1. The Next Revolution in Probes of Nanoscale Phenomena The Next Revolution in Probes of Nanoscale Phenomena Dawn Bonnell The University of Pennsylvania

2. Nano/Bio Interface Center A National Science Foundation Supported NSEC

3. Resolution Time/Temp Range Opportunities for Advances in Characterization

4. Structure Properties Dynamics Opportunities for Advances in Characterization

5. 140K 10 nm Exploiting Ferroelectric Polarization Separating Atomic Lattice and Charge Lattice Functional Oxides Bridging Biological and Functional Systems Towards properties at atomic resolution Molecules at Interfaces Nano Letters 06, 07, PRL 08 PRL 02, APL 03,Nano Letters 05, PRL 05,Nano Letters 06, Physics Today 08, ACS Nano 2008 PRB 07 Adv Mat 2008 PRL 2008

6. 72.0eV 2x2 c2x2 89 eV Kolpak, Li, Rappe, Bonnell, PRL 2008 BaTiO 3 (100) stability limits

8. Bonnell, ACS Nano Sept 2008 Davis group, Bonnell group, Morita group, Hartmann group, Eguchi et al, Bonnell Group, Cho Group, Kalinin Group Functional Imaging: What are the limits?

9. Resistance/conductance at the  ngstrom level Interface contact resistance of single molecule layer Dielectric function of molecular monolayer 2 nd harmonic of electrostatic force 3 rd,4 th harmonics in near field scattered light Piezo response at pm sensitivity and nm resolution 3-D tracking of single molecule dynamics 3-D Imaging of internal structure Probing “Continuum” Properties at High Spatial Resolution

10. Probing “Continuum” Properties at High Spatial Resolution Resistance/conductance at the  ngstrom level Interface contact resistance of single molecule layer Dielectric function of molecular monolayer 2 nd harmonic of electrostatic force 3 rd,4 th harmonics in near field scattered light Piezo response at pm sensitivity and nm resolution 3-D tracking of single molecule dynamics 3-D Imaging of internal structure

11. A B ~2 nm ~0.5 pA Conductance of 1.2 nm HfO films on Si 2-5 pA at 0.5-1.5V Ultimate Spatial Resolution Limits of Continuum Properties APL 2009

12. Stress as a field focusing mechanism APL 2009

13. Density of statesDefect energies Injection barriers, defect energies and DoS at sub nm resolution

14. Contact Potential and Molecular Orientation Dielectric Function of Single Molecule Layers

15. Dependence of Contact Potential at Molecule-Electrode on Interfaces Molecular Orientation nm Nikiforov, et al NanoLetters 2007

16. Molecular structures determined by nc- AFM: F 0 = 180 kHz,  f =150 Hz, Black-to-white contrast 0.04 nm (a), 0.05 nm (c), and T = 80 K. 5,15-bis(2’,6’-bis(3,3-dimethyl-1- butyloxy)phenyl)porphyrin assembles into two structures on graphite: 1.Ring is parallel to the surface 2.Ring is perpendicular to the surface Local Properties of Molecular Interfaces porphyrin on HOPG Nikiforov, Schnaider, Zerwek, Park, Therein, Eng, Bonnell NanoLetters 2007

17. Extracting Dielectric Properties of Molecular Layers Ex: Higher harmonics

18. Spatially Resolved Dielectric Function: Scattering near field Real part of the dielectric function Imaginary part of the dielectric function Nikiforov, et al 2008

19. Contact Potential and Molecular Orientation Dielectric Function of Single Molecule Layers

20. Phaseless 3D Optical Nanoimaging A.A. Govyadinov, G.Y. Panasyuk, J.C. Schotland Physical Review Letters 103, 213901 (2009) Conventional Optics Near-Field Optics ?  Can not image the interior Images nanostructures at the surface  Can not image nanostructures Physical Review Focus 24, story 18 (2009) ? ? ? ? Phaseless 3-D Nanoimaging Images nanostructures at the surface Images the interior SNOM tip

21. Phaseless 3D Optical Nanoimaging A.A. Govyadinov, G.Y. Panasyuk, J.C. Schotland Subwavelength resolution in three dimensions No phase controlled illumination or phase measurements, only power Recover both real and imaginary parts of complex-valued susceptibility z x ztzt n>1 n=1 ti p sampl e Plane wave Power

22. Bonnell, ACS Nano Sept 2008 Davis group, Bonnell group, Morita group, Hartmann group, Eguchi et al, Bonnell Group, Cho Group, Kalinin Group Functional Imaging: What are the limits?

23. Structure Properties Dynamics

24. Structure Properties Dynamics Spatial resolution In situ imaging in liquid in cells 3-D internal structure optical tomography electron holography Conductance/impedance/capacitance Piezoelectricity/ferroelectricity/ferromagnitism Dielectric function Mech. force/strain Absorption Bond vibration phonons Mins secs  secs nano secs femto secs

25. Structure Properties Dynamics Morphology evolution Domain wall motion Atomic diffusion Activation energies

26. Structure Properties Dynamics Scanning Probe Microscopies Resolution In situ 3-D

27. Structure Properties Dynamics Spectroscopies SERS absorption fluorescence EDXS UPS etc

28. Structure Properties Dynamics Resolution In situ 3-D 

29. Structure Properties Dynamics 

30. Structure Properties Dynamics Spatial resolution In situ imaging in liquid in cells 3-D internal structure optical tomography electron holography Conductance/impedance/capacitance Piezoelectricity/ferroelectricity/ferromagnitism Dielectric function Mech. force/strain Absorption Bond vibration phonons Mins secs  secs nano secs femto secs The Next Revolution

31. Global Networking A seed group of investigators from England, Korea, Germany, and 8 institutions in the US met in 2006 at a workshop at Penn to outline the mission and initial project goals The site has found immediate use in facilitating outcomes of an EU/US joint commission workshop (Ispara, Italy June 2008) on nanobiotechnology and by the US DoE. Monthly live forums engage members from 72 countries Probe Pedia www.nanoprobenetwork.org

32. International Community

33. Multiple Modulation SPM: An Oscillating Electrical Signal

34. Structure Properties Dynamics Resolution In situ 3-D

35. Structure Properties Dynamics

36. Structure Properties Time resolution