Piezoresponse Force Microscopy (PFM) -

Introduction, Principles and

Instrumental Aspects of Piezoresponse
Force Microscopy by NT-MDT
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Topics Covered
Introduction
Principles and Instrumental Aspects of Piezoresponse Force Microscopy
(PFM)
Basic Principles of PFM
History of PFM
Elementary theory of PFM
Contrast Mechanism in Piezoresponse Force Microscopy
Artifacts in PFM Acquisition
Polarization Patterning and Self-Assembly via PFM
Piezoresponse and Pseudoferroelectricity in ZnO
Electromechanics of Biological Systems
Nanoscale Studies of Multiferroic Materials
Conclusions

Introduction
Ferroelectrics are a subclass of piezoelectrics, namely, materials that
experience mechanical deformation under applied voltage or charging under
mechanical force. Ferroelectrics exhibit a wide range of functional properties,
including high and switchable electric polarization, strong piezoelectricity, high
non-linear optical activity, outstanding pyroelectricity, and notable non-linear
dielectric behavior. These properties are indispensable for the applications in
numerous electronic devices such as sensors, actuators, IR detectors,
microwave filters and, recently, non-volatile memories, to name a few. Due to
this unique combination of properties researchers and engineers have been
focusing on visualization of ferroelectric domains (areas with unique
polarization direction) at different scales.

Recent advances in synthesis and fabrication of micro-and nanoscale

ferroelectrics brought to life new physical phenomena and devices that need
to be studied and understood at this scale. As structure dimensions are
getting smaller, ferroelectrics exhibit a pronounced size effect manifesting
itself in a significant deviation of the properties of low-dimensional structures
from their bulk analogs. In this sense, ferroelectrics are similar to magnetic
materials since surface energy cannot be neglected in small volumes and
long-range dipole interaction is significantly modified in reduced geometries. It
also depends on whether a ferroelectric is confined in one-, two-, or all
threedimensional structures.

Following the miniaturization challenge, novel techniques are required for the
evaluation of ferroelectric and piezoelectric properties with the high, ultimately
nanoscale resolution. Many fundamental issues have nowadays to be
addressed such as effect of the geometry confinement on ferroelectric and
piezoelectric properties, relationship between local piezoresponse and
macroscopic properties, as well as microscopic mechanisms of polarization
switching, domain stability and degradation, including polarization phenomena
at the interface.
Beyond the novel nanoscale applications, functionality of ferroelectric films,
polycrystalline ceramics, and even single crystals is often dominated by
defects that act as nucleation and pinning centers for moving domain walls
and thus determine the piezoresponse. In addition, the unique
electromechanical properties of relaxor ferroelectrics (materials with giant
strain and dielectric constant) originate from the interplay of polarization with
chemical and charge disorder on the nanometer scale. Finally, there is a novel
class of multiferroics where polarization is coupled to the magnetization at the
local scale.

To address the fundamental mechanisms underpinning the functionality of

ferroelectric materials and devices, domain structures and their evolution
under bias have to be studied at the micro and nanometer scales. The rapid
development of scanning probe microscopy and, especially, Piezoresponse
Force Microscopy (PFM) has resulted in a fabulous advancement in this area
as will be highlighted below after the short description of the method.

Principles and Instrumental Aspects of Piezoresponse

Force Microscopy (PFM)
Basic Principles of PFM
The PFM approach for probing piezo-and ferroelectric properties at the
nanoscale is based on the strong coupling between polarization and
mechanical dispacement. Apparently, coupling can be addressed by applying
a highly localized electric field to the material and probing the resultant minute
surface displacements with a picometer precision (Fig. 1).
 Figure 1. Schematic of the Piezoresponse Force Microscopy arrangement
where both ac and dc voltages are applied to the metallized tip and
mechanical displacement is measured via conventional AFM method.

Common AFM provides an ideal platform for local piezoeffect study due to
high vertical resolution and high localization of electric field at the junction
between the metalized tip and the surface. Hence, PFM is a contact-
mode AFM in which an electrically biased conductive AFM tip is used as a
probe of local electromechanical coupling via the converse piezoelectric
effect. Remarkably, the basic image formation mechanism in PFM is
complementary to force-based AFM methods (force is applied and the tip
deflection is measured) and scanning tunneling microscopy (STM) (bias is
applied and a current is measured).

History of PFM
Following the invention of STM and AFM, the first examples of measuring a
bias-induced deformation due to piezoelectricity with a scanning probe were in
1991 where piezoresponse was studied using scanning acoustic microscopy
and STM . Later on, the first papers on piezoelectric measurements and
ferroelectric domain visualization by AFMhave appeared. Following this a
series of pioneer results have been obtained by Takata et al (using strain
imaging via tunneling acoustic microscopy), Franke et al , Kolosov et al and
Gruverman et al. The work by Gruverman with coauthors is particularly
important because it demonstrated imaging and switching in common
ferroelectrics and coining the terms 'Piezoresponse' and 'PFM' which have
now become standard. In the past 15 years,PFM has become the premier tool
for studying static and dynamic properties of ferroelectric materials, as
evidenced by a number of recent books and reviews.

Elementary theory of PFM

In PFM, a voltage is applied to the conductive tip as

Vtip = VDC+ VAC cos(t)

Here VDC is the dc bias (switching bias), VAC is the ac bias (probing bias) and
is the AC bias frequency (driving frequency). As the sample expands and
contracts due to the converse piezoelectric effect, the tip deflection is
monitored using a lock-in amplifier so that the tip oscillation

A = A0 + A1 cos(t + )

where A0 is the static surface displacement and is the phase shift between
the driving voltage VAC and the voltage induced deformation A1 = d33eff V +
AC

(C/z) (VDC - V5)VAC. The first term is the true piezoresponse due local
piezoelectric deformation described by the effective piezocoefficient d33eff and
the second term is a local electrostatic deformation caused by both local and
non-local Maxwell stress.20 Vs stands for the surface potential and C is the
total capaciatance of the cantilever-sample system.
The PFM amplitude provides information on the magnitude of the local
electromechanical coupling, while the PFM phase image gives local
polarization orientation. Typically the imaging resolution of PFM is less than ~
10-30 nm as determined from half of the width of a domain wall in the
mixed PFM signal, PR = A1 cos () that is mostly used for the characterization
( is ether close to 0 or to 180). The resolution is limited by the tip-sample
contact area (nominally determined by the radius of the tip apex), though
additional mechanisms for broadening such as electrostatic interactions and
the formation of a liquid neck in the tip-surface junction are possible.

Contrast Mechanism in Piezoresponse Force

Microscopy
The contrast mechanism and detection of ferroelectric domain patterns
with PFM is based on the fact that ferroelectric materials are necessarily
piezoelectric. Basically, the cantilever performs three kinds of displacements:
(i) vertical deflection as a result of the out-of plane force due to d33eff coefficient,
(ii) torsion (caused by shear piezocoefficient d15eff ), and (iii) buckling from the
interaction with the surface when an in-plane force acts along the cantilever
axis. The first type of deformations are referred to as out-of-plane (or
vertical PFM, or VPFM) measurements.

If the polarization and applied electric field are parallel (Fig. 2a), the
deformation is positive (expansion) and piezoresponse signal is in phase
with VAC. On the contrary, if the applied electric field is antiparallel to the
spontaneous polarization, this will cause piezoelectric to contract with the
consequent lowering of the cantilever (Fig. 2b). The electric field and the
piezoresponse signal are shifted in phase by 180. Similarly, the direction of
the polarization for the in-plane polarized ferroelectric grain can be deduced
via a relevant (shear) piezoelectric coefficient d15eff (Fig. 2c,d). In this case, the
applied electric field causes a shear deformation of the grain, which is
transferred via the friction forces to the torsional movement of the cantilever.
These measurements will be further denoted as in-plane (or lateral PFM, or
LPFM) measurements.
Due to the cantilever asymmetry, polarization in the direction of cantilever axis
can only be recorded by physically rotating the sample by 90 along the z-axis
and repeating the in-plane measurement. By acquiring all three components
of the piezoresponse signal, it is possible to perform at least semiquantitative
reconstruction of polarization orientation. However, precise orientation of
polarization can be calculated only if all the components of the piezoelectric
tensor are known. The first attempt to relate the amplitude of the
piezoresponse signal to the orientation of the ferroelectric polarization has
been undertaken by Harnagea and Pignolet and detailed formalism has been
later developed by Kalinin et al. A careful analysis of the movement of the
cantilever must be done with respect to its orientation relative to the
crystallographic axes of the sample, allowing a clear attribution of the
observed domain contrast to the driving forces. In the case of composite
materials as ferroelectric polymer blended with particles or ferroelectric hybrid
(organic-inorganic) materials this problem is approached by knowing the
electromechanical behavior of each component.
Figure 2. Piezoelectric effect in a tetragonal ferroelectric investigated by PFM.
(a) Electric field aligned parallel to the spontaneous polarization leads to a
lifting of the cantilever due to the d33 effect (out-of-plane signal). (b) The
antiparallel alignment of the electric field and the spontaneous polarization
leads to a vertical contraction and a horizontal expansion of the ferroelectric.
(c), (d) Electric field applied orthogonal to the polarization results in a shear
movement due to the d15 coefficient. This movement causes a torsional
deformation of the cantilever forcing the laser spot to move horizontally (in-
plane signal).

Artifacts in PFM Acquisition

Unfortunately an unambiguous separation of the out-of-plane and in-plane
acquisition channels is not always possible. This results in the cross-talk
between both channels and misinterpreatation of the results irrespectively
whether the cross-talk is of the mechanical or electrical reason. Although most
commercially available AFMs are supplied with the programs capable to
compensate the images during processing, PFM cross-talk correction is not
included. NT-MDT (in cooperation with the University of Bonn) has developed
a simple electronic circuit where the cross-talk compensation is done by
simple signal processing of the in-plane and out-plane signals in the situation
where either of them is present. The results shown below illustrate the
situation where only in-plane signal is present. The out-of-plane PFM signal is
fully compensated by the compensating circuit.

Figure 3. Topogaphy (a), out-of-plane PFM (b) and in-plane PFM (c) signals
without (right image) and with (left image) cross-talk compensator in FF
peptide nanotubes where only in-plane signal should be observed (Images
courtesy of I. Bdikin and A. Kholkin, University of Aveiro, Portugal).

Polarization Patterning and Self-Assembly via PFM

Currently, the research is conducted to discover new types of materials that
may assemble into uniquely functioning devices. The cornerstone of such
studies is a vigorous synthetic effort that allows freedom to design, so that
new structural types can be created. An unanswered question is how to
devise general methods to assemble and to interconnect organic and
biological structures into functioning molecular scale devices. To attain these
critical interconnections, a new type of assembly must be developed allowing
to attach different molecular species on the surface in the predetermined
locations. Novel approach that was recently suggested is based on the
assembly of nanostructures directed by atomic (ferroelectric) polarization on
the surface. This is often referred to as ferroelectric lithography. Ferroelectric
polarization can be indeed used to assemble various organic and inorganic
species and to create nanostructures with controlled properties. As an
example, we show here that P(VDF-TrFE), ultrathin films deposited by the
Langmuir-Blodgett technique can be used as templates for the assembly of
various phospholipids, which are the essential components of cell
membranes. Both imaging and patterning could be done by PFM, so that the
nanoscale patterns can be created. These were revealed by the formation of
homogeneous and stable rounded blobs with diameters in the range 0.5-3m.

In this way, ferroelectric polymer films were polarized by the application of

various voltages via a conducting PFM tip and PFM images were then
obtained showing controlled polarization distribution. After this, the
phospholipid (1,2-di-O-hexadecyl- sn-glycero-3-phosphocholine) molecules
were deposited from the solution. Conventional atomic force
microscopy experiments were then performed to assess the selectivity of the
deposition process. It was observed that the deposition process is very
sensitive to the concentration of the solution. The selective deposition was
observed mainly at the polarization boundaries where the selectivity reached
a maximum value of about 20-40% (Fig. 4a). The pospholipid lines could be
also directly deposited by the PFM tip as a nanoscale pen (Fig. 4b) and
polarization can be also reversed in a phospholipid layer
Figure 4. (a) Polarization-driven assembly of the pospholipids on the surface
of P(VDF-TrFE) films via PFM, (b) Pospholipid lines written and visualized by
PFM and (c) ferroelectric domains writeen on the surface of phospholipid/
P(VDF-TrFE) bilayer films. Courtesy Alejandro Heredia, Igor Bdikin and Andrei
Kholkin (University of Aveiro, Portugal).

Piezoresponse and Pseudoferroelectricity in ZnO

Zinc oxide (ZnO) is a well-known n-type semiconductor material having
remarkable electronic and optical properties with great potential for micro-and
optoelectronics. Highly resistive c-axis-oriented ZnO films are also of interest
for various piezoelectric applications (e.g. as sensors, actuators, high-
frequency acoustic transducers, etc) due to their notable and stable
piezoelectric properties. Recently, ZnO has become a material of choice for
piezoelectric harvesting devices because of the ease of growth in the nanorod
and nanobelt geometries. However, the piezoelectric properties of ZnO are
not well understood and characterized, especially in the case of polycrystalline
films having mixed orientation of the grains and weak (if any) unipolarity. The
example of the detailed investigation of piezoelectric properties of ZnO films is
given in Fig. 5. Each grain is characterized by the contrast related to relevant
piezoelectric coefficient, grain orientation, and clamping effect of other grains.
Using PFM it was possible to obtain piezoelectric maps of the surface by
measuring the response in vertical and 2 orthogonal lateral directions (Fig. 5a-
c) and, based on the piezoelectric contrast, to deconvolute the orientation and
polarity of each individual grain (Fig. 5c). For the first time, ferroelectric-like
hysteresis was discovered in nominally pure ZnO (Fig. 5e) thus proving its
pseudoferroelectric properties as predicted recently by Tagantsev.
 Figure 5. Topography (a) and nanoscale piezoelectric maps in polycrystalline
ZnO films (b-c) obtained by pulsed laser deposition. Polarity map (c)
represents polarization (with sign) and orientation of individual grains while (g)
demonstrates ferroelectric-like hysteresis in nominally undoped films.
Courtesy Igor Bdikin and Andrei Kholkin (University of Aveiro, Portugal).

Electromechanics of Biological Systems

Piezoelectricity which stems from the non-centrosymmetric crystal structure is
an intrinsic property of most biopolymers, including proteins and
polysaccharides. Piezoelectric behaviour has been observed in a variety of
biological systems, including calcified and connective tissues and plants,
dentine, bones etc. Understanding the relationship between physiologically
generated electric fields and mechanical properties on the molecular, cellular,
and tissue levels has become the main motivation of studying piezoelectricity
in biological systems. The interest is also due to the fact that pizoelectrically
active biomaterials can be used as nanoscale sensors, actuators and
transducers fully compatible with the biological environment. In addition, the
strong orientation dependence of the piezoelectric effect is extremely
important for the investigation of complex hierarchical structure in biological
materials. It has been recently observed that short aromatic peptides self-
assembled in the nanscale tubular geometries with a very high piezoeleffect
(comparable to that in LiNbO3, one of the mostly used inorganic transducer
materials). Figure 6 presents topography image of the nanotube (a),
schematic of the polarization and measurement arrangement by PFM (b)
and PFMcontrast for oppositely oriented nanotubes where the d33eff (shear)
piezoelectric coefficient is only responsible for the electromechanical coupling.
The advantage of PFM is a high resolution and possibility to measure local
piezoelectric effect in complex geometries. The strong and robust
piezoelectric activity in bioinspired PNTs (never seen in the past) makes them
promising candidates for future generations of "green" nanopiezoelectrics that
might be extensively used in biomedical and medical applications. It is
foreseen that these biocompatible and rigid nanotubes (as well as arrays of
thereof) may serve as the key elements for future biosensors allowing direct
contact with human tissue.
 Figure 6. Topography (a), measurement arrangement (b), and piezoelectric
contrast (c) in FF peptide nanotubes (courtesy Igor Bdikin and Andrei Kholkin,
University of Aveiro, Portugal).

Nanoscale Studies of Multiferroic Materials

Multiferroics - materials which simultaneously have magnetic and ferroelectric
ordering - attract now a considerable interest both because of fascinating
physics and promising applications. One of the proposed driving mechanisms
for ferroelectricity is the occurrence of charge ordering (CO) in mixed
manganites combined with bond dimerization in order to break inversion
symmetry. Considering that the polarization in these solids can exist in
nanoscale volumes, Piezoresponse Force Microscopy can be used for
studying bias-induced ferroelectric properties both below and above CO
phase transition. Such bias-induced ferroelectricity studied via PFM may also
be important for creating artificial multiferroic materials and memory cells.
These experiments help to undertand the role of charge/orbital and magnetic
ordering on the electrical polarization and assess the nature of the new source
of multiferroicity. These exeriments were recently performed on the well-
known (La,Sr)MnO3 mixed manganites and indeed a ferroelectric state was
found at room temperatures, i.e., much higher than expected for CO phase
transitions. Figure 7 exemplifies the bias field-induced ferroelectric island in
the centrosymmetric manganite "sea". This confirms that high enough electric
field could break a symmetry and induce polar state due to local "electric"
doping of the material.

Figure 7. Nanoscale ferroelectric island induced by the PFM tim in

La0.89Sr0.11MnO3manganite (a) and piezoresponse hysteresis loops showing
polarization reversibility. Courtesy Igor Bdikin and Andrei Kholkin (University of
Aveiro, Portugal).

Conclusions
While the initial application of PFM was mainly to image ferroelectric domains
significant in a few important but quite rare ferroelectric materials,
the PFM can be currently applied to a large variety of materials including
biomaterials and ionic conductors. Coupled electromechanical properties are
inherent in hundreds of inorganic materials (even centrosymmetric at a
macroscopic scale) and similarly in biological materials. The evolution
of PFM provides a new window into the behavior of a wide range of materials.
Equally important, the developments in PFM are part of a larger trend toward
extreme high spatial resolution in quantification of electromagnetic properties.
Several classes of functional properties are now probed at sub-nm resolution.
In most cases the properties are represented by single scalar numbers like
resistivity, conductivity, surface potential, charge density, etc. PFM is unique in
that it carries this strategy into the realm of complex tensor properties.
Significant advances of PFM (possible but unknown yet) are expected in the
realm of new materials and devices based on them.