Creation of damage-free ferroelectric nanocapacitors via focused ion beam milling

We present a novel method for creating damage-free ferroelectric nanostructures with a focused ion beam milling machine. Using a standard e-beam photoresist followed by a dilute acid wash, nanostructures ranging in size from 1 mu m down to 250 nm were created in a 90 nm thick lead zirconate titanate ( PZT) wafer. Transmission electron microscopy and piezoresponse force microscopy ( PFM) confirmed that the surfaces of the nanostructures remained damage free during fabrication, and showed no gallium implantation, and that there was no degradation of ferroelectric properties. In fact DC strain loops, obtained using PFM, demonstrated that the nanostructures have a higher piezoresponse than unmilled films. As the samples did not have any top hard mask, the method presented is unique as it allows for imaging of the top surface to understand edge effects in well-defined nanostructures. In addition, as no post-mill annealing was necessary, it facilitates investigation of nanoscale domain mechanisms without process-induced artefacts.

Domains in three-dimensional ferroelectric nanostructures

We report the experimental measurement of domains in single- crystal nanocolumns of ferroelectric BaTiO3, together with a theory of domain size scaling in three- dimensional structures which explains the observations.

The effect of flexoelectricity on the dielectric properties of inhomogeneously strained ferroelectric thin films

Recent experimental measurements of large flexoelectric coefficients in ferroelectric ceramics suggest that strain gradients can affect the polarization and permittivity behaviour of inhomogeneously strained ferroelectrics. Here we present a phenomenological model of the effect of flexoelectricity on the dielectric constant, polarization, Curie temperature (T-C), temperature of maximum dielectric constant (T-m) and temperature of the onset of reversible polarization (T-ferro) for ferroelectric thin films subject to substrate-induced epitaxial strains that are allowed to relax with thickness, and the qualitative and quantitative predictions of the model are compared with experimental results for (Ba0.5Sr0.5)TiO3 thin films on SrRuO3 electrodes. It is shown that flexoelectricity can play an important role in decreasing the maximum dielectric constant of ferroelectric thin films under inhomogeneous in-plane strain, regardless of the sign of the strain gradient.

Evidence for two-phase regions in BST thin films from capacitance-voltage data

The Curie-Weiss plots of reciprocal dielectric constant versus temperature, in Ba0.5Sr0.5TiO3 films grown onto SrRuO3 lower electrodes by pulsed-laser deposition, show two minima below film thicknesses of 280 nm. This double minima implies possible mixed phases in the thin films. A graphical plot of capacitance for decreasing dc voltage versus that of increasing dc voltage shows a well-defined triangular shape for both Pb(Zr0.4Ti0.6)O-3 and SrBi2Ta2O9 thin films. However, for a 175-nm-thick Ba0.5Sr0.5TiO3 thin film, the plot shows an overlapping of two triangles, suggesting mixed phases. This graphical method appears to be effective in detecting structural subtleties in ferroelectric capacitors.

The effect of tungsten trioxide thin films at ferroelectric-electrode boundaries on fatigue behaviour

A conventional thin film capacitor heterostructure, consisting of sol-gel deposited lead zirconium titanate (PZT) layers with sputtered platinum top and bottom electrodes, was subjected to fatiguing pulses at a variety of frequencies. The fatigue characteristics were compared to those of a similarly processed capacitor in which a ~20nm tungsten trioxide layer had been deposited, using pulsed laser deposition, between the ferroelectric and upper electrode. The expectation was that, because of its ability to accommodate considerable oxygen non-stoichiometry, tungsten trioxide (WO3) might act as an efficient sink for any oxygen vacancies flushed to the electrode-ferroelectric boundary layer during repetitive switching, and hence would improve the fatigue characteristics of the thin film capacitor. However, it was found that, in general, the addition of tungsten trioxide actually increases the rate of fatigue. It appears that any potential benefit from the WO3, in terms of absorbing oxygen vacancies, is far outweighed by it causing dramatically increased charge injection in the system.

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.

On the nature of the silver phases of Ag/Al2O3 catalysts for reactions involving nitric oxide

The nature of the silver phases of Ag/Al2O3 catalysts (prepared by silver nitrate impregnation followed by calcination) was investigated by X-ray diffractograms (XRD), transmission electron microscopy (TEM) and UV-VIS analyses and related to the activity of the corresponding materials for the oxidation of NO to NO2. The UV-VIS spectrum of the 1.2 wt.% Ag/Al2O3 exhibited essentially one band associated with Ag+ species and the NO2 yields measured over this material were negligible. A 10 wt.% Ag/Al2O3 material showed the presence of oxidic species of silver (as isolated Ag+ cations and silver aluminate), but the UV-VIS data also revealed the presence of some metallic silver. The activity for the NO oxidation to NO2 of this sample was moderate. The same 10% sample either reduced in H-2 or used for the C3H6-selective catalytic reduction (SCR) of NO showed a significantly larger proportion of silver metallic phases and these samples displayed a high activity for the formation of NO2. These data show that the structure and nature of the silver phases of Ag/Al2O3 catalysts can markedly change under reaction feed containing only a fraction of reducing agent (i.e. 500 ppm of propene) in net oxidizing conditions (2.5% O-2). The low activity for N-2 formation during the C3H6-SCR of NO (reported in an earlier study) over the high loading sample can. therefore, he related to the presence of metallic silver. which is yet a good catalyst for NO oxidation to NO2. The reverse observations apply for the oxide species observed over the low loading sample, which is a good SCR catalyst but do not oxidize NO to NO2. (C) 2002 Elsevier Science B.V. All rights reserved.

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.

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.