Mass-Producible Nanoparticle Assemblies on Polymer Templates using by alllona

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									     @                                                        University of   Cincinnati




  Mass-Producible Nanoparticle Assemblies on
Polymer Templates using Nanoinjection Molding:
Opportunities and Challenges for NanoBiosensors


  Chong H. Ahn, Michael J. Rust, Se Hwan Lee, and Joon Sub Shim


             Center for BioMEMS and Nanobiosystems
         Department of Electrical and Computer Engineering
               Department of Biomedical Engineering
                    University of Cincinnati
                       Cincinnati OH 45219


                      Center for BioMEMS and Nanobiosystems
BioMEMS @                                                     University of Cincinnati




              Smart Point-of-Care Diagnostics
            for Home Care or Emergency Room




                      Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                          University of Cincinnati




         Wristwatch Type Point-of-Care Testing

                           Inlet ports
     Biochemical sensors
     (underneath)




    sPROMs
                                         Integrated Disposable            Biochip Analyzer
                                         Biochip Cartridge                for Multi-analyte
  Air-bursting                                    Watch &
                                                                          Detection
  “Detonator”                                     Display cap
                                                                         Wrist watch band

  Pressurized
  air bladders




     Microneedle
     array


                                                                          Action buttons

                                 Center for BioMEMS and Nanobiosystems
BioMEMS @                                                 University of Cincinnati




       “SMART” Lab-on-a-Chip and Analyzer




                  Center for BioMEMS and Nanobiosystems
BioMEMS @                                           University of Cincinnati




            Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                      University of Cincinnati


              Polymer Lab-on-a-Chip with
            Heterogeneous Nano Biosensors




                                                             Iron Catalyst
                                                                      Au/Ti electrode




                                                             Ni Pattern Nanotube
                                                                 1μm


                     Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                      University of Cincinnati



              Polymer Lab-on-a-Chip with
            Heterogeneous Nano Biosensors
                                      Nano gaps,
                                      Electrochmical
                                      nanobiosesnors




                                                                             Self-assembled
                                                                             carbon nano wires
                                                             Iron Catalyst
                                                                      Au/Ti electrode
                     Functional nano particles,
                     colloidal beads,
                     biomolecules, nano
                     molecular blocks                        Ni Pattern Nanotube
                                                                 1μm


                     Center for BioMEMS and Nanobiosystems
BioMEMS @                                                           University of Cincinnati



           Mass-Producible Nano Devices
    on Polymer for NanoBiosensors: Opportunities
   Mass Producible Nano Manufacturing? (Top-down + Bottom-up)
      Mass-producible nano injection molding techniques
        o High throughput nano patterns or templates
        o Low cost nanodevices or biochips
      Self-assembled micro/nano particles on polymer lab-on-a-chip:
       nanocolumns, nanospots, or nanowires
      Nanoelectrodes or nanocondcutors on polymer templates
   Heterogeneous NanoBiosensors? (Micro + Multi Nano)
      New transduction mechanisms with extremely high sensitivity
      Embedded functional column for point-of-care (POC) health
       monitoring – on-site separation or sample prep
      Self-assembled nanoelectrodes or nanowires – ultra high sensitive
       electrochemical sensor
      Biosensor with self-assembled and functionalized CNTs.

                            Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                                     University of Cincinnati




    Plastic Nano Injection Molding Techniques
                                      Mold block                             Mold structure




                                                                                                Hot plastic




                                        Injection nozzle
   Mold structure
   on molder block



                                                              Injection Molding Process
                                                                –   Heat granular plastic material
                                                                –   Inject softened plastic into mold
                                                                –   Plastic cooling down
                                                                –   Open mold halves and eject part
       Injection molded plastic structure


                                      Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                                                            University of Cincinnati




            Multilane Polymer CE Microchip

                                                                      0.5                                            FITC             FL
                                                                     0.45
                                                                      0.4
                                                                     0.35                                       35    36    37   38        39     40   41   42




                                                     Intensity (V)
                                                                      0.3
                                                                     0.25
                                                                      0.2
                                                                     0.15
                                                                      0.1
                                                                     0.05
                                                                       0
                                                                            0   50   100   150      200       250          300                  350         400

                                                                                                 Time (sec)




       ■    Electropherogram of 25 µM Fluorescein and 50 µM FITC separation on CE chip.
       ■    0.03 % Poly(ethylene oxide) (PEO) in 0.1 x Tris/boric acid/EDTA (TBE) buffer solution
       ■    Reproducibility in terms of migration time was achieved within 1.50 % range.
       ■    The reservoir shape difference did not show significant difference in the separation
            efficiency.
       ■    However semi-conical shaped reservoir would be more preferable, when many patterns
            need to be packed in small area because of enough spacing at bonding sight while
            providing sufficiently large sample volumes (>33 μl).

                                     Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                          University of Cincinnati




        Fully Packed CE Device for On-site Analysis

                                    D
                C

            B
                    A

                            Detection Point

                                                                        Silica bead packed channels


  ■   Channel filling with buffer solution only by the capillary action of the
      packed channel: Bubble free initial conditioning
  ■   Easy and flexible liquid sample injection on chip without injection pump
      or vacuum suction
  ■   Fully packed silica beads dominantly controls the EOF: Stable EOF can
      be achieved.
  ■   Effective on-chip CE separation in simple
  ■   Provide hand-held on-chip CE separation for on-site or point-of-care
      analysis
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BioMEMS @                                                                       University of Cincinnati




         Colloidal Self-Assembly Crystallization
                     Hydrophilic treated
                       microchannel




                      Monodisperse                              Stir bar
                   colloidal silica beads
                          solution




           Self-assembly of colloidal suspension in a microchannel
           Filling through hydrophilic treated plastic microchannels
           2D or 3D periodic array of a uniform colloidal silica suspension
           Capillary forces, convective particle flux during solvent evaporation

                                        Center for BioMEMS and Nanobiosystems
BioMEMS @                                                               University of Cincinnati




            Self-Assembly Collidal Bead Packing




       ■     Well defined silica bead packing for whole channels
             o   100 um width, 40 um height channels
             o   800 nm diameter silica beads



                                Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                    University of Cincinnati




   Fully Packed CE Device for On-site Analysis

                                          Cover wafer
                                          COC (Tg = 80˚C)




                                          Patterned wafer
                                          COC (Tg = 136˚C)

                   Bead packed channels


       ■    Destruction of silica packing by pressure is critical
            o   Topas COC 5013 (Tg = 136 ˚C, for patterned plate) and 8007 (Tg = 80 ˚C,
                for cover plate) are used.
            o   85 ˚C for 20 minutes without pressure  gently pressed for another 20
                minutes  cool down while holding the pressure.


                                     Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                                                          University of Cincinnati




                                Fully Packed CE Device for On-site Analysis
                                1200

                                                           F
                                                                                                   A: arginine
                                1000
                                                                                                   F: FITC
                                 800
                                                                                                   P: phenylalanine
                                                                                                   G: glycine
      in te n sity (co u n t)




                                 600
                                                                                                   G*: glutamic acid
                                                                                                   0.25mM each
                                 400                   A
                                                                P
                                                                    G                              20 mM Na2B4O7 running
                                                                                                        buffer (pH 9.2)
                                 200
                                                                                G*



                                   0
                                         0     20          40              60        80

                                                    tim e (se c)



                       ■               Separation of FITC-derivatized amino acid mixture
                       ■               Sample loading (A:+200V) with pinching (C and D:+170V,
                                       B:gorund)
                       ■               Separation (C:+200V) with back pushing (A and B:+70V)
                       ■               Detected at 2.5 mm far from the channel cross
                                                                        Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                         University of Cincinnati



                     Fully Packed CE device and
                      Electrochemical Detection

                               3.5 cm

                          SW                   CE



                 0.5 cm          1.2 cm
     2 cm   BR                                           BW




                          SR
                                          WE        RE




                                          Center for BioMEMS and Nanobiosystems
BioMEMS @                                                        University of Cincinnati




            Fully Packed CE device and
             Electrochemical Detection




                          (a)                              (b)




                   (c)                               (d)


                   Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                     University of Cincinnati




            Fully Packed CE Device for On-site
                        Analysis




               Uric acid


                           Ascorbic acid




      On-site Uric Acid and Ascorbic Acid Detection with the Lab Chip


                                      Center for BioMEMS and Nanobiosystems
BioMEMS @                                                             University of Cincinnati




       Mass-Producible Nano Devices on Polymer
        for Nanobiosensors: Challenging Issues
       Nano Manufacturing using Nano Injection Molding
           Nano Injection Molding Techniques
            o Nanofabrication of nano master molder – electroplating or metal
              deposition: reproducibility and durability
            o Influence of thermal expansion coefficient (TEC) of polymer and
              mold for injected nano templates


           Self-assembled micro/nano beads on polymer
            o Understanding assembly dynamics
            o In-situ monitoring of the assembly condition of the colloidal
              beads during assembly
            o Analysis of dynamics of the surface energy
            o In-situ measurement of the surface characterization and
              interactions between nano particles and nano/micro channels.

                              Center for BioMEMS and Nanobiosystems
BioMEMS @                                                    University of Cincinnati




     Interdigitated Array (IDA) Nanoelectrodes
     as an Ultrahigh sensitive Electrochemical
                       Sensor

             “Nanoparticle Assemblies As A
            Conductor on Polymer Templates”




                     Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                                        University of Cincinnati




      IDA Electrode as Electrochemical Sensor

                                                                                  Substrate
                                     Reference Counter
                                     Electrode Electrode

  Potentiostat

                                                              Enzyme
                                                                                       Product
            IDA Electrode




                       A                                                          e-
                                            -                                                    e-
                       Amperometer          +
  Potentiostat
                                                                              Anode       Cathode




                                          Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                                                                 University of Cincinnati




               IDA Electrode with Nano Gaps?
     IDA nano electrode                                 Assuming D = 6 10-6 cm2/s
      improves the response                L m icro
                                                    2       6
                                                      1  10  1  10
                                                                      6

      time and the redox cycling t m icro  D  6  10  6  10  4 s  1 . 6 ms
      efficiency (and thus signal
                                                    1
      magnitude)                      f                300 Hz
                                                           micro
                                                                            2 t micro
            Electrode1         Electrode2

                           R
                                                                                    10  10         10  10
                                                                            2                 9                    9
                     R             R                               L nano
                2e                     2e              t nano                                                          s  0 . 16 us
                                                                                        6  10           10
                                                                                                   6          4
                                                                     D
                     O             O
                           O                                                1
                                                         f nano                     3 MHz
                                                                      2 t nano
                         L=10 nm
                     Or, L=1 um                  i nano / i micro  2 ef nano / 2 ef micro  10 , 000



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BioMEMS @                                                                            University of Cincinnati




            Geometry of Electrochemical Sensor

                                                   Working electrode 1
                                A



                   Reference
                   electrode                                      Auxiliary
                                                                  electrode



                                                           A’
            Reference Working                                                 Auxiliary
            electrode electrode 1              Working electrode 2            electrode



                                         500 um




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BioMEMS @                                                                                  University of Cincinnati




                          IDA Micro/Nano Electrodes

                 250 um                                                                  250 um

                              Working                                              WE1
                              electrodes
                                                             RE                                AE




                                                                          WE2
        Reference
        electrode                          Auxiliary
                                           electrode
                      Micro-IDA                                          Nano-IDA
            1.     Almost same electrode surface area for interdigitated array
            2.     All fingers are confined in a ring-band region (outer radius=250 µm, inner
                   radius = 30 µm)


                                           Center for BioMEMS and Nanobiosystems
BioMEMS @                                                         University of Cincinnati




            Nanofabricated IDA Nanoelectrodes
                      (ebeam based)




                    1m




                          Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                                                                   University of Cincinnati




       Outputs for IDA Micro/Nano Electrodes

                                      2
                                                ■ Data using nanoelectrode               R2nano=0.994
                                 10              Data using microelectrode
                                                                                                   R2micro=0.99
                                      1
                                                                                                   6
                                 10
            Decay Rate (V/sec)




                                 10
                                      0            Y=5.004 +0.833 X


                                  -1
                                 10


                                  -2
                                 10
                                                          Y=3.504 +0.818
                                                                                                              3
                                                          X
                                  -3
                                 10        -9        -8           -7       -6       -5        -4         -3            -2
                                      10           10        10          10       10        10          10        10
                                                                       Concentration (M)




                                                          Center for BioMEMS and Nanobiosystems
BioMEMS @                                                               University of Cincinnati



                      Nanoparticle Assemblies
        Surfaces functionalized with nanoparticle assemblies can be
         applied for:
            –   Biosensors                  300 nm
            –   Photonics
            –   Electronics
            –   Catalysis




        Requirements
            –   Assembly of multiple types, sizes, and shapes of nanoparticles
            –   Nano-scale precision
            –   Uniform over large areas
            –   Mass-producible fabrication methods
            –   Low-cost polymer substrates


                                Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                                   University of Cincinnati




       Nanoparticle Assembly: Silica and then Gold

                                             PMMA



            E-beam writing of PMMA pattern   Ni
                                             substrate




                   Ni/Fe electroplating




                      Liftoff PMMA
                                             COC



               Injection molding with COC




                  Nanostructured COC




                                                    Center for BioMEMS and Nanobiosystems
BioMEMS @                                                           University of Cincinnati




                   Nanoinjection Molding
                  Nano Mold                            Polymer Replica



            (a)                                 (b)


                                                        300 nm
                  300 nm




                           Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                            University of Cincinnati



                       Nanoparticle Assembly
                                                               91.8 nm




                                                                 0 nm
                                                                         0 µm   1.13 µm




        New technique for nanoparticle
         assembly on polymer nano-
         template
        Can produce assemblies of
         multiple nanoparticle:
            – types
            – sizes
            – configurations                          300 nm


                               Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                                 University of Cincinnati




                       Size-Selective Assembly
                  80 nm deep                                                 55 nm deep
                                                                             55 nm deep


                           200 nm                                                    200 nm


  80 nm                                                55 nm




                           200 nm                                                    200 nm

                                                       55 nm
  80 nm




          80 nm SiO2 nanoparticles                  *80 nm silica nanoparticles excluded from 55 nm
                                                        deep patterns
          22 nm SiO2 nanoparticles
                                     Center for BioMEMS and Nanobiosystems
BioMEMS @                                                      University of Cincinnati




            Nanoparticle Assembly




                   300 nm


                      Assembly of 80 nm silica nanoparticles




               Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                       University of Cincinnati



   Uniformity and Multiple Nanoparticle Types
                      200 nm                                           200 nm




        1 µm   80 nm SiO2 nanoparticles            3 µm       55 nm Sb2O5 nanoparticles



                      200 nm                                           200 nm




        3 µm   22 nm SiO2 nanoparticles              1 µm        86 nm Au nanoparticles

                               Center for BioMEMS and Nanobiosystems
 BioMEMS @
nitiator solution (SE100, Sigma-Aldrich) and pipetting onto the polymer template for 1 min. After rinsing in de-ionized water, the template was dried in nitr
                                                                                                                                University of Cincinnati
                                                                         • Results



          Nanoelectrodes by Silver Electroless Deposition

          •The self-assembled electrodes with gold nanoparticles did show
          very poor conductivity and reproducibility – compelling desires.

          •Explored new method, which utilizes nanostructured polymer
          templates for the selective patterning of silver, which is deposited
          by electroless plating.

          •Polymer chip surface was activated by gold (Au) sputter, as non-
          conducting film of Au (< 10 nm) to serve as the catalyst for the
          electroless deposition of Ag.

          •Ag electroless deposition was performed on selectively over the
          nano templated channels.




                                                          Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                 University of Cincinnati


     Nanoelectrodes by Silver Electroless Deposition




    Fabrication process for silver nanoelectrodes on polymer template: (a) fabrication of
                         (a)                                (b)
    polymer template by nanoinjection molding; (b) electroless deposition and patterning
    of silver by mechanical wiping.

                                Center for BioMEMS and Nanobiosystems
BioMEMS @
 Results from fabrication: (a) SEM image of Ag nanoelectrodes in IDA format. (b) High-magnification SEM image of Ag nanoelectrodes in polymer         University
                                                                                                                                                template.          of Cincinnati




                    Nanoelectrodes by Electroless Deposition




                 10 µm
                                                                                                  300 nm




                 Results from fabrication: (a) SEM image of Ag nanoelectrodes in IDA format. (b)
                 High-magnification SEM image of Ag nanoelectrodes in polymer template.



                                                                  Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                                      University of Cincinnati




            Nanoelectrodes by Electroless Deposition

                                 300


                                 250
                Thickness (nm)




                                 200


                                 150


                                 100


                                 50


                                  0
                                       0   1        2        3        4       5        6   7
                                                            Time (min)



                                               Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                             University of Cincinnati




       Measured Resistance of Nanowires on Chip
                                                          8


                                                          6


                                                          4


                                                          2
               Current (mA)




                                                          0
                              -1.5   -1       -0.5            0       0.5         1   1.5
                                                         -2


                                                         -4


                                                         -6


                                                         -8
                                                       Voltage (V)

            0.1 ~ 10 mohms of resistance was reproducibly attained.


                                          Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                                                                      University of Cincinnati




            Hope to Get This Again on Polymer !!

                                         2
                                                   ■ Data using nanoelectrode               R2nano=0.994
                                    10              Data using microelectrode
                                                                                                      R2micro=0.99
                                         1
                                                                                                      6
                                    10
               Decay Rate (V/sec)




                                    10
                                         0            Y=5.004 +0.833 X


                                     -1
                                    10


                                     -2
                                    10
                                                             Y=3.504 +0.818
                                                                                                                 3
                                                             X
                                     -3
                                    10        -9        -8           -7       -6       -5        -4         -3            -2
                                         10           10        10          10       10        10          10        10
                                                                          Concentration (M)




                                                             Center for BioMEMS and Nanobiosystems
BioMEMS @                                                 University of Cincinnati




     Fluidic Self-Assembly of Carbon Nanotube
         by Magnetic Attraction on Catalyst




                  Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                University of Cincinnati


        Fluidic Assembly of CNT by Magnetic
             Attraction on Metal Catalyst
            ■ Commonly used metal catalyst for the synthesis of CNT
                – Ni, Fe, Co
            ■ Ferromagnetic characteristic of metal catalysts
            ■ Catalysts located at the one end of nanotube
            ■ Nanotube synthesized on iron (Fe) catalyst were tried
              No pre-processing on nanotube for assembly


                                                                     Ni Pattern


                                                                     Catalyst



                                                                     Nanotube
                                       100 nm
                   500 nm


                             Center for BioMEMS and Nanobiosystems
BioMEMS @                                                                                             University of Cincinnati




   Precise Self-Assembly of Carbon Nanotube
                                                               Flowing direction
            Ni pattern       Au/Ti Electrode
                                                                         Fe Catalyst     Nanotube




                   SiO2 / Si Substrate
                                                                                    Magnetic Field
      (a) Fabrication of Ni pattern on Au/Ti electrodes
                                                                 (b) CNT flowing guided by PDMS channel




         Induced
         magnetic field                                                            Fluidic aligning




                           Magnetic Field                                             Magnetic Field
         (c) Magnetic attraction on Fe catalyst                   (d) Parallel aligning with flowing direction


                                            Center for BioMEMS and Nanobiosystems
BioMEMS @                                                          University of Cincinnati




       Precisely assembled CNT on electrode

                          Au/Ti
            Iron Catalyst electrode




                                   Nanotube

              Ni Pattern

                                                       1μm

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BioMEMS @                                                                                               University of Cincinnati



                                       Electrical Characterization
        ■ Showing stable ohmic contact with Au/Ti electrode (Metallic MWNT)
        ■ No additional metal depostion is required (No post-processing)
        ■ Annealing Effect
           o Reduce the contact resistance
                         o       Measured resistance = 39.28 kΩ  28.68 kΩ
                                                               40

                                                               30

                                                               20
            C u rren t (u A )




                                                               10
                                                                                                          B efore
                                                                 0
                                                                                                          A fter
                                -1.2   -0.9   -0.6    -0.3           0          0.3   0.6   0.9   1.2
                                                              -10

                                                              -20

                                                              -30

                                                              -40

                                                             V o lta g e (V )



                                                     Center for BioMEMS and Nanobiosystems
BioMEMS @                                                          University of Cincinnati




                     Challenging Issues
  Mass-Manufacturaable Nano Functional Column and Biosensors
   Manufacturing precise master nanomold and replica
   Precise nano templates or its surface modification for the precise
  assembly of nanomolecules
   In-situ monitoring of assembling process and characterization of
  assembled structures

     Reproducible and reliable conductivity for metal nanoparticles
     Conductivity improvement of self-assembled metal nanoparticles

   Assembly precision control for self-assembled CNTs
   Reliable conductivity and functionalization of the self assembled
  CNT

     Innovative interface between microsystem and nanodevices
                           Center for BioMEMS and Nanobiosystems
BioMEMS @                                                          University of Cincinnati




      Summary Recommendation for 2020
     Manufacturable functional nanodevices or nanosystems could be
      achievable from the combination of top-down and bottom-up
      approaches.

     Mass-producible nano biochips and lab chips would come from
      nano-templates and self-assembly approaches.

     New interfacial methods and approaches between micro and nano
      devices should be focused and explored in future.

     Manufacturable process and devices should be comprehensively
      considered for the development of mass-producible nanodevices or
      systems at the beginning.


                           Center for BioMEMS and Nanobiosystems
BioMEMS @                                                              University of Cincinnati




                          Acknowledgements

             DARPA, MicroFlumes & BioFlips Program, DoD

             NSF/EPDT Program, #0622036
               NSF/BES Program, #0330075

             NIH/NIEHS, R01 ES015446-01
               NIH – Biochips, R01 GM69547
               NIH/NIBIB – SBIR with Siloam Biosciences Inc.




                               Center for BioMEMS and Nanobiosystems

								
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