Piezoresponse Force Microscopy_ Fields below the Surface

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					Novel biopiezoelectric materials for
   sensor/actuator applications
                 Andrei Kholkin
  Center for Ceramic and Composite Materials &
  Department of Ceramics and Glass Engineering
               University of Aveiro
                    Portugal




                                                 1
             Ciência 2010, July 6th, 2010
                            Outline



•   Introduction
•   Piezoelectric effect in biosystems
•   Strong piezoelectricity in peptide nanotubes
•   Ferroelectricty in aminoacids
•   Lipids on ferroelectric susbtrates
•   Conclusions




                                                   2
               Electromechanics and the Origins of Physics


 1771




                                          Electric Field




                                                                            Force
     Luigi Galvani

           18th Century                                             21st Century
In the beginning, there was electromechanics…
                                                           And now is the time to revisit it
                                                                                               3
              Nanoscale Electromechanics: Future and Perspectives




Special Issue in MRS Bulletin, Sept. 2009:                                                4
“Electromechanics on the Nanometer Scale: Emerging Phenomena, Devices and Applications”
                                Electromechanical Coupling
Direct piezoelectric effect                                                  -q                    +q
                                                                                         k
                              Inverse piezoelectric effect

                                                                                                        E
                                                                             External electric field

                                                                         F                                  F

                                                                                  External force
                                                                      Electrostatic force:     Fel  2qE
   Charge = Force • d33
                                    Strain = Bias • d33               Change in bond geometry:
   In crystals, d33 ranges                                              dl  F  Fel  k  F k  2qE k
   from ~2 pm/V (quartz) to ~500 pm/V (PZT)
• Electromechanical coupling is ubiquitous in systems        Estimate for single chemical bond:
with polar bonds, if not forbidden by symmetry               l  1A                    d  9.6 pm V
• Surfaces, interfaces, and low dimensional systems          q  0.3e                   or
with broken symmetry will have unusual forms of                                         d  9.6 C N
electromechanical coupling                                   k  100 N m


                                                                                                        5
                     Electromechanics: The Next Frontier
                                 Grains and
                                  Domains




                                        300 nm             Cho et al.,
                                                                          Unit cell
        Quartz Crystal                                     APL 2005

1m      0.1 m   10 mm    1 mm 0.1 mm 10 μm       1 μm     0.1 μm 10 nm     1 nm         1Å

     We need to understand structure and electromechanical behavior on
          the micron, nanometer, and ultimately molecular levels!

                              Tissues



                                                  5 µm

           Mouse                                        Cell
                                                                         Molecule

                                                                                    6
                           Probing NanoElectromechanics
In macroscopic systems, we measure response to the uniform external field (interferometry, etc)


     Field
                  Strain




                                                 Piezoresponse Force Microscopy
                                                     Application of AC bias to the tip
                                                      Vtip = Vdc+Vaccos(t)
In nanoscale systems, we need                         results in cantilever deflection
• Displacements of order of ~pm
                                                      d = d0+A(,Vdc)Vaccos(t+)
• Currents of order of ~fA
• Length scales of ~1-10 nm                           due to piezoelectric effect

                           PFM = Nanoelectromechanics
                                                                                                  7
                                                                                                                                                                                    1.2µm



                                                                                                                                                     Domain writing (BaTiO3)
                                               Domain imaging                                                                Piezoresponse Force
                                                   (SBT)                                                                         Microscopy                                                         Domain dynamics
                                                                                                                                                                                                     and evolution
                                          60                                         2800
Surface dielectric constant,  ( a.u. )




                                                                                        Macroscopic dielectric constant, 



                                                                        o
                                                            Tmax~ 40 C
                                          50

                                                         Tmax           Tmax         2400
                                          40
                                                                                                                                                    6
                                          30                                                                                                        4       Active
                                                                                                                              Piezoresponse, a.u.




                                                                                     2000
                                                                                                                                                            Grain
                                          20                                                                                                        2

                                          10                                                                                                        0
                                                                                     1600

                                          0
                                                                                                                                                    -2                          Inactive
                                               40   80      120       160      200                                                                                              Grain
                                                                  o                                                                                 -4
                                                    Temperature, C
                                                                                                                                                         -10 -8 -6 -4 -2 0 2 4      6   8 10
                                                                                                                                                                      Tip bias, V
                                                                                                                                                                                                 6.0µm
d33 temperature dependences                                                                                                                         PFM spectroscopy
          (PLZT)                                                                                                                                                                               Local FFT analysis
                                                                                                                                                                                                               8
                                                                                                                                                                                                    (PLZT)
               Electromechanical Phenomena in Biosystems

                             1771: Galvani – discovery of electricity
1771                         1954: Iitaka – piezoelectricity in glycine
                             1957: Fukada – piezoelectricity in bones
                             1996: Gruverman - Piezoresponse Force Microscopy in bones
                         Since 1955, it was shown that many biomaterials, including collagen and
                         cellulose, are piezoelectric. This piezoelectric activity was postulated to be
                         directly related to biochemical functionality.

       Bones remodel to respond to external stimuli (Wolff law):
Bones: d24 = 2-10 pC/N (similar to quartz)
As we know, bones regenerate

 Teeth: d24 = 0.2 pC/N
 And teeth don’t…

 A number of approaches for bone
 treatments (osteoporosis, fracture)
 were suggested using periodic fields

                                                                                                    9
                            Nanoelectromechanics of Human Tooth
Dentine and enamel are based on hydroxyapatite, but have different mechanical properties as they
differ by the content of organic fibers. Topography           Elasticity        Piezoelectricity
                                                           AFAM Amplitude        PFM Amplitude




                                 Pulp
       Soft                                   300 nm
       Piezoelectric
        Hard                    Dentine
        Non-piezoelectric




                                              300 nm
                                 Enamel




                                             300 nm

                                                                                                 10
                      Proteins and peptides: folding and aggregation
There are at least 20 distinct human diseases that are associated with amyloid fibril
formation: regular fibrillar structures micrometers in length, a few nanometers in diameter
The Peptides Aggregate Into Amyloid Fibrils-NATURAL BIOLOGICAL NANOTUBES
  T. Kowalewski, D. Holtzman,               The transition from the native state conformation
  PNAS, Biophysics, 1996                                     to amyloid fibrils
                                             Soluble                             Insoluble
                                      Peptides and Proteins                    Amyloid Fibrils




  Alzheimer filaments diam.
  10-15 nm , few mm length                                                Amyloid Fibrils, X-ray
  Alzheimer’s b-amyloid peptide
  K. Dill, H. Chan, Nature Struct.   M. Hayden, S. Tyagi, JOP, 2001
  Biology, 1997




                                     Endocrine pancreas,
  TTR amyloid fibril                                                                       11
                                     amyloid fibrils
  in cerebrospinal fluid                                                Makin, O. S., Febs J. 2005
                       Short aromatic dipeptides from solution
The core recognition motif of Aβ peptide (Alzheimer’s disease) the diphenylalanine element.
Dipeptide NH2-Phe-Phe-COOH (FF) is self assembled into well ordered peptide nanotubes
       Diphenylalanine-Bio-inspired Molecules-Self-Assembly PNT
Fast evaporation from aqueous solution, (M. Reches, E. Gazit, Science, 2003)
                             E. Gazit, et al, Science,
                             2003
                            Aqueous solution




                  Fast evaporation from organic solution
               M. Reches, E. Gazit, Nature Nantechnology, 2006

          Numerous nucleation due to
          supersaturation state



                                                                                    12
   M. Reches, E. Gazit, Nature Nanotechnology, 2006
                                                          Unidirectional Growth
  Nanopiezotronics




Z. Wang et al, Advanced Materials (2009)
       Self-assembled bio nanostructures




2 mm

         FF- Solution Growth – CICECO - UA
           Testing nanoscale piezoelectricity in peptides




                                 Piezoelectric coefficients:
                                   Peptide Nanotubes:
                            d15 ~ 70 pm/V d33 ~ 7 pm/V
                                    Lithium Niobate:
                            d15 ~ 74 pm/V d33 ~ 16 pm/V

                                                     Dielectric Anisotropy
High piezoelectric anisotropy                          d15  11
           d 15                                            
           d 33
                  10
                ~ 15                                   d 33  33
                                                                             15
Kholkin et al, ACS Nano (2010)                  M. Davis, et al, JAP, 2007
                                PFM on bundles of vertical nanotubes




                                                                                   Topography




                    0
                         Uac = 10 V
                         f = 50 kHz

                   -20
d33 eff ( a.u. )




                   -40




                   -60


                         -100         -50      0        50   100
                                            Udc ( V )


                                  Piezohysteresis                  Piezocontrast          16
Irreversible phase transition into centrosymmetric phase

                            Second Harmonic Generation                                                    Piezoresponse Force Microscopy
                                                                                                                               5
                            6000                                                     25
                                                                                                                               4
                            5000
 SHG intensity (arb. un.)




                                                                                     20
                                                                 MD calculations




                                                                                          2 2




                                                                                                            d15 eff ( a.u. )
                            4000




                                                                                          P , ( mC/cm )
                                                                      - Heating                                                3
                                                                      - Cooling      15
                            3000
                                                                                                                               2
                                                                                     10




                                                                                          2
                            2000

                                                                                     5                                         1
                            1000

                              0                                                      0                                         0
                                   0     20    40    60   80    100    120   140   160                                             0   20   40    60   80    100    120   140   160
                                                    Temperature (ºC)                                                                             Temperature (ºC)




                                                                                   P61  Pmmm


                                                          AC = 41.692 Ǻ                                                  Corthorhombic = 41.072 Ǻ
                                                    B)

                                          Ps
                                                                       C)
                                        A)                       D)
                                       Ahexagonal = 24.071 Ǻ                                                                   Borthorhombic = 24.147 Ǻ


                                                                                                                                                                                      17
                                                                 Heredia et al, J. Phys. D (submitted)
Polarization switching in annealed tubes: ferroelectricity in
                           action
                                                                                                              -180 V, 10 s




                                          20

                                          15
                 Piezoresponse ( a.u. )




                                          10

                                           5

                                           0

                                           -5

                                          -10

                                          -15

                                          -20

                                                -200   -150   -100   -50       0       50   100   150   200

                                                                           Udc ( V )
                                                                                                                             18
                                   Aminoacid glycine
                                                                         C2H5NO2


              N           C


                                           History:
             H                   O          1820 Discovery by Henri Braconnot
                                            1905 Fischer discovered b phase
                                            1930 Albrecht and Gorey identified  phase
                                            1954  glycine discovered by Iitaka (piezoelectric)
                                    
                     b

 The principal function of glycine is as a precursor to proteins. It is also a building block
to numerous natural products
 Found in the comet Wild 2 thus confirming the theory of panspermia



                                                                                                 19
                    Ferroelectric domains in glycine
          Mixture of  and  phases grown from solution




5.0µm                         5.0µm                       5.0µm



   Topography                  Out-of-plane                   In-plane

                Separate micro islands representing  phase

                                                          5.0µm




                                                                         20
       Ferroelectric switching in glycine


                                                        1.2




                              Diameter ( mm )
                                                                                     500nm
                                                        0.8




                                                        0.4

                                                                  500nm




                                                        0.0
                                                              0           5     10           15        20     25
                                                                                - Udc ( V )

                                                                     Domain size vs. bias
                                                         30


Poling with increasing bias                              20



                                     d33 eff ( a.u. )
                                                         10


                                                          0


                                                         -10


                                                         -20

                                                                  -15     -10   -5        0        5    10   15
                                                                                       Udc ( V )


                                                                  Ferroelectric hysteresis
                                                                                                                   21
    Glycine grown at low temperature
           +30 V, 10 s




х                              х




х                              х

        1.2µm                          1.2µm


           -30 V, 10 s

                                               22
           Molecular dynamic simulations (AMBER)
                                                         20


                                                         10




                                      d33 eff ( a.u. )
                                                          0


                                                         -10


                                                         -20


Theory                                                         7   8          9    10
                                                                                         Experiment
                                                                                        11
                                                                       Udc ( V )




                                                                                                23
         Collaboration with Vincent Meunier, Oak Ridge Natl. Lab.
           Polarization-induced lithography with bio materials



screening         adsorbed               + + +               - -- -
                                        + + +             -       -
 charge             internal
                                         - - -              + + +

polarization charge                       -PS                   PS

                                           + -+ +         - - -
Potential variation at the surface      -       -       + + +
                                          - - -          + + +



                                     Selective deposition can be driven by
                                     a combination of surface charge,
                                     surface potential and surface dipoles.
                                                                         24
                 Deposition of phospholipids on P(VDF-TrFE)




    PVDF-TrFE                PVDF-TrFE              PVDF-TrFE                 PVDF-TrFE

                                                   Deposition of         Drying and scanning
Scan while applying     Polarization created
                                                 phospholipids from             again
   electric field     in ferroelectric polymer
                                                     solution

                                                                      Selective local reactivity in
                                                                            poled regions



                                                                                                25
Selective deposition of phospolipids onto ferroelectrics




   1,2-Di-O-hexadecyl-sn-glycero-3-phosphocoline           26
    Patterning and manipulation with phospholipids
Bare PVDF-TrFE           PVDF-TrFE/lipid               Domain size vs. V




       Writing phospholipid lines on top of ferroelectric polymer

    1,2-Di-O-hexadecyl-sn-glycero-3-phosphocoline                          27
                   CONCLUSIONS


 Surprisingly, some organic biomaterials are
not only piezoelectric but also ferroelectric
 Polarization writing is possible in aminoacids
 Peptides may be used as a source of
piezoelectric charge in nanogenerators
 Lipids become ferroelectric in contact with
P(VDF-TrFE)


                                                   28

				
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