WO2007005525A1 - Coated article with transparent conductive oxide film doped to adjust fermi level, and method of making same - Google Patents
Coated article with transparent conductive oxide film doped to adjust fermi level, and method of making same Download PDFInfo
- Publication number
- WO2007005525A1 WO2007005525A1 PCT/US2006/025379 US2006025379W WO2007005525A1 WO 2007005525 A1 WO2007005525 A1 WO 2007005525A1 US 2006025379 W US2006025379 W US 2006025379W WO 2007005525 A1 WO2007005525 A1 WO 2007005525A1
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- WIPO (PCT)
- Prior art keywords
- dopant
- transparent conductive
- film
- conductive film
- coated article
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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
- C23C14/06—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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/216—ZnO
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/24—Doped oxides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3289—Noble metal oxides
- C04B2235/3291—Silver oxides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/402—Aluminium
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/408—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
- C04B2235/9653—Translucent or transparent ceramics other than alumina
Definitions
- This invention relates to a coated article including a transparent conductive oxide (TCO) film that is doped to adjust the Fermi level, and a method of making the same.
- a TCO such as zinc aluminum oxide (ZnAlO x ) or the like is doped with an acceptor or co-dopant such as. silver (Ag) or the like.
- the silver co-dopant prevents or reduces self-compensation of the primary dopant by native defects as well as promotes declustering of the primary dopant (e.g., Al) thereby freeing up space in the sublattice and permitting more Al to function as a donor.
- conductivity of the TCO film can be improved.
- this technique also permits good quality TCO inclusive films to be deposited at low temperatures (e.g., via sputtering).
- Coated articles according to certain example non-limiting embodiments of this invention may be used in applications such as solar cells, oven doors, defrosting windows, or other types of windows in certain example instances.
- sputter-depositing a TCO inclusive film at a low temperature e.g., less than about 150 degrees C, more preferably less than about 100 degrees C, and possibly at approximately room temperature
- a low temperature e.g., less than about 150 degrees C, more preferably less than about 100 degrees C, and possibly at approximately room temperature
- the use of both the primary dopant and the co-dopant in depositing (e.g., sputter-depositing) the TCO inclusive film prevents or reduces the formation of compensating native defects in a wide-bandgap semiconductor material during the impurity introduction by controlling the Fermi level at or proximate the edge of the growth.
- the provision of the co-dopant promotes declustering of the primary dopant, thereby freeing up space in the metal sublattice and permitting more Al to function as a charge carrier so as to improve conductivity of the film. Accordingly, the use of the co-dopant permits the primary dopant to be more effective in enhancing conductivity of the TCO inclusive film, without significantly sacrificing visible transmission characteristics. Furthermore, the use of the co-dopant improves crystallinity of the TCO inclusive film and thus the conductivity thereof, and grain size may also increase which can lead to increased mobility.
- the TCO film may be sputter-deposited on a glass substrate (either directly or indirectly) at approximately room temperature.
- a glass substrate either directly or indirectly
- a zinc oxide based film includes Al as a primary dopant and Ag as a co-dopant.
- the Al is the primary charge provider.
- Ag facilitates the introduction of the primary donor dopant (Al).
- Certain example embodiments of this invention may also use the ability of silver to promote the uniform or substantially uniform distribution of donor- like dopants in wide-bandgap II- VI compounds, thereby allowing one to increase the effective dopant concentration in a poly-crystalline film.
- silver is used as a co-dopant in certain example embodiments of this invention, it is possible to use another Group IB, IA or V element such as Cu or Au instead of or in addition to silver as the co-dopant.
- a method of making a coated article including a transparent conductive film comprising: providing a glass substrate; sputtering at least one target comprising each of zinc, aluminum and silver in an atmosphere comprising oxygen so as to form a transparent conductive film on the glass substrate.
- a method of making a coated article including a transparent conductive film comprising: providing a substrate; sputtering at least one target comprising each of zinc, a primary metal dopant, and a co-dopant of at least one Group IB, IA or V element, wherein the sputtering is performed in an atmosphere comprising oxygen so as to form a transparent conductive film comprising zinc, oxygen, the primary metal dopant and the co-dopant on the substrate.
- a coated article comprising: a transparent conductive film provided on a glass substrate; and wherein the transparent conductive film comprises zinc aluminum oxide that is doped with silver in order to enhance electrical properties of the film.
- a coated article comprising: a transparent conductive film provided on a substrate; and wherein the transparent conductive film comprises MAl oxide that is doped with silver in order to enhance electrical properties of the film.
- the metal M may be Zn or the like in certain example embodiments.
- FIGURE 1 is a cross-sectional view of a coated article according to an example embodiment of this invention.
- FIGURE 2 is a schematic diagram of a method of making a coated article according to an example embodiment of this invention.
- Coated articles including conductive layer(s) may be used in applications such as solar cells, oven doors, defrosting windows, or other types of windows in certain example instances.
- the conductive layers discussed herein may be used as electrodes in solar cells, as heating layers in defrosting windows, as solar control layers in windows, or the like.
- Fig. 1 is a cross-sectional view of a coated article according to an example embodiment of this invention.
- the coated article includes glass substrate 1 and transparent electrically conductive layer 3 that is provided on the substrate.
- Glass 1 may be soda-lime-silica glass in certain example embodiments of this invention, although other types of glass may instead be used.
- conductive film 3 may be of or include a transparent conducive oxide (TCO).
- TCO transparent conducive oxide
- other layers may be provided between the glass substrate 1 and the transparent conductive layer 3.
- Layer 3 is said to be on the substrate 1, regardless of whether other layer(s) are provided therebetween.
- the coated article has a visible transmission of at least about 30%, more preferably of at least about 50%, and even more preferably of at least about 70%.
- TCO inclusive film In certain example embodiments of this invention, TCO inclusive film
- the film 3 is sputter-deposited onto substrate 1 at a low temperature (e.g., less than about 150 degrees C, more preferably less than about 100 degrees C, and possibly at approximately room temperature) so as to include both a primary dopant and a co- dopant.
- the film 3 may be zinc oxide based, the primary dopant may be Al, and the co-dopant may be Ag.
- the TCO film 3 may be of or include ZnAlO x :Ag, where Ag is the co-dopant.
- Al is the primary charge carrier dopant.
- the amount of primary dopant (e.g., Al) in the film 3 may be from about 0.5 to 7%, more preferably from about 0.5 to 5%, and most preferably from about 1 to 4% (atomic %).
- the amount of co-dopant (e.g., Ag) in the film 3 may be from about 0.001 to 3%, more preferably from about 0.01 to 1%, and most preferably from about 0.02 to 0.25% (atomic %).
- the TCO inclusive film e.g., ZnAlO x :Ag 3
- the TCO inclusive film e.g., ZnAlO x :Ag 3
- the Fermi level is lowered at the growth edge by the addition of a small amount of acceptor impurity (such as Ag) so it prevents the formation of the compensating (negative in this case) species, such as zinc vacancies.
- the mobility of atoms is reduced and the probability of the point defect formation is primarily determined by the respective energy gain.
- Silver atoms in this particular case tend to occupy interstitial sites where they play role of predominantly neutral centers, forcing Al atoms to the preferable zinc substitutional sites, where Al plays the desired role of shallow donors, thus eventually raising the Fermi level.
- the provision of the co-dopant (Ag) promotes declustering of the primary dopant (Al), thereby freeing up space in the metal sublattice of the film 3 and permitting more primary dopant (Al) to function as a charge provider so as to improve conductivity of the film.
- Fig. 2 is a schematic diagram illustrating an example of how the TCO inclusive film 3 may be sputter-deposited on substrate 1 according to an example embodiment of this invention.
- the TCO film 3 may be sputter-deposited on glass substrate 1 (either directly or indirectly) at approximately room temperature.
- the glass substrate may move in direction 8 under the sputtering target 5 so as to permit the film 3 to be formed thereon.
- a sputtering target(s) 5 is provided.
- the sputtering target may be a rotatable magnetron type sputtering target, or alternatively may be a planar sputtering target, or any other suitable type of sputtering target.
- the target 5 is made of or includes ZnAlAg, where Zn is the primary metal of the target, Al is the primary dopant, and Ag is the co-dopant.
- the target 5 is characterized by Zn>Al>Ag, where at least 50% of the target is made up of Zn (more preferably at least 70%, and most preferably at least 80%).
- the amount of primary dopant (e.g., Al) in the target 5 may be from about 0.5 to 7%, more preferably from about 0.5 to 5%, and most preferably from about 1 to 4% (atomic %); and the amount of co-dopant (e.g., Ag) in the target 5 may be from about 0.001 to 3%, more preferably from about 0.01 to 1%, and most preferably from about 0.02 to 0.25% (atomic %).
- the target is typically sputtered in an atmosphere include oxygen gas (e.g., O 2 ).
- the atmosphere in which the target is sputtered may include a mixture of oxygen and argon gas.
- the oxygen from the atmosphere contributes to forming the "oxide" nature of the film 3 on the substrate.
- gases e.g., nitrogen
- some of this may end up in the film 3 on the substrate.
- the sputtering target 5 may be a ceramic target.
- target 5 may be of or include ZnAlAgO x .
- a ceramic target may be advantageous in this respect because less oxygen gas would be required in the atmosphere in which the target is sputtered (e.g., and more Ar gas for example could be used).
Abstract
Description
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2610979A CA2610979C (en) | 2005-07-05 | 2006-06-29 | Coated article with transparent conductive oxide film doped to adjust fermi level, and method of making same |
BRPI0612688-0A BRPI0612688A2 (en) | 2005-07-05 | 2006-06-29 | Item coated with doped transparent conductive oxide film to adjust fermi level and method for its manufacture |
EP06785848A EP1919837A1 (en) | 2005-07-05 | 2006-06-29 | Coated article with transparent conductive oxide film doped to adjust fermi level, and method of making same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/173,157 US7628896B2 (en) | 2005-07-05 | 2005-07-05 | Coated article with transparent conductive oxide film doped to adjust Fermi level, and method of making same |
US11/173,157 | 2005-07-05 |
Publications (1)
Publication Number | Publication Date |
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WO2007005525A1 true WO2007005525A1 (en) | 2007-01-11 |
Family
ID=37433755
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2006/025379 WO2007005525A1 (en) | 2005-07-05 | 2006-06-29 | Coated article with transparent conductive oxide film doped to adjust fermi level, and method of making same |
Country Status (5)
Country | Link |
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US (2) | US7628896B2 (en) |
EP (1) | EP1919837A1 (en) |
BR (1) | BRPI0612688A2 (en) |
CA (1) | CA2610979C (en) |
WO (1) | WO2007005525A1 (en) |
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US7628896B2 (en) * | 2005-07-05 | 2009-12-08 | Guardian Industries Corp. | Coated article with transparent conductive oxide film doped to adjust Fermi level, and method of making same |
US8679302B2 (en) | 2005-11-14 | 2014-03-25 | Guardian Industries Corp. | Silicon titanium oxide coating, coated article including silicon titanium oxide coating, and method of making the same |
WO2007118204A2 (en) * | 2006-04-06 | 2007-10-18 | Applied Materials, Inc. | Reactive sputtering zinc oxide transparent conductive oxides onto large area substrates |
US8298380B2 (en) | 2006-05-23 | 2012-10-30 | Guardian Industries Corp. | Method of making thermally tempered coated article with transparent conductive oxide (TCO) coating in color compression configuration, and product made using same |
US7674662B2 (en) * | 2006-07-19 | 2010-03-09 | Applied Materials, Inc. | Process for making thin film field effect transistors using zinc oxide |
US8734621B2 (en) | 2007-01-16 | 2014-05-27 | Alliance For Sustainable Energy, Llc | Transparent conducting oxides and production thereof |
US8747630B2 (en) * | 2007-01-16 | 2014-06-10 | Alliance For Sustainable Energy, Llc | Transparent conducting oxides and production thereof |
US20080254613A1 (en) * | 2007-04-10 | 2008-10-16 | Applied Materials, Inc. | Methods for forming metal interconnect structure for thin film transistor applications |
US7927713B2 (en) * | 2007-04-27 | 2011-04-19 | Applied Materials, Inc. | Thin film semiconductor material produced through reactive sputtering of zinc target using nitrogen gases |
JP5718052B2 (en) | 2007-08-02 | 2015-05-13 | アプライド マテリアルズ インコーポレイテッドApplied Materials,Incorporated | Thin film transistor using thin film semiconductor material |
US8980066B2 (en) * | 2008-03-14 | 2015-03-17 | Applied Materials, Inc. | Thin film metal oxynitride semiconductors |
US8253012B2 (en) * | 2008-03-17 | 2012-08-28 | Alliance For Sustainable Energy, Llc | High quality transparent conducting oxide thin films |
US8143093B2 (en) * | 2008-03-20 | 2012-03-27 | Applied Materials, Inc. | Process to make metal oxide thin film transistor array with etch stopping layer |
US7879698B2 (en) * | 2008-03-24 | 2011-02-01 | Applied Materials, Inc. | Integrated process system and process sequence for production of thin film transistor arrays using doped or compounded metal oxide semiconductor |
US8258511B2 (en) | 2008-07-02 | 2012-09-04 | Applied Materials, Inc. | Thin film transistors using multiple active channel layers |
US20100133094A1 (en) * | 2008-12-02 | 2010-06-03 | Applied Materials, Inc. | Transparent conductive film with high transmittance formed by a reactive sputter deposition |
US20100163406A1 (en) * | 2008-12-30 | 2010-07-01 | Applied Materials, Inc. | Substrate support in a reactive sputter chamber |
US9139465B2 (en) | 2009-08-04 | 2015-09-22 | Lehigh University | Conductive doped metal-glass compositions and methods |
WO2011037829A2 (en) | 2009-09-24 | 2011-03-31 | Applied Materials, Inc. | Methods of fabricating metal oxide or metal oxynitride tfts using wet process for source-drain metal etch |
US8840763B2 (en) * | 2009-09-28 | 2014-09-23 | Applied Materials, Inc. | Methods for stable process in a reactive sputtering process using zinc or doped zinc target |
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CN107253826B (en) * | 2017-05-22 | 2020-08-04 | 美的集团股份有限公司 | Heat insulation glass, preparation method thereof and electric appliance |
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- 2006-06-29 BR BRPI0612688-0A patent/BRPI0612688A2/en not_active IP Right Cessation
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- 2006-06-29 EP EP06785848A patent/EP1919837A1/en not_active Withdrawn
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Also Published As
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US20070007125A1 (en) | 2007-01-11 |
CA2610979C (en) | 2011-05-03 |
US7989072B2 (en) | 2011-08-02 |
US20100040892A1 (en) | 2010-02-18 |
EP1919837A1 (en) | 2008-05-14 |
BRPI0612688A2 (en) | 2010-11-30 |
US7628896B2 (en) | 2009-12-08 |
CA2610979A1 (en) | 2007-01-11 |
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