WO2010132612A2 - Metal-coated shrinkable polystyrene and methods for using same - Google Patents

Metal-coated shrinkable polystyrene and methods for using same Download PDF

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Publication number
WO2010132612A2
WO2010132612A2 PCT/US2010/034613 US2010034613W WO2010132612A2 WO 2010132612 A2 WO2010132612 A2 WO 2010132612A2 US 2010034613 W US2010034613 W US 2010034613W WO 2010132612 A2 WO2010132612 A2 WO 2010132612A2
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WO
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Prior art keywords
metal
alternatively
nanometers
metal surface
textured
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PCT/US2010/034613
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French (fr)
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WO2010132612A3 (en
Inventor
Michelle Khine
Diep Nguyen
Chi-Cheng Fu
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The Regents Of The University Of California
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Publication of WO2010132612A2 publication Critical patent/WO2010132612A2/en
Publication of WO2010132612A3 publication Critical patent/WO2010132612A3/en

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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
    • C23C14/0005—Separation of the coating from the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/068—Polyalkylene glycols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00835—Comprising catalytically active material

Definitions

  • thermoplastic material such as printable pre- stressed polystyrene (PS) sheets.
  • PS printable pre- stressed polystyrene
  • thermoplastic materials contract to a fraction of their size when heated, the mismatch in stiffness between a metal thin film and the carrier thermoplastic material substrate is leveraged. As the thermoplastic material retracts, it carries the stiffer thin metal layer with it, causing the stiffer, non-shrinkable film to buckle (wrinkle) or petal.
  • the methods disclosed herein has been informed by theoretical work that addresses the scaling relationship between the length scales of the wrinkles or petals
  • this invention provides methods for using a device, wherein the comprises, or alternatively consists essentially of, or yet further consists of a heat-shrunk thermoplastic base having a high-surface area textured metal surface, wherein the textured metal surface in the three-dimensional shape of a wrinkle or petal, has an average height from about 100 nanometers to about 5 micrometers.
  • the thermoplastic base has been separated or removed from the wrinkle or petal.
  • the textured metal surface comprises, or alternatively consists essentially of, or yet further consists of at least one metal selected from the group consisting of silver, gold and copper.
  • Methods to prepare the devices are also provided.
  • the methods comprise, or alternatively consist essentially of, or yet further consist of:
  • thermoplastic base is been separated or removed from the wrinkle or petal.
  • this invention provides a method for catalyzing a reaction, comprising, or alternatively consisting essentially of, or yet further consisting of, contacting the reaction substrates with a device comprising a high-surface area textured metal surface, wherein the textured metal surface has an average height from about 100 nanometers to about 5 micrometers.
  • the high-surface area textured metal surface further comprises a thermoplastic material.
  • the textured metal surface comprises at least one metal selected from the group consisting of silver, gold and copper.
  • the textured metal surface comprises two or more metals selected from the group consisting of silver, gold and copper.
  • the devices can be used to catalyze reactions that are one or more of surface enhanced catalysis, stereoselective reaction, water-gas shift reactions.
  • This invention also provides a method to inhibit microbial growth in a solution, comprising, or alternatively consisting essentially of, or yet further consisting of, contacting the solution with a device comprising a high-surface area textured silver metal surface, wherein the textured silver metal surface has an average height from about 100 nanometers to about 5 micrometers.
  • the heat sensitive thermoplastic material is uniaxially or biaxially biased prior to performing steps a) and b) and/or during step b).
  • the metal is deposited by sputter coating, evaporation or chemical vapor deposition and is deposited in a thickness from about 2 nanometers to about 100 nanometers.
  • the metal is any suitable metal, for example one or more of the group of silver, gold or copper.
  • the material is reduced by heating or other suitable method to achieve a surface texture in the range of from about 100 nanometers to about 5 micrometers.
  • Kits for preparing the devices and methods for use are further provided. BRIEF DESCRIPTION OF THE FIGURE
  • Figures IA to 1C are SEM images of biaxial (Figure IA) and uniaxial (Figure IB) nanopetals and nanowrinles created by wrinkling bimetallic films (40 nanometer gold on the top of 40 nanometer silver).
  • Figure IA shows the petals at 20 ⁇ m and the inset at 3 ⁇ m.
  • Figure IB shows wrinkles at 20 ⁇ m and the inset at 3 ⁇ m.
  • Figure 1C is a wide-field epiflourescence image and corresponding intensity profile along the lines of dyes on a glass plate (on left) and on uniaxial petals (on right).
  • Figures 2A to 2C also show fabrication of nanowrinkles.
  • Figure 2A shows the schematic of fabricating biaxial (left) and unixial (right) petals.
  • the SEM images of biaxial ( Figures 2B) and uniaxial (Figure 2C) wrinkles on a shrunk polystyrene sheet covered with a bimetallic layer of 40nm-thick silver and 40 nm-thick gold.
  • compositions and methods include the recited elements, but do not exclude others.
  • Consisting essentially of when used to define compositions and methods shall mean excluding other elements of any essential significance to the combination when used for the intended purpose. Thus, a composition consisting essentially of the elements as defined herein would not exclude trace contaminants or inert carriers.
  • Consisting of shall mean excluding more than trace elements of other ingredients and substantial method steps for preparing the microfluidic device. Embodiments defined by each of these transition terms are within the scope of this invention.
  • thermoplastic material is intended to mean a plastic material which shrinks upon heating.
  • the thermoplastic materials are those which shrink uniformly without distortion.
  • Shrinky-Dink is a commercial thermoplastic which is used a children's toy. The shrinking can be either biaxially (isotropic) or uniaxial (anisotropic) by inhibiting reduction in size in one direction by clamping, for example.
  • thermoplastic materials for inclusion in the methods of this invention include, for example, high molecular weight polymers such as acrylonitrile butadiene styrene (ABS), acrylic, celluloid, cellulose acetate, ethylene-vinyl acetate (EVA), ethylene vinyl alcohol (EVAL), fluoroplastics (PTFEs, including FEP, PFA, CTFE, ECTFE, ETFE), ionomers kydex, a trademarked acrylic/PVC alloy, liquid crystal polymer (LCP), polyacetal (POM or Acetal), polyacrylates (Acrylic), polyacrylonitrile (PAN or Acrylonitrile), polyamide (PA or Nylon), polyamide-imide (PAI), polyaryletherketone (PAEK or Ketone), polybutadiene (PBD), polybutylene (PB), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), Polycyclohexylene Dimethylene Terephthalate (PC
  • a "metal" for use in this invention includes but is not limited to platinum, gold, titanium, silver, copper, a dielectric substance, a paste or any other suitable metal or combination thereof.
  • suitable dielectric substances include metal oxides, such as aluminum oxide, titanium dioxide, silver oxide and silicon dioxide.
  • suitable pastes include conductive pastes such as silver pastes.
  • the metal can be applied to the thermoplastic material by a variety of methods known to one skilled in the art, such as printing, sputtering and evaporating.
  • evaporating is intended to mean thermal evaporation, which is a physical vapor deposition method to deposit a thin film of metal on the surface of a substrate. By heating a metal in a vacuum chamber to a hot enough temperature, the vapor pressure of the metal becomes significant and the metal evaporated. It recondenses on the target substrate.
  • sputtering is intended to mean a physical vapor deposition method where atoms in the target material are ejected into the gas phase by high-energy ions and then land on the substrate to create the thin film of metal.
  • the metal can be applied to the thermoplastic material using "pattern transfer.”
  • pattern transfer refers to the process of contacting an image-forming device, such as a mold or stamp, containing the desired pattern with an image-forming material to the thermoplastic material. After releasing the mold, the pattern is transferred to the thermoplastic material.
  • image-forming device such as a mold or stamp
  • the pattern is transferred to the thermoplastic material.
  • high aspect ratio pattern and sub-nanometer patterns have been demonstrated.
  • Such methods are well known in the art (Sakurai, et al., US Patent 7,412,926; Peterman, et al., US Patent 7,382,449; Nakamura, et al., US Patent 7,362,524; Tamada, US Patent 6,869,735).
  • micro-contact printing refers to the use of the relief patterns on a PDMS stamp to form patterns of self-assembled monolayers (SAMs) of an image-forming material on the surface of a thermoplastic material through conformal contact.
  • SAMs self-assembled monolayers
  • Micro-contact printing differs from other printing methods, like inkjet printing or 3D printing, in the use of self-assembly (especially, the use of SAMs) to form micro patterns and microstructures of various image-forming materials.
  • a "patterning device” is intended to be broadly interpreted as referring to a device that can be used to convey a patterned cross-section, corresponding to a pattern that is to be created in a target portion of the substrate.
  • a "pattern” is intended to mean a mark or design.
  • a “solution” is intended to refer to a substantially homogeneous mixture of a solute, such as a solid, liquid, or gaseous substance, with a solvent, which is typically a liquid.
  • the solution can be either aqueous or non-aqueous.
  • suitable solutes in solutions include fluorescent dyes, biological compounds, such as proteins, DNA and plasma, and soluble chemical compounds.
  • suitable solids include beads, such as polystyrene beads, and powders, such as a metal powder.
  • a “suspension” is intended to refer to a substantially heterogeneous fluid containing a solid, wherein the solid is dispersed throughout the liquid, but does not substantially dissolve.
  • the solid particles in a suspension will typically settle as the particle size is large, compared to a colloid, where the particle size is small such that the suspension does not settle.
  • suitable suspensions include biological suspensions such as whole blood, cell compositions, or other cell containing mixtures. It is contemplated that any solution, solid or suspension can be mixed using the mixers disclosed herein, provided that the solid has a particle size sufficiently small to move throughout the channels in the mixer.
  • the preparation of the textured metal wrinkle and nanopetal surface comprises, or alternatively consists essentially of, or yet further consists of the steps of: a) depositing a metal onto a thermoplastic material; and b) reducing the surface area of the receptive material by at least about 60% until wrinkles form or the metal on the material cracks, thereby forming the textured metal nanopetals.
  • Steps a) and b) prepare a metal surface on the thermoplastic material.
  • Methods for preparing a metal wrinkled surface can be found in PCT Patent Application No. PCT/US08/083283, which is incorporated by reference in its entirety.
  • Metal petals are formed by using layers of metals or different metals and reducing the thermoplastic material until the metal surface cracks open, thereby producing a "petaled" surface.
  • the depositing of the metal onto heat sensitive thermoplastic receptive material is by evaporating, which is a physical vapor deposition method to deposit a thin film of metal on the surface of a substrate.
  • evaporating is a physical vapor deposition method to deposit a thin film of metal on the surface of a substrate.
  • the metal is deposited on the thermoplastic, it is placed in an oven, or similar device, to be heated, and upon heating, because of the stiffness incompatibility between the metal and the shrinking thermoplastic, petals form.
  • the spacing between the metal petals can be controlled by the amount of heating, and hence shrinkage.
  • the thermoplastic material is a heat sensitive thermoplastic receptive material which in one aspect is to be uniaxially or biaxially stressed upon heating and/or alternatively, uniaxially or biaxially pre-stressed prior to heating.
  • the shrinking can be either biaxially (isotropic) or uniaxial (anisotropic) by inhibiting reduction in size in one direction by clamping, for example.
  • Petal or wrinkle height can be controlled by adjusting the metal film thickness.
  • Fig. 17 of the PCT application PCT/US08/083283 shows a plot of the maximum average petal height as a function of metal layer thickness. Therefore, one can easily predict the spacing between and height of the metal petals by adjusting the thickness of metal deposited onto the thermoplastic material and the time the thermoplastic material is heated.
  • the thickness of metal deposited onto the thermoplastic material can be easily controlled using the metal deposition methods disclosed herein by adjusting parameters such as time, temperature, and the like. Such methods are well known to one of skill in the art.
  • the metals can be the same or different or and/or alternatively deposited in multiple layers in a thickness from about 0.1 nm, or alternatively about 0.2 nm, or alternatively about 0.25 nm, or alternatively about 0.3 nm, or alternatively about 0.35 nm, or alternatively about 0.4 nm, or alternatively about 0.45 nm, or alternatively about 0.5 nm, or alternatively about 0.55 nm, or alternatively about 0.6, or alternatively about 0.7 nm, or alternatively about 75 nm, or alternatively about 0.8 nm, or alternatively about 0.85 nm, or alternatively about 0.9 nm, or alternatively about 1 nm, or alternatively about 2 nm, or alternatively about 3 nm or alternatively about 4 nm, or alternatively about 5 nm, or alternatively about 7.5 nm, or alternatively about 8, or alternatively about 10 nm, or alternatively about 15 nm, or alternatively
  • the thickness of metal deposited onto the thermoplastic material can be easily controlled using the metal deposition methods disclosed herein by adjusting parameters such as time, temperature, and the like. Such methods are well known to one of skill in the art.
  • Various heights of the metal wrinkles and/or nanopetals can be achieved from about 0.1 nanometers to about 100 nanometers.
  • the height of the metal is about 2 nanometers.
  • the height of the metal is about 5 nanometers, or alternatively, about 10 nanometers, or alternatively, about 20 nanometers, or alternatively, about 30 nanometers, or alternatively, about 40 nanometers, or alternatively, about 50 nanometers, or alternatively, about 60 nanometers, or alternatively, about 70 nanometers, or alternatively, about 80 nanometers, or alternatively, about 90 nanometers, or alternatively, about 100 nanometers.
  • petal heights can be achieved from about 100 nanometers to about 5 micrometers.
  • the height of the metal is about 200 nanometers.
  • the height of the metal is about 200 nanometers, or alternatively, about 300 nanometers, or alternatively, about 500 nanometers, or alternatively, about 700 nanometers, or alternatively, about 1 micrometer, or alternatively, about 2 micrometers, or alternatively, about 3 micrometers, or alternatively, about 4 micrometers, or alternatively, less than about 5 micrometers.
  • the directionality of the wrinkles and/or petals is controlled by grooving the substrate prior to metal deposition.
  • the directionality of the petals can be controlled by monodirectional shrinking using a uniaxially biasing thermoplastic receptive material.
  • the method to prepare a textured metal surface further comprises first heating a heat sensitive thermoplastic receptive material under conditions that reduce the size of the thermoplastic receptive material biaxially by at least about 60%, followed by uniaxially biasing the thermoplastic receptive material to shrink along one axis or dimension prior to depositing a metal onto a heat sensitive thermoplastic receptive material, and reducing the material by at least about 60%, thereby preparing a textured metal surface.
  • any metal can be deposited onto the thermoplastic material to fabricate the metal wrinkles and/or petals disclosed herein.
  • the metal is at least one of platinum, gold, titanium, silver, copper, a dielectric substance, a paste or any other suitable metal or combination thereof.
  • suitable dielectric substances include metal oxides, such as aluminum oxide, titanium dioxide, silver oxide and silicon dioxide.
  • suitable pastes include conductive pastes such as silver pastes.
  • the metal can be deposited in a given pattern or design. For example, the metal can be deposited to only a desired area of the thermoplastic receptive material to form isolated metal sections or 'islands' on the thermoplastic material.
  • the metal is deposited by one or more of sputtering, evaporation or chemical vapor deposition.
  • Sputtering is a physical vapor deposition method where atoms in the target material are ejected into the gas phase by high-energy ions and then land on the substrate to create the thin film of metal.
  • the metal is deposited in a desired pattern.
  • thermoplastic materials are those which shrink uniformly without substantial distortion.
  • Suitable thermoplastic materials for inclusion in the methods of this invention include, for example, high molecular weight polymers such as acrylonitrile butadiene styrene (ABS), acrylic, celluloid, cellulose acetate, ethylene-vinyl acetate (EVA), ethylene vinyl alcohol (EVAL), fluoroplastics (PTFEs, including FEP, PFA, CTFE, ECTFE, ETFE), ionomers kydex, a trademarked acrylic/PVC alloy, liquid crystal polymer (LCP), polyacetal (POM or Acetal), polyacrylates (Acrylic), polyacrylonitrile (PAN or Acrylonitrile), polyamide (PA or Nylon), polyamide- imide (PAI), polyaryletherketone (PAEK or Ketone), polybutadiene (PBD),
  • ABS acrylonitrile butadiene styrene
  • EVA ethylene-vinyl a
  • Heat can be used to reduce the size of the thermoplastic material 5 by at least 65%, or alternatively, at least 70%, or alternatively, at least 75%, or alternatively, at least 80%, or alternatively, at least 85%, or alternatively, at least 90%.
  • the thermoplastic material is reduced to achieve a surface texture having a periodicity in the range of from about 10 nanometers to about 5 micrometers.
  • the thermoplastic material is reduced to achieve a surface texture having a periodicity in the range of from about 10 nanometers to about 600 nanometers.
  • the pre-stressed thermoplastic material is reduced to achieve a surface texture having a periodicity in the range of from about 15 nanometers to about 100 nanometers.
  • the pre-stressed thermoplastic material is reduced to achieve a surface texture having a periodicity selected from the group consisting of about 15 nanometers, about 30 nanometers, about 60 nanometers, and about 600 nanometers.
  • the heat sensitive thermoplastic material is reduced by heating.
  • the temperature used to heat and reduce the size of the thermoplastic material is from about 100 0 C to about 250 0 C, or alternatively from about 120 0 C to about 220 0 C, or alternatively from about 150 0 C to about 200 0 C, or alternatively from about 180 0 C to about 190 0 C, or alternatively about 185°C.
  • the methods disclosed herein are capable of fabricating various devices to be used in applications such as molecular detection, optical devices, filters and sorters, high-surface area conductors and actuators, molecular detection, optical devices, filters and sorters, high- surface area conductors and actuators, metrology, surface-enhanced Raman scattering (SERS), metal-enhanced fluorescence (MEF), and extraordinary light transmission. Exploitation of these and other plasmon-induced effects have benefited numerous applications, including near-field optical microscopy, sub-wavelength photonics, biochemical sensing and solar energy harvesting.
  • this invention also provides a device comprising a heat-shrunk thermoplastic base having a textured metal surface in the form of a metal wrinkle or metal petal (See Figure 1), wherein the texture has an average height from about 100 nanometers to about 0.1 micrometers.
  • the texture has an average height of about 100 nanometers, or alternatively, about 100 nanometers, or alternatively, about 300 nanometers, or alternatively, about 500 nanometers, or alternatively, about 700 nanometers, or alternatively, about 1 micrometer, or alternatively, about 2 micrometers, or alternatively, about 3 micrometers, or alternatively, about 4 micrometers, or alternatively, less than about 5 micrometers, as low as 0.1 nanometers, as described above.
  • the thermoplastic base has been removed from the metal wrinkles and/or petals.
  • Metal height can be controlled by adjusting the metal film thickness. Therefore, one can easily predict the spacing between and height of the wrinkle or petal by adjusting the thickness of metal deposited onto the thermoplastic material and the time the thermoplastic material is heated.
  • the thickness of metal deposited onto the thermoplastic material can be easily controlled using the metal deposition methods disclosed herein by adjusting parameters such as time, temperature, and the like. Such methods are well known to one of skill in the art.
  • This invention provides substrates of metal wrinkles and/or nanopetals which means of manufacture is considerably faster and significantly less expensive and more robust than other means of achieving such metal nano-structures (including self-assembly method, focus ion beam lithography and e-beam lithography) (Lakowicz, J.R. (2008) Analyst 133:1308-1346).
  • the sharp edges of wrinkles and petals enables concentration and localization of an electromagnetic field.
  • the devices are promising materials for surface plasmon-based sensing applications, such as metal enhanced fluorescence (MEF) and surface enhanced Ramon spectroscopy (SERS) (Lakowicz (2008) supra, Ko, H. et al. (2008)).
  • the inventors first results show that after deposited dyes on the petals, a 7- fold enhancement on fluorescence intensity can be achieved (Fig. 1C).
  • the strong plasmons on the surface of nanopetals can resonance well with fluorophors.
  • Such huge enhancement makes nanopetals as good substrates for single molecules detection.
  • SERS applications the strong localized electromagnetic filed on the sharp edges would enhance Ramon signals of molecules for label-free bimolecular detection (Lakowicz, J.R. et al. (2008), supra.).
  • Nanoparticles are the typical materials for nanocatalysis due to their large surface area (Xu, W. et al. (2008) Nature Materials 7(12):992-996 and Chen, M.S. et al. (2006) Accounts of Chemical Res. 39(10):739-746). They have been applied on catalyzing many chemical reactions to improve synthesis efficiency, pollutant removal and et al. However, after catalysis, it is not easy to remove nanoparticles to get pure productions. Here, these wrinkles and petals, immobilized on the substrates, are free of this problem. The large surface area of petals would be suitable materials for catalysis, such as active for CO oxidation (Chen, M.S. et al. (2006), supra.)
  • Metallic thin films and nanostructures exhibit remarkable optical properties which originate in their ability to support coherent electronic oscillations at their interfaces with surrounding dielectric media (Maier, S. A., et al. (2005) J Appl Phys 98: 1-10). These supported plasmons can be spatially confined (Localized Surface Plasmon Resonance, LSPR) or free to propagate along the interface boundary (Surface Plasmon Polaritons, SPP).
  • LSPR Localized Surface Plasmon Resonance
  • SPP Surface Plasmon Polaritons
  • SERS surface-enhanced Raman scattering
  • MEF metal-enhanced fluorescence
  • SPPs allow directional flow of energy when combined with suitably designed metallic nanostructures to mediate radiative energy transfer over distances of 10 ⁇ 4 -10 ⁇ 7 m (Jeffrey N., et al. (2008) Nature Mater 7: 442-453, Anthony J., et al. (2008) Appl. Phys. Lett. 92: 013504/1-3).
  • Surface-enhanced catalysis is based on enhanced-surfaces area, thus can be applicable to heat-induced buckling of metal-coated biaxially-stressed polystyrene sheets, i.e. gold wrinkles and petals.
  • the polystyrene substrates may be required to be removed due to the high temperature operating condition. This can be done by dissolving the polystyrene with Toluene and washing with de-ionized water.
  • the metal petals or wrinkles are contacted with the reactants under suitable conditions and serve to catalyze the reaction and can be easily removed.
  • Metal coated surfaces can be use to drive stereoselective reactions based on the preferential differences of chemical bonds to the metallic surfaces and the available surface area of reaction which will consequently affect the reaction rate.
  • gold wrinkles and petals can potentially be used for the transfer of stereoselectivity from catalyst to product (Bongers, N. et al. (2008) Angew. Chem. Int. Ed., 47:2178-2181).
  • the devices of this invention can be used for catalysis of endo-cycloisomerization of ⁇ - and ⁇ -hydroxyallenes to five- and six-membered heterocyclics by gold (I) and gold (III) using a modification of the methods disclosed in Bongers, N. et al.
  • Highly conductive metals of high surface area can be used as heat sources and sinks to direct the flow of thermal energy.
  • This principle can be applied to microfluidic devices where wrinkles and petals can be incorporated within the microfluidic devices to control the flow of heat alter reaction rate.
  • This process may also be applied to sensors where high- surface area metals can be used as temperature sensors to monitor reaction rates.
  • Example of such applications would be the use platinum-containing metal wrinkles and petals can be used with microfluidic chips and integrated with heaters and sensors to make enhanced- surface area conductive metal, i.e. methanol reformers for on-chip hydrogen production using a modification of the technology previously disclosed in Pattekar, A. et al.
  • the devices can be used in a process by which hydrogen atoms are stripped from methanol in a high temperature cracker. Water-Gas Shift Reactions
  • the devices can be used for the production of hydrogen gas fuel from the catalytic cracking of gasoline or natural gases, gasoline and natural gas reformers.
  • the devices can be used to lower the carbon monoxide contamination of the hydrogen product through a process known as water-gas shift (WGS) reaction using modification of the methods disclosed in Rebrov, V. E. et al. (2008) Catalysis Today, 138:210-215; Kuperman, A. et al. Method for making hydrogen using a gold containing water-gas shift catalyst,US Patent 7,169,376; Idakiev, V. et al. (2004) Appl. Catal. A., 270: 135; Idakiev, V. et al.
  • WGS water-gas shift
  • Carbon Oxide (CO) contamination is typically around 8-12% and can be reduced to below 1% using water-gas shift reactions. This reaction is carried out at 200-280 0 C. This is based on hydrogen production and may be integrated into the microfluidic chip listed above.
  • Silver-containing devices and devices coated with silver and/or nanocrystallines will produce silver cations, AgO, and free radicals in cell culture medium which are highly antimicrobial with little effect on mammalians cells (Kleps, I. et al. (2007) Materials Science and Engineering, C 27:1439-1443 and Fu-Ren, F. et al. (2004) J. Chem. Phys., Vol. 120(12)).
  • silver wrinkles into cell culture chips will provide an enhanced-surface for production of anti-microbial agents applicable in long term cell culture.
  • This invention further provides a kit comprising, or alternatively consisting essentially of, or yet further consisting of the materials necessary to perform the method described above.
  • the kit comprises, or alternatively consists essentially of, or yet further consists of a thermoplastic material and instructions for making the device.
  • the kits further comprise one or more metals.
  • the kit provides instructions for making and using the apparatus described above and incorporated herein by reference.
  • this invention provides a method for assaying or screening for new materials and methods having the same function of the inventions as described herein. In this aspect, the new materials and/or methods are used in the methods as described herein and compared to the performance of the devices of this invention.

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Abstract

Methods of using a device is provided that contains a heat-shrunk thermoplastic base having a high-surface area textured metal surface, wherein the textured metal surface has an average height from about 100 nanometers to about 5 micrometers.

Description

METAL-COATED SHRINKABLE POLYSTYRENE AND METHODS FOR USING SAME
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit under 35 U.S. C. § 119(e) of U.S. Provisional Serial No. 61/178,005, filed May 13, 2009, the content of which is incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] The invention disclosed herein related to the field of micro fabrication.
BACKGROUND OF THE INVENTION
[0003] Throughout this disclosure, various technical and patent publications are referenced to more fully describe the state of the art to which this invention pertains. These publications are incorporated by reference, in their entirety, into this application.
SUMMARY OF THE INVENTION
[0004] Disclosed herein is a simple and ultra-rapid technique to controllably create complex nano- to micro- scale patterns on a receptive thermoplastic material, such as printable pre- stressed polystyrene (PS) sheets. Because thermoplastic materials contract to a fraction of their size when heated, the mismatch in stiffness between a metal thin film and the carrier thermoplastic material substrate is leveraged. As the thermoplastic material retracts, it carries the stiffer thin metal layer with it, causing the stiffer, non-shrinkable film to buckle (wrinkle) or petal. The methods disclosed herein has been informed by theoretical work that addresses the scaling relationship between the length scales of the wrinkles or petals
(wavelengths and amplitudes) and the thickness of the metal film, material properties of the film and substrate and the overall shrinking strain produced (Cerda, E., et al., (2002) Nature,
419: 579-598, Huang, Z., et al., (2004) Phys. Rev. E, 70: 030601). The length scales arise from a competition between the elastic bending energy of the film and the elastic energy of deformation of the substrate. By this method, plasmon-active wrinkles or petals are created with a large range of wavelengths (> 30x) and periodicity, directionality and aspect ratios, and even patterns. While there have been several demonstrations of metal wrinkles on polymers, all have reported considerably larger wrinkle wavelengths (Yoo P.J., et al., (2002) Adv. Mater., 18:1383-1387, Bowden N, et al., (1999) Appl. Phys. Lett. 75: 2557-2559, Huck W.T.S., et al., (2000) Langmuir 16: 3497-3501 Watanabe M., et al., (2004) J. Polym. Sci. Part B: Polym. Phys. 42: 2460-2466 (2004), Watanabe M., (2005) J. Polym. Sci. Part B: Polym. Phys; 43: 1532-1537, Volynskϋ A.L., et al., (2000) J. Mater. Sci. 35: 547-554). Using the methods disclosed herein, petals from less than 100 nanometers to greater than 5 microns can be created.
[0005] Because these surfaces demonstrate tunable LSPR resonance, it holds potential as a low cost and robust substrate for surface enhanced sensing and spectroscopy. In addition, because the surfaces exhibit hierarchical self-assembly, broad band response can be achieved. Moreover, the unidirectional features allow the possibility of energy harvesting and radiative transfer on the same device by SPP.
[0006] Thus, in one aspect, this invention provides methods for using a device, wherein the comprises, or alternatively consists essentially of, or yet further consists of a heat-shrunk thermoplastic base having a high-surface area textured metal surface, wherein the textured metal surface in the three-dimensional shape of a wrinkle or petal, has an average height from about 100 nanometers to about 5 micrometers. In one aspect, the thermoplastic base has been separated or removed from the wrinkle or petal. For the purpose of illustration only, the textured metal surface comprises, or alternatively consists essentially of, or yet further consists of at least one metal selected from the group consisting of silver, gold and copper.
[0007] Methods to prepare the devices are also provided. The methods comprise, or alternatively consist essentially of, or yet further consist of:
a) depositing a metal onto a heat sensitive thermoplastic receptive material; and
b) reducing the material by at least about 60% until wrinkles and/or cracks form in the metal deposited on the receptive material,
thereby preparing a textured metal surface. [0008] In one aspect, the thermoplastic base is been separated or removed from the wrinkle or petal.
[0009] Thus, this invention provides a method for catalyzing a reaction, comprising, or alternatively consisting essentially of, or yet further consisting of, contacting the reaction substrates with a device comprising a high-surface area textured metal surface, wherein the textured metal surface has an average height from about 100 nanometers to about 5 micrometers. In one aspect, the high-surface area textured metal surface further comprises a thermoplastic material. In another aspect, the textured metal surface comprises at least one metal selected from the group consisting of silver, gold and copper. In a yet further aspect, the textured metal surface comprises two or more metals selected from the group consisting of silver, gold and copper.
[0010] The devices can be used to catalyze reactions that are one or more of surface enhanced catalysis, stereoselective reaction, water-gas shift reactions.
[0011] This invention also provides a method to inhibit microbial growth in a solution, comprising, or alternatively consisting essentially of, or yet further consisting of, contacting the solution with a device comprising a high-surface area textured silver metal surface, wherein the textured silver metal surface has an average height from about 100 nanometers to about 5 micrometers.
[0012] In one aspect, the heat sensitive thermoplastic material is uniaxially or biaxially biased prior to performing steps a) and b) and/or during step b).
[0013] In performing the methods, the metal is deposited by sputter coating, evaporation or chemical vapor deposition and is deposited in a thickness from about 2 nanometers to about 100 nanometers. The metal is any suitable metal, for example one or more of the group of silver, gold or copper. During the method, the material is reduced by heating or other suitable method to achieve a surface texture in the range of from about 100 nanometers to about 5 micrometers.
[0014] Kits for preparing the devices and methods for use are further provided. BRIEF DESCRIPTION OF THE FIGURE
[0015] Figures IA to 1C are SEM images of biaxial (Figure IA) and uniaxial (Figure IB) nanopetals and nanowrinles created by wrinkling bimetallic films (40 nanometer gold on the top of 40 nanometer silver). Figure IA shows the petals at 20 μm and the inset at 3 μm. Figure IB shows wrinkles at 20 μm and the inset at 3 μm. Figure 1C is a wide-field epiflourescence image and corresponding intensity profile along the lines of dyes on a glass plate (on left) and on uniaxial petals (on right).
[0016] Figures 2A to 2C also show fabrication of nanowrinkles. Figure 2A shows the schematic of fabricating biaxial (left) and unixial (right) petals. The SEM images of biaxial (Figures 2B) and uniaxial (Figure 2C) wrinkles on a shrunk polystyrene sheet covered with a bimetallic layer of 40nm-thick silver and 40 nm-thick gold.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0017] As used herein, certain terms may have the following defined meanings.
[0018] As used in the specification and claims, the singular form "a," "an" and "the" include plural references unless the context clearly dictates otherwise.
[0019] As used herein, the term "comprising" is intended to mean that the compositions and methods include the recited elements, but do not exclude others. "Consisting essentially of when used to define compositions and methods, shall mean excluding other elements of any essential significance to the combination when used for the intended purpose. Thus, a composition consisting essentially of the elements as defined herein would not exclude trace contaminants or inert carriers. "Consisting of shall mean excluding more than trace elements of other ingredients and substantial method steps for preparing the microfluidic device. Embodiments defined by each of these transition terms are within the scope of this invention.
[0020] A "thermoplastic material" is intended to mean a plastic material which shrinks upon heating. In one aspect, the thermoplastic materials are those which shrink uniformly without distortion. A "Shrinky-Dink" is a commercial thermoplastic which is used a children's toy. The shrinking can be either biaxially (isotropic) or uniaxial (anisotropic) by inhibiting reduction in size in one direction by clamping, for example. Suitable thermoplastic materials for inclusion in the methods of this invention include, for example, high molecular weight polymers such as acrylonitrile butadiene styrene (ABS), acrylic, celluloid, cellulose acetate, ethylene-vinyl acetate (EVA), ethylene vinyl alcohol (EVAL), fluoroplastics (PTFEs, including FEP, PFA, CTFE, ECTFE, ETFE), ionomers kydex, a trademarked acrylic/PVC alloy, liquid crystal polymer (LCP), polyacetal (POM or Acetal), polyacrylates (Acrylic), polyacrylonitrile (PAN or Acrylonitrile), polyamide (PA or Nylon), polyamide-imide (PAI), polyaryletherketone (PAEK or Ketone), polybutadiene (PBD), polybutylene (PB), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), Polycyclohexylene Dimethylene Terephthalate (PCT), polycarbonate (PC), polyhydroxyalkanoates (PHAs), polyketone (PK), polyester polyethylene (PE), polyetheretherketone (PEEK), polyetherimide (PEI), polyethersulfone (PES), polysulfone polyethylenechlorinates (PEC), polyimide (PI), polylactic acid (PLA), polymethylpentene (PMP), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyphthalamide (PPA), polypropylene (PP), polystyrene (PS), polysulfone (PSU), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and spectralon.
[0021] A "metal" for use in this invention includes but is not limited to platinum, gold, titanium, silver, copper, a dielectric substance, a paste or any other suitable metal or combination thereof. Examples of suitable dielectric substances include metal oxides, such as aluminum oxide, titanium dioxide, silver oxide and silicon dioxide. Examples of suitable pastes include conductive pastes such as silver pastes.
[0022] The metal can be applied to the thermoplastic material by a variety of methods known to one skilled in the art, such as printing, sputtering and evaporating. The term "evaporating" is intended to mean thermal evaporation, which is a physical vapor deposition method to deposit a thin film of metal on the surface of a substrate. By heating a metal in a vacuum chamber to a hot enough temperature, the vapor pressure of the metal becomes significant and the metal evaporated. It recondenses on the target substrate. As used herein, the term "sputtering" is intended to mean a physical vapor deposition method where atoms in the target material are ejected into the gas phase by high-energy ions and then land on the substrate to create the thin film of metal. Such methods are well known in the art (Bowden et al. (1998) Nature (London) 393: 146-149; Bowden et al. (1999) Appl. Phys. Lett. 75: 2557-2559; Yoo et al. (2002) Adv. Mater. 14: 1383-1387; Huck et al. (2000) Langmuir 16: 3497-3501; Watanabe et al. (2004) J. Polym. Sci. Part B: Polym. Phys. 42: 2460-2466; Volynskii et al. (2000) J. Mater. Sci. 35: 547-554; Stafford et al. (2004) Nature Mater. 3: 545-550; Watanabe et al. (2005) J. Polym. Sci. Part B: Polym. Phys. 43: 1532-1537; Lacour, et al. (2003) Appl. Phys. Lett. 82: 2404-2406).
[0023] In addition, the metal can be applied to the thermoplastic material using "pattern transfer." The term "pattern transfer" refers to the process of contacting an image-forming device, such as a mold or stamp, containing the desired pattern with an image-forming material to the thermoplastic material. After releasing the mold, the pattern is transferred to the thermoplastic material. In general, high aspect ratio pattern and sub-nanometer patterns have been demonstrated. Such methods are well known in the art (Sakurai, et al., US Patent 7,412,926; Peterman, et al., US Patent 7,382,449; Nakamura, et al., US Patent 7,362,524; Tamada, US Patent 6,869,735).
[0024] Another method for applying the image forming material includes, for example "micro-contact printing". The term "micro-contact printing" refers to the use of the relief patterns on a PDMS stamp to form patterns of self-assembled monolayers (SAMs) of an image-forming material on the surface of a thermoplastic material through conformal contact. Micro-contact printing differs from other printing methods, like inkjet printing or 3D printing, in the use of self-assembly (especially, the use of SAMs) to form micro patterns and microstructures of various image-forming materials. Such methods are well known in the art (Cracauer, et al., US Patent 6,981,445; Fujihira, et al., US Patent 6,868,786; Hall, et al., US Patent 6,792,856; Maracas, et al., US Patent 5,937,758).
[0025] A "patterning device" is intended to be broadly interpreted as referring to a device that can be used to convey a patterned cross-section, corresponding to a pattern that is to be created in a target portion of the substrate.
[0026] A "pattern" is intended to mean a mark or design.
[0027] A "solution" is intended to refer to a substantially homogeneous mixture of a solute, such as a solid, liquid, or gaseous substance, with a solvent, which is typically a liquid. The solution can be either aqueous or non-aqueous. Examples of suitable solutes in solutions include fluorescent dyes, biological compounds, such as proteins, DNA and plasma, and soluble chemical compounds. Examples of suitable solids include beads, such as polystyrene beads, and powders, such as a metal powder. A "suspension" is intended to refer to a substantially heterogeneous fluid containing a solid, wherein the solid is dispersed throughout the liquid, but does not substantially dissolve. The solid particles in a suspension will typically settle as the particle size is large, compared to a colloid, where the particle size is small such that the suspension does not settle. Examples of suitable suspensions include biological suspensions such as whole blood, cell compositions, or other cell containing mixtures. It is contemplated that any solution, solid or suspension can be mixed using the mixers disclosed herein, provided that the solid has a particle size sufficiently small to move throughout the channels in the mixer.
[0028] All numerical designations, e.g., pH, temperature, time, concentration, and molecular weight, including ranges, are approximations which are varied ( + ) or ( - ) by increments of 0.1. It is to be understood, although not always explicitly stated that all numerical designations are preceded by the term "about". It also is to be understood, although not always explicitly stated, that the reagents described herein are merely exemplary and that equivalents of such are known in the art.
[0029] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as "up to," "at least," "greater than," "less than," and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above.
MODES FOR CARRYING OUT THE INVENTION
Methods for Preparing the Textured Surfaces
[0030] The preparation of the textured metal wrinkle and nanopetal surface comprises, or alternatively consists essentially of, or yet further consists of the steps of: a) depositing a metal onto a thermoplastic material; and b) reducing the surface area of the receptive material by at least about 60% until wrinkles form or the metal on the material cracks, thereby forming the textured metal nanopetals.
[0031] Steps a) and b) prepare a metal surface on the thermoplastic material. Methods for preparing a metal wrinkled surface can be found in PCT Patent Application No. PCT/US08/083283, which is incorporated by reference in its entirety. Metal petals are formed by using layers of metals or different metals and reducing the thermoplastic material until the metal surface cracks open, thereby producing a "petaled" surface.
[0032] In certain embodiments, the depositing of the metal onto heat sensitive thermoplastic receptive material is by evaporating, which is a physical vapor deposition method to deposit a thin film of metal on the surface of a substrate. By heating a metal in a vacuum chamber to a hot enough temperature, the vapor pressure of the metal becomes significant and the metal evaporated. It recondenses on the target substrate. The height of the metal is dependent on length of processing time. The thermoplastic substrate must be far enough from the source such that the plastic does not heat up during deposition.
[0033] After the metal is deposited on the thermoplastic, it is placed in an oven, or similar device, to be heated, and upon heating, because of the stiffness incompatibility between the metal and the shrinking thermoplastic, petals form. The spacing between the metal petals can be controlled by the amount of heating, and hence shrinkage.
[0034] In one embodiment, the thermoplastic material is a heat sensitive thermoplastic receptive material which in one aspect is to be uniaxially or biaxially stressed upon heating and/or alternatively, uniaxially or biaxially pre-stressed prior to heating. The shrinking can be either biaxially (isotropic) or uniaxial (anisotropic) by inhibiting reduction in size in one direction by clamping, for example.
[0035] Petal or wrinkle height can be controlled by adjusting the metal film thickness. Fig. 17 of the PCT application PCT/US08/083283 shows a plot of the maximum average petal height as a function of metal layer thickness. Therefore, one can easily predict the spacing between and height of the metal petals by adjusting the thickness of metal deposited onto the thermoplastic material and the time the thermoplastic material is heated. The thickness of metal deposited onto the thermoplastic material can be easily controlled using the metal deposition methods disclosed herein by adjusting parameters such as time, temperature, and the like. Such methods are well known to one of skill in the art.
[0036] In addition, the metals can be the same or different or and/or alternatively deposited in multiple layers in a thickness from about 0.1 nm, or alternatively about 0.2 nm, or alternatively about 0.25 nm, or alternatively about 0.3 nm, or alternatively about 0.35 nm, or alternatively about 0.4 nm, or alternatively about 0.45 nm, or alternatively about 0.5 nm, or alternatively about 0.55 nm, or alternatively about 0.6, or alternatively about 0.7 nm, or alternatively about 75 nm, or alternatively about 0.8 nm, or alternatively about 0.85 nm, or alternatively about 0.9 nm, or alternatively about 1 nm, or alternatively about 2 nm, or alternatively about 3 nm or alternatively about 4 nm, or alternatively about 5 nm, or alternatively about 7.5 nm, or alternatively about 8, or alternatively about 10 nm, or alternatively about 15 nm, or alternatively about 20 nm, or alternatively about 25 nm, or alternatively about 30 nm, or alternatively about 35 nm, or alternatively about 40 nm, or alternatively about 45 nm, or alternatively about 50 nm, or alternatively about 55 nm, or alternatively about 60 nm, or alternatively about 65 nm, or alternatively about 70 nm or alternatively about 75 nm, or alternatively about 85 nm, or alternatively about 90 nm, or alternatively about 95 nm, or alternatively about 100 nm, or alternatively about 105 nm, or alternatively about 110 nm or alternatively about 120 nm, or alternatively about 125 nm, or alternatively about 130 nm, or alternatively about 135 nm, or alternatively about 140 nm, or alternatively about 145 nm, or alternatively about 150 nm, or alternatively about 155 nm, or thicker. Therefore, one can easily predict the spacing between and height of the metal petals by adjusting the thickness of metal deposited onto the thermoplastic material and the time the thermoplastic material is heated. The thickness of metal deposited onto the thermoplastic material can be easily controlled using the metal deposition methods disclosed herein by adjusting parameters such as time, temperature, and the like. Such methods are well known to one of skill in the art.
[0037] Various heights of the metal wrinkles and/or nanopetals can be achieved from about 0.1 nanometers to about 100 nanometers. In an particular embodiment, the height of the metal is about 2 nanometers. In an alternative embodiment, the height of the metal is about 5 nanometers, or alternatively, about 10 nanometers, or alternatively, about 20 nanometers, or alternatively, about 30 nanometers, or alternatively, about 40 nanometers, or alternatively, about 50 nanometers, or alternatively, about 60 nanometers, or alternatively, about 70 nanometers, or alternatively, about 80 nanometers, or alternatively, about 90 nanometers, or alternatively, about 100 nanometers.
[0038] In some embodiments, petal heights can be achieved from about 100 nanometers to about 5 micrometers. In an particular embodiment, the height of the metal is about 200 nanometers. In an alternative embodiment, the height of the metal is about 200 nanometers, or alternatively, about 300 nanometers, or alternatively, about 500 nanometers, or alternatively, about 700 nanometers, or alternatively, about 1 micrometer, or alternatively, about 2 micrometers, or alternatively, about 3 micrometers, or alternatively, about 4 micrometers, or alternatively, less than about 5 micrometers.
[0039] In addition, the directionality of the wrinkles and/or petals is controlled by grooving the substrate prior to metal deposition. Alternatively, the directionality of the petals can be controlled by monodirectional shrinking using a uniaxially biasing thermoplastic receptive material. In one embodiment, the method to prepare a textured metal surface further comprises first heating a heat sensitive thermoplastic receptive material under conditions that reduce the size of the thermoplastic receptive material biaxially by at least about 60%, followed by uniaxially biasing the thermoplastic receptive material to shrink along one axis or dimension prior to depositing a metal onto a heat sensitive thermoplastic receptive material, and reducing the material by at least about 60%, thereby preparing a textured metal surface.
[0040] It is contemplated that any metal can be deposited onto the thermoplastic material to fabricate the metal wrinkles and/or petals disclosed herein. In some embodiments, the metal is at least one of platinum, gold, titanium, silver, copper, a dielectric substance, a paste or any other suitable metal or combination thereof. Examples of suitable dielectric substances include metal oxides, such as aluminum oxide, titanium dioxide, silver oxide and silicon dioxide. Examples of suitable pastes include conductive pastes such as silver pastes. Depending on the intended use of the metal surface, it may be desired that the metal be deposited in a given pattern or design. For example, the metal can be deposited to only a desired area of the thermoplastic receptive material to form isolated metal sections or 'islands' on the thermoplastic material. Methods for the controlled deposition of metals are well known in the art. [0041] The periodicity of the wrinkles and/or petals as the wavelength of the metal scale according to the thickness to the 3/4th power. Therefore, tighter waves and/or petals are achieved by changing the thickness, or height of the metal layer.
[0042] In some embodiments, the metal is deposited by one or more of sputtering, evaporation or chemical vapor deposition. Sputtering is a physical vapor deposition method where atoms in the target material are ejected into the gas phase by high-energy ions and then land on the substrate to create the thin film of metal.
[0043] In some embodiments, the metal is deposited in a desired pattern.
[0044] It is contemplated that any thermoplastic material can be used in the methods disclosed herein. In one aspect of the disclosed invention, the thermoplastic materials are those which shrink uniformly without substantial distortion. Suitable thermoplastic materials for inclusion in the methods of this invention include, for example, high molecular weight polymers such as acrylonitrile butadiene styrene (ABS), acrylic, celluloid, cellulose acetate, ethylene-vinyl acetate (EVA), ethylene vinyl alcohol (EVAL), fluoroplastics (PTFEs, including FEP, PFA, CTFE, ECTFE, ETFE), ionomers kydex, a trademarked acrylic/PVC alloy, liquid crystal polymer (LCP), polyacetal (POM or Acetal), polyacrylates (Acrylic), polyacrylonitrile (PAN or Acrylonitrile), polyamide (PA or Nylon), polyamide- imide (PAI), polyaryletherketone (PAEK or Ketone), polybutadiene (PBD), polybutylene (PB), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), Polycyclohexylene Dimethylene Terephthalate (PCT), polycarbonate (PC), polyhydroxyalkanoates (PHAs), polyketone (PK), polyester polyethylene (PE), polyetheretherketone (PEEK), polyetherimide (PEI), polyethersulfone (PES), polysulfone polyethylenechlorinates (PEC), polyimide (PI), polylactic acid (PLA), polymethylpentene (PMP), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyphthalamide (PPA), polypropylene (PP), polystyrene (PS), polysulfone (PSU), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC) and spectralon. In one embodiment, the thermoplastic material is polystyrene.
[0045] Heat can be used to reduce the size of the thermoplastic material 5 by at least 65%, or alternatively, at least 70%, or alternatively, at least 75%, or alternatively, at least 80%, or alternatively, at least 85%, or alternatively, at least 90%. [0046] In some embodiments, the thermoplastic material is reduced to achieve a surface texture having a periodicity in the range of from about 10 nanometers to about 5 micrometers.
[0047] In some embodiments, the thermoplastic material is reduced to achieve a surface texture having a periodicity in the range of from about 10 nanometers to about 600 nanometers. In one aspect, the pre-stressed thermoplastic material is reduced to achieve a surface texture having a periodicity in the range of from about 15 nanometers to about 100 nanometers. In yet another aspect, the pre-stressed thermoplastic material is reduced to achieve a surface texture having a periodicity selected from the group consisting of about 15 nanometers, about 30 nanometers, about 60 nanometers, and about 600 nanometers.
[0048] In some embodiments, the heat sensitive thermoplastic material is reduced by heating. In some embodiments, the temperature used to heat and reduce the size of the thermoplastic material is from about 1000C to about 2500C, or alternatively from about 1200C to about 2200C, or alternatively from about 1500C to about 2000C, or alternatively from about 1800C to about 1900C, or alternatively about 185°C.
Devices
[0049] The methods disclosed herein are capable of fabricating various devices to be used in applications such as molecular detection, optical devices, filters and sorters, high-surface area conductors and actuators, molecular detection, optical devices, filters and sorters, high- surface area conductors and actuators, metrology, surface-enhanced Raman scattering (SERS), metal-enhanced fluorescence (MEF), and extraordinary light transmission. Exploitation of these and other plasmon-induced effects have benefited numerous applications, including near-field optical microscopy, sub-wavelength photonics, biochemical sensing and solar energy harvesting.
[0050] Thus, this invention also provides a device comprising a heat-shrunk thermoplastic base having a textured metal surface in the form of a metal wrinkle or metal petal (See Figure 1), wherein the texture has an average height from about 100 nanometers to about 0.1 micrometers. In one embodiment, the texture has an average height of about 100 nanometers, or alternatively, about 100 nanometers, or alternatively, about 300 nanometers, or alternatively, about 500 nanometers, or alternatively, about 700 nanometers, or alternatively, about 1 micrometer, or alternatively, about 2 micrometers, or alternatively, about 3 micrometers, or alternatively, about 4 micrometers, or alternatively, less than about 5 micrometers, as low as 0.1 nanometers, as described above. In one aspect, the thermoplastic base has been removed from the metal wrinkles and/or petals.
[0051] Metal height can be controlled by adjusting the metal film thickness. Therefore, one can easily predict the spacing between and height of the wrinkle or petal by adjusting the thickness of metal deposited onto the thermoplastic material and the time the thermoplastic material is heated. The thickness of metal deposited onto the thermoplastic material can be easily controlled using the metal deposition methods disclosed herein by adjusting parameters such as time, temperature, and the like. Such methods are well known to one of skill in the art.
Industrial Applicability
[0052] This invention provides substrates of metal wrinkles and/or nanopetals which means of manufacture is considerably faster and significantly less expensive and more robust than other means of achieving such metal nano-structures (including self-assembly method, focus ion beam lithography and e-beam lithography) (Lakowicz, J.R. (2008) Analyst 133:1308-1346). The sharp edges of wrinkles and petals enables concentration and localization of an electromagnetic field. Thus, the devices are promising materials for surface plasmon-based sensing applications, such as metal enhanced fluorescence (MEF) and surface enhanced Ramon spectroscopy (SERS) (Lakowicz (2008) supra, Ko, H. et al. (2008)). For MEF applications, previous studies show that bimetallic films can extend the penetration depth of surface plasmon to increase the amount of molecules in the enhanced region (Ong, B.H. et al. (2007) Lab on a Chip 7(4):506-512). This technique utilizes metallic nanostructures in which the plasmons resonate with the fluorophores to increase their fluorescence emission intensities. A typical ~10-fold enhancement has been applied to improve detection of DNA hybridization and immunoassay. (Malicka J. et al. (2003) Biochem. And Biophysical Res. Comm. 306(l):213-218 and Asian, K. et al. (2005) 16(1): 55-62. The inventors first results show that after deposited dyes on the petals, a 7- fold enhancement on fluorescence intensity can be achieved (Fig. 1C). The strong plasmons on the surface of nanopetals can resonance well with fluorophors. Such huge enhancement makes nanopetals as good substrates for single molecules detection. For SERS applications, the strong localized electromagnetic filed on the sharp edges would enhance Ramon signals of molecules for label-free bimolecular detection (Lakowicz, J.R. et al. (2008), supra.).
[0053] Nanoparticles are the typical materials for nanocatalysis due to their large surface area (Xu, W. et al. (2008) Nature Materials 7(12):992-996 and Chen, M.S. et al. (2006) Accounts of Chemical Res. 39(10):739-746). They have been applied on catalyzing many chemical reactions to improve synthesis efficiency, pollutant removal and et al. However, after catalysis, it is not easy to remove nanoparticles to get pure productions. Here, these wrinkles and petals, immobilized on the substrates, are free of this problem. The large surface area of petals would be suitable materials for catalysis, such as active for CO oxidation (Chen, M.S. et al. (2006), supra.)
[0054] Moreover, all these applications can be easily integrated into Shrinky-Dinks based microfluidic devices, disclosed in PCT/US08/083283 which were developed by the inventors. A significant plasmon effect and large surface area, together with the high throughput of lab-on-chip technique, makes the wrinkles and petals promising low-cost substrates for ultra-sensitive and -fast detection for biomedical applications.
[0055] Metallic thin films and nanostructures exhibit remarkable optical properties which originate in their ability to support coherent electronic oscillations at their interfaces with surrounding dielectric media (Maier, S. A., et al. (2005) J Appl Phys 98: 1-10). These supported plasmons can be spatially confined (Localized Surface Plasmon Resonance, LSPR) or free to propagate along the interface boundary (Surface Plasmon Polaritons, SPP). The enhanced electromagnetic fields associated with these modes form the basis of many observed optical phenomena arising from highly enhanced absorption and scattering cross- sections when incident radiation couples to the plasmonic oscillations. These include surface-enhanced Raman scattering (SERS), metal-enhanced fluorescence (MEF), and extraordinary light transmission (Xu, H., et al. (1999) Phys. Rev. Lett. 83: 4357 - 4360, Shuming N., et al. (1997) Science 275: 1102-1106, Song, J.-H., et al. (2005) Nano Lett. 5: 1557-1561). Exploitation of these and other plasmon-induced effects have benefited numerous applications, including near-field optical microscopy, sub-wavelength photonics, biochemical sensing and solar energy harvesting (Okamoto, K., et al. (2006) J. Opt. Soc. Am. B 23: 1674-1678, Ebbesen, T. W., et al. (1998) Nature 391 : 667-669, Barnes, W. L., et al. (2004) Phys. Rev. Lett. 92: 107401-4). In addition to these, SPPs allow directional flow of energy when combined with suitably designed metallic nanostructures to mediate radiative energy transfer over distances of 10~4 -10~7 m (Jeffrey N., et al. (2008) Nature Mater 7: 442-453, Anthony J., et al. (2008) Appl. Phys. Lett. 92: 013504/1-3).
[0056] A wide variety of platforms have been used for fabrication of structures capable of supporting plasmonic modes, with the most popular approach being deposition of Au or Ag thin films or nanoparticles (1 and 2D arrays) on inert substrates (Joseph R., et al. (2006) Appl. Phys. Lett. 89: 153120/1-3, Anton Kuzyk, et. al., (2007) Optics Express 15: 9908- 9917, Andrew, P., et al. (2004) Science 306: 1002-1005). The techniques used, however, are typically labor intensive nanofabrication and expensive methods such as electron beam lithography and ion beam milling. While there are some effective bottom-up manufacturing approaches using pre-patterned substrates for nanoparticle deposition, such as rippled silicon or faceted alumina, it is believed that there has been no approach as cost-effective and amenable to large-scale production as the one disclosed herein (H. Raether, "Surface Plasmons on Smooth and Rough Surfaces and on Gratings", Springer, Berlin, (1988) Murray, W. A., et al. (2004) Phys. Rev. B 69: 165407/1-7).
Surface-Enhanced Catalysis
[0057] Surface-enhanced catalysis is based on enhanced-surfaces area, thus can be applicable to heat-induced buckling of metal-coated biaxially-stressed polystyrene sheets, i.e. gold wrinkles and petals. In some embodiments, e.g., for microfluidic heating applications, the polystyrene substrates may be required to be removed due to the high temperature operating condition. This can be done by dissolving the polystyrene with Toluene and washing with de-ionized water. The metal petals or wrinkles are contacted with the reactants under suitable conditions and serve to catalyze the reaction and can be easily removed. One such application is the fluorogenic reaction of resazurin, whereby gold catalyzes the reduction of the non-fluorescent resazurin to the fluorescent production resorufm (Xu, W. et al. (2008) Nature Materials (7):992-996). This reaction is based on the available surface area of the catalyst and the turnover rate of the reactants, thus utilization of metallic wrinkles and petals within a microfluidic chip can potentially be used as a platform for micro -analysis of biologically activity and environmental contaminants, such as cell proliferation, and hydrocarbon contaminants which can reduce the surround medium. Stereoselective Reactions
[0058] Metal coated surfaces can be use to drive stereoselective reactions based on the preferential differences of chemical bonds to the metallic surfaces and the available surface area of reaction which will consequently affect the reaction rate. Thus gold wrinkles and petals can potentially be used for the transfer of stereoselectivity from catalyst to product (Bongers, N. et al. (2008) Angew. Chem. Int. Ed., 47:2178-2181). For the purpose of illustration only and by way of example, the devices of this invention can be used for catalysis of endo-cycloisomerization of α- and β-hydroxyallenes to five- and six-membered heterocyclics by gold (I) and gold (III) using a modification of the methods disclosed in Bongers, N. et al. (2008) Angew. Chem. Int. Ed., Vol. 47, 2178-2181; Hoffmann-Roder, A. et al. (2001) Org. Lett, 3: 2537-2538; Krause, N. et al. (2002) Synthesis, 1759-1774: Hyland, C. J. T. et al. (2006) J. Org. Chem. 71 : 8658-8660; Patil, N. T. et al. (2006) Tetrahedron Lett., 47: 4749-4751; and Zhang, Z. et al. (2006) J. Am. Chem. Soc, 128:9066- 9073). The metal petals or wrinkles are contacted with the reactants under suitable conditions and serve to catalyze the reaction and can be easily removed.
Heat Sources And Sinks In Microfluidic Devices
[0059] Highly conductive metals of high surface area can be used as heat sources and sinks to direct the flow of thermal energy. This principle can be applied to microfluidic devices where wrinkles and petals can be incorporated within the microfluidic devices to control the flow of heat alter reaction rate. This process may also be applied to sensors where high- surface area metals can be used as temperature sensors to monitor reaction rates. Example of such applications would be the use platinum-containing metal wrinkles and petals can be used with microfluidic chips and integrated with heaters and sensors to make enhanced- surface area conductive metal, i.e. methanol reformers for on-chip hydrogen production using a modification of the technology previously disclosed in Pattekar, A. et al. (2004) Journal of Microelectromechanical Systems, 13(1) and "Modeling, design and control of silicon based microchemical systems," in 2002 AIChE Annual Meet., Indianapolis, IN, Nov. 3-6 (2002). The devices can be used in a process by which hydrogen atoms are stripped from methanol in a high temperature cracker. Water-Gas Shift Reactions
[0060] The devices can be used for the production of hydrogen gas fuel from the catalytic cracking of gasoline or natural gases, gasoline and natural gas reformers. For example, when gold comprises the wrinkles or petals, the devices can be used to lower the carbon monoxide contamination of the hydrogen product through a process known as water-gas shift (WGS) reaction using modification of the methods disclosed in Rebrov, V. E. et al. (2008) Catalysis Today, 138:210-215; Kuperman, A. et al. Method for making hydrogen using a gold containing water-gas shift catalyst,US Patent 7,169,376; Idakiev, V. et al. (2004) Appl. Catal. A., 270: 135; Idakiev, V. et al. (2006) Appl. Catal. B. 270:178; Idakiev, V. et al., (2007) Catal. Today, 128:223; Sakurai, H. et al. (1997) Chem. Commun., 3: 271; and Boccuzzi, F. et al. (2002) Catal. Today, 75: 169. Carbon Oxide (CO) contamination is typically around 8-12% and can be reduced to below 1% using water-gas shift reactions. This reaction is carried out at 200-280 0C. This is based on hydrogen production and may be integrated into the microfluidic chip listed above.
Cell Culture Substrate
[0061] Silver-containing devices and devices coated with silver and/or nanocrystallines will produce silver cations, AgO, and free radicals in cell culture medium which are highly antimicrobial with little effect on mammalians cells (Kleps, I. et al. (2007) Materials Science and Engineering, C 27:1439-1443 and Fu-Ren, F. et al. (2004) J. Chem. Phys., Vol. 120(12)). Thus the integration of silver wrinkles into cell culture chips will provide an enhanced-surface for production of anti-microbial agents applicable in long term cell culture.
Kits
[0062] This invention further provides a kit comprising, or alternatively consisting essentially of, or yet further consisting of the materials necessary to perform the method described above. In one aspect, the kit comprises, or alternatively consists essentially of, or yet further consists of a thermoplastic material and instructions for making the device. In one aspect, the kits further comprise one or more metals. The kit provides instructions for making and using the apparatus described above and incorporated herein by reference. [0063] In another aspect, this invention provides a method for assaying or screening for new materials and methods having the same function of the inventions as described herein. In this aspect, the new materials and/or methods are used in the methods as described herein and compared to the performance of the devices of this invention.
Experimental
[0064] As shown in Figure 1 , for biaxial nanopetals, 40-nm-thick silver and subsequent 40- nm-thick gold are deposited on a Shrinky-Dink sheet (or KSF50-C; Grafix , 2cm x 1 cm ) using a sputter (SEM coating system; Polaron). To avoid preheating of the substrate, this step is separated to 4 cycles and each cycle (including 10 seconds of sputtering and 20 seconds of cooling) deposits 2.5 nm of gold. After deposition, heating at 1600C for 6 minutes in an oven induces retraction of the substrate and causes the non-shrinkable gold film to form biaxial wrinkles. Wrinkling induced cracks make it possible to create nanopetals (Fig. IA). For uniaxial wrinkles or petals, before heating two short-edges of a gold-coated sheet are clamped by clips (2" binder clips; OfficeMax) to ensure it can only retract in the other direction (Fig. IB).
[0065] While the present invention is exemplified and illustrated by the use of polystyrene sheets to fabricate channel structures and molds, it would be obvious to those of skill in the art that any thermoplastic receptive material that can be patterned to control the dimensions of the channel defining walls and thereby their size, can be used to fabricate the devices disclosed and claimed herein. In addition, although several other embodiments of the invention are described herein in detail, it will be understood by those skilled in the art that variations may be made thereto without departing from the spirit of the invention or the scope of the appended claims.

Claims

What is Claimed is:
1. A method for catalyzing a reaction, comprising contacting the reaction substrates with a device comprising a high-surface area textured metal surface, wherein the textured metal surface has an average height from about 100 nanometers to about 5 micrometers.
2. The method of claim 1, wherein the high- surface area textured metal surface further comprises a thermoplastic material.
3. The method of claim 1 or 2, wherein the textured metal surface comprises at least one metal selected from the group consisting of platinum, silver, gold and copper.
4. The method of any of claims 1 to 3, wherein the textured metal surface comprises two or more metals selected from the group consisting of platinum, silver, gold and copper.
5. The method of claim 2, wherein the thermoplastic material is one or more high molecular weight polymer selected from the group of acrylonitrile butadiene styrene (ABS), acrylic, celluloid, cellulose acetate, ethylene -vinyl acetate (EVA), ethylene vinyl alcohol (EVAL), fluoroplastics (PTFEs, including FEP, PFA, CTFE, ECTFE, ETFE), ionomers kydex, a trademarked acrylic/PVC alloy, liquid crystal polymer (LCP), polyacetal (POM or Acetal), polyacrylates (Acrylic), polyacrylonitrile (PAN or Acrylonitrile), polyamide (PA or Nylon), polyamide-imide (PAI), polyaryletherketone (PAEK or Ketone), polybutadiene (PBD), polybutylene (PB), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), Polycyclohexylene Dimethylene Terephthalate (PCT), polycarbonate (PC), polyhydroxyalkanoates (PHAs), polyketone (PK), polyester polyethylene (PE), polyetheretherketone (PEEK), polyetherimide (PEI), polyethersulfone (PES), polysulfone polyethylenechlorinates (PEC), polyimide (PI), polylactic acid (PLA), polymethylpentene (PMP), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyphthalamide (PPA), polypropylene (PP), polystyrene (PS), polysulfone (PSU), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC) and spectralon.
6. The method of any of claims 1 to 5, wherein the reaction catalyzed by the device is one or more of surface enhanced catalysis, stereoselective reaction, water-gas shift reactions.
7. A method to inhibit microbial growth in a solution, comprising contacting the solution with a device comprising a high-surface area textured silver metal surface, wherein the textured silver metal surface has an average height from about 100 nanometers to about 5 micrometers.
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