Nanoscale ferroelectrics machined from single crystals

This paper summarises some of the most recent work that has been done on nanoscale ferroelectrics as a result of a joint collaborative research effort involving groups in Queen's University Belfast, the University of Cambridge and the University of St. Andrews. Attempts have been made to observe fundamental effects of reduced size, and increasing morphological complexity, on ferroelectric behaviour by studying the functional response and domain characteristics in nanoscale single crystal material, whose size and morphology have been defined by Focused Ion Beam (FIB) patterning. This approach to nanoshape fabrication has allowed the following broad statements to be made: (i) in single crystal BaTiO3 sheets, permittivity and phase transition behaviour is not altered from that of bulk material down to a thickness of similar to 75 nm; (ii) in single crystal BaTiO3 sheets and nanowires changes in observed domain morphologies are consistent with large scale continuum modeling.

Characteristics of the interfacial capacitance in thin film Ba0.5Sr0.5TiO3 capacitors with SrRuO3 and (La, Sr)CoO3 bottom electrodes

Thin film Ba0.5Sr0.5TiO3 (BST) capacitors of thickness similar to75 nm to similar to1200 nm, with Au top electrodes and SrRuO 3 (SRO) or (La, Sr)CoO3 (LSCO) bottom electrodes were fabricated using Pulsed Laser Deposition. Implementing the "series capacitor model," bulk and interfacial capacitance properties were extracted as a function of temperature and frequency. 'Bulk' properties demonstrated typical ceramic behaviour, displaying little frequency dependence and a permittivity and loss peak at 250 K and 150 K respectively. The interfacial component was found to be relatively temperature and frequency independent for the LSCO/BST capacitors, but for the SRO/BST configuration the interfacial capacitance demonstrated moderate frequency and little temperature dependence below T similar to 300 K but a relatively strong frequency and temperature dependence above T similar to3 00 K. This was attributed to the thermal activation of a space charge component combined with a thermally independent background. The activation energy for the space charge was found to be E-A similar to 0.6 eV suggesting de-trapping of electrons from shallow level traps associated with a thin interfacial layer of oxygen vacancies, parallel to the electrodes.

Thin film capacitor cut from single crystals using focused ion beam milling

The focused ion beam microscope (FIB) has been used to fabricate thin parallel-sided ferroelectric capacitors from single crystals of BaTiO3 and SrTiO3. A series of nano-sized capacitors ranging in thickness from similar to660 nm to similar to300 nm were made. Cross-sectional high resolution transmission electron microscopy (HRTEM) revealed that during capacitor fabrication, the FIB rendered around 20 nm of dielectric at the electrode-dielectric interface amorphous, associated with local gallium impregnation. Such a region would act electrically in series with the single crystal and would presumably have a considerable negative influence on the dielectric properties. However, thermal annealing prior to gold electrodes deposition was found to fully recover the single crystal capacitors and homogenise the gallium profile. The dielectric testing of the STO ultra-thin single crystal capacitors was performed yielding a room temperature dielectric constant of similar to300, as is the case in bulk. Therefore, there was no evidence of a collapse in dielectric constant associated with thin film dimensions.

Progressive loss of ferroelectricity under bipolar pulsed fields and experimental determination of non-switchable polarization in Au/Ba0.5Sr0.5TiO3/SrRuO3 thin-film capacitors

175 nm-thick Ba0.5Sr0.5TiO3 (BST) thin film fabricated by pulsed laser deposition (PLD) technique is found to be a mixture of two distributions of material. We discuss whether these two components are nano-regions of paraelectric and ferroelectric phases, or a bimodal grain-size distribution, or an effect of oxygen vacancy gradient from the electrode interface. The fraction of switchable ferroelectric phase decreases under bipolar pulsed fields, but it recovers after removal of the external fields. The plot of capacitance in decreasing dc voltage (C(Vdown arrow) versus that in increasing dc 61 voltage C(Vup arrow) is a superposition of overlapping of two triangles, in contrast to one well-defined triangle for typical ferroelectric SrBi2Ta2O9 thin films.

Understanding thickness effects in thin film capacitors

Pulsed Laser Deposition (PLD) was used to make Au/(Ba0.5Sr0.5)TiO3/(La0.5Sr0.5) CoO3/MgO thin film capacitor structures. Functional properties were studied with changing BST thickness from similar to1265 nm to similar to63 nm. The dielectric constant was found to decrease, and migration of T-m (the temperature at which the dielectric constant is maximum) to lower temperatures occurred as thickness was reduced. Curie-Weiss plots of the as-obtained dielectric data, indicated that the Curie temperature was also systemmatically progressively depressed. Further, fitting to expressions previously used to describe diffuse phase transitions suggested increased diffuseness in transformation behaviour as film thickness decreased. This paper discusses the care needed in interpreting the observations given above. We make particular distinction between the apparent Curie-temperature derived from Curie-Weiss plots of as-measured data, and the inherent Curie temperature determined after correction for the interfacial capacitance. We demonstrate that while the apparent Curie temperature decreases as thickness decreases, the inherent Curie temperature is thickness independent. Thickness-invariant phase transition behaviour is confirmed from analysis of polarisation loops, and from examination of the temperature dependence of the loss-tangent. We particularly note that correction of data for interfacial capacitance does not alter the position of T-m. We must therefore conclude that the position of T-m is not related simply to phase transformation behaviour in BST thin films.

Maximum of dielectric permittivity caused by structural transition in ferroelectric BaTiO3-SrTiO3 superlattices

We invoke the onset of dislocations along the BaTiO3-SrTiO3 interface as reported by Wunderlich et al. to explain the non-monotonic behaviour of the dielectric permittivity as a function of superlattice periodicity and the less than four-fold in-plane symmetry at the dielectric maximum. At a periodicity of about 10/10, depending on composition and growth mechanism, several groups report a maximum of dielectric permittivity. In addition to that we observe in-plane symmetry less than tetragonal for 10/10 superlattices by HR-XRD, in contrast to initial low-resolution data from Tabata et al. thus challenging the assumption of unrelaxed strain all the way through the superlattice. The aim of this article is to link both effects to the increasing volume fraction of conducting layers close to the interface in series with the superlattice layers.

Switching dynamics in ferroelectric thin films: An experimental survey

We have conducted a broad survey of switching behavior in thin films of a range of ferroelectric materials, including some materials that are not typically considered for FeRAM applications, and are hence less studied. The materials studied include: strontium bismuth tantalate (SBT), barium strontium titanate (BST), lead zicronate titanate (PZT), and potassium nitrate (KNO3). Switching in ferroelectric thin films is typically considered to occur by domain nucleation and growth. We discuss two models of frequency dependence of coercive field, the Ishisbashi-Orihara theory where the limiting step is domain growth and the model of Du and Chen where the limiting step is nucleation. While both models fit the data fairly well the temperature dependence of our results on PZT and BST suggest that the nucleation model of Du and Chen is more appropriate for the experimental results that we have obtained.

Size Effects on Thin Film Ferroelectrics: Experiments on Isolated Single Crystal Sheets

Thin lamellae were cut from bulk single crystal BaTiO3 using a Focused Ion Beam Microscope. They were then removed and transferred onto single crystal MgO substrates, so that their functional properties could be measured independent of the original host bulk ferroelectric. The temperature dependence of the capacitance of these isolated single crystal films was found to be strongly bulk-like, demonstrating a sharp Curie anomaly, as well as Curie-Weiss behaviour. In addition, the sudden change in the remanent polarisation as a function of temperature at TC was characteristic of a first order phase change. The work represents a dramatic improvement on that previously published by M. M. Saad, P. Baxter, R. M. Bowman, J. M. Gregg, F. D. Morrison & J. F. Scott, J. Phys: Cond. Matt., 16 L451-L456 (2004), as critical shortcomings in the original specimen geometry, involving potential signal contributions from bulk BaTiO3, have now been obviated. That the functional properties of single crystal thin film lamellae are comparable to bulk, and not like those of conventionally deposited heteroegenous thin film systems, has therefore been confirmed.

Origin of Ferroelastic domains in Free-Standing Single Crystal Ferroelectric Films

The origin of the unusual 90 degrees ferroelectric/ferroelastic domains, consistently observed in recent studies on mesoscale and nanoscale free-standing single crystals of BaTiO3 [Schilling , Phys. Rev. B 74, 024115 (2006); Schilling , Nano Lett. 7, 3787 (2007)], has been considered. A model has been developed which postulates that the domains form as a response to elastic stress induced by a surface layer which does not undergo the paraelectric-ferroelectric cubic-tetragonal phase transition. This model was found to accurately account for the changes in domain periodicity as a function of size that had been observed experimentally. The physical origin of the surface layer might readily be associated with patterning damage, seen in experiment; however, when all evidence of physical damage is removed from the BaTiO3 surfaces by thermal annealing, the domain configuration remains practically unchanged. This suggests a more intrinsic origin, such as the increased importance of surface tension at small dimensions. The effect of surface tension is also shown to be proportional to the difference in hardness between the surface and the interior of the ferroelectric. The present model for surface-tension induced twinning should also be relevant for finely grained or core-shell structured ceramics.

The Influence of Point Defects and Inhomogeneous Strain on the Functional Behaviour of Thin film Ferroelectrics

An attempt has been made to unequivocally identify the influence that inhomogeneous strain fields, surrounding point defects, have on the functional properties of thin film ferroelectrics. Single crystal thin film lamellae of BaTiO3 have been integrated into capacitor structures, and the functional differences between those annealed in oxygen and those annealed in nitrogen have been mapped. Key features, such as the change in the paraelectric-ferroelectric phase transition from first to second order were noted and found to be consistent with mean field modeling predictions for the effects of inhomogeneous strain. Switching characteristics appeared to be unaffected, suggesting that point defects have a low efficacy in domain wall pinning.

Ferroelectrics at the Nanoscale

There are several factors which make the investigation and understanding of nanoscale ferroelectrics particularly timely and important. Firstly, there is a market pressure, primarily from the electronics industry, to integrate ferroelectrics into devices with progressive decreases in size and increases in morphological complexity. This is perhaps best illustrated through the roadmaps for product development in FeRAM (Ferroelectric Randorn Access Memory) where the need for increases in bit density will require a move from 2D planar capacitor structures to 3D trenched capacitors in the next few years. Secondly, there is opportunity for novel exploration, as it is only relatively recently that developments in thin film growth of complex oxides, self-assembly techniques and high-resolution 'top-down' patterning have converged to allow the fabrication of isolated and well-defined ferroelectric nanoshapes, the properties of which are not known. Thirdly, there is an expectation that the behaviour of small scale ferroelectrics will be different from bulk, as this group of functional materials is highly sensitive to boundary/surface conditions, which are expected to dominate the overall response when sizes are reduced into the nanoscale regime. This feature article attempts to introduce some of the current areas of discovery and debate surrounding studies on ferroelectrics at the nanoscale. The focus is directed primarily at the search for novel size-related properties and behaviour which are not necessarily observed in bulk.

Imaging domains in BaTiO3 single crystal nanostructures: comparing information from transmission electron microscopy and piezo-force microscopy

This article compares and contrasts information
obtained, using transmission electron microscopy (TEM)
and piezo-force microscopy (PFM), on domain configurations
adopted in single crystal lamellae of BaTiO3, that had
been cut directly from bulk using a focused ion beam
microscope with top and bottom surfaces parallel to
{100}pseudocubic. Both forms of imaging reveal domain
walls parallel to {110}pseudocubic, consistent with sets of 90
domains with dipoles oriented parallel to the two
\001[pseudocubic directions in the plane of the lamellae.
However, the domain width was observed to be dramatically
larger using PFM than it was using TEM. This suggests
significant differences in the surface energy densities
that drive the domain formation in the first place, that could
relate to differences in the boundary conditions in the two
modes of imaging (TEM samples are imaged under high
vacuum, whereas PFM imaging was performed in air).
Attempts were made to map local dipole orientations
directly, using a form of ‘vector’ PFM. However, information
inferred was largely inconsistent with the known
crystallography of the samples, raising concern about the
levels of care needed for accurate interpretation of PFM
images.

Domains in Ferroelectric Nanodots

Almost free-standing single crystal mesoscale and nanoscale dots of ferroelectric BaTiO3 have been made by direct focused ion beam patterning of bulk single crystal material. The domain structures which appear in these single crystal dots, after cooling through the Curie temperature, were observed to form into quadrants, with each quadrant consisting of fine 90° stripe domains. The reason that these rather complex domain configurations form is uncertain, but we consider and discuss three possibilities for their genesis: first, that the quadrant features initially form to facilitate field-closure, but then develop 90° shape compensating stripe domains in order to accommodate disclination stresses; second, that they are the result of the impingement of domain packets which nucleate at the sidewalls of the dots forming “Forsbergh” patterns (essentially the result of phase transition kinetics); and third, that 90° domains form to conserve the shape of the nanodot as it is cooled through the Curie temperature but arrange into quadrant packets in order to minimize the energy associated with uncompensated surface charges (thus representing an equilibrium state). While the third model is the preferred one, we note that the second and third models are not mutually exclusive.