WO2000055388A2 - Method and apparatus for arc deposition - Google Patents
Method and apparatus for arc deposition Download PDFInfo
- Publication number
- WO2000055388A2 WO2000055388A2 PCT/US2000/003028 US0003028W WO0055388A2 WO 2000055388 A2 WO2000055388 A2 WO 2000055388A2 US 0003028 W US0003028 W US 0003028W WO 0055388 A2 WO0055388 A2 WO 0055388A2
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- WIPO (PCT)
- Prior art keywords
- plasma
- reactant
- chamber
- substrate
- nozzle
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/228—Gas flow assisted PVD deposition
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32422—Arrangement for selecting ions or species in the plasma
Definitions
- the present invention relates generally to a method and apparatus for deposition of reagents, and more particularly to an arc plasma deposition method and apparatus in which the reagents are evaporated into the plasma.
- PC polycarbonate
- UV radiation ultraviolet
- CVD chemical vapor deposition
- gaseous reagents which contain the desired constituents of the film.
- Energy required to pyrolyze the reactants is supplied by heating the substrate.
- the substrate is heated to a relatively high temperature, in the range of about 500 - 2000° F. These temperatures preclude application of the CVD process to heat sensitive substrate materials such as PC.
- PECVD plasma enhanced chemical vapor deposition
- PVD Physical vapor deposition
- Plasma spray can obtain the rates needed at high temperatures but not at the temperatures where PC is stable.
- coatings tend to be highly stressed and porous.
- Reactive sputtering can be achieved at the desired substrate temperatures, but the deposition rates are too slow for a cost effective process.
- Thermal or electron beam evaporation can provide high deposition rates, but generally produce coatings with low adhesion due to low energy ions. Thermal and electron beam evaporation are also unable to provide simultaneous coating of two sides of a substrate.
- Wire arc deposition is another coating method in which an arc is generated between a cathode and a wire of the material to be deposited.
- the wire is instantly melted, and the droplets are deposited onto the substrate.
- This method can deliver high coating rates, but the coatings typically have poor transparency and are porous.
- the films are also typically relatively thick, e.g. greater than the size of the droplets.
- a conventional approach to protection of the PC material is to use an organic UV absorber within a silicone hardcoat.
- the problem with this approach is that the organic UV absorbers degrade with time, thereby losing their ability to protect the PC.
- UV filter coating materials include zinc oxide (ZnO) and titanium dioxide (Ti0 2 ). These materials, however, have been conventionally deposited by sputtering which typically has a very low rate.
- ZnO zinc oxide
- Ti0 2 titanium dioxide
- U.S. Patent No. 4,871,580 describes a conventional sputtering technique whereby a solid source material is sputtered into a plasma. However, this technique results in a much slower deposition rate, and thus may not be practical for commercial applications.
- the present invention provides a method of coating a substrate, comprising the steps of generating a plasma which flows toward the substrate, evaporating a metallic reactant, and introducing the evaporated metallic reactant into the flowing plasma to project the metallic reactant onto the substrate.
- the present invention also provides an apparatus for depositing a coating on a substrate comprising a first chamber, an anode and a cathode for generating an arc in the first chamber, a second chamber to house the substrate, the second chamber being in fluid communication with the first chamber, a pump for reducing the pressure in the second chamber to a value below the pressure in the first chamber such that a plasma generated by the anode and the cathode flows into the second chamber toward the substrate, and an evaporator which evaporates a metallic reactant into the flowing plasma.
- the present invention also provides an evaporator comprising an evaporator chamber, a heating element in thermal contact with the evaporator chamber, a conduit mounted on the evaporator chamber to provide passage of a metal wire from a wire supply to said evaporator chamber, a motor adapted to feed the metal wire into said evaporator chamber; and a gas supply line coupled to the conduit.
- the present invention also provides a method for coating first and second sides of a substrate comprising generating a first plasma which flows toward the first surface of the substrate, generating a second plasma which flows toward the second surface of the substrate, evaporating a metallic reactant introducing the evaporated metallic reactant into the first plasma to project the metallic reactant onto the first surface of the substrate, and introducing a second reactant into the second plasma to project the second reactant onto the second surface of the substrate.
- Figure 1 is flow chart of a method according to one embodiment of the present invention.
- Figure 2 is a schematic cross-section of an example arc plasma deposition apparatus according to one embodiment of the present invention.
- Figure 3 is a cross-section view of a plasma generator and a nozzle according to one embodiment of the present invention.
- Figure 4 shows a cross-section view of ring-type inlet.
- Figure 5A shows a schematic view of the arc plasma deposition apparatus including an evaporation supply line according to one embodiment of the present invention.
- Figure 5B shows a schematic view of the arc plasma deposition apparatus including a modified evaporator according to one embodiment of the present invention.
- Figure 6 shows a schematic view of the arc plasma deposition apparatus including a distal evaporation inlet according to an alternative embodiment of the present invention.
- Figure 7 shows a schematic view of the arc plasma deposition apparatus including a crucible inlet according to an alternative embodiment of the present invention.
- Figure 8 shows a schematic view of the arc plasma deposition apparatus including an electron-beam evaporation system according to an alternative embodiment of the present invention.
- Figure 9 shows a schematic view of the arc plasma deposition apparatus including a purging system according to an alternative embodiment of the present invention.
- Figure 10 shows a schematic view of an arc plasma deposition apparatus capable of simultaneously coating both sides of a substrate according to an alternative embodiment of the present invention.
- the present invention relates to a method for the high rate application of a coating onto a substrate.
- the present invention relates to an arc plasma deposition technique for coating a UV filter material, such as zinc oxide (ZnO), indium zinc oxide (IZO), or aluminum zinc oxide (AZO) onto a glass or a polycarbonate sheet suitable for architectural or automotive glazing applications.
- This arc plasma deposition technique can yield excellent coating performance with high transparency, high UV absorbency, and low haze.
- this UV filter material is superior to prior ZnO filters and can be improved further by doping the ZnO composition with dopants, such as aluminum or indium, resulting in a coating material having the properties of improved stability, electrical conductivity, and a strong absorption band at about 350 nanometers (nm).
- dopants such as aluminum or indium
- an arc is generated in a first chamber between a cathode and an anode.
- the anode has a central aperture, typically in the form of a portion of a diverging cone, which opens into a low pressure second chamber.
- An inert carrier gas, introduced proximate to the cathode, is ionized by the arc between the cathode and anode to form a plasma.
- the plasma flows into the second chamber at high velocity as a plasma jet due to the pressure difference between the chambers.
- the second chamber may include a diverging, e.g. conical, nozzle which extends from the diverging aperture of the anode.
- the nozzle at its narrow end concentrates the plasma and reagents to enhance chemical reactions and reduce diffusion of the reagents in the second chamber.
- the area of the plasma is substantially increased to provide a larger deposition area.
- the present invention also relates to an apparatus that facilitates the high rate application of a UV filtering coating onto a substrate.
- an optically clear adherent coating can be deposited on one or both sides of a substrate using an arc plasma deposition apparatus with an evaporator for evaporating a reactant into the plasma.
- a zinc-based coating can be deposited onto the substrate at a controllable but sufficiently high rate.
- the resulting coated substrate has the characteristics of good transparency, good chemical stability, low haze, and high UV absorbency and/or infrared (IR) reflection.
- One embodiment provides a ZnO coating doped with indium (In) or aluminum (Al) that can be deposited at a high rate by a combined thermal evaporation and arc plasma deposition process.
- This method results in the formation of a transparent, electrically conductive, UV filter on a surface of the substrate.
- a polycarbonate (PC) substrate coated with ZnO can have an absorbency value in the UV (e.g., at 350 nanometers) from about 1.22 to about 4.55, for example.
- Absorbency also referred to as "optical density” or "OD" is defined as log(l/l 0 ), where l
- a first reactant is evaporated.
- the evaporated reactant is introduced or fed into a plasma jet.
- the evaporated reactant is deposited on a surface of the substrate.
- step 1 can be achieved by a physical vapor deposition (PVD) technique.
- PVD techniques include thermal evaporation and sputtering techniques.
- the basic mechanism of PVD is an atom-by-atom transfer of material from the solid phase to the vapor phase and back to the solid phase upon deposition on a substrate surface.
- a substance such as a metal
- This heating creates a vapor that contains a gaseous phase of the original solid substance.
- This reactant can then be introduced or fed into a plasma in step 2.
- the first reactant of step 1 can be a metal.
- the metal is selected from a group that includes zinc (Zn), zinc alloys, indium (In), titanium (Ti), cerium (Ce), and aluminum (Al).
- Zn is preferred for purposes of the present invention because of its absorption characteristics in the ultraviolet (UV) region of the electromagnetic spectrum.
- Zn is also acceptable for purposes of the present invention due to its melting point temperature and vapor pressure characteristics.
- the method of Fig. 1 can also be utilized for depositing coatings for other applications.
- metals such as Al and silver (Ag), utilized to filter out IR radiation, may also be deposited by the method of the present invention, as described in U.S. Serial No. (GE Docket No. RD-25,973), entitled "Infrared Reflecting
- an evaporator comprises a metal crucible.
- a nickel crucible with a tantalum (Ta) liner can be utilized as a suitable evaporator.
- the crucible can be wrapped with a heating element to control its temperature.
- the crucible is used to heat a metal reactant, such as Zn or a Zn alloy.
- a metal reactant such as Zn or a Zn alloy.
- Other metals with similar UV absorption characteristics can also be utilized in the method of the present invention as would be apparent to one of skill in the art given the present description.
- step 1 can further include the step of controlling the vapor pressure of the reactant. It has been observed that the vapor pressure of the reactant plays an important role in optimizing a coating deposition run. By controlling the vapor pressure, the deposition rate of the reactant onto the substrate can be more precisely controlled.
- One way to control the vapor pressure is to monitor and vary the temperature of the crucible. For example, as the vapor pressure of Zn is increased, more Zn is available for delivery into the plasma. With more Zn being delivered to the plasma, a high deposition rate of a Zn-based coating compound can be achieved. For example, when Zn has a vapor pressure of 100 milliTorr, it has a corresponding melting point of 405 degrees centigrade. Other metals, with similar vapor pressure characteristics, can be utilized in the method of the present invention.
- step 2 can be achieved by introducing, injecting or feeding the evaporated reactant directly into a plasma via a reactant or reagent supply line.
- the plasma comprises a plasma stream or plasma jet.
- a first inlet or opening can be provided to allow the flow of the first reactant into the plasma.
- the plasma can be created by a plasma generator, as discussed below.
- the first inlet can be located at or in close proximity to the anode of the plasma generator or, alternatively, at a distal point from the plasma generator.
- the first inlet can be used to introduce an evaporated metal such as zinc to the plasma jet.
- a second inlet can be located at or in close proximity to the anode of the plasma generator or, alternatively, at a distal point from the plasma generator.
- This second inlet can be used to introduce a second reactant, e.g. an oxidant such as oxygen, sulfur, or nitrous oxide to the plasma jet.
- a second reactant e.g. an oxidant such as oxygen, sulfur, or nitrous oxide
- the Zn vapor reactant enters the plasma and reacts with the oxygen supplied to the plasma.
- Oxygen is ionized by electron impact collisions or collisions with ionized inert gases, such as Argon (Ar), comprising the plasma or carrier gas.
- Argon Argon
- the substrate typically comprises a polymer resin.
- the substrate may comprise a polycarbonate.
- Polycarbonates suitable for forming the substrate are well- known in the art and generally comprise repeating units of the formula:
- R is a divalent aromatic radical of a dihydric phenol (e.g., a radical of 2,2-bis(4-hydroxyphenyl)-propane, also known as bisphenol A) employed in the polymer producing reaction; or an organic polycarboxylic acid (e.g. terphthalic acid, isophthaiic acid, hexahydrophthalic acid, adipic acid, sebacic acid, dodecanedioic acid, and the like).
- a dihydric phenol e.g., a radical of 2,2-bis(4-hydroxyphenyl)-propane, also known as bisphenol A
- organic polycarboxylic acid e.g. terphthalic acid, isophthaiic acid, hexahydrophthalic acid, adipic acid, sebacic acid, dodecanedioic acid, and the like.
- These polycarbonate resins are aromatic carbonate polymers which may be prepared by reacting one or more dihydric phenols
- Aromatic carbonate polymers may be prepared by methods well known in the art as described, for example, in U.S. Patent Nos. 3,161 ,615; 3,220,973; 3,312,659; 3,312,660; 3,313,777; 3,666,614; 3,989,672; 4,200,681 ; 4,842,941 ; and 4,210,699, all of which are incorporated herein by reference.
- the substrate may also comprise a polyestercarbonate which can be prepared by reacting a carbonate precursor, a dihydric phenol, and a dicarboxylic acid or ester forming derivative thereof.
- Polyestercarbonates are described, for example, in U.S. Patent Nos. 4,454,275; 5,510,448; 4,194,038; and 5,463,013.
- the substrate may also comprise a thermoplastic or thermoset material.
- suitable thermoplastic materials include polyethylene, polypropylene, polystyrene, polyvinylacetate, polyvinylalcohol, polyvinylacetal, polymethacrylate ester, polyacrylic acids, polyether, polyester, polycarbonate, cellulous resin, polyacrylonitrile, polyamide, polyimide, polyvinylchloride, fluorine containing resins and polysulfone.
- suitable thermoset materials include epoxy and urea melamine.
- Acrylic polymers are another material from which the substrate may be formed.
- Acrylic polymers can be prepared from monomers such as methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and the like.
- Substituted acrylates and methacrylates such as hydroxyethyl acrylate, hydroxybutyl acrylate, 2-ethylhexylacrylate, and n-butylacrylate may also be used.
- Polyesters can also be used to form the substrate.
- Polyesters are well-known in the art, and may be prepared by the polyesterification of organic polycarboxylic acids (e.g., phthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, terphthalic acid, isophthaiic acid, sebacic acid, dodecanedioic acid, and the like) or their anhydrides with organic polyols containing primary or secondary hydroxyl groups (e.g., ethylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol).
- organic polycarboxylic acids e.g., phthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, terphthalic acid, isophthaiic acid, sebacic acid, dodecanedioic acid, and the like
- organic polyols containing primary or secondary hydroxyl groups e.g
- Polyurethanes are another class of materials which can be used to form the substrate.
- Polyurethanes are well-known in the art, and are prepared by the reaction of a polyisocyanate and a polyol.
- useful polyisocyanates include hexamethylene diisocyanate, toluene diisocyanate, MDI, isophorone diisocyanate, and biurets and triisocyanurates of these diisocyanates.
- useful polyols include low molecular weight aliphatic polyols, polyester polyols, polyether polyols, fatty alcohols, and the like.
- Examples of other materials from which the substrate may be formed include acrylonitrile-butadiene-styrene, glass, VALOX® (polybutylenephthalate, available from General Electric Co.), XENOY® (a blend of LEXAN® and VALOX®, available from General Electric Co.), polyestercarbonate (PPC), polyethersulfone (PES) (sold under the trademark "Radel®” by Amoco), polyethe mide (PEI or polyimide) (sold under the trademark "Ultem®” by the General Electric Company), and the like.
- the substrate can be precoated with a silicone hardcoat or a polymerized organosilicon layer, for example.
- silicone hardcoats are described in U.S. Patent No. 4,842,941 , which is hereby incorporated by reference.
- a polycarbonate sheet coated with a silicone hardcoat is also available as MR7 from the General Electric Company.
- polymerized organosilicon layers are described in U.S. Serial No. (GE Docket No. RD-25993), entitled “Multilayer Article and Method of Making by Arc Plasma Deposition", by lacovangelo et al., filed on the same day as the present application, which is hereby incorporated by reference.
- the substrate can be formed in a conventional manner, for example by injection molding, extrusion, cold forming, vacuum forming, blow molding, compression molding, transfer molding, thermal forming, and the like.
- the article may be in any shape and need not be a finished article of commerce, that is, it may be sheet material or film which would be cut or sized or mechanically shaped into a finished article.
- the substrate may be rigid or flexible.
- the substrate may be transparent or not transparent.
- step 2 can also be achieved by feeding several reactants directly into a plasma via a number of reagent supply lines and corresponding inlets or openings, which can be operated individually or in combination. Separate inlets can be provided for each of the reactants to be deposited on the substrate.
- a first inlet allows the flow of evaporated Zn or Zn-alloy into the plasma
- a second inlet allows the flow of oxygen (0 2 ) into the plasma
- a third inlet allows the flow of evaporated indium or aluminum into the plasma.
- These reactants then combine or react in the plasma to form a compound that is deposited on the substrate.
- the compound In-ZnO (IZO) or AI:ZnO (AZO) is formed in the plasma and is deposited onto the substrate.
- Other gas reactants and solid reactants can be utilized as will be apparent to those of skill in the art.
- the substrate prior to initiating deposition, is mounted on a support in a first chamber.
- a carrier or plasma gas such as Ar
- Ar is introduced into a second chamber containing a cathode and an anode adjacent the first chamber, which may include an aperture.
- Other inert gases such as noble gases or nitrogen can be utilized to generate the plasma.
- the pressure in the first chamber is reduced below the pressure in the second chamber.
- a potential difference is then applied between the cathode and the anode.
- a carrier gas plasma arc or jet is created that extends from the second chamber to the substrate in the first chamber through the aperture in the anode.
- step 1 can either be modified or avoided altogether by utilizing an organometallic source for Zn, In, and/or Al in addition to or instead of the evaporation technique.
- organometallic sources such as diethyl zinc (DEZ), dimethyl zinc (DMZ), triethyl indium (TEI), trimethyl indium (TMI), triethyl aluminum (TEA), and trimethyl aluminum (TMA), and the like, can be injected into the oxygen argon plasma in step 2.
- the organometallics are broken down by the plasma energy and are reacted with the ionized oxygen to form ZnO, IZO, or AZO.
- the arc plasma deposition apparatus 4 comprises a plasma generation chamber 10 (also referred to as a plasma generator) and a deposition (or treatment) chamber 11.
- the deposition chamber 11 contains a substrate 20 mounted on a temperature controlled support 22.
- the deposition chamber also contains an outlet 23 for pumping and a door 7 for loading and unloading the substrate 20.
- Door 7 may be mounted on a hinge to swing open and is preferably placed in the front of the deposition chamber where the plasma generation chamber 10 is mounted.
- the support 22 may be positioned at any position in area 21 of chamber 11. According to one embodiment that produces acceptable results, the substrate 20 is positioned at a distance of about 15 centimeters (cm) to about 70 cm from the anode 19. Preferably, the substrate is positioned about 25 cm from anode 19. The substrate is typically perpendicular to the flow of the plasma jet.
- Chamber 11 also optionally comprises a retractable shutter 24.
- the shutter may be positioned by a handle 25 or by a computer controlled positioning mechanism.
- the shutter 24 may also contain a circular aperture to control the diameter of the plasma that emanates from the plasma generation chamber 10 towards the substrate 20.
- Chamber 11 may also optionally comprise magnets or magnetic field generating coils (not shown) adjacent to chamber walls to direct the flow of the plasma.
- chamber 11 may also contain a nozzle 18.
- nozzle 18 can be designed either with or without one or more injectors incorporated in its design. The combination of the nozzle and the injectors is sometimes referred to herein as an injection nozzle or nozzle- injector.
- Nozzle 18 allows an improved control of the injection, io ⁇ ization and reaction of the reactants to be deposited on the substrate 20.
- the nozzle 18 helps define a suitable confinement area in which the reaction takes place. The nozzle 18 assures the deposition of the coating composition on the substrate 20 and prevents formation of powdery reactant deposits on the substrate 20.
- Nozzle 18 can be either cylindrical or conical in shape.
- the nozzle 18 has a conical shape with a divergent angle (measured from one inside surface to the opposite inside surface) of about 40 degrees and a length defined along the central axis of the cone of about 16 cm.
- nozzle 18 may have a variable cross section, such as conical-cylindrical- conical or conical-cylindrical.
- the nozzle 18 may have a divergent angle either greater than or less than 40 degrees and a length other than 16 cm.
- the divergent angle of nozzle 18 may range from greater than 0 degrees to about 60 degrees to produce acceptable results.
- the nozzle may also be omitted entirely, as would be apparent to one of skill in the art given the present description.
- nozzle 18 can also be varied in order to optimize the extent of reaction, the coating area, and/or the thermal load on the substrate.
- nozzle 18 can be designed, as shown in Fig. 2, with a diverging (or conical) shape. This conical shape provides for a larger coating area onto the substrate.
- optically clear coatings i.e., not partially opaque due to a powder-like coating on the surface of the substrate
- optically clear coatings of about 30 centimeters in diameter have been deposited on a PC substrate.
- Nozzle 18 can comprise stainless steel, or any other metal, such as tungsten, or other group V-VI metals, that can withstand high operating temperatures without melting.
- nozzle 18 can comprise a ceramic or the like, which can withstand extremely high operating temperatures.
- the nozzle 18 can be designed to be suitable for use with a variety of plasma generating devices.
- nozzle 18 can be utilized in a wall stabilized arc plasma torch having at least one electrically isolated plate located between the cathode and the anode.
- nozzle 18 can be designed to be suitable for use with multi-plate wall stabilized arc devices, such as described in U.S. Patent Nos. 4,948,485 and 4,957,062, each hereby incorporated by reference in their entirety.
- Chamber 11 also contains at least one reactant supply line.
- chamber 11 may contain a first supply line 12 (e.g., for oxygen) and a second supply line 14 (e.g., for zinc) to deposit a ZnO film on the substrate 20.
- Chamber 11 may also include a third supply line 16 to introduce another reactant, such as indium or aluminum, to the plasma stream in order to deposit IZO or AZO on the substrate.
- the supply lines 12, 14, 16 preferably communicate with the nozzle 18 and supply reactants into the plasma flowing through the nozzle 18.
- Chamber 11 also contains vacuum pumps (not shown) for evacuating the chamber.
- Chamber 10 is shown in more detail in Figure 3.
- the plasma generation chamber 10 contains at least one cathode 13, a plasma gas supply line 17 and an anode 19.
- Chamber 10 typically comprises more than one cathode 13.
- the cathodes 13 may comprise tungsten or thorium doped tungsten tips. The added thorium allows the temperature of the tips to be maintained below the melting point of tungsten, thus avoiding contamination of the plasma with tungsten atoms.
- the cathodes 13 may be surrounded by a cathode housing 5 to isolate each cathode 13 from the walls of the cathode support plate 28 and to provide for water cooling.
- the cathode housing 5 may comprise a shell surrounding an isolating mantle made from an insulating material such as quartz.
- the cathodes 13 are separated from the anode 19 by at least one cascade plate 26.
- the cascade plate(s) preferably comprise copper discs containing a central aperture having a shape which corresponds to the shape of the anode aperture.
- Chamber 10 also contains at least one plasma gas supply line 17.
- chamber 10 may also contain a purging gas supply line adjacent to the plasma gas supply line 17 to supply a purging or flushing gas to chambers 10 and 11 prior to supplying a plasma gas, as shown in Fig. 9.
- a purging gas supply line adjacent to the plasma gas supply line 17 to supply a purging or flushing gas to chambers 10 and 11 prior to supplying a plasma gas, as shown in Fig. 9.
- injection of the reactant can also take place in the plasma generation chamber 10 via supply line 17, while a purging or flushing gas can be injected via supply line 87, in order to facilitate continuous flushing of the reactor.
- the flushing gas comprises a single gas or a multiple gas mixture that does not release any fragments after separation that could damage the parts of the plasma generator.
- inert gases such as Ar, or gases such as hydrogen, can be utilized as the flushing gas.
- a plasma gas can be supplied through plasma gas supply line 17.
- the plasma gas may comprise a noble gas, nitrogen, ammonia, carbon dioxide, nitrous oxide, sulfur, or hydrogen, for example, or any combination thereof. If there is more than one plasma gas, then the plural gasses may be supplied through plural supply lines.
- the plasma gas comprises argon or a combination of argon and oxygen.
- the plasma gas in plasma generation chamber 10 is maintained at a higher pressure than the pressure in the deposition chamber 11 , which is continuously evacuated by a pump. An arc voltage is then applied between the cathode(s) 13 and the anode 19 to generate a plasma in the chamber 10.
- the plasma is then emitted as a supersonic plasma (also referred to as a plasma jet or plasma stream) through the anode 19 aperture into the deposition chamber 11 due to the pressure difference between chambers 10 and 11.
- a supersonic plasma also referred to as a plasma jet or plasma stream
- the volume through which the plasma flows from the chamber 10 into chamber 11 is also referred to herein as the plasma channel.
- the cathode support plate 28 is attached to the cascade plate(s) 26 and the anode 19 by an insulated bolt 27 or by other fasteners.
- the cascade plate 26 is electrically insulated from the cathode support plate 28 and the anode 19 by spacers 15.
- Spacers 15 comprise an electrically insulating material that can withstand the elevated temperatures.
- spacers 15 may comprise O-ring vacuum seals, polyvinilchloride rings, boron nitride rings, or the like.
- the cascade plate(s) 26 and anode 19 contain coolant channels 29 and 40, respectively.
- the channels 29, 40 typically have a circular shape within the bulk of the plate(s) 26 and anode 19, as shown in Figure 3. Coolant, such as chilled water supplied through a water supply line 6 flows through the channel 40 to cool the anode 19 during operation.
- a similar water supply line (not shown) is provided to supply water to the channel 29.
- Nozzle 18 is preferably attached to (or mounted on) anode 19.
- nozzle 18 can be securely mounted onto anode 19.
- nozzle 18 is screwed into the support portion 41 of anode 19 to provide a flush fit.
- Other means of mounting nozzle 18 to anode 19 will be apparent to one of skill in the art given the present description.
- nozzle 18 can be formed onto anode 19 as one contiguous unit.
- Nozzle 18 can optionally further include an integral or removable divergent portion, referred to as a nozzle extension 39, for confinement and further directing of the plasma and reactive species flow. Further confinement provided by the nozzle extension 39 helps to ensure the recirculation of the reactants within the plasma stream by preventing reactants from becoming too diffuse in the chamber.
- extension nozzle 39 can include an additional reactant supply line and inlet (not shown), for introducing an additional reactant to the plasma.
- an additional reactant such as sulfur or a mixed oxysulfide, can be introduced to the plasma stream at an inlet(s) located within nozzle extension 39.
- the nozzle 18 has a substantially similar degree of divergence (or expansion) as the cascade plate 26 and the anode 19.
- anode 19 can be configured as a conical-shaped nozzle.
- the nozzle 18 can vary according to the shape and geometry of the anode.
- nozzle 18 can have a flared or bell-shaped mouth at its distal end (the end furthest from anode 19).
- Various shapes can be utilized depending on the desired coating characteristics.
- anode 19 can also have a variety of shapes. Secured mounting for the anode can be achieved using one or more securing screws to mount the cathode housing to the cascade plates and anode.
- the exemplary nozzle 18 shown in the embodiment of Fig. 3 also provides for an increased deposition rate.
- shower-ring or slit injectors can be built into the nozzle for the delivery of gas and/or vapor reactants.
- the locations of the injectors can affect the degree of gas ionization, which can affect the extent of reaction of the reactants fed into the plasma.
- the locations of the reactant inlets can affect the chemical stoichiometry and structure of the coating deposited on the substrate.
- an inlet supplying an oxygen reactant, or the like, to the plasma stream is located on the nozzle 18 adjacent to the anode
- the reactant supply line(s) 12, 14 and 16 are in fluid communication with the nozzle 18.
- nozzle 18 includes one or more injectors coupled to the reactant supply line(s) 12, 14, and 16 providing for the delivery of the reactants into the plasma.
- the injectors may include ring shaped reactant supply channels connected to injection holes or a slit shaped injector.
- reactant supply line 14 connects to reactant supply channel 35 formed inside the body of nozzle 18.
- Reactant supply channel 35 contains a plurality of openings 34, which are preferably evenly distributed around the circumference of channel 35.
- the reactant flows from line 14 into the channel 35.
- the reactant then flows from the channel 35 simultaneously through openings 34 into deposition chamber space 21 from several directions.
- supply line 16 is connected to channel 33 and openings 32 and supply line 12 is connected to channel 31 and openings 30.
- the channel and openings may be omitted and the supply lines may deposit the reactants directly into the plasma.
- the reactants are supplied into the plasma through supply line(s) 12, 14, 16.
- oxygen gas may be supplied through line 12
- zinc may be supplied through line 14, and indium may be supplied through line 16 to form an IZO film on substrate 20.
- line 16 may be sealed if a ZnO film is to be deposited.
- Zinc and indium (and/or aluminum) may be supplied through the same line (14 or 16).
- the supply line location may be altered, and oxygen may be supplied through line 14 or 16 and evaporated zinc reactant through line 12. This arrangement, in which oxygen is supplied downstream from the Zn reactant, helps reduce the risk of ZnO forming on the Zn reactant injection holes or inlets.
- one or more additional supply lines can be connected to nozzle 18 and/or nozzle extension 39, to provide additional reactants and/or dopants to the plasma stream.
- the oxygen can be fed through the reactant supply line 14 which feeds openings (or injection holes) 34 through channel 35.
- Supply line 14 can also be used to feed reactants for doping the ZnO; e.g. TMA or TEA for aluminum or TEI or TMI for indium, or TMDSO or SiH 4 for Si.
- the zinc, indium and/or aluminum reactants are supplied to the plasma in the form of a vapor.
- ZnO and IZO coatings can be deposited onto a PC substrate at high rates by thermally evaporating Zn into the plasma. Oxygen and Zn can be reacted in the Ar plasma to form a substantially transparent ZnO layer on the substrate. Indium can be added to form an IZO layer. Additional reactants or dopants, such as sulfur can also be mixed into the coating composition to provide user desired results, such as forming a ZnS layer.
- metals having relatively low melting point temperatures are chosen. Metals having higher melting point temperatures can be utilized, however the temperature of the nozzle should be kept at an even higher temperature. If metals having higher melting point temperatures are chosen as a coating constituent, this choice may limit the types materials that can be utilized to form the injection nozzle.
- an exemplary injection nozzle configuration and structure includes both cylindrical and conical plasma channels and a two-stage conical channel with a cylindrical section in between.
- the angle of divergence of the injection nozzle can range from 0 degrees to about 60 degrees, for example.
- the opening of the plasma channel (i.e., the anode aperture) at the base of the anode can range from about 4 to about 7 mm in diameter. Alternatively, smaller diameter plasma channels can be used to coat small objects.
- the length of the example injection nozzle can range from about 1.5 cm to about 25 cm, thereby controlling the volume of the zone (within the plasma) in which the reaction of the constituent reactants can take place.
- the injection nozzle can also be a single integral construction.
- the nozzle extension 39 can also be incorporated into nozzle 18 as a single integral construction.
- the injection nozzle can be assembled from parts such as a stainless steel main body with injectors or inlets for introducing or feeding the reactants into the plasma, a copper or other metal adapter (not shown) for mounting nozzle 18 to the plasma generator, and a nozzle extension 39 attached to the downstream end of the main body to provide a suitable volume for the reaction zone which exists within the injection nozzle.
- an inlet such as a ring injector, can be built into the copper adapter for oxygen injection.
- the copper adapter can be plated, such as with nickel (Ni), gold (Au), or rhodium (Rh) plating, to resist oxidation.
- the metal supply line may be altered as shown in Fig. 5A.
- the metal supply line 14 (or 12 or 16, as necessary) is replaced by a conduit or tube 44, such as a stainless steel tube.
- the tube 44 is attached to an evaporator 45.
- evaporator 45 comprises a crucible, such as a nickel crucible with a tantalum liner.
- the crucible is surrounded by a heating element 47, such as a high resistance wire or radio frequency (RF) coils.
- the heating element is also wrapped around the tube 44.
- the heating element is kept at a temperature sufficient to prevent the reactant metal from solidifying in the tube 44.
- the heating element 47 also extends to the nozzle 18 to prevent the metal from solidifying therein.
- the nozzle 18 can be thermal wrapped to maintain a temperature above the melting point of a vapor reactant to prevent clogging, such as if the vapor were cooled to the point where the reactant returned to its solid phase.
- the metal reactant 48 is loaded into the evaporator 45 such that the reactant abuts the pipe 44.
- the heating element is activated to evaporate the metal reactant 48 into the pipe 44.
- the metal reactant is then fed into the plasma 50 from pipe 44 through channel 35 and openings 34.
- the metal reactant is zinc, which is commercially available in the form of Zn slugs.
- the metal reactant 48 may be a ln:Zn alloy, such as 2.5 atomic % ln:Zn.
- indium vapor may be supplied through a separate conduit than the zinc vapor.
- the second metal supply line 16 is replaced with a second tube 46 and a second crucible containing indium.
- the zinc and/or indium vapor enter the plasma, where its mixes with oxygen supplied through supply line 12.
- the metal and oxygen reactants mix in the plasma 50 to form ZnO or IZO which deposits on the substrate 20 as a thin film as the plasma strikes the substrate.
- organometallics such as diethyl zinc (DEZ), dimethyl zinc (DMZ), triethyl indium (TEI), trimethyl indium (TMI), trimethyl aluminum (TMA), and triethyl aluminum (TEA), and the like, can be utilized as sources for reactants that are introduced into the plasma stream. These reactants can be introduced into the plasma stream via, for example, supply line 16.
- DEZ diethyl zinc
- DMZ dimethyl zinc
- TEI triethyl indium
- TMI trimethyl indium
- TMA trimethyl aluminum
- TEA triethyl aluminum
- Fig. 5B Another embodiment of the present invention is shown in Fig. 5B.
- the metal reactant such as Zn
- evaporator 45 which comprises an evaporation chamber.
- Evaporator 45 is connected to conduit 44 to provide a flow of the evaporated reactant to injection holes 34.
- a Zn wire 52 is fed to the evaporator 45 through a wire feed conduit or hollow tube 51 connected to a wire feed supply 53, such as a spool of Zn wire.
- a wire feed conduit or hollow tube 51 connected to a wire feed supply 53, such as a spool of Zn wire.
- other metals can be utilized as the metal reactant, as described above.
- Wire feed supply 53 can be unspooled by a conventional motor 54.
- a motor 54 is driven at a constant rate to continuously feed wire 52 into evaporator 45.
- Ar gas can be fed through conduit 51 via tube 57. Argon is used to reduce back diffusion of oxygen, to carry the zinc vapors, and to dilute the zinc activity at the entrance to the plasma at injection holes 34.
- the arc plasma deposition apparatus of the present invention can be used in a batch mode.
- a metal reactant such as a slug of Zn or ln:Zn is placed within evaporator 45.
- Nozzle 18 is brought to thermal equilibrium while the evaporator is rapidly cycled up and down to start and stop reactant deposition.
- the evaporator 45 and nozzle 18 are brought to equilibrium via heating element 47.
- Wire 52 is fed into the evaporator 45 where it melts and evaporates into the plasma 50 at a constant rate proportional to the feed rate of the wire and the vapor pressure of the reactant at the evaporator temperature.
- the continuous mode is advantageous in that it minimizes any waste of the evaporated reactant.
- the evaporator can be kept at the proper elevated temperature for as long as a user desires.
- the feed rate of the reactant wire can also be varied accordingly. Of course, variations or combinations of these modes of operation can also be utilized to produce acceptable deposition runs, as will be apparent to those of skill in the art given the present description.
- At least one reactant inlet such as a metal reactant inlet 56 is located distal from the anode 19, as shown in Figure 6.
- Inlet 56 can be provided on a nozzle extension or at some further downstream area.
- the inlet 56 may have a ring shape with a wide aperture in the center of the ring.
- the inlet preferably contains a reactant supply channel 35 and reactant supply openings 34 similarly to the previous embodiment.
- the plasma 50 passes through the aperture in the inlet 56.
- the reactant is supplied to channel 35 through a supply line 14 if the reactant is a gas or through a pipe 44 and crucible 45 if the reactant is a vapor.
- the reactant 48 enters the plasma 50 from plural openings 34.
- the nozzle 18 may be omitted because the inlet 56 controls the shape and direction of the plasma 50, as well as the reaction zone.
- the reactant inlet may comprise a crucible 55, as shown in Figure 7.
- Solid Zn or ln:Zn alloy 58 may be evaporated from the crucible 55 directly into the plasma 50.
- the reactant source comprises an electron- beam evaporation system, as shown in Figure 8.
- An electron gun 68 emits a beam of electrons 60.
- the electron beam is directed toward a reactant target 61 by magnet(s) 59.
- the reactant target is a rotating wheel to allow uniform reactant release from the target 61.
- the reactant atoms 78 migrate toward the plasma 50 to be deposited on the substrate 20.
- the target 61 may comprise Zn, ln:Zn, AI:Zn, ZnO, IZO, for example, or any combination thereof. If the target 61 contains oxygen, then a separate source of oxygen may be omitted. Likewise, the injection nozzle 18 may be omitted.
- an arc plasma deposition apparatus 100 is configured with two plasma generation chambers 110 and 140 respectively. Unlike conventional PVD techniques, which rely on diffusion of a reactant vapor pool upwards towards a single surface of a substrate, the embodiment of Fig. 10 can simultaneously coat both surfaces of a substrate 120.
- the arc plasma deposition technique utilizes a plasma jet to transport the coating composition onto the substrate.
- the plasma generation chambers 110 and 140 respectively contain at least one cathode (113 and 143), a plasma gas supply line (117 and 147) and an anode (119 and 149). Chambers 110 and 140 are operated as discussed above.
- Chamber 111 contains a plurality of reactant supply lines.
- chamber 111 may contain supply lines 112 and 142 (for oxygen) and supply lines 114 and 144 (for zinc) to deposit a ZnO film on surfaces 121 and 122 of substrate 120.
- Chamber 111 may also contain supply lines 116 and 146 to introduce another reactant, such as In, to the plasma stream in order to deposit IZO on the substrate.
- the supply lines preferably communicate with the injection nozzles 118 and 148 and supply reactants into the plasma flowing through the nozzle in a similar manner as described above.
- Chamber 111 also contains vacuum pumps (not shown) for evacuating the chamber, such as at port 171.
- the arc plasma deposition apparatus included a copper anode separated from three needle-type cathodes of thoriated tungsten by at least one or a series of electrically isolated copper disks.
- Argon (Ar) was chosen as the plasma gas.
- a direct current (DC) voltage was applied to the electrodes to generate a plasma.
- the plasma expanded through the injection nozzle, similar to the embodiment shown in Fig. 3, into the treatment chamber at a reduced pressure thus forming a plasma jet.
- the injection nozzle was thermally wrapped, so that the temperature was maintained at about 850 degrees centigrade, which is above the melting point temperature of the zinc and indium reactants. This increased temperature of the injection nozzle also helped to reduce the risk of clogging.
- the substrate coated was a PC sheet.
- the substrates were cleaned in isopropyl alcohol and dried at 120 degrees in vacuum for at least 12 hours prior to deposition to degas the substrates.
- the substrate was supported on the plasma jet axis in the treatment chamber by a metal support stage.
- the support stage was located at a distance of about 25.5 cm from the anode.
- a retractable shutter was also utilized to regulate the exposure of the substrate to the plasma stream.
- Each chamber was pumped to less than 1 milliTorr and back flushed with nitrogen to about 500 Torr then pumped back down at least two times to remove residual moisture from the chamber prior to introduction of the reactants.
- Oxygen was introduced into the plasma via a reactant supply line and reactant inlet, such as those shown above in Fig. 3. This setup produced an oxygen/argon plasma.
- Coating runs 1-6 were conducted under a batch mode of operation.
- a zinc or a zinc-based alloy was thermally evaporated to produce a reactant vapor in an evaporator similar to that shown in Fig. 5A.
- the Zn-based reactant was then introduced into an injector of the nozzle into the plasma.
- the nozzle used in the experimental coating runs contained a series of gas passages to feed reactants into the plasma.
- the nozzle was coupled to the evaporator with a " stainless steel tube connected to one gas channel and set of injection holes.
- This steel tube had a cap on the end that fitted to a small nickel crucible with a Ta liner that was wrapped with a heating element to control it's temperature.
- Zinc and/or Zinc alloys such as ln:Zn were placed into the crucible and press fitted against the feed tube.
- the nozzle was also wrapped to keep it above the melting point of zinc to prevent clogging of the injection holes.
- the Zn or ln:Zn vapor reactant was introduced at a location down stream from the oxygen inlet site.
- the ZnO or IZO compound was formed in a so-called reaction zone of the plasma. For example, in Fig. 3, the reaction zone 38 occurs proximate to inlet 34.
- Run 7 was conducted in a continuous mode, using an evaporator similar to that shown in Fig 5B.
- zinc wire having a .017"-.057" diameter was fed into the evaporator by a wire feeder under motorized control through a stainless steel tube connected to the evaporator.
- Run 8 was made using an organometallic, rather than an evaporated reactant, in which the organometallic gas was introduced into the plasma by way of a reactant supply line.
- a shutter was retracted and the substrate was exposed to the reactant compound (in this experiment ZnO or IZO) plasma to initiate deposition.
- the rate of ZnO and IZO deposition was controlled by maintaining the temperature of the metal, e.g., controlling the vapor pressure of the metal.
- Evap refers to the material that was evaporated or fed to the nozzle
- Zn T refers to the temperature of the material being evaporated (the vapor pressure of the Zn and hence the rate in which the Zn is introduced into the plasma is proportional to this temperature) in degrees Celsius
- I refers to the anode-cathode (i.e., arc) current (in amperes), which in all cases was split evenly among the 3 cathodes
- Press refers to the deposition chamber pressure in milliTorr
- Ar refers to the argon flow rate in standard liters per minute (Ipm); 0 2 refers the oxygen flow rate in Ipm
- A refers to absorbency at 350 nm
- T is the transmission of light in units of percent (%)
- H refers to the measured haze (percentage of light scattering).
- the primary difference in depositing the Zn and ln:Zn materials was that Zn was melted for ZnO, and an alloy of 2.5% ln:Zn was melted for IZO. All runs were done with a working distance (anode to substrate) of about 25.5 cm. Depositions were done on both Lexan and glass. Deposits on glass were used to measure the absorbency (A) at 350 nanometers (nm). Absorbency was measured on a UNICAM UV-3 UV/Visible spectrophotometer. Haze measurements were made using a Gardner model XL-835 colorimeter.
- the rate was generally controlled by the vapor pressure of the metal, (compare runs 1 and 2 and also 4, 5, 6) however, it was also affected by the current supplied to the arc. In these examples, if the arc current is too low, the adhesion and properties of the coating are affected. If the arc current is too high, (compare runs 2 and 3) the deposition rate drops off significantly, presumably due to formation of ZnO powder in the plasma which is carried off to the pumps. The arc current also affects the degree of ionization of the oxygen. Therefore, the arc current can be controlled to optimize coating quality.
- the flow rate of oxygen affects the coating clarity or haze: if the flow rate is too low, the haze will be high.
- An exact calculation of the optimal ratio of 0:Zn could not be done because the exact flow rate of Zn is not known. However, an estimate based on the deposition rate and anticipated utilization of the zinc is about 5:1.
- the arc plasma deposition technique of the present invention has many advantages over PVD or conventional arc plasma deposition processes.
- demonstrated deposition rates can be as high as 4 ⁇ m/minute, while still maintaining an acceptable coating quality. Based on these results, even higher deposition rates can be achieved with optimization.
- Second, a very inexpensive, readily available and easily interchangeable source material can be used.
- the source material can comprise zinc or a zinc alloy.
- the coating can be electrically conductive which is useful for applications such as flat panel displays.
- both sides of a substrate can be coated simultaneously by projecting the reactants with two plasma jets, saving considerable time and eliminating the steps and equipment necessary to flip the substrate, mask the back side of the substrate, and recoat the substrate.
- DMZ or DEZ an organometallic gas
- DMZ or DEZ part of the energy of the plasma is imparted to break down the organometallic.
- zinc vapor or the like
- the technique of the present invention results in less thermal load to the substrate.
- excellent coating properties can be achieved such as higher UV absorbency than other conventional methods, excellent transmission in the visible, and low haze.
- the water soak stability of the coating is also improved, as described in the above-referenced copending application (GE RD-25,973).
- the present invention is particularly useful as part of an automotive glazing package. It is also useful for a variety of applications of PC needing extended weathering capability such as architectural windows, headlamps, airplane canopies, etc. Further, it is also useful for solar cells.
- the coated substrates can be utilized in various apparatus display windows such as TV screens, LCD screens, fiat panel displays, plasma display screens, and computer terminal screens and glare guards.
Abstract
Description
Claims
Priority Applications (4)
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EP00907176A EP1161574B1 (en) | 1999-03-17 | 2000-02-04 | Method and apparatus for arc deposition |
DE60007287T DE60007287T2 (en) | 1999-03-17 | 2000-02-04 | METHOD AND DEVICE FOR COATING BY ARCH DISCHARGE |
AT00907176T ATE256763T1 (en) | 1999-03-17 | 2000-02-04 | METHOD AND DEVICE FOR COATING BY ARC DISCHARGE |
JP2000605803A JP4733273B2 (en) | 1999-03-17 | 2000-02-04 | Arc deposition method and apparatus |
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US09/271,655 US6365016B1 (en) | 1999-03-17 | 1999-03-17 | Method and apparatus for arc plasma deposition with evaporation of reagents |
US09/271,655 | 1999-03-17 |
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JP (1) | JP4733273B2 (en) |
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EP2302423A2 (en) | 1999-03-17 | 2011-03-30 | SABIC Innovative Plastics IP B.V. | Infrared reflecting coatings |
KR100912981B1 (en) * | 2001-05-29 | 2009-08-20 | 가부시끼가이샤 테크노 료와 | Ionized Air Flow Discharge Type Non-Dusting Ionizer |
WO2003038141A2 (en) * | 2001-10-31 | 2003-05-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Method for producing a uv-absorbing transparent wear protection layer |
WO2003038141A3 (en) * | 2001-10-31 | 2003-10-23 | Fraunhofer Ges Forschung | Method for producing a uv-absorbing transparent wear protection layer |
US7390573B2 (en) | 2004-03-09 | 2008-06-24 | Exatec Llc | Plasma coating system for non-planar substrates |
US9702036B2 (en) | 2006-10-11 | 2017-07-11 | Oerlikon Surface Solutions Ag, Pfäffikon | Layer system with at least one mixed crystal layer of a multi-oxide |
EP3374542B1 (en) * | 2015-11-12 | 2020-07-15 | Inocon Technologie Gesellschaft m.b.H | Device for applying a coating |
Also Published As
Publication number | Publication date |
---|---|
ATE256763T1 (en) | 2004-01-15 |
DE60007287T2 (en) | 2004-10-21 |
DE60007287D1 (en) | 2004-01-29 |
JP4733273B2 (en) | 2011-07-27 |
JP2003518553A (en) | 2003-06-10 |
EP1161574A1 (en) | 2001-12-12 |
EP1161574B1 (en) | 2003-12-17 |
US6365016B1 (en) | 2002-04-02 |
WO2000055388A3 (en) | 2001-06-28 |
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