WO2005037418A2 - Processes for fabricating conductive patterns using nanolithography as a patterning tool - Google Patents
Processes for fabricating conductive patterns using nanolithography as a patterning tool Download PDFInfo
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- WO2005037418A2 WO2005037418A2 PCT/US2004/027631 US2004027631W WO2005037418A2 WO 2005037418 A2 WO2005037418 A2 WO 2005037418A2 US 2004027631 W US2004027631 W US 2004027631W WO 2005037418 A2 WO2005037418 A2 WO 2005037418A2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/44—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/38 - H01L21/428
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/06—Coating on selected surface areas, e.g. using masks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/161—Process or apparatus coating on selected surface areas by direct patterning from plating step, e.g. inkjet
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1666—Ultrasonics
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1667—Radiant energy, e.g. laser
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1678—Heating of the substrate
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
- H01L21/461—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/4763—Deposition of non-insulating, e.g. conductive -, resistive -, layers on insulating layers; After-treatment of these layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S438/00—Semiconductor device manufacturing: process
- Y10S438/929—Eutectic semiconductor
Definitions
- nanostructures of metals are needed to provide for smaller and faster computer chips and circuit boards, and metals can provide the required electrical conductivity to complete a circuit. Metals also can be used as catalysts. The processing of metals, however, can be difficult, and operating at the nanoscale can make matters even more difficult. Many methods are limited to micron level manufacturing. Many methods are limited by the need for electrochemical biases or very high temperatures. Moreover, many methods are limited by physical requirements of the deposition process such as ink viscosity. Better methods are needed to fabricate metallic nanostructures by means which provide for, among other things, alignment, ability to layer films and wires, high resolution, and versatility.
- the present invention provides a method of depositing a conductive coating in a desired pattern onto a substrate comprising: (a) depositing a precursor onto the substrate in the desired pattern by nanolithography with use of a tip coated with the precursor, (b) contacting the precursor with a ligand, (c) applying sufficient energy, optionally from an extended radiation source, to transfer electrons from the ligand to the precursor, thereby decomposing the precursor to form a conductive precipitate in the desired pattern and thus forming the conductive pattern directly on the substrate.
- the present invention also provides a method of printing a conductive metal in a desired pattern onto a substrate comprising: (a) drawing a metal precursor and ligand directly onto the substrate according to the desired pattern using nanolithography with use of a tip coated with a precursor; and
- the present invention also provides a nanolithographic method comprising depositing a metallic precursor from a tip onto a substrate to form a nanostructure and subsequently converting the precursor nanostructure to a metallic deposit.
- the deposition can be carried out without use of an electrical bias between the tip and substrate.
- the present invention also provides a nanolithographic method consisting essentially of: depositing an ink composition consisting essentially of a metallic precursor from a nanoscopic tip onto a substrate to form a nanostructure, and subsequently converting the metallic precursor of the nanostructure to a metallic form.
- a nanolithographic method consisting essentially of: depositing an ink composition consisting essentially of a metallic precursor from a nanoscopic tip onto a substrate to form a nanostructure, and subsequently converting the metallic precursor of the nanostructure to a metallic form.
- Basic and novel aspects of the invention are noted throughout this specification, but these aspects include that stamps and resists are not needed, electrochemical bias is not needed, expensive equipment not readily available for typical research laboratories and production facilities is not needed, and reaction between the substrate and the ink is not needed. Accordingly, compositions and inks can be formulated and patterned without these limitations.
- the present invention also provides a method of printing without use of electrochemical bias or reaction between the ink and substrate comprising depositing a metallic precursor ink composition onto a substrate from a tip in the form of a microstructure or nanostructure on the substrate to form an array having discreet objects separated from each other by about one micron or less, about 500 nm or less, or about 100 nm or less.
- the present invention also provides patterned arrays comprising a substrate and discreet nanoscopic and/or microscopic metal deposits thereon prepared by the methods according to this invention.
- the metal deposits can be, for example, rectangles, squares, dots, or lines.
- the present invention also provides methods of using these methods including, for example, preparing sensors, biosensors, and lithographic templates, as well as other applications described herein.
- Figure 1 illustrates AFM data of palladium structures according to the present invention in Working Example 1.
- FIG. 1 illustrates AFM data of palladium structures according to the present invention in Working Example 3.
- FIG. 3 illustrates AFM data of platinum structures according to the present invention in Working Example 4.
- Figure 4 illustrates AFM data of palladium structures according to the present invention in Working Example 5.
- Figure 5 illustrates AFM data of palladium structures according to the present invention in Working Example 5.
- DPNTM and DIP PEN NANOLITHOGRAPHYTM are trademarks of Nanolnk, Inc. and are used accordingly herein (e.g, DPN printing or DIP PEN NANOLITHOGRAPHY printing).
- DPN methods and equipment are generally available from Nanolnk, Inc. (Chicago, IL), .including the NScriptorTM which can be used to carry out the nanolithography according to the present invention.
- Direct- write technologies can be carried out by methods described in, for example, Direct-Write Technologies for Rapid Prototyping Applications: Sensors, Electronics, and Integrated Power Sources, Ed. by A. Pique and D.B. Chrisey, Academic Press, 2002. Chapter 10 by Mirkin, Demers, and Hong, for example, describes nanolithographic printing at the sub- 100 nanometer length scale, and is hereby incorporated by reference (pages 303-312). Pages 311-312 provide additional references on scanning probe lithography and direct- write methods using patterning compounds delivered to substrates from nanoscopic tips which can guide one skilled in the art in the practice of the present invention. This text also describes electrically conductive patterns.
- Nanolithography and nanofabrication is also described in Marc J. Madou's Fundamentals of Microfabrication, The Science of Miniaturization, 2 nd Ed, including metal deposition at pages 344-357.
- a protein can be directly patterned onto a substrate by DPN printing, or a template compound can be patterned which is used to bind a protein.
- DPN printing is an enabling nanofabrication/nanolithographic technology which allows one to practice fabrication and lithography at the nanometer level with exceptional control and versatility. This type of nanofabrication and nanolithography can be difficult to achieve with many technologies that are more suitable for micron scale work.
- the tip can be a nanoscopic tip. It can be a scanning probe microscopic tip including an AFM tip. It can be hollow or non-hollow. Ink can pass through the middle of a hollow tip, coating the end of the tip. The tip can be modified to facilitate printing of the precursor ink. In general, it is preferred that the tip does not react with the ink and can be used over extended periods of time.
- the patterns deposited by the nanolithography are not particularly limited by the shape of the pattern. Common patterns include dots and lines and arrays thereof. The height of the pattern can be, for example, about 10 nm or less, and more particularly about 5 nm or less.
- the lines can be, for example, about one micron wide or less, and more particularly, about 500 nm wide or less, and more particularly about 100 nm wide or less.
- dots can be, for example, about one micron wide in diameter or less, and more particularly, about 500 nm wide or less, and more particularly about 100 nm wide or less.
- the nanolithography is preferably carried out to form nanostructures, structures at a micron scale can be also of interest. For example, experiments used to pattern a structure of 1-10 square microns in area, such as a rectangle, square, dot, or line, can be useful in also designing experiments for smaller nanostructures.
- conductive patterns are formed with use of DPN printing with use of the following steps: 1) depositing a precursor such as, for example, a metal salt, onto a substrate in a desired pattern with use of a coated tip, 2) applying an appropriate ligand onto the substrate, wherein for example the ligand comprises a donor atom such as nitrogen, phosphorous, or sulfur, 3) applying sufficient energy to transfer electrons from the ligand to the precursor by, for example, radiant heat, thereby decomposing the precursor to form a precipitate such as, for example, a metal.
- Metal patterning processes and chemistries are disclosed in (1) U.S. Patent No. 5,980,998 to Sharma et al.
- the ink solution is generally contemplated herein to include a solvent and solute.
- the solvent can be any material capable of solvating the solute, but is generally contemplated to comprise an inexpensive, readily available, relatively non-toxic material such as water, various alcohols and so forth.
- the solute is generally contemplated to include at least two components which chemically react with one another under the influence of an energy source, such that a metal or other substance precipitates out of the solution.
- one component of the solute comprises a salt
- another component of the solute comprises an appropriate ligand.
- salt means any combination of an acid (A) and a base (B).
- metallic salts such as copper formate, acetate, acrylate, thiocyanate, and iodide.
- non-metallic salts such as ammonium formate and ammonium acrylate.
- the various components of the solution may be deposited on the substrate concurrently or sequentially, or in some combination of the two. Thus, it is contemplated that the salt may be deposited concurrently with the ligand, or separately from the ligand.
- the solvent may itself comprise or contribute one or more aspects of the salt or the ligand.
- ligand refers to any substance which can be thermally activated to displace one or more aspects of the salt in a redox reaction, such that AB+LAL+B, or AB+LA+BL.
- preferred ligands are non-crystalline, leave no non-metallic residue, and are stable under normal ambient conditions. More preferred ligands are also capable of taking part in redox reactions with a particular salt being used at reasonable temperatures, which are generally considered to be less than about 300°C.
- a preferred class of ligands are nitrogen donors, including, for example, cyclohexylamine.
- a number of other nitrogen donors and their mixtures may also be used. Examples are 3-picoline, lutidines, quinoline and isoquinoline, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctyl amine, and so forth. These are only a few examples, however, and many othe aliphatic primary, secondary and tertiary amines and/or aromatic nitrogen donors may also be used.
- Contemplated solutions may include other compounds besides salts and ligands. For example, a mixture of copper (II) formate in a nitrogen donor solvent with or without water and an alcohol may be used to facilitate transport from tip to substrate.
- a small amount of a solvent based polymer or a surfactant may also be useful additives for adjusting the rheology of the precursor solution to facilitate transport from tip to substrate, and to impart better film forming properties.
- larger amounts of high boiling solvents and/or additives such as triethylphosphate, Triton XI 00, glycerol, etc., are preferably to be avoided as these have a tendency to contaminate the film produced on account of incomplete pyrolysis over temperature sensitive substrates such as Kapton.TM. or paper.
- the substrate may be worthwhile to treat the substrate with a coupling agent to improve the adhesion of the deposited material to the substrate as a function of the coupling agent's modifying the hydrophobicity or hydrophilicity of the surface of the substrate.
- the salt contains a metal
- all metals are contemplated.
- Preferred metals include conductive elements such as copper, silver and gold, but also include semiconductors such as silicon and germanium.
- metals such as cadmium, chromium, cobalt, iron, lead, manganese, nickel, platinum, palladium, rhodium, silver, tin, titanium, zinc, etc. can be used.
- the term "metal” also includes alloys, metal/metal composites, metal ceramic composites, metal polymer composites, as well as other metal composites.
- the substrate can comprise virtually any substance upon which a compound can be deposited.
- contemplated substrates include metals and non-metals, conductors and non-conductors, flexible and inflexible materials, absorbent and non-absorbent materials, flat and curved materials, textured and non-textured materials, solid and hollow materials, and both large and small objects.
- Particularly preferred substrates are circuit boards, paper, glass, and metal objects. Viewed from another perspective, the wide breadth of contemplated substrates gives some indication of the scope of contemplated objects to which the present teachings may advantageously be applied.
- methods and apparatus taught herein may be used for a variety of applications, including multichip modules, PCMCIA cards, printed circuit boards, silicon wafers, security printing, decorative printing, catalysts, electrostatic shielding, hydrogen transport membranes, functionally gradient materials, production of nanomaterials, battery electrodes, fuel cell electrodes, actuators, electrical contacts, capacitors, and so forth.
- the methods and apparatus can be used as sensors and biosensors.
- the method and apparatus can be used to prepare templates for further lithography such as imprint nanolithography. Using the methods to connect nano wires and nanotubes is of particular interest.
- the substrate is contemplated to represent any suitable substrate, including especially a circuit board, which may or may not be installed in or form part of an electronic device such as a computer, disk drive or other data processing or storage device, a telephone or other communication device, and a battery, capacitor, charger, controller or other energy storage related device.
- Suitable energy sources contemplated herein include any source which is capable of effecting the desired chemical reaction(s) without causing excessive damage to the substrate or the coating.
- particularly preferred energy sources are radiative and convection heat sources, including especially infrared lamps and hot air blowers.
- Other suitable energy sources include electron beams, and radiative devices at non-IR wavelengths including x-ray, gamma ray and ultra-violet.
- Still other suitable energy sources include vibrational sources such as microwave transmitters.
- the various energy sources can be applied in numerous ways.
- the energy source is directed at the precursor/ligand deposited on the substrate.
- a heated ligand could be applied to a cold precursor, or a heated precursor could be applied to a cold ligand.
- Many advantages can be discerned from this invention including, for example, smooth surfaces, good coating adhesion, and control of coating thickness.
- Still another advantage of various embodiments of the present teachings is that coatings can be deposited with a purity of at least 80% by weight.
- the purity of the metal or other material intended to be included in the coating is at least 90%, in still more preferred embodiments the purity is at least 95%, and in most preferred embodiments the purity is at least 97%.
- Still another advantage of various embodiments of the present teachings is that coatings can be deposited with very little waste. In preferred embodiments at least 80% by weight of the material to be deposited on the substrate remains to form the desired pattern. For example, if copper (II) formate is used to produce a copper circuit, then at least 80% of the copper deposited on the substrate can remain to form the desired pattern, and no more than 20% of the copper is removed as "waste".
- the waste is no more than 10%, in still more preferred embodiments the waste is no more than 95%, and in most preferred embodiments the waste is no more than 3%.
- Still another advantage of various embodiments of the present teachings is low temperature operation. Metals, for example, can be deposited in desired patterns at temperatures of less than about 150°C, preferably less than about 100°C, more preferably less than about 75° C, and most preferably at ordinary room temperatures of room temperature (25-30°C).
- the redox or "curing" step can also be performed at relatively low temperatures below about 100°C, more preferably below about 75°C, and even as low as about 50°C. Even lower temperatures are also possible, although below about 50°C. the redox reaction tends to be too slow for most applications.
- inks or patterning compounds are of particular interest for the present invention: copper formate or copper acetate; silver sulfate; silver nitrate; silver tetrafluroborate; palladium chloride, acetate, and acetylacetonate; hexachloroplatinic(IV) acid; ammonium iron citrate; carboxylates, (pseudo- )halides, sulfates, and nitrates of zinc, nickel, cadmium, titanium, cobalt, lead, iron, and tin; irietalcarbonyl complexes, including chromium hexacarbonyl; amine bases, including cyclohexylamine, 3-picoline, (iso)quinoline, cyclopentylamine,
- deposition can be carried out with use of aqueous solutions as ink, wherein the solutions comprise water, metal salt, and a water-soluble polymer such as a polyalkylene oxide polymer having molecular weight of about 50,000 or less.
- Aqueous solutions can be also useful as carriers for the reducing agent.
- deposition of disodium palladium chloride in water with 10% polyethylene oxide (MW 10,000) via DPN printing on amino-silanized glass can be carried out (Schott Glass company), and subsequent chemical reduction to palladium metal using a reducing agent such as, for example, 0.03 M aqueous solution of dimethylamine:borane complex (DMAB).
- a reducing agent such as, for example, 0.03 M aqueous solution of dimethylamine:borane complex (DMAB).
- the concentration of the reducing agent can be varied to determine the best conditions for reduction.
- Atomic force micrographs of the patterns can be obtained before and after reduction.
- AFM imaging can be carried out with the tip which was used to deposit the structure or a different tip. If a different tip is used, the image can be better, particularly if the tip is selected or adapted for imaging rather than deposition.
- polymers which are of commercial use in printing inks can be used in the present invention.
- nanolithographic deposition can be carried out of palladium acetylacetonate (Pdacac) via DPN printing on an oxidized silicon substrate, and subsequent reduction by application of (1) a reducing agent, such as a liquid reducing agent like formamide, and (2) heat to the patterned surface.
- a reducing agent such as a liquid reducing agent like formamide
- Pd(acac) can be dissolved in an organic solvent including a halogenated solvent such as chloroform to form an ink for use in coating a solid tip or passing through a hollow tip.
- Heat treatment can be sufficient to carry out the reduction including temperatures of, for example, about 100°C to about 300°C or about 150°C.
- the heat time, temperature, and atmospheric conditions can be adjusted to achieve the desired pattern. Generally, a heat time of one to five minutes at 150°C can achieve a desired result.
- the stability of the deposited pattern can be examined by solvent rinsing, and the experimental conditions can be varied to improve the stability.
- Nanolithographic deposition experimental variables including substrate and ink composition, also can be varied to provide better resolution.
- AFM micrographs can be obtained before reduction and after application of heat including use of height scan analysis of the patterns.
- the imaging parameters can be varied to improve image resolution.
- a tip such as a gold coated tip can catalyze reduction of a metal salt directly on the cantilever.
- the tip composition can be varied to prevent this.
- an aluminum coated probe can be useful to avoid this reduction on the tip.
- the tips are preferably selected and adapted for long term use and avoid catalyzing reaction with the ink.
- the reduction of a nanolithographically patterned metal salt can be also carried out by vapor reduction rather than liquid phase reduction, wherein the reducing agent is converted to vapor form and passed over the patterned substrate.
- Heaters known in the art can be used to heat the reducing agent to a vapor state as needed. In some cases, this type of treatment can improve the preservation of the original pattern during reduction.
- deposition can be carried out for a silver salt emulsion consisting of ferric ammonium chloride, tartaric acid, silver nitrate, and water onto an amino- silanized glass substrate via DPN printing, followed by development by photoreduction under a UV lamp.
- AFM imaging can be carried out to show patterns.
- the reduction step can be carried out with sufficient heat and sufficient time to reduce the metal salt without use of a chemically reducing agent.
- temperatures below about 400°C can be used, or below about 200°C can be used.
- One skilled in the art can select temperatures and experiment accordingly based on a given ink system and pattern.
- the deposition methods according to this invention also can include one or more pre- deposition steps, one or more probe cleaning or chemical modification steps aimed at improving ink coating; and one or more deposition steps, which may use dip pen nanolithography printing technojogy; one or more post-deposition steps, including cleaning steps and inspection steps.
- Pre-deposition substrate surface treatment steps include but are not limited to (in no particular order):
- chemical cleaning such as, for example, piranha cleaning, basic etching (eg. hydrogen peroxide and ammonium hydroxide);
- Probe cleaning or modification steps include but are not limited to (in no particular order):
- chemical cleaning such as piranha cleaning, basic etching (eg. hydrogen peroxide and ammonium hydroxide),
- Deposition steps include but are not limited to the deposition of one or more inks e.g. by DPNTM printing or deposition with one or more probe(s).
- Possible inks include but are not limited to precursors, compounds that will form the bulk of the final pattern, catalysts, solvents, small molecule or polymeric carrier agents, host matrix materials, or sacrificial reducing agents, and mixtures of above materials. They may be deposited as thin films or as thick multilayers (formed by multiple deposition steps), with or without variation of the chemical composition from layer to layer.
- Post-deposition steps include but are not limited to (in no particular order):
- Heating of the substrate for example with a heat lamp, hot air blower, or hot plate,
- Irradiation of the substrate with electromagnetic radiation e.g., IR, visible, and UV light
- charged particles e.g. electrons, ions drawn from a gun or a plasma source. This process may occur in air, vacuum, or in solution, with or without photosensitizing agents,
- the metallic nanostructures can be in the form of conductive nanoscopic grids which can include nanowires.
- crossbar structures can be formed.
- Metallic layers can be formed on top of each other.
- Structures can be included to integrate the nanoscopic conductive patterns with microscopic and macroscopic testing methods. Resistors, capacitors, electrodes, and inductors can be used as desired to form a circuit. Semiconductors and transistors can be used as desired. Formation of multilayers can be carried out to increase the height of the structure. Different metals can be in different layers of the multilayer. The methods of the invention can be used to electrically connect electrodes. In sensor applications, for example, the metallic deposit can have a resistivity which is modified when an analyte of interest binds to the structure. In biosensor applications, for example, antibody-antigen, DNA hybridization, protein adsorption,-and other-molecular recognition events can be used to. trigger a change in resistivity.
- the methods of this invention can be also used for bar code applications.
- U.S. Patent No. 6,579,742 to Chen describes nanolithographic structures formed by imprinting for nanocomputing and microelectronics applications. Imprinting, however, can suffer from mold stickiness effects.
- USP 6,579,742 nanocomputing applications and structures can be carried out using the nanolithographic methods described herein, and this patent is incorporated by reference in its entirety.
- the substrate can be a protosubstrate as described in, for example, U.S. regular patent application no. 10/444,061 filed May 23, 2003 to Cruchon-Dupeyrat et al "Protosubstrates". This allows electrical conductivity of the printed structure to be examined by macroscopic methods.
- Oxidizing and reducing compounds can be mixed together, applied to the tip, and deposited on the substrate at selected locations by DPNTM printing or deposition.
- the ink mixture can be then heated (either by heating of the whole substrate or by local probe-induced heating).
- a metal salt and organic ligand cocktail can be used.
- a typical ink formulation can comprise a metal salt (e.g. carboxylate, nitrate, or halide) along with an appropriate organic Lewis base or ligand (amines, phosphines).
- Additives small molecules such as ethyleneglycol, polymers such as polyethyleneoxide, PMMA, polyvinylcarbazol, etc
- additives small molecules such as ethyleneglycol, polymers such as polyethyleneoxide, PMMA, polyvinylcarbazol, etc
- gentle heating in an ambient or inert environment e.g., 40-200°C
- This approach enables deposition of a variety of metals or metal oxides including, for example copper, under mild conditions with very little organic contaminant [see, for example, Sharma et al., U.S. Patent No.
- Example 1 One specific example of the use of this method used DPNTM printing or deposition to pattern palladium acetylacetonate dissolved in chloroform (1 mg/microliter; generally, almost saturated solutions of inks are desired) on oxidized silicon, glass, or amino-silanized glass. After patterning of the dots, a droplet (1 microlitre) of formamide was placed on the horizontal substrate and heated to 150°C for 2 min. The resulting metal patterns were stable towards solvent rinsing (including water, alcohols, and other non-polar organics) while the salt patterns prior to reduction were removed by solvent rinsing.
- Fig. 1 shows AFM images and a height scan of the patterns before (Fig. la) and after treatment (Fig. lb and lc) with formamide and heat.
- Example 2 Palladium nanopatterns were deposited by DPN printing and metallized by vapor reduction.
- a DPN ink consisting of palladium acetate in dimethylformamide was patterned onto silicon oxide using the DPN technique.
- the DPN pen used was a silicon nitride probe with a gold coating. This process also works well with aluminum coated DPN probes because the Al coating does not catalyze the reduction of the metal salt directly onto the cantilever as does the gold coated probes.
- Prior to patterning the silicon/silicon oxide wafer was cleaned by sonication in millipore water for 5 minutes. The patterned substrate was placed vertically in a conical polyethylene tube and 10 microlitres of formamide liquid was placed in the bottom of the tube.
- the tube was placed on a heating block and heated at 80°C for 30 min. so that the vapor caused reduction of the metal precursor. This method is useful because it preserves the metal pattern on the substrate.
- the resulting metal structures are resistive to solvent rinsing and other common methods of cleaning.
- Example 3 Palladium nanopatterns deposited by DPN metallized by chemical reduction.
- a DPN ink consisting of disodium palladium chloride in water with 10% polyethyleneoxide (MW 10,000) was patterned onto amino-silanized glass (Schott Glass company) using the DPN technique.
- the patterned substrate was exposed to a solution of 0.03M aqueous solution of dimethylamine:borane complex (DMAB) to cause reduction of the metal precursor to conducting metal.
- DMAB dimethylamine:borane complex
- the resulting metal structures are resistive to solvent rinsing.
- Fig. 2 shows AFM images and a height scan of the patterns before (2a) and after (2b, 2c) treatment with DMAB.
- Example 4 Platinum nanopatterns deposited by DPN metallized by chemical reduction.
- a DPN ink consisting of platinum tetrachloride in water was patterned onto amino-silanized glass (Schott Glass company) using the DPN technique.
- the patterned substrate was exposed to a solution of 0.03M aqueous solution of dimethylamine:borane complex (DMAB) to cause reduction of the - metal precursor to conducting metal.
- DMAB dimethylamine:borane complex
- the reduction reaction occurs within seconds of immersion.
- the resulting metal structures are resistive to solvent rinsing.
- Fig. 3 shows an AFM height scan of platinum nanostructures deposited by DPN and reduced by DMAB.
- Example 5 Palladium patterns deposited by DPN.
- a DPN ink consisting of palladium acetate in dimethylformamide was patterned onto silicon oxide using the DPN technique. Prior to patterning the substrate was cleaning in piranha solution for 15 min at 80°C. After patterning the substrate was heated using a hot plate in air for at least 1 minute. After heating the pattern was imaged by AFM.
- the resulting metal structures show high topography and are resistive to solvent rinsing and other common methods of cleaning.
- Fig. 4 and Fig. 5 shows a desired structure design (left figure) and actual patterns before reduction (center figures) and after thermal reduction (right figures). The imaging of these patterns, particularly those patterns already reduced, can be improved by, for example, using clean tips not used for deposition.
- Embodiment 1 A method of depositing a conductive coating in a desired pattern onto a substrate comprising: depositing a precursor onto the substrate in the desired pattern by nanolithography with use of a tip coated with the precursor, contacting the precursor with a ligand, applying sufficient energy to transfer electrons from the ligand to the precursor, thereby decomposing the precursor to form a conductive precipitate in the desired pattern and thus forming the conductive pattern directly on the substrate.
- Embodiment 2 The embodiment according to Embodiment 1, wherein the tip is a nanoscopic tip.
- Embodiment 3 The embodiment according to Embodiment 1, wherein the tip is a scanning probe microscopic tip.
- Embodiment 4 The embodiment according to Embodiment 1, wherein the tip is an atomic force microscope tip.
- Embodiment 5 The embodiment of Embodiment 1, wherein the coating comprises a metal with a purity of at least about 80%.
- Embodiment 6 The embodiment of Embodiment 1, wherein the coating comprises a metal with a thickness of less than about 10 angstroms.
- Embodiment 7 The embodiment of Embodiment 1, wherein the coating comprises a metal with a thickness of at least about 100 angstroms.
- Embodiment 8 The embodiment of Embodiment 1, wherein the precursor comprises a salt selected from the group consisting of a carboxylate, a halide, a pseudohalide, and a nitrate.
- Embodiment 9 The embodiment of Embodiment 1, wherein the precursor comprises a carboxylate.
- Embodiment 10 The embodiment of Embodiment 1, wherein the pattern comprises a circuit.
- Embodiment 11 The embodiment of Embodiment 1, wherein the ligand comprises a material selected from the group consisting of an amine, an amide, a phosphine, a sulfide, and an ester.
- Embodiment 12 The embodiment of Embodiment 1 wherein the ligand is selected from the group consisting of a nitrogen donor, a sulphur donor, and a phosphorous donor.
- Embodiment 13 The embodiment of Embodiment 1 wherein the precipitate comprises a metal.
- Embodiment 14 The embodiment of Embodiment 1, wherein the precipitate is selected from the group consisting of copper, zinc, palladium, platinum, silver, gold, cadmium, titanium, cobalt, lead, tin, silicon and germanium.
- Embodiment 15 The embodiment of embodiment 1, wherein the precipitate comprises an electrical conductor.
- Embodiment 16 The embodiment of embodiment 1, wherein the precipitate comprises an electrical semiconductor.
- Embodiment 17 The embodiment of Embodiment 1, wherein the substrate comprises a non-conductor.
- Embodiment 18 The embodiment of Embodiment 1 wherein the substrate comprises at least one of a conductor and a semiconductor.
- Embodiment 19 The embodiment of Embodiment 1, wherein the step of applying energy comprises applying heat.
- Embodiment 20 The embodiment of Embodiment 1, wherein the step of applying energy comprises applying infra red radiation or UV radiation.
- Embodiment 21 The embodiment of Embodiment 1, wherein the step of applying energy comprises applying vibrational energy.
- Embodiment 22 The embodiment of Embodiment 1, wherein the precursor comprises a salt selected from the group consisting of a carboxylate, a halide, a pseudo halide, a nitrate, and the ligand comprises a material selected from the group consisting of an amine, an amide, a phosphine, a sulfide and an ester.
- Embodiment 23 The embodiment of Embodiment 19, wherein the precipitate is selected from the group consisting of copper, zinc, palladium, platinum, silver, gold, cadmium, titanium, cobalt, lead, tin, silicon and germanium.
- Embodiment 24 The embodiment of Embodiment 19, wherein the step of applying energy comprises applying radiant heat.
- Embodiment 25 A method of printing a conductive metal in a desired pattern onto a substrate comprising: drawing a metal precursor and ligand directly onto the substrate according to the desired pattern using nanolithography with use of a tip coated with a precursor; and decomposing the precursor by applying energy to form the conductive metal in the desired pattern, without removing from the substrate a substantial quantity of the precursor, and without removing from the substrate a substantial quantity of the metal.
- Embodiment 26 The embodiment of Embodiment 25, wherein the metal pattern comprises a substantially pure metal, with impurities less than about 20% by weight.
- Embodiment 27 The embodiment of Embodiment 25, wherein the step of decomposing comprises thermally decomposing.
- Embodiment 28 The embodiment of Embodiment 25, wherein the step of decomposing comprises thermally decomposing at a temperature of less than about 300°C.
- Embodiment 29 The embodiment of Embodiment 25, wherein the metal is selected from the group consisting of an elemental metal, an alloy, a metal/metal composite, a metal ceramic composite, and a metal polymer composite.
- Embodiment 30 A nanolithographic method comprising: depositing a metallic precursor from a tip onto a substrate to form a nanostructure, and subsequently converting the precursor nanostructure to a metallic deposit.
- Embodiment 31 The embodiment according to Embodiment 30, wherein the deposition and conversion is carried out without use of an electrical bias between the tip and substrate.
- Embodiment 32 The embodiment according to Embodiment 30, wherein the deposition and conversion is carried out with use of a chemical agent other than the substrate.
- Embodiment 33 The embodiment according to Embodiment 30, wherein the tip is a nanoscopic tip.
- Embodiment 34 The embodiment according to Embodiment 30, wherein the tip is a scanning probe microscopic tip.
- Embodiment 35 The embodiment according to Embodiment 30, wherein the tip is an AFM tip.
- Embodiment 36 The embodiment according to Embodiment 35, wherein the deposition and conversion is carried out without use of an electrical bias between the tip and substrate.
- Embodiment 37 The embodiment according to Embodiment 30, wherein the method is repeated to form a multilayer.
- Embodiment 38 The embodiment according to Embodiment 30, wherein the tip is adapted to not react with the precursor.
- Embodiment 39 The embodiment according to Embodiment 30, wherein the method is used to connect at least one nanowire with another structure.
- Embodiment 40 The embodiment according to Embodiment 30, wherein the method is used to connect at least two electrodes.
- Embodiment 41 The embodiment according to Embodiment 30, wherein the method is used to prepare a sensor.
- Embodiment 42 The embodiment according to Embodiment 30, wherein the method is used to fabricate a lithographic template.
- Embodiment 43 The embodiment according to Embodiment 30, wherein the method is used to prepare a biosensor.
- Embodiment 44 A nanolithographic method consisting essentially of: depositing an ink composition consisting essentially of a metallic precursor from a nanoscopic tip onto a substrate to form a nanostructure, and subsequently converting the metallic precursor of the nanostructure to a metallic form.
- Embodiment 45 The embodiment according to Embodiment 44, wherein the conversion is a thermal conversion without use of a chemical agent.
- Embodiment 46 The embodiment according to embodiment 44, wherein the conversion is a chemical conversion carried out with use of a reducing agent.
- Embodiment 47 The embodiment according to embodiment 44, wherein the reducing agent is used in the vapor state to carry out the conversion.
- Embodiment 48 The embodiment according to embodiment 44, wherein the tip is an AFM tip.
- Embodiment 49 The embodiment according to embodiment 44, wherein the tip comprises a surface which does not react with the precursor.
- Embodiment 50 A method according to Embodiment 44, wherein the method is repeated a plurality of times to generate a multi-layer structure.
- Embodiment 51 A method of printing without use of electrochemical bias or reaction between the ink and substrate comprising depositing a metallic precursor ink composition onto a substrate from a tip in the form of a microstructure or nanostructure on the substrate to form an array having discreet objects separated from each other by about one micron or less.
- Embodiment 52 The embodiment according to Embodiment 51, further comprising the step of forming metal from the precursor.
- Embodiment 53 The embodiment according to embodiment 51, wherein the discreet objects are separated from each other by about 500 nm or less.
- Embodiment 54 The embodiment according to Embodiment 51 , wherein the discreet objects are separated from each other by about 100 nm or less.
Abstract
Description
Claims
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JP2006524826A JP4740850B2 (en) | 2003-08-26 | 2004-08-26 | Method for depositing conductive film of desired pattern on substrate |
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KR1020067003809A KR101084395B1 (en) | 2003-08-26 | 2004-08-26 | Processes for Fabricating Conductive Patterns Using Nanolithography as a Patterning Tool |
CA2537023A CA2537023C (en) | 2003-08-26 | 2004-08-26 | Processes for fabricating conductive patterns using nanolithography as a patterning tool |
HK07104046.9A HK1097954A1 (en) | 2003-08-26 | 2007-04-18 | Processes for fabricating conductive patterns using nanolithography as a patterning tool |
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US10/647,430 US7005378B2 (en) | 2002-08-26 | 2003-08-26 | Processes for fabricating conductive patterns using nanolithography as a patterning tool |
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Cited By (3)
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JP2010530126A (en) * | 2006-12-18 | 2010-09-02 | ノースウエスタン ユニバーシティ | Manufacturing method of microstructure and nano structure using etching resist |
JP2012528736A (en) * | 2009-06-05 | 2012-11-15 | ノースウェスタン ユニバーシティ | Silicon pen nanolithography |
CZ303566B6 (en) * | 2010-11-30 | 2012-12-12 | Deposition method of metallic nanoparticles onto substrate surface |
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CA2537023C (en) | 2012-02-07 |
KR101084395B1 (en) | 2011-11-18 |
US20040127025A1 (en) | 2004-07-01 |
EP1665360A2 (en) | 2006-06-07 |
JP2007503725A (en) | 2007-02-22 |
HK1097954A1 (en) | 2007-07-06 |
EP1665360A4 (en) | 2011-03-30 |
WO2005037418A3 (en) | 2006-03-23 |
KR20070026297A (en) | 2007-03-08 |
CA2537023A1 (en) | 2005-04-28 |
JP4740850B2 (en) | 2011-08-03 |
CN100583401C (en) | 2010-01-20 |
US7005378B2 (en) | 2006-02-28 |
CN1875469A (en) | 2006-12-06 |
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