5 μm/second. ### Claim 42 A plasma source forming a coating using plasma enhanced chemical vapor deposition (PECVD) comprising: i) a plurality of pairs of electron emitting surfaces, each pair comprising a first electron emitting surface and a second electron emitting surface separated by a gas-containing space, wherein a first restricted opening is disposed in the first electron emitting surface and a second restricted opening is disposed in the second electron emitting surface, wherein the first and second restricted openings are configured to face the substrate to be coated, wherein the first electron emitting surface and the second electron emitting surface are positioned so that a current comprising secondary electrons flows from the first electron emitting surface through the first restricted opening, through the gas containing space, and through the second restricted opening to the second electron emitting surface, ii) at least one precursor gas manifold supplying a precursor gas; iii) at least one reactant gas manifold supplying a reactant gas; iv) a power source to which each pair of electron emitting surfaces is electrically connected supplying a voltage that alternates between positive and negative to cause the voltage supplied to the first electron emitting surface of each pair to be out of phase with the voltage supplied to the second electron emitting surface of each pair and creating a current comprising electrons that flows between the electron emitting surfaces of each pair; and iv. one or more walls for pressure control, wherein the operating gas pressure between the first electron emitting surface and the second electron emitting surface is 1 millibar to 10−3 millibar; wherein the plurality of pairs of electron emitting surfaces are disposed adjacently in an array; wherein the current creates a two dimensional plasma between the electron emitting surfaces of each pair that is substantially uniform in two dimensions in the substantial absence of Hall current; wherein the at least one reactant gas manifold is positioned so that reactant gas flows along the electron emitting surfaces; wherein the at least one precursor gas manifold is positioned so that the precursor gas flows into the gas containing space separating the electron emitting surfaces; and wherein the plasma energizes, partially decomposes, or fully decomposes the precursor gas proximate to the substrate to be coated, and wherein the plasma source is able to produce a coating at a rate of deposition of at least 0.2 μm/second. ### Claim 43 (depends on 42) The plasma source of claim 42, wherein the first electron emitting surface and the second electron emitting surface of each pair are hollow cathodes. ### Claim 44 (depends on 42) The plasma source of claim 42, wherein the first electron emitting surface and the second electron emitting surface of at least one pair are comprised of a porous material. ### Claim 45 (depends on 42) The plasma source of claim 42, wherein the electron emitting surfaces are at a temperature of at least 600° C. to 2000° C. ### Claim 46 (depends on 42) The plasma source of claim 42, wherein the electron emitting surfaces are at a temperature of at least 800° C. to 1200° C. ### Claim 47 (depends on 42) The plasma source of claim 42, further comprising electrical insulators that electrically isolate conductive regions other than the electron emitting surfaces. ### Claim 48 (depends on 42) The plasma source of claim 42, further comprising a secondary electrode that generates a secondary electric field, wherein the secondary electric field is projected into the gas containing space through which the current passes. ### Claim 49 (depends on 48) The plasma source of claim 48, wherein the secondary electric field accelerates electron and ion movement in the gas containing space through which the current passes. ### Claim 50 (depends on 42) The plasma source of claim 42, further comprising a magnetic field source proximate to the gas containing space, wherein the magnetic field source projects a magnetic field into the gas containing space such that the plasma formed is densified by the magnetic field in the gas containing space. ### Claim 51 (depends on 42) The plasma source of claim 42, wherein the power source is a bipolar power source. ### Claim 52 (depends on 51) The plasma source of claim 51, wherein the bipolar power source supplies an alternating voltage. ### Claim 53 (depends on 51) The plasma source of claim 51, wherein the bipolar power source supplies a pulsed voltage. ### Claim 54 (depends on 42) The plasma source of claim 42, wherein the plasma created by the plasma source is at least 0.5 meters in length. ### Claim 55 (depends on 42) The plasma source of claim 42, wherein the plasma created by the plasma source is at least one meter in length. ### Claim 56 (depends on 42) The plasma source of claim 42, wherein the plasma created by the plasma source is linear. ### Claim 57 (depends on 42) The plasma source of claim 42, wherein the plasma created by the plasma source is two-dimensional. ### Claim 58 (depends on 42) The plasma source of claim 42, wherein the gas containing space contains at least one of a precursor gas and a reactant gas. ### Claim 59 (depends on 42) The plasma source of claim 42, wherein the precursor gas comprises one of metals, transition metals, boron, carbon, silicon, germanium, selenium, and combinations thereof. ### Claim 60 (depends on 42) The plasma source of claim 42, wherein the reactant gas comprises one of oxygen, nitrogen, halogens, hydrogen, and combinations thereof. ### Claim 61 (depends on 42) The plasma source of claim 42, wherein the plasma source is able to produce the coating at a rate of deposition of at least 0.3 μm/second. ### Claim 62 (depends on 42) The plasma source of claim 42, wherein the plasma source is able to produce the coating at a rate of deposition of at least 0.5 μm/second. ### Claim 63 (depends on 1) The plasma source of claim 1, comprising a plurality of manifolds positioned consecutively, wherein each manifold supplies one or more precursor gases. ### Claim 64 (depends on 22) The plasma source of claim 22, comprising a plurality of manifolds positioned consecutively, wherein each manifold supplies one or more precursor gases. ### Claim 65 (depends on 42) The plasma source of claim 42, comprising a plurality of manifolds, wherein each manifold supplies one or more precursor gases. ### Claim 66 (depends on 1) The plasma source of claim 1, wherein the at least one precursor gas manifold comprises a tube. ### Claim 67 (depends on 1) The plasma source of claim 1, wherein the at least one reactant gas manifold comprises a tube. ### Claim 68 (depends on 22) The plasma source of claim 22, wherein the at least one precursor gas manifold comprises a tube. ### Claim 69 (depends on 22) The plasma source of claim 22, wherein the at least one reactant gas manifold comprises a tube. ### Claim 70 (depends on 42) The plasma source of claim 42, wherein the at least one precursor gas manifold comprises a tube. ### Claim 71 (depends on 42) The plasma source of claim 42, wherein the at least one reactant gas manifold comprises a tube. ### Claim 72 A plasma source forming a coating using plasma enhanced chemical vapor deposition (PECVD) comprising: i) a first electron emitting surface and a second electron emitting surface separated by a gas containing space, wherein a first restricted opening is disposed in the first electron emitting surface and a second restricted opening is disposed in the second electron emitting surface, wherein the first and second restricted openings are configured to face the substrate to be coated, wherein the first electron emitting surface and the second electron emitting surface are positioned so that a current comprising secondary electrons flows from the first electron emitting surface through the first restricted opening, through the gas containing space, and through the second restricted opening to the second electron emitting surface; ii) at least one precursor gas manifold supplying precursor gas; iii) at least one reactant gas manifold supplying reactant gas; iv) a power source to which the electron emitting surfaces are electrically connected supplying a voltage that alternates between positive and negative to cause the voltage supplied to the first electron emitting surface to be out of phase with the voltage supplied to the second electron emitting surface and creating a current comprising electrons that flows between the electron emitting surfaces; and v) one or more walls for pressure control, wherein the operating gas pressure between the first electron emitting surface and the second electron emitting surface is 1 millibar to 10−3 millibar; wherein the current creates a plasma between the electron emitting surfaces that is substantially uniform over its length in the substantial absence of Hall current; wherein the at least one reactant gas manifold is positioned so that reactant gas flows along the electron emitting surfaces; and wherein the plasma energizes, partially decomposes, or fully decomposes the precursor gas proximate to the substrate to be coated, and wherein the plasma source is able to produce a coating at a rate of deposition of at least 0.2 μm/second. ### Claim 73 (depends on 72) The plasma source of claim 72, wherein the at least one precursor gas manifold comprises a tube. ### Claim 74 (depends on 72) The plasma source of claim 72, wherein the at least one reactant gas manifold comprises a tube. ### Claim 75 (depends on 72) The plasma source of claim 72, wherein the first electron emitting surface and the second electron emitting surface are each hollow cathodes. ### Claim 76 (depends on 1) The plasma source of claim 1, wherein the electron emitting surfaces are separated from each other by at least 1 millimeter to 0.5 meters. ### Claim 77 (depends on 22) The plasma source of claim 22, wherein the hollow cathodes are separated from each other by at least 1 millimeter to 0.5 meters. ### Claim 78 (depends on 42) The plasma source of claim 42, wherein the electron emitting surfaces of each pair are separated from each other by at least 1 millimeter to 0.5 meters. ### Claim 79 (depends on 72) The plasma source of claim 72, wherein the electron emitting surfaces are separated from each other by at least 1 millimeter to 0.5 meters. ### Claim 80 (depends on 1) The plasma source of claim 1, wherein the electron emitting surfaces are separated by a dark space. ### Claim 81 (depends on 22) The plasma source of claim 22, wherein the hollow cathodes are separated by a dark space. ### Claim 82 (depends on 42) The plasma source of claim 42, wherein the electron emitting surfaces of each pair are separated by a dark space. ### Claim 83 (depends on 72) The plasma source of claim 72, wherein the electron emitting surfaces are separated by a dark space. ### Claim 84 (depends on 80) The plasma source of claim 80, wherein the dark space is filled with an insulating material. ### Claim 85 (depends on 81) The plasma source of claim 81, wherein the dark space is filled with an insulating material. ### Claim 86 (depends on 82) The plasma source of claim 82, wherein the dark space is filled with an insulating material. ### Claim 87 (depends on 83) The plasma source of claim 83, wherein the dark space is filled with an insulating material.