Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41F—PRINTING MACHINES OR PRESSES
  • B41F17/00—Printing apparatus or machines of special types or for particular purposes, not otherwise provided for
• • 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
• • 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
• • 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
• • 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
  • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
  • H05K3/0079—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the method of application or removal of the mask
• • 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
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/04—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching
  • H05K3/046—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching by selective transfer or selective detachment of a conductive layer
  • H05K3/048—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching by selective transfer or selective detachment of a conductive layer using a lift-off resist pattern or a release layer pattern
• • 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
  • H05K3/1258—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 using a substrate provided with a shape pattern, e.g. grooves, banks, resist pattern
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/60—Forming conductive regions or layers, e.g. electrodes
  • H10K71/611—Forming conductive regions or layers, e.g. electrodes using printing deposition, e.g. ink jet printing
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K99/00—Subject matter not provided for in other groups of this subclass
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
  • B41M2205/14—Production or use of a mask
• • 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
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0242—Shape of an individual particle
  • H05K2201/0257—Nanoparticles
• • 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
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/01—Tools for processing; Objects used during processing
  • H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
  • H05K2203/0108—Male die used for patterning, punching or transferring
• • 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
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/05—Patterning and lithography; Masks; Details of resist
  • H05K2203/0502—Patterning and lithography
  • H05K2203/0537—Transfer of pre-fabricated insulating pattern

Definitions

• This invention pertains to a method for forming a pattern of functional material on a substrate, and in particular, the method uses an elastomeric stamp having a relief surface to form a pattern of open area on the substrate where the functional material is applied.
• Microelectronic devices have long been prepared by photolithographic processes to form the necessary patterns. According to this technique a thin film of conducting, insulating, or semiconducting material is deposited on a substrate and a negative or positive photoresist is coated onto the exposed surface of the material. The resist is then irradiated in a predetermined pattern, and irradiated or non-irradiated portions of the resist are washed from the surface to produce a predetermined pattern of resist on the surface. To form a pattern of a conducting metal material, the metal material that is not covered by the predetermined resist pattern is then etched or removed. The resist pattern is then removed to obtain the pattern of metal material. Photolithography, however, is a complex, multi-step process that is too costly for the printing of plastic electronics.
• the SAM acts as an etch resist when the inked substrate is then immersed in a metal etching solution and all but the SAM protected metal areas are etched away to the underlying substrate. The SAM is then stripped away leaving the metal in the desired pattern.
• a method of transferring a material to a substrate, particularly for light emitting devices, is disclosed by Coe-Sullivan et al. in WO 2006/047215. The method includes selectively depositing the material on a surface of a stamp applicator and contacting the surface of the stamp applicator to the substrate.
• the stamp applicator may be textured, that is have a surface with a pattern of elevations and depressions, or may be featureless, that is, having no elevations or depressions.
• the material is a nanomaterial ink, which includes semiconductor nanocrystals. Direct contact printing of the material on the substrate eliminates the steps associated with printing of SAM in which excess material that does not form the desired microcircuitry pattern from the substrate is etched away or removed.
• Direct microcontact printing of SAM of thiol materials or other materials such as those described in WO 2006/047215 may be achievable in microelectronic devices and components having a high density of features.
• microcontact printing of devices and components having the pattern of fine resolution lines of functional material separated by relatively large featureless areas where no functional material resides can be problematic.
• the stamp can sag in areas between features where the density of features is low or the separation of between features is large.
• Sagging of the relief surface of the stamp is a phenomenon in which a lowermost surface of recessed areas of the relief structure collapse or sag toward an uppermost surface of the raise areas. Sagging may also be called roof collapse of the stamp. Sagging of the relief surface can cause the recessed areas to print material where there should be no material.
• the elastic nature of stamp may contribute to sagging in featureless areas.
• the stamp used for microcontact printing is elastomeric in order for the stamp to sufficiently contact the substrate while conforming to various surfaces including on cylindrical or spherical surfaces, or discontinuous or multiplanar surfaces.
• the features of the stamp may have an aspect ratio (determined by the width of features divided by height of features on the stamp) such that sagging is caused in the recessed areas between the pattern of fine resolution line features.
• a method for forming a pattern of a functional material such as a conductor, semiconductor, or dielectric material, onto a substrate. It is also desirable for such method to have the ease of microcontact printing with an elastomeric stamp, but not be limited to printing onto metals. It is also desirable for such a method to avoid the problem of transfer of the functional material in featureless areas of the pattern.
• Figure 5 is a sectional elevation view of the elastomeric stamp having the layer of mask material on the raised surface of the relief structure contacting a substrate.
• Figure 6 is a sectional elevation view of the elastomeric stamp separating from the substrate, and transferring the mask material on the raised surface to the substrate to form a pattern of mask material.
• Figure 7 is a sectional elevation view of the substrate with the pattern of mask material on a platform of a spin coater as one embodiment of applying a functional material to open areas on the substrate that are not covered by the pattern of mask material.
• the present invention provides a method to form a pattern of a functional material on a substrate for use in electronic applications.
• the method is applicable to the pattern formation of a variety of electronic materials, including conductors, semiconductors, and dielectrics, as the functional material.
• the method is not limited to the application by elastomeric stamps of thiol materials as a mask material.
• the method is capable of forming the pattern of the functional material onto a variety of substrates over large areas typically with at least 1 to 5 micron line resolution, and thus is particularly capable of forming microcircuitry.
• the method employs the ease of printing with an elastomeric stamp having a relief structure to transfer a mask material, without sagging or substantial sagging of the stamp and undesired transfer of material to the substrate.
• the present method is not limited to only embodiments where the raised surface/s has a width greater than the width of the recess surface/s.
• the present method is applicable to forming patterns of functional material regardless of the relative dimensions of the raised surfaces and the recessed surfaces of the stamp.
• the stamp may be formed in conventional fashion as understood by those skilled in the art of microcontact printing.
• a stamp may be fabricated by molding and curing a layer of a material on a master having a surface presenting a relief form (that is in opposite of the stamp relief structure).
• the stamp may be cured by exposure to actinic radiation, heating, or combinations thereof.
• A-B-A block copolymers include but is not limited to poly(styrene-butadiene-styrene) and poly(styrene-isoprene-styrene).
• the polymeric material may be elastomeric or may become elastomeric upon curing.
• the material forming the elastomeric stamp is photosensitive such that the relief structure can be formed upon exposure to actinic radiation.
• photosensitive encompasses any system in which the photosensitive composition is capable of initiating a reaction or reactions, particularly photochemical reactions, upon response to actinic radiation.
• chain propagated polymerization of a monomer and/or oligomer is induced by either a condensation mechanism or by free radical addition polymerization. While all photopolymerizable mechanisms are contemplated, photosensitive compositions useful as elastomeric stamp material will be described in the context of free-radical initiated addition polymerization of monomers and/or oligomers having one or more terminal ethylenically unsaturated groups.
• Monomers that can be used in the composition activated by actinic radiation are well known in the art, and include, but are not limited to, addition-polymerization ethylenically unsaturated compounds.
• the addition polymerization compound may also be an oligomer, and can be a single or a mixture of oligomers.
• the composition can contain a single monomer or a combination of monomers.
• the monomer compound capable of addition polymerization can be present in an amount less than 5%, preferably less than 3%, by weight of the composition.
• the elastomeric stamp is composed of a photosensitive composition that includes a fluorinated compound that polymerizes upon exposure to actinic radiation to form a fluorinated elastomeric-based material.
• Suitable elastomeric-based fluorinated compounds include, but are not limited to, perfluoropolyethers, fluoroolefins, fluorinated thermoplastic elastomers, fluorinated epoxy resins, fluorinated monomers and fluorinated oligomers that can be polymerized or crosslinked by a polymerization reaction.
• the fluorinated compound has one or more terminal ethylenically unsaturated groups that react to polymerize and form the fluorinated elastomeric material.
• the support has a thickness between 2 to 50 mils (0.0051 to 0.13 cm).
• the support is in sheet form, but is not limited to this form.
• the support is transparent or substantially transparent to the actinic radiation at which the photosensitive composition polymerizes.
• Examples of materials suitable for use as the mask material for functional materials that are in organic solution include but are not limited to, alkyd resins; gelatin; poly(acrylic acid); polypeptides; proteins; polyvinyl pyridine); polyvinyl pyrrolidone); hydroxy polystyrene; polyvinyl alcohol); polyethylene glycol; chitosan; poly(styrene-co-vinyl pyridine); poly(butyl acrylate-co-vinyl pyridine); aryl amines and fluorinated aryl amines; cellulose and cellulose derivatives; dispersions of acrylate and/or methacrylate emulsions; and combinations and copolymers thereof.
• Suitable substrates include, for example, a metallic film on a polymeric, glass, or ceramic substrate, a metallic film on a conductive film or films on a polymeric substrate, metallic film on a semiconducting film on a polymeric substrate.
• suitable substrates include, for example, glass, indium-tin-oxide coated glass, indium-tin-oxide coated polymeric films; polyethylene terephthalate, polyethylene naphthalate, polyimides , silicon, and metal foils.
• Semiconducting materials include light-emitting quantum dots.
• a bulk material generally has constant physical properties regardless of its size, but for nanoparticles this is often not the case. Size dependent properties are observed such, as quantum confinement in semiconductor particles, surface plasmon resonance in some metal particles and superparamagnetism in magnetic materials.
• the functional material includes but is not limited to semi-solid nanoparticles, such as liposome; soft nanoparticles; nanocrystals; hybrid structures, such as core-shell nanoparticles.
• the functional material includes nanoparticles of carbon, such as carbon nanotubes, conducting carbon nanotubes, and semiconducting carbon nanotubes. Metal nanoparticles and dispersions of gold, silver and copper are commercially available from Nanotechnologies, and ANP.
• the printing form precursor can be exposed to actinic radiation, such as an ultraviolet (UV) or visible light, to cure the layer 20.
• actinic radiation exposes the photosensitive material through the transparent support 16.
• the exposed material polymerizes and/or crosslinks and becomes a stamp or plate having a solid elastomeric layer with a relief surface corresponding to the relief pattern on the master.
• suitable exposure energy is between about 10 and 20 Joules on a 365nm Miner exposure unit.
• Actinic radiation sources encompass the ultraviolet, visible, and infrared wavelength regions. The suitability of a particular actinic radiation source is governed by the photosensitivity of the photosensitive composition, and the optional initiator and/or the at least one monomer used in preparing the stamp precursor.
• stamp precursor is in the UV and deep visible area of the spectrum, as they afford better room-light stability.
• suitable visible and UV sources include carbon arcs, mercury-vapor arcs, fluorescent lamps, electron flash units, electron beam units, lasers, and photographic flood lamps.
• the most suitable sources of UV radiation are the mercury vapor lamps, particularly the sun lamps. These radiation sources generally emit long-wave UV radiation between 310 and 400 nm.
• Stamp precursors sensitive to these particular UV sources use elastomeric-based compounds (and initiators) that absorb between 310 to 400 nm.
• the substrate 34 having the layer of the functional material 46 and the mask pattern 40 is placed in a bath 50 containing a solution 52 that is a solvent for the mask material 32.
• the pattern 40 of mask material 32 lifts off from the substrate 34 and/or dissolves in the solution bath 50.
• the functional material 46 that resided on the mask pattern 40 also is removed with the mask material 32, and the functional material 46 that resided in the open areas 42 remains on the substrate 34.
• the functional material 46 that resides on the substrate 34 in the open areas 42 creates a pattern 55 of functional material 46 for the electronic device or component.
• the substrate 34 with the pattern 55 of functional material 46 is being heated as one embodiment of further treating.
• the functional material 46 is metal nanoparticles that need to be sintered by heating in order to render the pattern 55 conductive.
• the following example demonstrates a method to form a pattern on a substrate.
• Silver nanoparticles are formed into a pattern onto a flexible base that can provide a functional source-drain level of a thin film transistor.
• Elastomeric stamp preparation A support for the elastomeric stamp was prepared by applying a layer of a UV curable optically-clear adhesive, type NOA73, (purchased from Norland Products; Cranbury, NJ) at a thickness of 5 microns onto a 5 mil (0.0127 cm) Melinex® 561 polyester film support by spin coating at 3000 rpm and then curing by exposure to ultraviolet radiation (350-400 nm) at 1.6 watts power (20 mWatt/cm 2 ) for 90 seconds in a nitrogen environment.
• a UV curable optically-clear adhesive type NOA73
• the sacrificial masking material on the raised surface of the relief pattern of the elastomeric stamp transferred to the substrate and formed a mask pattern on the substrate. Recessed areas in the stamp did not contact the substrate, and therefore the substrate had open areas where there was no mask material.
• the pattern of masking material had a thickness of 27nm as measured with a profiler.
• the mask pattern of the printed sacrificial masking material was the positive of the pattern on the master (that is, the printed mask pattern is the same as the pattern of recessed areas of the master). Patterning of functional material:
• the stamp was separated from the substrate at room temperature resulting in the transfer of the P4VP from the raised surfaces of the stamp's relief pattern onto the substrate.
• the thickness of P4VP pattern was 30 nm when measured with profiler.
• Patterning of functional material Silver ink, type DGH with 45% solids by weight, was purchased from Anapro (Korea). The silver ink had silver nanoparticles of about 20 nm in diameter. The ink was diluted to 18% by weight with toluene. The dilute silver dispersion was then sonicated for 10 minutes using tip a sonicator and filtered twice with 0.2 micron PTFE filter. The silver solution was spun coated onto the substrate having the mask pattern of the sacrificial P4VP material at 2000 rpm for 60 seconds.
• Example 3 The following example demonstrates the method for forming a pattern of a functional material onto a flexible film.
• the functional material is an organic semiconducting material of a polythiophene.
• the following example demonstrates the method of forming a pattern of functional material using an elastomeric stamp to print a sacrificial mask material.
• the functional material is silver nanoparticles that form a pattern on a flexible film substrate.
• the master and the elastomeric stamp were prepared as described in Example 1.
• the relief pattern on the stamp had the same dimensions as those reported for Example 1.
• a master was prepared with a pattern using a negative photoresist, SU-8 type 2 (from MICRO CHEM 1 Newton, MA) and the same photomask as used in Example 1.
• the stamp made from this master had the raised surface for direct printing the functional material onto the substrate.
• the photoresist was diluted with gamma butyrolactone with weight ratio of 7:3 and filtered using 1.0 micron of PTFE.
• the solution was spun coated onto a silicon wafer at 3000 rpm, dried at 65°C 1min and further pre-baked at 95°C for 1 min.
• the pre-baked photoresist was exposed with an Miner (365nm) for 5 seconds followed by post-baking at 95°C hotplate for 1 min.

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• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Chemical & Material Sciences (AREA)
• Nanotechnology (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Crystallography & Structural Chemistry (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Mathematical Physics (AREA)
• Theoretical Computer Science (AREA)
• Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
• Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

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• 2006
  • 2006-08-23 US US11/508,806 patent/US20080047930A1/en not_active Abandoned
• 2007
  • 2007-08-08 WO PCT/US2007/017670 patent/WO2008024207A1/en not_active Ceased
  • 2007-08-08 DE DE602007009544T patent/DE602007009544D1/de active Active
  • 2007-08-08 KR KR1020097005450A patent/KR20090042848A/ko not_active Ceased
  • 2007-08-08 CN CN2007800311719A patent/CN101505969B/zh not_active Expired - Fee Related
  • 2007-08-08 EP EP07811203A patent/EP2054233B1/en not_active Not-in-force
  • 2007-08-08 JP JP2009525554A patent/JP2010502010A/ja active Pending

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