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

Nano/Bio Interface Center A National Science Foundation Supported NSEC

Resolution Time/Temp Range Opportunities for Advances in Characterization

Structure Properties Dynamics Opportunities for Advances in Characterization

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

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

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?

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

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

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

Stress as a field focusing mechanism APL 2009

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

Contact Potential and Molecular Orientation Dielectric Function of Single Molecule Layers

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

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

Extracting Dielectric Properties of Molecular Layers Ex: Higher harmonics

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

Contact Potential and Molecular Orientation Dielectric Function of Single Molecule Layers

Phaseless 3D Optical Nanoimaging A.A. Govyadinov, G.Y. Panasyuk, J.C. Schotland Physical Review Letters 103, (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

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

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?

Structure Properties Dynamics

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

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

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

Structure Properties Dynamics Spectroscopies SERS absorption fluorescence EDXS UPS etc

Structure Properties Dynamics Resolution In situ 3-D 

Structure Properties Dynamics 

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

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

International Community

Multiple Modulation SPM: An Oscillating Electrical Signal

Structure Properties Dynamics Resolution In situ 3-D

Structure Properties Dynamics

Structure Properties Time resolution