Multiple Modulation and Higher

Harmonics Probing Complex Properties

(including Scanning Impedance)

Dawn A. Bonnell,
S-H. Kim, R. Shao, D. Strachen, C. Staii,
A. T. Johnson

The University of Pennsylvania

NSF: NIRT, NSEC, MRSEC

 Tip Modulation
The Ideal Probe mechanical
electrical
optical
Detection
Sample stimulation Higher order harmonics
dc + high frequency ac lateral modulation Multiple harmonics
Back gate modulation Frequency dependence
Frequency dependence Optical + electrical
Dc + modulated magnetic field Optical + mechanical
Single wavelength optical Wavelength dependence
Wavelength modulation

Temperature
Chemical environment

electrostatic/mag
surface potential, SIM, NIS
netic interactions
+ V1 + V2 sin(ωt)
+- - -
+ - --
PFM, SCM ,SSRM
+
Van der Waals interactions

Mechanically driven electrostatically driven

 Not Only Structure ….. Also Properties

Functional Oxide Structure

CH3-CO-S-Benzen-(Zn-prophyrin)3

STM
topography

STM current image Height =5nm

Diameter =2nm
Spin and Charge: La
Manganates
Biomolecules on Surfaces
Separating Atomic Lattice and
Charge Lattice: Potassium
Molybdate
140K

10 nm

Atomic Structure and Ferroelectric

Polarization; BaTiO3
Scanning Impedance Microscopy
exploiting sample perturbation and frequency dependence
electrons trapped at an interface
band energies in a nanotube

Higher Harmonics
dielectric constant of a thin film
dielectric constant of nanowires
density of states of nanotubes

Higher Harmonics in Tip Scattered Optical Signal

dielectric function of porphyrin
An Oscillating Electrical Signal

1 ∂C (z ) ⎡
F (z ) = ⎢ (Vdc − Vsurf )
2
+ Vac2 [1 − sin (2ωt )] + 2(Vdc − Vsurf )Vac cos(ωt )⎥
1 ⎤
2 ∂z ⎣ 2 ⎦
1 ∂C ( z ) ⎡
Fdc (z ) =
2 ∂z ⎣ ⎢ V(dc − V surf )
2 1 2⎤
+ Vac ⎥
2 ⎦

∂C (z ) 1 ∂C ( z ) 2
F1ω ( z ) = (Vdc − Vsurf )Vac F2 ω ( z ) =
4 ∂z
Vac
∂z
An Oscillating Electrical Signal

∂C (z ) 1 ∂C ( z ) 2
F1ω ( z ) = (Vdc − Vsurf )Vac F2 ω ( z ) =
4 ∂z
Vac
∂z

Scanning Surface Potential Microscopy/Kelvin Force Microscopy

Scanning Impedance Microscopy
Gated Scanning Impedance
An Oscillating Electrical Signal

∂C (z ) 1 ∂C ( z ) 2
F1ω ( z ) = (Vdc − Vsurf )Vac F2 ω ( z ) =
4 ∂z
Vac
∂z

New Variants of SSPM/KFM and EFM

Dielectric function
Quantum capacitance
Density of states
 Scanning Impedance Microscopy: a local probe
Vtip = Vdc + Vac cos (ωt ) Vtip = Vdc

Vlat = Vdc Vlat = Vdc + Vac cos(ωt )

V1 V2 ϕ1, A1 ϕ2, A2
Vsurf = Vs + Vac cos(ωt + ϕ c ) Rd
R Rd R ωγ R R
tan (ϕ ) = Cd
ω 2 − ω 02

V V 148 O hm
0 .4 Phase 0 .4O h m

ω
520
0
10

Amplitude, a.u.
1 .5 k O h m
0 .2 0 .2
φ gb ) deg

Amplitude 4 .7 k O h m
Phase,

0 .0
10
-1 0 .0
tan(

-0 .2
-2
R C-0 .2
10
-0 .4 -0 .4
3
0 1 05 1100 4 15 1 0 5
D
F is , μc m
r etaqnucee n y, H z

Kalinin and Bonnell, Appl. Phys. Lett., 2001, Shao, Kalinin, Bonnell, APL 2003
US patent
Grain Boundary Structure

24o

Sr

Ti
0.5n
m

Aberration corrected STEM image of a SrTiO3

34nm {100}
bicrystal and calculated charge density

3
1000
2 oC for 15 min in
Z[nm]

vacuum:
1 details show up in
surface
0
steps.
0 50 100 150
X[nm]
Fine Structure at the Grain Boundary

24o

2nm

34nm {100}
Temperature Dependent SIM Identifies an Interface Induced Ferroelectric
Phase Transition in SrTiO3
5
148 Ohm 1.8x10
5
520 Ohm 1.5x10
0 5
10 1.5 kOhm
1.2x10
4
9.0x10

R,Ω
4.7 kOhm 4
6.0x10
tan( φ gb )

-1
10 4
3.0x10
0.0
-2
10
ω 50 100 150200250 300350
R C T,K
3 4 5
10 10 10
Frequency, Hz
12

C , m /F
2
9

-1
6
50 100 150 200 250 300
T, K
Scanning surface potentiometry Curie-Weiss Law:
−1
C gb ∝ T − TC and TC=40K

Shao, Duscher, Chisholm, Bonnell, PRL (2005)

 Direct Imaging of the Boundary Potential

200nm 40
Surface Potential, mV

80

Surface Potential,mV
40

-4 0 VGB≈-100mV
0
-8 0

0 200 400 600 800 1000

L a te ra l d is ta n c e ,n m 98K
30K

-40
2 0 0 nm
293K
100
Surface Potential, mV

50 -80
0
V≈120mV 0 500 1000
-5 0
VGB≈-40mV
Lateral distance,nm
-1 0 0
0 200 400 600 800 1000
L a te r a l d is ta n c e ,n m
 Temperature Dependent Transport Reveals Collapse of the
Interface Potential Barrier in SrTiO3
o
10
-2 24
o

RGrain (Ωm2)
40 36.8 -6
10

RGB (Ωm2)
grain
Surface Potential,mV

-3
10
0 -7
10

98K 30K -4
10 -8
-40 10

293K
-5 -9
10 10
-80
0 500 1000 0 50 100 150 200 250 300
Lateral distance,nm T(K)

Shao, Duscher, Chisholm, Bonnell, PRL (2005)

Interface charge determined from first principles calculations and transport
measurements are in good agreement

Sr

Ti
0.5nm

Aberration corrected Z DFT calculations

contrast TEM

Boundary charge=0.06C/m2
That is 0.3 electron/unit cell
That is 0.8 electrons/Ti unit Field Induced Dipole Alignment

Shao, Duscher, Chisholm, Bonnell, PRL (2005)

 Temperature Dependent Transport Reveals Collapse of the
Interface Potential Barrier in SrTiO3
o
10
-2 24
o

RGrain (Ωm2)
40 36.8 -6
10

RGB (Ωm2)
grain
Surface Potential,mV

-3
10
0 -7
10

98K 30K -4
10 -8
-40 10

293K
-5 -9
10 10
-80
0 500 1000 0 50 100 150 200 250 300
Lateral distance,nm T(K)

Shao, Duscher, Chisholm, Bonnell, PRL (2005)

Interface charge determined from first principles calculations and transport
measurements are in good agreement

Sr

Ti
0.5nm

Aberration corrected Z DFT calculations

contrast TEM

Boundary charge=0.06C/m2
That is 0.3 electron/unit cell
That is 0.8 electrons/Ti unit Field Induced Dipole Alignment

Shao, Duscher, Chisholm, Bonnell, PRL (2005)

 Nanoimpedance Spectroscopy

Laser Detecto Topo AFM

r Controller
Tip
Z(ω), θ(ω)

Impedance Two-terminal measurements

Analyzer
HP4294A
|Z| θ
Single-terminal measurements 2
2 1
1

200
Z = Z e iθ 3 3
-Zim (R2C2 )
−1 (c) (e)
150
-20o
(R1C1 )−1 14M 19M -
-Zim(kΩ )

Ω Ω 90
o
100
-Zre 1
2
|Z|
1 2
θ

R1 R1+R2
50
3 3

0 (d) (f)
0 100 200 300 400
Zre(kΩ ) 6.1M 18M - -
Ω Ω 90 10o
o

Shao, et al, APL 2003

 Scanning Gate Microscopy Scanning Impedance Microscopy
Deflection at ω
Laser Detector Laser Detector
Lock-in AFM
Vdc, tip Tip Controller
Out
Vac, ω ϕ(ω) and A(ω)
Lock-in
SiO2
Current

Backgate Reference at ω
Ref. Controller Backgate Function
Lock-in Generator

An ac bias is applied across the molecular wire

A bias is applied across the molecular A dc bias is applied to the tip

wire.
The phase and amplitude of the consequent
A dc bias is applied to the tip. cantilever oscillation are the images.
+
The current across the sample as a
function of tip position is the image.

An independent bias can be applied to

the back electrode to gate the signal
+ Vi -
Scanning Impedance on
Reduced Dimension Structures Samples
from
Craighead &
MacDiarmid
Groups

Nikiforov, Liu, Bellan, Craighead, Bonnell

Nano Letters 2005
Scanning Impedance on
Reduced Dimension Structures

Ec
Ev
EF +
Vi
-
SIM Determines the Electronic Structure of Individual Defects in
Molecular Wires and Nanotubes

SGM SIM amplitude

(current through the nanotube) (local potential amplitude)
V tip α R
Spot diameter : D i = Vi* κ + 1

where: κ SiO = 3 . 9
2

C tip − surface
α = ~ 1 . 33
C free _ sphere

R = Tip radius ~ 20 nm

Freitag, Johnson, Kalinin, Bonnell, Phys Rev Lett (2002)

 Electronic Structure of Individual Defects

Quantum electrostatics
Tip
C1
Φtube = Vsurf
C1 + C2 + Cq
C1
Tube C1 Cq - quantum capacitance
C1, C2 – geometric capacitances
C2 Cq
C2

Onset of depletion
Gate
ΔΦtube = Vi

S. Lyrui, Appl. Phys. Lett. 52, 501 (1988),

M. Freitag, S.V. Kalinin, A.T. Johnson, D.A. Bonnell, PRL (2002)
SIM Determines the Electronic Structure of Individual Defects in
Molecular Wires and Nanotubes

SGM SIM amplitude

(current through the nanotube) (local potential amplitude)
V tip α R
Spot diameter : D i = Vi* κ + 1

where: κ SiO = 3 . 9
2

C tip − surface
α = ~ 1 . 33
C free _ sphere

R = Tip radius ~ 20 nm

Freitag, Johnson, Kalinin, Bonnell, Phys Rev Lett (2002)

Defect contrast is related to the local electronic structure

SGM

SIM

Increasing tip bias

600 Defect 1
Defect 2
Spot diameter (nm)

500
Defect 3 Defect Slope [nm/V] Vi [mV] Vi* [meV]
400 Defect 4
1 83.6 ± 3.6 65 20
300
2 39.1 ± 0.4 139 40
200 3 26.4 ± 1.1 206 55
100 4 53.0 ± 1.2 102 30
0
0 2 4 6 8
Tip bias (V)

M. Freitag, S.V. Kalinin, A.T. Johnson, D.A. Bonnell, PRL (2002)

An Oscillating Electrical Signal

∂C (z ) 1 ∂C ( z ) 2
F1ω ( z ) = (Vdc − Vsurf )Vac F2 ω ( z ) =
4 ∂z
Vac
∂z

New Variants of SSPM/KFM and EFM

Dielectric function
Quantum capacitance
Density of states
Simultaneous topographic signal, 1st harmonic and 2nd harmonic detection
Implemented on custom designed Omicron VT AFM/STM

2ω

Differential
capacitance

Effectively 2 lock-in signals

Additional filters on the frequency demodulator signal
Simultaneous imaging of topography, surface potential (1ω), and
differential capacitance (2ω) of high-k oxide film (2nm HfO2 on Si).

topography

topography

1ω 2ω
0.002ω (Df)

1ω 2ω

Omicron UHV VT-AFM/STM

Low dimensional systems exhibit discontinuities in the
density of states

[ ]
2
QF ∂
ϕ≅ Vtip
2
Ctotal ( z ,Vtip )
2k ∂z 2 ϕ

Vtip

C tt ( z ) C Q ( z , V tip ) C0 (z)L

Vtip

DE
2
*J. Heo and M. Bockrath, APL 5, 853 (2005).
CQ = Ltip e DE
**D. Gekhtman et al. Physical Review Letters 82, 3887 (1999).
Combine EFM Feedback Detection with low
amplitude electric signal detection

1
ϕ ≅ ϕ (V0 ) + ϕ ′(V0 ) ⋅ ΔV0 sin ωt + ϕ ′′(V0 ) ⋅ (ΔV0 ) 2 sin 2 ωt
2

Vtip = V0 + ΔV0 sin ωt

ϕ →V Lock-in
In
sin ωt
Ref In
ϕ (2ω )

AFM computer
Real Time 2nd harmonic of carbon nanotubes

tube

bare substrate
Combine EFM Feedback Detection with low
amplitude electric signal detection

C. Staii, N. J. Pinto, A. T. Johnson, Nano

Lett. 4, 859 (2004)
There is much information in the ‘long range’
interactions; it is not simple to extract it!!
Combining multiple modulations of tip signals and sample perturbations
yields new information
Scanning Impedance Microscopy
Nano Impedance Spectroscopy
trap state time constants
dielectric anomalies

Accessing higher harmonics with multiple signals yields complex properties

Surface Potential vs Dielectric Constant
polarizability !!!

Exploiting boundary conditions related to sample configuration can yield

fundamental information.
Quantum Capacitance Defect electronic structure
Density of States Quantization at Interfaces