Three-Dimensional Electric Field Probing of Ferroelectrics on the Nanometer Scale Using Scanning Force Microscopy

L. M. Eng1 , S. Grafstrm1 , Ch. Loppacher1, F. Schlaphof1 , S. Trogisch1 , o A. Roelofs2 , and R. Waser2

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Institute of Applied Photophysics, University of Technology Dresden, D-01062 Dresden, Germany Institut fr Werkstoe der Elektrotechnik, University of Technology, u D-52056 Aachen, Germany

Abstract. Nanoscale investigations of ferroic systems are currently of clue interest in device fabrication and analysis. We show that scanning force microscopy (SFM) is of valuable help in addressing questions of both dynamic and static stability of domains and domain walls. In this contribution polarization sensitive modes of SFM, i.e. piezoresponse force microscopy (PFM) and Kelvin force probe microscopy (KPFM) are contrasted for the internal and external electric eld measurements. These techniques provide unique resolution of the sample topography including chemical heterogeneity and the domain wall width, recording of hysteresis loops on the nanometer scale, as well as the transient response when inducing ferroelectric domain switching. Emphasis is laid onto the future possibilities in measuring device limiting physical properties which are related to interface problems. Here SPM tools applied to the local inspection provide unique insight to this problematic.

Introduction

High-resolution studies of ferroelectric and ferroelastic domains and domain walls gain in importance when following the path of miniaturization for ferroelectric memory (FeRAM) application and integration [1,2]. Therefore, clue interest has to be addressed to the characterization of ferroelectric properties on the nanometer scale. Parameters like the spontaneous or remanent polarization, the coercive threshold eld, retention and fatigue [3,4], as well as the temporal behavior upon domain switching of areas measuring less than 100 nm in diameter [5,6] are emphasized. Unfortunately, macroscopic or mesoscopic measurements using the dielectric displacement method are not suitable because the switched charge is comparable, or smaller than the intrinsic noise level in these systems. Although extended conductive electrodes could possibly overcome this limitation for thin lm applications, the leakage current at grain boundaries or pin holes [7] as well as the non-continuous
To whom correspondence should be addressed. Phone: +49 (351) 463 4389 Fax: +49 (351) 463 7065. eMail: eng@iapp.de
B. Kramer (Ed.): Adv. in Solid State Phys. 41, 287298 (2001) c Springer-Verlag Berlin Heidelberg 2001

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texture of these lms demand possibilities of performing such a testing well inside single grains. This contribution shows the track to determine the surface polarization and other parameters with a lateral resolution of < 20 nm by applying sophisticated methods being derived from scanning force microscopy (SFM). Although many methods involving scanning probe instruments have been proposed in order to retrieve data on the ferroelectric domain distribution like the eective domain wall width, the surface chemical heterogeneity, and the surface structure and morphology down to the atomic scale, only SFM and the near-eld scanning optical microscope (NSOM) may contribute eectively to both a qualitative and quantitative understanding of spontaneous polarization at the sample surface Ps and the polarization variation Py (x) over domain walls apparent at the sample surface. Still some big eort has to be undertaken in order to achieve this goal. Table 1 summaries the possibilities when investigating ferroelectric, ferroelastic and charged domain walls with scanning probe instruments, i.e. SFM, NSOM, and scanning tunneling microscopy (STM). The latter though is of help only when dealing with a nite surface conductivity of the dielectric system (i.e. chemical reduction or oxidation) and will not be considered in this contribution. As shown in Tab. 1 the dierentiation of ferroelectric domains having antiparallel or orthogonal polarization may be carried out relying on mechanical, optical, and/or electrical properties. Nevertheless, an experimental resolution below 1 nm or even on the atomic scale so far was shown to be possible only when using SFM in contact to the sample surface. The most recent eorts though report on promising results that a resolution < 5 nm for any mode mentioned in Tab. 1 should be possible. This then will considerably help inspecting ferroelectric and/or dielectric interfaces on the nanometer scale. From Tab. 1 it seems to be easily possible to dierentiate ferroelectric domains with dierent polarization orientation at the sample surface down to a resolution of 1 nm. Many of these modes possess the ability of atomic resolution. This may be sucient for the inspection of dielectric systems. For ferroelectrics, though, we need an additional proof of true ferroelectric behavior on that small a length scale. We would like to mention that it is absolutely not sucient simply to monitor the dielectric responsivity [8] although the resolution achieved by measuring the dielectric susceptibility distribution may be comparable (the domain distribution though may deviate dramatically from the dielectric distribution). What we need are methods that proof the nanoscale switching properties by monitoring for instance the dielectric hysteresis loop and the transient response behavior both in bulk ferroelectrics and ultra-thin ferroelectric lms [9] down to domains of measuring less than 20 nm in diameter. Luckily, such a mode is provided by operating the SFM in the piezoresponse mode (PFM).

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Table 1. Status of investigating physico-chemical properties of ferroelectrics with scanning probe instruments. Abbreviations used are: nc-SFM: non-contact force microscopy; EFM: electric force microscopy; PFM: piezoresponse force microscopy; NSOM: near-eld scanning optical microscopy; KPFM: Kelvin probe force microscopy; STM: scanning tunneling microscopy nanoscale aspect topography, texture and morphology domains SFM mode any SFM mode contact mode friction nc-SFM EFM PFM 3-dimensional domain distribution PFM NSOM quantitative polarization determination KPFM nc-SFM spectroscopy surface chemistry friction nc-SFM KPFM PFM surface layer nc-SFM NSOM STM optical indicatrix hysteresis NSOM PFM nc-SFM transient response PFM nc-SFM domain type ferroelastic ferroelastic C+, C C+, C C+, C any any any C+, C C+, C any C+, C C+, C C+, C C+, C any any any C+, C any C+, C

2 Internal Electric Field Measurements with Piezoresponse Force Microscopy (PFM)

A very common way to measure the polarization distribution in a ferroelectric sample is based on deducing the piezoelectric response signal from the material under investigation [10]. On the nanometer scale the top electrode is formed by the conductive SFM tip itself, while the bottom electrode is still of macroscopic shape. This set-up allows the unambiguous dierentia-

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tion between individual ferroelectric grains [4] and to investigate even noncontinuous ferroelectric thin lms [11]. Unless for macroscopic probing this method never leads to an electrical short-circuit between the top and bottom electrode and thus enables the nanoscopic analysis of domain switching. Another advantage of piezoresponse force microscopy (PFM) to deduce polarization information is the fact that this method does not rely on mea suring the displacement current D upon domain switching. First, this signal may be partially screened by surface or bulk conductivity when biasing the dielectric capacitor. Secondly, D may become very small or practically nonmeasurable when investigating thin lms having nanoscale electrodes, i.e. an electrode area of < 100 nm in diameter. The piezoresponse signal therefore oers a nice and easy to adapt way of transforming the piezoelectric response of the dynamically vibrating sample into a mechanically measurable signal. Basically the resolution depends only on factors like the geometrical amplication and electronic signal processing. Also, we recently showed that PFM provides a true 3-dimensional polarization analysis of heterogeneous structures (grains) having any orientation, as documented by single crystal investigations [12] and inspection of ceramic powders [13]. Nevertheless, some eort has to be invested into the interpretation of such PFM measurements. As described above the mechanical response signal of the cantilever couples to the internal electric eld distribution, or rather to say to the polarization P by means of the piezoelectric displacement of the crystal. In doing so, the following points have to be considered: the the the the the the eective electric eld distribution eective surface area contact potential presence of a thin water layer on top of both tip and sample electric eld penetration into the sample, and lateral coupling between dierent grains.

Imagine a tip having a 10 nm tip radius which stays in rm contact to the sample surface, the latter being a thin ferroelectric lm of 50 nm thickness. Clearly the lateral eld distribution (and hence the PFM signal) will be very inhomogeneous due to both the variable surface morphology and the chemical variation of the material on the nanometer scale. The tip therefore always measures a mediated value with the main contribution stemming from the central part which is electrically clamped under the tip. This situation, however, is not comparable to the case of a freely vibrating disc, since there is mechanical clamping to neighbouring unit cells along the lateral direction. Due to the inhomogeneous electric eld distribution, the vibration amplitude therefore radially decreases in a uniform way. Furthermore, the eld heterogeneity is inuenced by the eective contact area between tip and sample. Since both these two surfaces generally possess a topologically non-equivalent morphology, a rm contact always leaves some voids lled with a low k material like air or dust (in comparison to the relatively high dielectric constant of

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the ferroelectric thin lm; actually let us forget for a while that every surface may wet with a thin water lm under ambient conditions). Again the electric eld distribution will vary on a local scale with every tip or sample surface asperity inducing a locally increased eld density. This local eld may further be modied in the case of chemically nonequivalent materials. Since surface oxidation and reduction changes the chemical surface potential dramatically (by (di)electric screening) the eective potential drop between the tip and sample is dicult to deduce. Also the possible occurrence of surface reconstruction belongs to the same category of eects. In this respect a thin polar water lm would have a similar eect by introducing a Helmholtz double layer to screen the electric eld. Finally the penetration depth into the ferroelectric material may be very undened on the local scale. Imagine a non-isotropic 3-dimensional distribution of ferroelectric grains with arbitrary crystallographic orientation. Consequently the dielectric matrix will be non-symmetric and the electric eld distribution inside the sample be very heterogeneous. Furthermore, our observations when using the piezoresponse mode even showed that the connection to the counter electrode is not necessary at all [14]. In fact, the eld drops within a distance of approximately 50 - 80 nm as found experientially for BaTiO3 and similar samples [14]. Hence the PFM signal stems from a thin surface volume only, dramatically depending though on the eective morphology (grains), the electronic coupling between grains, and the dielectric susceptibility. Although these points may severely aect the image quality and interpretation, PFM is practically that SFM mode which nowadays is most often used for the domain analysis and characterization on the nanometer scale. Nevertheless, the tensorial behavior of the eective electric eld distribution has not been taken into account so far. Mostly the theoretical modelling of this complex problem results to be very time consuming. On the other hand, PFM also oers the possibility to directly deduce experimentally the coupling between the perpendicular and lateral piezoelectric behavior. This is by applying PFM to the torsional bending of the cantilever and recording the dynamical changes. Nevertheless, since the successful operation of the latter SFM mode was rst demonstrated [12,13] only rarely have such measurements been performed [11], denitely because of a lack in know-how, experimental skills, and technical possibilities. Again we strictly state that the knowledge of the full dielectric tensor is a real must in order to fully understand the PFM mode. Therefore the complete set of piezoelectric or dielectric constants needs to be investigated on the nanometer scale.

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3 3-D Hysteresis Probing on the Nanometer Scale Using PFM

As pointed out in the previous paragraph PFM is based on the local piezoelectric variations when applying a small electric modulation eld. If the electric eld distribution would be homogeneous like in an innite plate capacitor, the measured piezoelectric value exactly corresponds to the d33 constant of the material. In PFM we measure though a combined signal being d33 +f (d31 , d15 ) where any cross talk in the form of lateral expansion and torsion is taken into account via d31 and d15 . Luckily the function f becomes small as we approach a lm thickness comparable to the tip radius of 40 nm. This is because the lm thickness is of the same order as the contact area between tip and surface. Furthermore, for some special materials like BaTiO3 in the tetragonal phase and other perovskites the correction f (d31 , d15 ) becomes negligible [15]. Hence under these restrictions, the piezoresponse signal may be directly related to the spontaneous or remanent polarization in a pseudocubic ferroelectric material based on nanoscale properties by d33 = 2Q33 PS (1)

where Q is the electrostrictive coecient, and 33 is the dielectric permittivity of the material. Provided that both Q and 33 are known adequately [16] we are able to directly relate the evaluated d33 to the polarization P [17] and hence to the dielectric displacement D on the macroscopic scale. Instead of using D we show here that mapping the hysteresis of small ferroelectric domains is equally possible by recording the PFM signal as a function of applied electric eld (equivalent to some C-V characteristics). Figure 1 illustrates the case for a 150 nm thick PbTiO3 lm from which we were unable to record macroscopic hysteresis loops by monitoring D( E ) due to the non-continuous lm growth [11]. Nevertheless, when recording the

Fig. 1. Hysteresis loops on PbTiO3 thin lms of 150 nm thickness deduced by PFM. Note the excellent ferroelectric switching properties on the nanometer scale

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PFM signal as a function of E we observe a symmetric switching behavior with Ec and Ec measuring 1.8 V and 1.8 V, respectively. Please note from Fig. 1 that the PbTiO3 lm was sandwiched between a Pt bottom electrode and the p-doped conductive silicon cantilever tip. As shown the PFM signal gives a symmetric signal both along the eld direction and with respect to the PFM response. Therefore both an imprint eect and a nonvanishing PFM signal due to surface charging and residual dipoles are not observed [7]. This example illustrates that PFM may well be suited for the material characterization beyond the 100 nm scale, both in the lateral and the perpendicular dimension. In a recent investigation we showed that domain switching is even possible for grains measuring 70 nm in diameter and 30 nm in thickness, only [18]. As was for domain mapping with PFM, hysteresis switching with PFM is possible under the same restrictions concerning the electric eld distribution. Additionally the time dependent E -eld applied between tip and counter electrode for switching may induce a lateral domain mobility and growth process [9] mostly because of the 3-dimensional tip geometry. Nevertheless, as pointed out in this example, the lateral tip shaft (not the tip diameter) plays a secondary role when investigating ultra-thin ferroelectric lm switching.

4 Access to Surface Chemistry with Kelvin Probe Force Microscopy (KPFM)

Unless probing the internal electric eld made up by the surface polarization charge as described in section 2, an external electric eld is always built up above the sample surface provided that dielectric screening is non-existent or non-ecient. Any change in surface morphology or surface structure both physically and chemically eectively acts in damping this electric eld vector outside the solid. It was suggested that the external electric eld therefore would be screened completely. Nevertheless, the fact that many external methods like powder decoration, etc. have been proposed and eectively applied in order to prove the existence of ferroelectric domains, shows that there is mostly a small but measurable contribution to this external electric eld. This forms the bases for the successful application of true non-contact [19,20] or electric force microscopy (EFM) [21] on the nanometer scale. Clearly though, the surface charge density being the source of the external electric eld may be dierent from the polarization charge responsible for building up the internal electric eld, as was investigated and described in section 2 using PFM. Reasons for that are the presence of surface layers surface reconstruction mass transportation perpendicular to the sample surface

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and others. Here we present a novel method of quantitatively governing electrical data, i.e. the eective surface potential dierence between anti-parallel ferroelectric domains, by means of Kelvin probe force microscopy (KPFM). Figure 2 shows two images of the Sol-Gel grown PbTiO3 surface which were recorded simultaneously in the so-called KPFM mode. Here the dynamically vibrating cantilever is electrically hooked up to an additional feedback regulator, the Kelvin force sensor, which minimizes the Coulomb force interaction between tip and sample surface. For a given tip-sample geometry any electric interaction gives rise to a potential dierence between the two electrodes aecting the overall force interaction F by F = 1 C ()2 2 z (2)

with C the tip-sample capacitance and z the mean tip sample distance. As indicated in equ. 2 both a negative and positive potential dierence aect our measurement similarly (always attractive force) showing the quadratic behavior of the Coulomb force term. In ordinary non-contact SFM though, both the tip and sample surface potential are electrically not controlled. Moreover when investigating ferroelectrics having a bound surface charge density, any arbitrary tip potential being dierent from the local sample surface potential directly leads to an additional force term in our non-contact interaction (equ. 2). The interpretation of data recorded by EFM or non-contact SFM therefore always suer from this point, specically when Coulomb forces dominate the local force contribution. Figure 2a) shows the sample topography of the PbTiO3 lm where the extra Coulomb force interaction (equ. 2) now was completely balanced (i.e. F = 0 in equ. 2). Here topological changes are displayed in a gray scale contrast with dark showing topographically low areas and bright features representing elevations. Please note that the overall roughness is very smooth (< 30 nm). Nevertheless, such small a value is only reportable when the additional force contribution, the Kelvin potential, stemming from the Coulomb interaction between tip and sample (see equ. 2) is completely cancelled [22]. This is achieved for Fig. 2a) by adjusting the tip potential above every point of measurement by means of an auxiliary feedback loop as described above. Note that experimentally the potential = U0 + US sin(t) was used with U0 = tip sample , the tip sample contact potential dierence, and US sin(t) the modulation voltage which was applied in order to nd the potential minimum of U0 . In general the contact potential is highly material dependent and related to the work function of the pure material. Also the condition of the surface, such as the presence of a contamination layer, adsorbates [23] or an additional surface dipole moment plays an essential role. Mobile charges therefore immediately act to locally compensate the surface polarization. Another severe point is the tip voltage which may induce some band bending [24]. The latter though is negligible in our experiment because = 0.

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Fig. 2. Kelvin probe force microscopy on Sol-Gel grown PbTiO3 : (a) topography (zscale black-white: 30 nm), (b) electric surface potential, z-range +/- 100 mV; Prole across 5 grains showing the topography (grey) and the sample bias (black) applied by the feedback controller in order to minimize the Coulomb force interaction

Most adequately the electric potential is divided up into two parts which is = + with the Volta potential, and the surface potential [25] accounting for the presence of monopolar and dipolar electrostatic charges at the sample surface, respectively. Such a model fully accounts for the situation in ferroelectric systems: we observe a net bound surface charge which in the limit though may also be regarded as a surface dipole having the counter charge being accumulated on the opposite sample surface. Furthermore, the KPFM method results in balancing any electrostatic eld wherever it might arise from. Hence these measurements present the eective and quantitatively correct eld distribution above the sample surface. Please note that due to charge compensation and variable geometry, the KPFM signal may be strongly distant dependent. The Kelvin signal which was recorded simultaneously to Fig. 2a) on the Sol-Gel grown PbTiO3 sample is displayed in Fig. 2b). As seen we observe a net potential dierence from - 100 mV (negative, black areas) to + 100 mV (positive, bright polarized areas). The potential dierence species the bound surface charge density. When comparing the sample topography and KPFM images it becomes obvious that the grains are randomly oriented. In fact the transition regions at the grain boundaries appears to be very sharp showing

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the surface potential to switch sign on a lateral scale less than 20 nm (see cross-sections taken from Fig. 2a) and b), respectively). KPFM therefore promises to be a powerful tool when inspecting the surface charge distribution.

5 Future Aspects in Nanoscale Investigations of Ferroelectrics

As pointed out in the last paragraph it is the surface features at interfaces which control the switching properties and retention within a ferroelectric thin lm [26]. Therefore a big need in exploring the nanoscale surface and interface properties is given from which the following information should be deduced: the the the the the the the the the surface chemical potential surface density of electronic states surface polarization surface and bulk conductivity as well as conduction mechanism surface layer thickness surface layer chemical isotropy surface reconstruction surface dielectric constant and optical properties defect density on the nanometer scale, etc.

In order to achieve these goals there are many valuable experimental approaches on the nanometer scale where SPM technology is involved. For instance are the nanoscale optical properties far from being understood or investigated thoroughly: measuring the optical birefringence, absorption, uorescence or Raman signal directly reveals information on the surface chemistry as well as their polarity. On the other hand, a clear correlation between optical and electronic methods has to be established, starting with combined NSOM and SFM/STM experiments in order to explore the electro-optic contributions including surface conductive processes, etc.. Finally, the above discussion clearly showed that PFM seems to be one of the universal modes in order to inspect the internal electric eld of ferroics on the nanometer scale. However, little is known so far from the basic physical mechanisms when the inhomogeneous electric eld dropping over the ferroic sample couples to the apparent local lattice distortion. Both theoretical simulations as well as the development of less invasive methods are needed in order to check for consistency in PFM and macroscopic probing.

Conclusions

We demonstrate that Kelvin probe force microscopy (KPFM) reveals a quantitative way of obtaining the surface potential on C + and C surfaces in

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ferroelectric crystals. Avoiding surface contamination and decoration therefore enables a quantitative conclusion on the amount of surface charge built up at the sample surface. This is of valuable help when investigating domain switching on the nanometer scale as shown with piezoresponse measurements (PFM) by scanning force microscopy on thin PbTiO3 lms. Acknowledgement We gratefully acknowledge nancial support by the German Research Society under grant-Nr. EN 434 /2-1.

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