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WO2010132611A2 - Nanopétales métalliques texturées - Google Patents

Nanopétales métalliques texturées Download PDF

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Publication number
WO2010132611A2
WO2010132611A2 PCT/US2010/034612 US2010034612W WO2010132611A2 WO 2010132611 A2 WO2010132611 A2 WO 2010132611A2 US 2010034612 W US2010034612 W US 2010034612W WO 2010132611 A2 WO2010132611 A2 WO 2010132611A2
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WO
WIPO (PCT)
Prior art keywords
metal
alternatively
nanometers
thermoplastic material
acrylic
Prior art date
Application number
PCT/US2010/034612
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English (en)
Other versions
WO2010132611A3 (fr
Inventor
Michelle Khine
Original Assignee
The Regents Of The University Of California
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Publication date
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Publication of WO2010132611A2 publication Critical patent/WO2010132611A2/fr
Publication of WO2010132611A3 publication Critical patent/WO2010132611A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • 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

Definitions

  • This invention provides a device comprising, or alternatively consisting essentially of, or yet further consisting of a heat-shrunk thermoplastic base having a high-surface area textured metal surface, wherein the textured metal surface comprises a plurality of cracks and has an average height from about 100 nanometers to about 5 micrometers.
  • 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.
  • Other molecules can be affixed or conjugated to the metal surface, such as a luminescent molecule, a fluorescent molecule or a catalyst.
  • Methods to prepare the devices 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 cracks form in the metal deposited on the receptive material, thereby preparing a textured metal surface.
  • the heat sensitive thermoplastic material is uniaxially biased prior to performing steps a) and b) and/or during step b).
  • layers of metals or by layering with different metals having slightly different stiffness one can controllably induce cracking of the metal surface to produce petal-like, high surface area substrates.
  • the devices have sharper nanostructures that can be used, inter alia, as higher field enhancements such as field emitters.
  • 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.
  • the method also requires affixing or conjugating to the metal surface one or more of a luminescent molecule, a fluorescent molecule or a catalyst.
  • Kits for preparing the devices and methods for use are further provided.
  • Figures IA to 1C are scanning electron microscope (SEM) images of biaxial (a) and uniaxial (b) nanopetals created by wrinkling bimetallic films (40 nanometer gold on the top of 40 nanometer silver).
  • the 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).
  • 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).
  • 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 (AB
  • 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 (also referred to as the thermoplastic material) 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 "crack" intends an interruption of the continuity of a surface.
  • the preparation of the textured 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 the metal on the material cracks, thereby forming the textured metal nanopetals.
  • Steps a) and b) prepare a metal nanopetal 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.
  • step a) can be repeated before step b) and each time the metal can be the same or different.
  • the thermoplastic material is a heat sensitive thermoplastic receptive material which in one aspect is to be uniaxially or biaxially stressed upon heating or alternatively, uniaxially or biaxially pre-stressed prior to heating.
  • 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.
  • 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 or the metal 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 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 receptive material to fabricate the metal 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.
  • 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 receptive material. Methods for the controlled deposition of metals are well known in the art.
  • 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 receptive 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%.
  • 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, 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.
  • Petal height can be controlled by adjusting the metal film 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.
  • This invention provides substrates of 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 petals enable the applicants to concentrate and localize electromagnetic field.
  • the nanopetals 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).
  • MEF metal enhanced fluorescence
  • SERS surface enhanced Ramon spectroscopy
  • bimetallic films can extend the penetration depth of surface plasmon to increase the amount of molecules in the enhanced region.
  • Nanoparticles are the typical materials for nanocatalysis due to their large surface area.
  • these nanopetals, 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).
  • thermoplastic material such as printable pre-stressed polystyrene (PS) sheets.
  • PS printable pre-stressed polystyrene
  • the methods disclosed herein has been informed by theoretical work that addresses the scaling relationship between the length scales of the 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 petal length scales arise from a competition between the elastic bending energy of the film and the elastic energy of deformation of the substrate.
  • plasmon-active petals are created with a large range of wavelengths (> 30x) and periodicity, directionality and aspect ratios, and even patterns.
  • this petaled surface demonstrates tunable LSPR resonance, it holds potential as a low cost and robust substrate for surface enhanced sensing and spectroscopy.
  • the petals exhibit hierarchical self-assembly, broad band response can be achieved.
  • the unidirectional features allow the possibility of energy harvesting and radiative transfer on the same device by SPP.
  • the nanopetals provided in the present disclosure are distinguished from those devices by provided a greater or enhanced surface area due to the exposure of surfaces of the metal which are originally in contact with the thermoplastic base. Further, applicants' data show a 7- fold enhancement on fluorescence intensity can be achieved from deposited dyes on the nanopetals (Fig. 1C). Further, several thousand folds of increase in intensity at the edges or
  • kits 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 kit further comprises one or more metals for forming the nanopetals. 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.
  • 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.
  • bimetallic structures on the surface of memory polymers are also attained in order to achieve sharp bi-layered uniaxial and biaxial nanopetals.
  • the sharp edges of the nanopetals exhibit remarkable increase of emission intensity of fluorescent molecules.
  • Several thousand fold increase in intensity at the edges or "hotspots" of both uniaxial and biaxial nanopetals have been observed.
  • the fluorescence intensities observed at the hotspots are brief bursts of intensity as the molecules diffuse through the structures. These bursts are below the resolution limit of our optics and possibly be due to single molecular emission.
  • the intensity of the bursts increases non-linearly with increase laser intensity suggesting that the events may be attributable to stimulated emission, excited-state absorption, or saturation intensity dependent 2-photon emission cross-section.
  • a decrease is also seen in the excited-state lifetime of the fluorescence particles, fluorescein, revealing strong plasmonic interactions.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)

Abstract

L'invention concerne un dispositif qui comprend une base thermoplastique thermorétractée présentant une surface métallique texturée à grande surface active. La surface métallique texturée a une hauteur moyenne comprise entre environ 100 nanomètres et environ 5 micromètres. L'invention concerne également des procédés de fabrication et d'utilisation du dispositif.
PCT/US2010/034612 2009-05-13 2010-05-12 Nanopétales métalliques texturées WO2010132611A2 (fr)

Applications Claiming Priority (2)

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US17791609P 2009-05-13 2009-05-13
US61/177,916 2009-05-13

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WO2010132611A2 true WO2010132611A2 (fr) 2010-11-18
WO2010132611A3 WO2010132611A3 (fr) 2011-02-03

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103499561A (zh) * 2013-10-14 2014-01-08 厦门大学 一种表面增强拉曼光谱基底材料及其制备方法
CN103521754A (zh) * 2013-10-14 2014-01-22 厦门大学 一种表面增强拉曼光谱基底材料的制备方法
US8828302B2 (en) 2011-02-07 2014-09-09 The Regents Of The University Of California Preparation and use of nanowrinkles
US9452564B2 (en) 2011-02-07 2016-09-27 The Regents Of The University Of California Multi-scale wrinkles for functional alignment of stem cells and cardiac derivatives
US9522820B2 (en) 2007-11-13 2016-12-20 The Regents Of The University Of California Processes for rapid microfabrication using thermoplastics and devices thereof
US9625819B2 (en) 2011-05-27 2017-04-18 The Regents Of The University Of California Photolithography on shrink film
CN118931224A (zh) * 2024-10-15 2024-11-12 浙江原邦材料科技有限公司 一种复合材料及其制备方法和用途

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9522820B2 (en) 2007-11-13 2016-12-20 The Regents Of The University Of California Processes for rapid microfabrication using thermoplastics and devices thereof
US8828302B2 (en) 2011-02-07 2014-09-09 The Regents Of The University Of California Preparation and use of nanowrinkles
US9452564B2 (en) 2011-02-07 2016-09-27 The Regents Of The University Of California Multi-scale wrinkles for functional alignment of stem cells and cardiac derivatives
US9625819B2 (en) 2011-05-27 2017-04-18 The Regents Of The University Of California Photolithography on shrink film
CN103499561A (zh) * 2013-10-14 2014-01-08 厦门大学 一种表面增强拉曼光谱基底材料及其制备方法
CN103521754A (zh) * 2013-10-14 2014-01-22 厦门大学 一种表面增强拉曼光谱基底材料的制备方法
CN118931224A (zh) * 2024-10-15 2024-11-12 浙江原邦材料科技有限公司 一种复合材料及其制备方法和用途

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