[go: up one dir, main page]

WO2003024712A1 - Conducteur transparent haute transmission durable a faible ohm - Google Patents

Conducteur transparent haute transmission durable a faible ohm Download PDF

Info

Publication number
WO2003024712A1
WO2003024712A1 PCT/US2002/025980 US0225980W WO03024712A1 WO 2003024712 A1 WO2003024712 A1 WO 2003024712A1 US 0225980 W US0225980 W US 0225980W WO 03024712 A1 WO03024712 A1 WO 03024712A1
Authority
WO
WIPO (PCT)
Prior art keywords
indium
zinc
composite
atomic percent
zinc oxide
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.)
Ceased
Application number
PCT/US2002/025980
Other languages
English (en)
Inventor
Mohtashim Saif
Hassan Memarian
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CPFilms Inc
Original Assignee
CPFilms Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by CPFilms Inc filed Critical CPFilms Inc
Priority to EP02775710A priority Critical patent/EP1451009A1/fr
Publication of WO2003024712A1 publication Critical patent/WO2003024712A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides

Definitions

  • the present invention pertains to the field of transparent electrical conductive coatings made of indium zinc oxide which are applied to transparent substrates, especially flexible transparent polymeric film substrates.
  • the invention also pertains to the method of making the coated substrates and the use of the coated substrates in electronic devices which require transparent conductive oxide (TCO) films having excellent electrical conductivity, mechanical durability and high transparency.
  • TCO transparent conductive oxide
  • Such electronic devices include transparent electrodes, electroluminescent lamps, EMI/RFI shielding, liquid crystal displays, touch screens, heat mirrors and transparent window heaters.
  • ITO indium oxide-tin oxide
  • RI refractive index
  • ITO generally has desirable optical properties, e.g. , ultraviolet (UN) radiation absorption below 330 (nm), high visible light transmission, and infrared (IR) radiation reflection at 800-1500 nm.
  • 6,028,654 discloses a liquid crystal display with ITO transparent electrodes having a surface resistivity of 20-70 ohms/square.
  • a drawback to ITO films is a tendency to absorb blue light which results in a yellow or green tint. This absorption of visible light increases with film thickness.
  • ITO has an inherent bulk resistivity of about 0.0004 ohm-centimeter.
  • Lower resistance can be obtained by providing films with greater thickness.
  • Highly conductive ITO films can be readily applied to rigid transparent substrates such as glass and polycarbonate.
  • ITO films on flexible substrates have diminished structural integrity with increased thickness.
  • increasing the thickness is required to provide a film having lower resistance.
  • This increased thickness makes it difficult to achieve durable, highly conductive ITO films on flexible substrates.
  • the diminished structural integrity is manifest by reduced adhesion between the ITO coating and the substrate and a high radius of curl due to ITO brittleness.
  • ITO with low structural integrity has low tolerance for further handling and/or etching.
  • ITO is routinely used in many applications, the limitation of ITO coatings at higher thicknesses leads to more stress in the film and also produces a pronounced color which makes its use prohibitive in some applications.
  • IZO indium zinc oxide
  • U.S. Patent No. 5,972,527 and EPO 677,593 Al disclose transparent electrically conductive layers of indium zinc oxide on various substrates.
  • the indium zinc oxide coating used in U.S. Patent No. 5,972,527 and EPO 677,593 Al contains indium and zinc having an atomic ratio (In/In +Zn) of 0.5-0.9. In other words the percentage of indium atoms in the indium zinc oxide is 50-90 % based upon the total number of indium and zinc atoms in the indium zinc oxide.
  • Carter et al. discloses in European patent application EP0707320 Al transparent conductors which comprise zinc-indium oxide (40-75 atomic % indium) deposited onto glass and quartz substrates. Such films are said to be useful as transparent electrodes, particularly in the blue region.
  • Minami et al. disclose in Japanese Kokai HEI 8 [1996]-264021 transparent conductive films which are obtained by sputtering indium zinc oxide (5-45 atomic % zinc) onto substrates at a temperature of 350 °C.
  • Moldonado et al. disclose (J. Vac. Sci. Technol. A 15(6) Nov/Dec 1997 p. 2905) that substrate temperature is the most important parameter which influences the physical properties of indium zinc oxide films. Moldonado et al. disclose the spray deposition of an indium zinc oxide (3 atomic % indium) film on glass substrates at 675 °K (412°C) and 800°K (527°C).
  • Minami et al. also disclose Thin Solid Films 290-291 (1996) 1-5) that the minimum resistivity is achieved when indium zinc oxide films are prepared by DC magnetron sputtering and that the composition at which minimum resistivity can be attained depends upon the substrate temperature.
  • Figure 1 of Minami et al. illustrates resistivity as a function of the atomic ratio of Zn/(In+Zn) at deposition temperatures of room temperature and 350°C.
  • U.S. Patent No. 5,206,089 discloses a glass substrate coated with a layer of transparent conductive material.
  • the transparent conductive material is a mixed oxide of indium and zinc containing 10-34 atomic % indium.
  • the coating is obtained by pyrolysis of powdered compounds of indium and zinc in contact with a substrate heated to a high temperature.
  • U.S. Patent No. 5,443,862 describes a process for treating thin semiconducting layers of metal oxide.
  • the treatment comprises subjecting the thin semi-conducting layer to an ion beam.
  • Various semi-conducting layers are described including indium oxide doped with tin, tin oxide doped with fluorine and zinc oxide doped with indium (ZnO:In).
  • U.S. Patent No. 5,470,618 discloses a zinc oxide based transparent conductive film containing a small amount (0.4 to 8 atomic %) of gallium or gallium oxide. It is said that the gallium or gallium oxide may be replaced by indium or indium oxide.
  • U.S. Patent No. 5,589,274 discloses a thermal controlled coating which is applied like a paint to a substrate.
  • the coating comprises a silicone polymeric matrix having doped zinc oxide particles distributed therein.
  • Dopants include aluminum, gallium, indium, boron, zinc, tin or hydrogen.
  • U.S. Patent No. 6,040,056 discloses a transparent substrate which is coated with a transparent electrically conductive film.
  • the electrically conductive film is a laminate which contains reflection preventing layers and one or more metal layers.
  • the metal layers are silver or metal which comprises silver as the main component.
  • the reflection preventing layer comprises a composite oxide of zinc and indium.
  • the atomic ratio of indium and zinc expressed as zinc/(indium+zinc) in the reflection preventing layers is 0.03 to 0.9.
  • the transparent electrically conductive film having the silver and IZO layers is structured to provide a sheet resistance of about 2.5 ohms per square to 1.5 ohms per square.
  • the laminated structure of the electrically conductive film has a structure to provide a sheet resistance of 1.5 ohms per square or lower.
  • a transparent flexible polymeric substrate coated with an electrically conductive film of IZO which has improved conductivity, mechanical durability and optical clarity which cannot be achieved with indium tin oxide coatings or other indium zinc oxide coatings on the flexible polymeric substrates.
  • This ratio may be expressed as an atomic percent by multiplying the ratio by 100.
  • the atomic percent zinc used in this invention is 0.01 % to 9.99 %.
  • the atomic percent of Zn is relative to the total amount of In and Zn, then the atomic percent zinc when added to the atomic percent indium will equal 100% .
  • the IZO coating has an atomic percent of In which is 97 % with a corresponding atomic percent of Zn which is 3 % (referred to herein as having the atomic percent ratio 97:3).
  • the transparent electrically conductive film or coating on the transparent flexible polymeric substrate has a sheet resistance which is at least 3 ohms per square up to about 1000 ohms per square.
  • the IZO coating is transparent and electrically conductive.
  • the invention is directed to an electrically conductive composite device which comprises a flexible transparent polymeric sheet having a transparent electrically conductive film or coating of IZO thereon.
  • the transparent electrically conductive film or coating consists of a layer of transparent electrically conductive IZO without any other layers therein.
  • a metal layer or layers i.e. , metal in the elemental state
  • a primer layer which in some cases may be a metal as further described herein, may be interposed between the IZO layer and the polymeric substrate. Since the primer layer is between the IZO film and the polymeric material, it is not within the IZO coating.
  • an IZO coating which includes a metal layer therein is the electrically conductive film described in U.S. Patent No. 6,040,056.
  • the transparent electrically conductive film is a laminate which includes one or more silver layers with IZO layers on both surfaces thereof.
  • the transparent electrically conductive film of Patent No. 6,040,056 includes a silver layer within the IZO material.
  • the embodiments of the present invention wherein the transparent electrically conductive coating has a sheet resistance which is more than 3 ohms per square is further distinguished from the electrically conductive coating of U.S. Patent No. 6,040,056 which has a maximum sheet resistance of 2.5 ohms per square.
  • the IZO film coating of the present invention is sputter coated at a low temperature which does not result in degradation (e.g. , melting, discoloration, decomposition or other loss of properties) of the polymeric sheet which would occur at high temperature sputtering such as the 350 °C sputter coating temperature used by Minami et al. in Japanese Kokai Hei 8[ 1996] -264021. Such a high temperature would destroy the polymeric substrates used in the present invention.
  • the ratio 97:3 with respect to IZO referred to in the figures and elsewhere in this application means that the IZO has 3 atomic percent Zn based on the total number of In and Zn atoms and 97 atomic percent In based on the total number of In and Zn atoms and thus has an atomic percent ratio (In:Zn) which is 97 : 3 (ratio of atomic percents) .
  • the ratio 90 : 10 with respect to IZO referred to in the figures and elsewhere in this application means that the IZO has 10 atomic percent Zn based on the total number of In and Zn atoms and 90 atomic percent In based on the total number of In and Zn atoms and thus has an atomic percent ratio (In:Zn) which is 90: 10 (ratio of atomic percents).
  • the ratio 90:10 with respect to ITO referred to in the figures (figures 15-17) and elsewhere in this application means that the ITO has 10 weight percent Sn and 90 weight percent In based on the total weight of In and Sn and thus has a weight percent ratio (In:Sn) which is 90: 10 (ratio of weight percents).
  • the ratio of the atomic percent of indium to the atomic percent of zinc is 97:3.
  • IZO coatings having an atomic percent of Zn, calculated as described above, which is less than 3 atomic percent zinc based on the total number of zinc and indium atoms in the IZO.
  • the IZO conductive coatings of the present invention may include any of the conventional dopants which are used in this field of technology.
  • dopants such as Sn, Al, Sb, B etc. , may also be added to further improve the optical and/or electronic properties of the deposited films.
  • Figure 1 illustrates resistivity as a function of zinc content for IZO films which is known from the prior art.
  • Figure 2 depicts schematically a sputter roll coater which can be used to deposit the IZO coating used in the present invention.
  • Figure 3 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for an IZO film having a sheet resistance of 20 ohms per square, sputter coated onto a transparent substrate by reactive sputter coating from indium and zinc metal target in an oxygen containing atmosphere.
  • Figure 4 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for an IZO film having a sheet resistance of 30 ohms per square, sputter coated onto a transparent substrate by reactive sputter coating from indium and zinc metal target in an oxygen containing atmosphere.
  • Figure 5 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for an IZO film having a sheet resistance of 100 ohms per square, sputter coated onto a transparent substrate by reactive sputter coating from indium and zinc metal target in an oxygen containing atmosphere.
  • Figure 6 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for an IZO film having a sheet resistance of 200 ohms per square, sputter coated onto a transparent substrate by reactive sputter coating from indium and zinc metal target in an oxygen containing atmosphere.
  • Figure 7 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for an IZO film having a sheet resistance of 300 ohms per square sputter coated onto a transparent substrate by reactive sputter coating from indium and zinc metal target in an oxygen containing atmosphere.
  • Figure 8 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for an IZO film having a sheet resistance of 20 ohms per square, sputter coated onto a transparent substrate by sputter coating from an IZO ceramic target.
  • Figure 9 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for an IZO film having a sheet resistance of 30 ohms per square, sputter coated onto a transparent substrate by sputter coating from an IZO ceramic target.
  • Figure 10 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for an IZO film having a sheet resistance of 100 ohms per square, sputter coated onto a transparent substrate by sputter coating from an IZO ceramic target.
  • Figure 11 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for an IZO film having a sheet resistance of 200 ohms per square, sputter coated onto a transparent substrate by sputter coating from an IZO ceramic target.
  • Figure 12 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for an IZO film having a sheet resistance of 300 ohms per square, sputter coated onto a transparent substrate by sputter coating from an IZO ceramic target.
  • Figure 13 is a graph which shows the percent transmission versus wavelength and the percent reflection versus wavelength for a variety of films which have a sheet resistance of 20 ohms per square (IZO films having In:Zn atomic percent ratios of 97:3 and 90: 10 based on the total number of In and Zn atoms.
  • Figure 14 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for a variety of films which have a sheet resistance of 30 ohms per square (IZO films having In:Zn atomic percent ratios of 97:3 and 90: 10 and an ITO (indium tin oxide) film having an In:Sn weight percent ratio of 90: 10.
  • the weight percent ratio of 90: 10 for ITO is the ratio of weight percent In to the weight percent Sn wherein each weight percent is based on the total weight of In and Sn.
  • Figure 15 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for a variety of films having a sheet resistance of 100 ohms per square (IZO films having an In:Zn atomic percent ratios of 97:3 and 90: 10, an indium tin oxide (ITO) film having In:Sn weight percent ratio of 90: 10 and an indium oxide (InO x ) film.
  • IZO films having an In:Zn atomic percent ratios of 97:3 and 90: 10
  • ITO indium tin oxide
  • ITO indium tin oxide
  • InO x indium oxide
  • Figure 16 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for a variety of films having a sheet resistance of 200 ohms per square (IZO films having In:Zn atomic percent ratios of 97:3 and 90:10, an ITO film having an In:Sn weight percent ratio of 90: 10 and an indium oxide film.
  • Figure 17 is a graph which shows the percent transmission versus wavelength and percent reflection versus wavelength for a variety of films having a sheet resistance of 300 ohms per square (IZO films containing In:Zn atomic percent ratios of 97:3 and 90: 10, an ITO film having an In:Sn weight percent ratio of 90: 10 and an indium oxide InO x film.
  • IZO films containing In:Zn atomic percent ratios of 97:3 and 90: 10 an ITO film having an In:Sn weight percent ratio of 90: 10 and an indium oxide InO x film.
  • Figure 18 is a cross-sectional representative of an embodiment of the invention which comprises an IZO film of the invention coated onto a transparent flexible polymeric substrate.
  • Figure 19 is a cross-sectional illustration of another embodiment of the invention which corresponds to the embodiment illustrated in Figure 18 with a primer layer interposed between the IZO film and the transparent flexible polymeric substrate.
  • references to atomic percent ratios of In:Zn refer to the ratio of the atomic percent of In to the atomic percent of Zn wherein each of the atomic percents are with reference to the total number of In and Zn atoms.
  • the atomic percent ratio is 97:3
  • the atomic percent of In is 97% based on the number of In atoms relative to the total number of In and Zn atoms
  • the atomic percent of Zn is 3 % based on the total number of Zn atoms relative to the total number of In and Zn atoms.
  • the atomic percent ratio of In:Zn which is 90: 10 means that the atomic percent of In is 90% based on the total number of In atoms relative to the total number of In and Zn atoms and the atomic percent of Zn is 10% based on the number of Zn atoms relative to the total number of In and Zn atoms.
  • ITO indium tin oxide
  • atomic percent ratio with respect to ITO material means that the material contains 90% by weight of In with respect to the total weight of In and Sn and 10% by weight of Sn with respect to the total weight of In and Sn.
  • the ratio 90: 10 with respect to ITO refers to the above described weight percent ratio
  • the ratios 97:3 and 90: 10 with respect to IZO refers to the above-described atomic percent ratios.
  • InO x coatings Such coatings are referred to herein as InO x coatings. It will be appreciated by those skilled in the art that such coatings have a less than stoichiometric amount of oxygen so that the indium oxide is electrically conductive.
  • the value of x in the formula InO x therefore refers to the amount of oxygen which is less than the stoichiometric amount of oxygen and which allows the indium oxide to be electrically conductive.
  • the transparent flexible polymeric substrate used in the present invention may be any of the commonly employed polymeric substrates which are typically used in electrically conductive composites which employ a transparent electrically conductive oxide (TCO) coating.
  • TCO transparent electrically conductive oxide
  • An example of such a polymeric material is polyethylene terephthalate (PET).
  • Sputtering is advantageously used to deposit the indium zinc oxide film so that high temperatures and other physical and chemical conditions which could harm the polymeric substrate can be avoided.
  • Sputtering is particularly advantageous because it can be used to deposit the IZO layer onto the polymeric substrate at ambient or room temperature (e.g., about 70°F). Any conventional sputtering method and apparatus may be used; it being understood that the ratio of In to Zn requires the use of a target which has a corresponding In:Zn ratio.
  • Sputtering coaters which advance a polymeric sheet or web from one roll to another roll with one or more sputtering stations positioned in the path of the sheet or web are particularly advantageous because the substrate can be sputter coated with the IZO layer in one pass of the sheet as it advances from one roll to the other roll.
  • Such sputtering coaters are well known and are commercially available.
  • An example of such a sputtering device is shown in U.S. Patent No. 4,977,013, the specification of which is incorporated herein by reference.
  • the IZO coated polymeric sheets described herein were made by using the sputter coater illustrated in figure 2.
  • the sputtering target may be an indium-zinc alloy.
  • the sputtering When sputtering with an indium-zinc alloy, the sputtering is performed in an atmosphere which contains oxygen according to well known techniques so that the deposited IZO material has the desired oxides of indium and zinc which are transparent and electrically conductive.
  • the sputtering conditions required to produce a transparent electrically conductive IZO coating are well known to those skilled in the art.
  • IZO coatings sputter coated by reactive sputtering using a metal target e.g., indium-zinc alloy
  • metal target e.g., indium-zinc alloy
  • the sputtering may use a zinc oxide-indium oxide ceramic (e.g. , a sintered mixture of zinc oxide and indium oxide powder).
  • IZO Coatings obtained by sputter coating from a ceramic target may be referred to herein as "ceramic" IZO.
  • the sputtering is done in a closed loop using plasma emission monitoring especially when sputtering from a metal target in an oxidizing atmosphere.
  • Plasma emission monitors and the use thereof and regulating the amount of oxygen during reactive sputtering procedures are well known to those skilled in the art.
  • a description of a suitable plasma emission monitor which can be used in the present invention is described in the publication by Patel et al. ; Methods of Monitoring and Control of Reactive ITO Deposition Process on Flexible Substrates with DC Sputtering; Society of Vacuum Coaters; 39th Annual Technical Conference Proceedings (1996) ISSN 0737-5921; pp.. 441-445.
  • the text of the aforementioned publication is incorporated herein by reference.
  • Figure 18 illustrates an embodiment of the invention which comprises transparent electrically conductive IZO film 1 adhered directly to transparent flexible polymeric sheet or film 2.
  • Figure 19 illustrates an embodiment of the invention wherein primer layer 3 is interposed between IZO film 1 and polymeric sheet 2.
  • the primer layer which may be interposed between the IZO film and the polymeric substrate may also be deposited by a conventional sputtering procedure.
  • the same sputtering apparatus and temperature used for applying the IZO film may also be used to apply the primer layer.
  • the primer layer improves the adhesion between the IZO and the polymeric substrate.
  • the primer layer is a metal or an oxide or nitride thereof.
  • the primer layer has a thickness of .5 to 100 nm, more preferably .5 to 50 nm.
  • the primer layer is made from a material selected from the group consisting of Ti, Cr, Ni, C, Zr, Hf, Ta, W, Al, oxides of any of the aforementioned metals, nitrides of any of the aforementioned metals and mixtures of any of the aforementioned metals, oxides or nitrides.
  • suitable oxides include Ti0 2 , A1 2 0 3 , Ta 2 0 5 , etc.
  • Suitable nitrides include TiN, ZrN, etc.
  • the IZO film of the present invention may be doped with small amounts of other conventional doping elements to further improve the optical-electronic properties thereof.
  • Such elements may include Sn, Sb, Al and others which are will known to those skilled in the art as dopants in this field of technology.
  • the atomic percentage of these elements can vary from 0.1 % to 10% depending on the application wherein the atomic percentage of the dopant is based upon the total number of zinc atoms , indium atoms and dopant atoms . It is expected that this type of tertiary alloy composition may provide additional benefits and improve the overall properties of the deposited films.
  • the dopants are advantageously included in the target (alloy or ceramic) so that the sputter coated layer contains the dopant metal therein.
  • the layer of indium zinc oxide which is coated onto the transparent flexible polymeric substrate has a sheet resistance of from 3 to 30 ohms per square.
  • the composite film which comprises the layer of IZO coated on a flexible transparent polymeric substrate has a light transmission at 550 nanometers of at least 75 % and is essentially crack free after rolling over a 3 mm diameter mandril.
  • the IZO coatings of the present invention preferably have bulk resistivities of less than 2.0 x 10 "4 ohm centimeter, visible light transmission which is greater than 85% and low yellow index.
  • the IZO film which is coated onto the substrate has 0.01 to 9.99 atomic % zinc therein based upon the total number of indium and zinc atoms in the IZO film.
  • the IZO film has 1 to 8 atomic % zinc, more preferably 2 to 6 atomic % zinc, and even more preferably 2 to 4 atomic % zinc.
  • the IZO coated polyester films of the invention have an IZO coating which is applied at a thickness which produces low surface resistivity, e.g., less than 100 ohms per square, and a low yellow index, e.g. , less than 15 YID.
  • the IZO coated polyester films of the present invention have enhanced mechanical properties including enhanced adhesion, low curl, extreme flexibility and machinability.
  • the preferred IZO coated polyester film of this invention has a surface resistance in the range of 3-50 ohms per square, more preferably 3-30 ohms per square or even more preferably 3-20 ohms per square and most preferably 3-10 ohms per square.
  • the sputter coated IZO films or coatings of the present invention have enhanced transparency in the visible region of the electromagnetic spectrum.
  • the mechanical properties of the IZO film of the present invention are superior than other transparent conductive coatings. These excellent mechanical properties are extremely important where room temperature sputtering is needed in roll-to-roll flexible films, especially for applications that need less than 50 ohms per square sheet resistance.
  • the IZO coatings of the invention were sputter coated onto a flexible polymeric film at room temperature using metallic indium/zinc target.
  • the transparent conductive film produced by this sputtering procedure met all the optical requirements compared to that of ITO film with low absorption and less yellowness than ITO.
  • the mechanical properties, however, were much superior compared to ITO film.
  • the IZO film of the invention showed good adhesion, good mechanical durability /flexibility, curl and excellent machinability with good etching properties especially for films which have less than 20 ohms per square sheet resistance.
  • the spectral optical properties i.e.
  • absorptance, reflectance and transmittance) of the IZO coated flexible substrate composites made in accordance with this invention are determined by conventional procedures using a spectro-photometer.
  • the surface resistivity or sheet resistance as it is sometimes called, of the IZO films of the present invention are measured in the conventional manner.
  • the surface resistivity or sheet resistance is set forth in units of ohms per square.
  • the methodology for measuring the sheet resistance is well known to those skilled in the art.
  • a 2 point probe is satisfactory.
  • a 4 point probe method is sometimes recommended for surface resistivities of less than 10 ohms per square, a 2 point probe method may be used for the IZO materials of the present invention.
  • Transverse strip means that a sample is cut across the width of a continuous web with a short dimension (5 cm) in the direction of web motion during coating.
  • a useful probe comprises 5 cm long cylindrical conductive elastomer electrodes for contacting the IZO surface where the elastomer electrodes are spaced 5 cm apart by mounting them in a metal channel supported by a rigid insulator.
  • Such conductive elastomers are well known to those skilled in the art and are commercially available from Chomerics.
  • Surface resistivity is determined by cleaning electrodes and electrodes that contact surfaces, e.g., metal channels and IZO surface, with a suitable solvent such as isopropyl alcohol.
  • the IZO coated flexible substrate is placed IZO-side up on a flat surfaced rubber mat.
  • the probe is placed on the IZO coating, loaded to about 6.9 kiloNewtons per square meter (1 psi) with the 5 cm length of the electrodes extending across the 5 cm width of the strip. Resistance measured in ohms is "ohms per square".
  • Example 1 This example illustrates the deposition of an IZO coating on a flexible polyester substrate.
  • a roll of 0.18 millimeter (7 mil) thick polyethylene terephthalate (PET) film was threaded through a roll-to-roll laboratory sputtering coater illustrated in Figure 2.
  • the IZO coating was applied to the moving web of PET film by sputtering from an indium: zinc alloy target of atomic percent ratio of 97:3.
  • the drum width is 40 cm (16 in) and the cathode size is 38 cm x 11 cm (15 in x 4.5 in).
  • the first pass was used to condition/clean the PET surface by glow discharge plasma.
  • the PET film was run through the coater in a second pass at various line speeds to deposit IZO at various thickness (and surface resistivity).
  • the PET with IZO coating of about 30 ohms per square was run through the coater in a third pass to provide an IZO coating of about 20 ohms per square. All three passes were run with a single pump down to operating pressure and the film was re-wound after each pass. Sputtering parameters for all three passes are set out below in Tables 1-3. Table 1
  • the IZO coated PET substrates prepared according to this Example 1 were evaluated for spectral optical properties according to ASTM Standard E424 (Test Method for Solar Energy Transmittance and Reflectance of Sheet Materials) over the 316nm to 2765nm spectral range using a spectrophotometer calibrated according to ASTM Standard E275 (Recommended Practice for Describing and Measuring Performance of Spectrophotometers).
  • Spectral reflectance (%R) and transmittance (%T) were measure; absorptance (% A) was determined from the Kirchoff relationship where the sum of absorptance, reflectance and transmittance equals unity.
  • a yellowness index (YID) was determined from the CIE 1976 (L*a*b*) color space.
  • the spectral optical properties are reported in Table 4. Table 4
  • the IZO coated PET substrates prepared according to this Example 1 were evaluated for mechanical properties, i.e. adhesion of IZO coating to the PET substrate, abrasion resistance of the surface of the IZO coating, flatness of the IZO coated PET substrate (reported as "curl") and machinability.
  • Machinability is measured by observing for cracks in the IZO coating by back lit microscope after drawing the coated substrate over a 3 mm (1/8 inch) diameter mandrel. All of the IZO coated PET substrates of Example 1 showed no cracks indicating excellent machinability.
  • the IZO coated PET Substrates of Example 1 were tested for environmental resistance by measuring surface resistivity after (a) exposure to ambient (room temperature/humidity) conditions for 24 hours, (b) exposure to high temperature, i.e. , 80°C in an oven for 24 hours and (c) exposure to humidity, i.e. 95 % relative humidity at 65 °C for 24 hours.
  • the surface resistivity for the before and after environmental exposure is reported in Table 5 for each of the nominal resistivity rated IZO coated PET substrates.
  • this atomic percent ratio is a ratio of atomic percents; i.e. , the ratio of the atomic percent of indium to the atomic percent of Zn wherein the percentage of In and Zn atoms is based upon the total number of In and Zn atoms.
  • the method and apparatus described in Example 1 was used except that the atmosphere was increased to 2.0m Torr with an argon/oxygen ratio increased to 70:6; and, the plasma power was doubled. Sputtering parameters for three passes are set out below in Tables 6-8. Table 6
  • the IZO coated PET substrates prepared according to the Example 2 were evaluated for spectral optical properties, mechanical properties and environmental resistance as described in Example 1.
  • the Spectral optical properties are reported in Tables 9 and 10.
  • the IZO coated PET substrates prepared in Example 2 were also tested for environmental resistance with results reported in Table 10.
  • InO x , ITO (90: 10), IZO (90: 10) and IZO (97:3) films of various sheet resistances were prepared using the sputter coater of figure 2 wherein the coating was deposited onto the substrate using DC magnetron sputtering. This comparison demonstrates the superior mechanical properties of IZO (97:3) compared to InO x , ITO (90: 10) and IZO (90: 10).
  • IZO metallic shows best flexibility results and is thinnest to achieve same ohms/sq. compared with IZO (90: 10) and ITO (90: 10).
  • 30 ohms/sq. IZO (97:3) has lower stress and more flexibility compared to IZO (90: 10) and ITO (90: 10).
  • Optical spectrum of 30 ohms/sq. shows that IZO (97:3) is thinner than all 30 ohms/sq. IZO (90: 10), and ITO (90: 10).
  • Optical spectrum of 100 ohms/sq. transparent conductors shows that 100 ohms/sq. IZO (97:3) and IZO (90: 10) thickness are close while ITO (90: 10) and InO x are thicker.
  • the flexibility and durability of 100 ohms/sq. IZO (97:3) is good due to thinner thickness achieved at the same resistance.
  • Table 15 shows all 300 ohms/sq. sheet resistance transparent conductors with the exception of InO x shows good durability and flexibility.
  • Figure 17 shows IZO (97:3) is superior to all other 300 ohms/sq. transparent conductors as it is thinner than other Transparent Conductors to achieve the same 300 ohms/sq.
  • IZO coatings of this invention show the advantages of IZO coatings of this invention.
  • the IZO coatings having the In:Zn atomic percent ratio of 97:3 showed excellent optical quality with a low yellow index, e.g. compared to ITO coatings.
  • Mechanical properties were much superior to those of ITO coated flexible substrates.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne un composite souple électroconducteur qui comprend une feuille polymère souple transparente (2) enduite d'un revêtement électroconducteur transparent (1) à base d'oxyde de zinc et d'indium. La teneur en zinc du revêtement à base d'oxyde de zinc et d'indium est comprise entre 0,01 et 9,99 en terme de pourcentage atomique par rapport à la quantité totale d'indium et de zinc dans l'oxyde. Par ailleurs, le revêtement à base d'oxyde de zinc et d'indium présente une résistance de couche comprise entre 3 et 1000 ohms par carré. Le revêtement électroconducteur à base d'oxyde de zinc et d'indium est déposé par pulvérisation sur ladite feuille.
PCT/US2002/025980 2001-09-14 2002-09-13 Conducteur transparent haute transmission durable a faible ohm Ceased WO2003024712A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02775710A EP1451009A1 (fr) 2001-09-14 2002-09-13 Conducteur transparent haute transmission durable a faible ohm

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US95144701A 2001-09-14 2001-09-14
US09/951,447 2001-09-14

Publications (1)

Publication Number Publication Date
WO2003024712A1 true WO2003024712A1 (fr) 2003-03-27

Family

ID=25491692

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2002/025980 Ceased WO2003024712A1 (fr) 2001-09-14 2002-09-13 Conducteur transparent haute transmission durable a faible ohm

Country Status (2)

Country Link
EP (1) EP1451009A1 (fr)
WO (1) WO2003024712A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2924723A1 (fr) * 2007-12-11 2009-06-12 Centre Nat Rech Scient Support solide revetu d'au moins un film de metal et d'au moins une couche d'oxyde transparent et conducteur pour la detection par spr et/ou par une methode electrochimique
DE102010004991A1 (de) 2010-01-19 2011-07-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 80686 Verfahren zum Vakuumbeschichten eines Substrates mit einem transparenten leitfähigen Metalllegierungsoxid sowie eine transparente leitfähige Schicht aus einem Metalllegierungsoxid
EP2393955A4 (fr) * 2009-02-04 2015-04-22 Heliovolt Corp Procédé de fabrication d'un film d'oxyde conducteur transparent contenant de l'indium, cibles métalliques utilisées dans le procédé et dispositifs photovoltaïques utilisant lesdits films
CN113956022A (zh) * 2021-11-30 2022-01-21 郑州大学 一种锌掺杂氧化铟粉体、溅射靶材及其制备方法
CN115976481A (zh) * 2022-12-23 2023-04-18 南京航空航天大学 一种靶材、金属钽表面复合梯度陶瓷涂层的制法及其所得涂层

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08264021A (ja) * 1995-03-26 1996-10-11 Gunze Ltd 透明導電膜
US6420032B1 (en) * 1999-03-17 2002-07-16 General Electric Company Adhesion layer for metal oxide UV filters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08264021A (ja) * 1995-03-26 1996-10-11 Gunze Ltd 透明導電膜
US6420032B1 (en) * 1999-03-17 2002-07-16 General Electric Company Adhesion layer for metal oxide UV filters

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MINAMI T.: "Highly transparent and conductive ZnO-In2O3 thin films prepared by d.c. magnetron sputtering", THIN SOLID FILMS 290-291, 1996, pages 1 - 5, XP000693798 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2924723A1 (fr) * 2007-12-11 2009-06-12 Centre Nat Rech Scient Support solide revetu d'au moins un film de metal et d'au moins une couche d'oxyde transparent et conducteur pour la detection par spr et/ou par une methode electrochimique
WO2009074660A1 (fr) * 2007-12-11 2009-06-18 Centre National De La Recherche Scientifique (Cnrs) Support solide revetu d'au moins un film de metal et d'au moins une couche d'oxyde transparent et conducteur pour la detection par spr et/ou par une methode electrochimique
EP2393955A4 (fr) * 2009-02-04 2015-04-22 Heliovolt Corp Procédé de fabrication d'un film d'oxyde conducteur transparent contenant de l'indium, cibles métalliques utilisées dans le procédé et dispositifs photovoltaïques utilisant lesdits films
DE102010004991A1 (de) 2010-01-19 2011-07-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 80686 Verfahren zum Vakuumbeschichten eines Substrates mit einem transparenten leitfähigen Metalllegierungsoxid sowie eine transparente leitfähige Schicht aus einem Metalllegierungsoxid
WO2011088875A1 (fr) 2010-01-19 2011-07-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de revêtement sous vide d'un substrat par un oxyde d'alliage métallique conducteur transparent et couche conductrice transparente faite d'un oxyde d'alliage métallique
CN113956022A (zh) * 2021-11-30 2022-01-21 郑州大学 一种锌掺杂氧化铟粉体、溅射靶材及其制备方法
CN115976481A (zh) * 2022-12-23 2023-04-18 南京航空航天大学 一种靶材、金属钽表面复合梯度陶瓷涂层的制法及其所得涂层

Also Published As

Publication number Publication date
EP1451009A1 (fr) 2004-09-01

Similar Documents

Publication Publication Date Title
EP0781076B1 (fr) Laminé transparent conducteur et élément électroluminescent
EP0030732B1 (fr) Film transparent électriquement conducteur et procédé pour sa fabrication
EP0049083B1 (fr) Pellicule stratifiée
KR100726747B1 (ko) 전자파 차폐 적층체 및 이를 이용한 디스플레이 장치
EP1720175B1 (fr) Film conducteur transparent et mat riau de base conducteur transparent utilisant ledit film
EP2115185A1 (fr) Corps stratifié conducteur et son procédé de préparation
Sahu et al. Development of ZnO-based transparent conductive coatings
JP4010587B2 (ja) 透明導電性積層体及びそれを用いたエレクトロルミネッセンス発光素子
KR101884643B1 (ko) 아연이 도핑된 주석산화물계 투명 전도성 산화물, 이를 이용한 다층 투명 전도막 및 그 제조 방법
EP1451009A1 (fr) Conducteur transparent haute transmission durable a faible ohm
JP7451505B2 (ja) 透明導電性フィルムの製造方法
JP3511337B2 (ja) 透明導電性積層体及びその製造方法
Lee et al. Heat treatment effects on electrical and optical properties of ternary compound In 2 O 3–ZnO films
JPH07249316A (ja) 透明導電膜および該透明導電膜を用いた透明基体
JP2002343150A (ja) 透明導電性フィルム及びその製造方法
JP2000108244A (ja) 透明導電膜とその製造方法および透明導電膜付き基体
JPH06251632A (ja) 屈曲性に優れた透明導電性フィルムおよびその製造法
KR20150080849A (ko) 복합체 투명 전극
KR101174359B1 (ko) 금속층을 포함하는 다성분 금속산화물계 투명전극 및 그 제조방법
Reddy et al. Development and environmental stability of ITO thin film for spacecraft application
WO2021187575A1 (fr) Film conducteur transmettant la lumière et film conducteur transparent
JP7534374B2 (ja) 透明導電性フィルムの製造方法
US12156330B2 (en) Light-transmitting electroconductive film and transparent electroconductive film
CN115315758B (zh) 透明导电性薄膜
WO2023042848A1 (fr) Film conducteur transparent

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY BZ CA CH CN CO CR CU CZ DE DM DZ EC EE ES FI GB GD GE GH HR HU ID IL IN IS JP KE KG KP KR LC LK LR LS LT LU LV MA MD MG MN MW MX MZ NO NZ OM PH PL PT RU SD SE SG SI SK SL TJ TM TN TR TZ UA UG UZ VC VN YU ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZM ZW AM AZ BY KG KZ RU TJ TM AT BE BG CH CY CZ DK EE ES FI FR GB GR IE IT LU MC PT SE SK TR BF BJ CF CG CI GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2002775710

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2002775710

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 2002775710

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP