Interplay between proton ordering and ferroelectric polarization in H-bonded KDP-type crystals

The origin of ferroelectricity in KH2PO4 (KDP) is studied by first-principles electronic structure calculations. In the low-temperature phase, the collective off-centre ordering of the protons is accompanied by an electronic charge delocalization from the near and localization at the far oxygen within the O-H...O bonds. Electrostatic forces. then, push the K+ ions towards off-centre positions, and induce a macroscopic polarization. The analysis of the correlation between different geometrical and electronic quantities, in connection with experimental data. supports the idea that the role of tunnelling in isotopic effects is irrelevant. Instead, geometrical quantum effects appear to play a central role. (C) 2001 Elsevier Science B.V. All rights reserved.

Intrinsic dielectric response in ferroelectric nano-capacitors

Measurements on 'free-standing' single-crystal barium titanate capacitors with thickness down to 75 nm show a dielectric response typical of large single crystals, rather than conventional thin films. There is a notable absence of any broadening or temperature shift of the dielectric peak or loss tangent. Peak dielectric constants of similar to25 000 are observed, and Curie-Weiss analysis demonstrates first order transformation behaviour. This is in dramatic contrast to results on conventionally deposited thin film capacitor heterostructures, which show large dielectric peak broadening and temperature shifts (e.g. Parker et al 2002 Appl. Phys. Lett. 81 340), as well as an apparent change in the nature-of the paraelectric-ferroelectric transition from first to second order. Our data are compatible with a recent model by Bratkovsky and Levanyuk (2004 Preprint cond-mat/0402100), which attributes dielectric peak broadening to gradient terms that will exist in any thin film capacitor heterostructure. The observed recovery of first order transformation behaviour is consistent with the absence of significant substrate clamping in our experiment, as modelled by Pertsev et al (1998,Phys. Rev. Lett. 80 1988), and illustrates that the second order behaviour seen in conventionally deposited thin films cannot be attributed to the effects of reduced dimensionality in the system, nor to the influence of an intrinsic universal interfacial capacitance associated with the electrode- ferroelectric interface.

First-principles study of ferroelectricity and isotope effects in H-bonded KH2PO4 crystals

By means of extensive first-principles calculations we studied the ferroelectric phase transition and the associated isotope effect in KH2PO4 (KDP). Our calculations revealed that the spontaneous polarization of the ferroelectric phase is due to electronic charge redistributions and ionic displacements which are a consequence of proton ordering, and not vice versa. The experimentally observed double-peaked proton distribution in the paraelectric phase cannot be explained by a dynamics of only protons. This requires, instead, collective displacements within clusters that include also the heavier ions. These tunneling clusters can explain the recent evidence of tunneling obtained from Compton scattering measurements. The sole effect of mass change upon deuteration is not sufficient to explain the huge isotope effect. Instead, we find that structural modifications deeply connected with the chemistry of the H bonds produce a feedback effect on tunneling that strongly enhances the phenomenon. The resulting influence of the geometric changes on the isotope effect agrees with experimental data from neutron scattering. Calculations under pressure allowed us to analyze the issue of universality in the disappearance of ferroelectricity upon compression. Compressing DKDP so that the distance between the two peaks in the deuteron distribution is the same as for protons in KDP, corresponds to a modification of the underlying double-well potential, which becomes 23 meV shallower. This energy difference is what is required to modify the O-O distance in such a way as to have the same distribution for protons and deuterons. At the high pressures required experimentally, the above feedback mechanism is crucial to explain the magnitude of the geometrical effect.

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.

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.

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.

Phonons, Instabilities and Origin of Polarization in KDP Crystals

The -phonons of KH2PO4 (KDP) and its deuterated analog DKDP are studied via first-principles linear response calculations. The paraelectric phase shows two instabilities. One for a z-polarized mode, which leads to the spontaneous polarization Ps of the ferroelectric phase. The other corresponds to a two-fold degenerate xy-polarized mode. Other phonons are analyzed, which couple to the ferroelectric one at large amplitudes and are relevant for the ferroelectric transition. We show that Ps is mainly of electronic nature, since it arises mostly from an off-diagonal component of the Born effective charge tensor of H, with minor contribution from P atoms displacements.

Regular nanodomain vertex arrays in BiFeO3 single crystals

Domain patterns consisting of triangular nanodomains of less than 50 nm size, arranged into long regular vertex arrays separated by stripe domains, were observed by (scanning and high-resolution) transmission electron microscopy and piezoresponse force microscopy in BiFeO3 single crystals grown from solution flux. Piezoresponse force microscopy analysis together with crystallographic analysis by selected area and nanobeam electron diffraction indicate that these patterns consist of ferroelectric 109 degrees domains. A possibility for conserving Kittel's law is discussed in terms of the patterns being confined to the skin layer observed recently on BiFeO3 single crystals.

Thickness independence of true phase transition temperatures in barium strontium titanate films

The functional properties of two types of barium strontium titanate (BST) thin film capacitor structures were studied: one set of structures was made using pulsed-laser deposition (PLD) and the other using chemical solution deposition. While initial observations on PLD films looking at the behavior of T-m (the temperature at which the maximum dielectric constant was observed) and T-c(*) (from Curie-Weiss analysis) suggested that the paraelectric-ferroelectric phase transition was progressively depressed in temperature as BST film thickness was reduced, further work suggested that this was not the case. Rather, it appears that the temperatures at which phase transitions occur in the thin films are independent of film thickness. Further, the fact that in many cases three transitions are observable, suggests that the sequence of symmetry transitions that occur in the thin films are the same as in bulk single crystals. This new observation could have implications for the validity of the theoretically produced thin film phase diagrams derived by Pertsev [Phys. Rev. Lett. 80, 1988 (1998)] and extended by Ban and Alpay [J. Appl. Phys. 91, 9288 (2002)]. In addition, the fact that T-m measured for virgin films does not correlate well with the inherent phase transition behavior, suggests that the use of T-m alone to infer information about the thermodynamics of thin film capacitor behavior, may not be sufficient. (C) 2004 American Institute of Physics.

Perovskite lead zirconium titanate nanorings: Towards nanoscale ferroelectric

Rings of perovskite lead zirconium titanate (PZT) with internal diameters down to similar to 5 nm and ring thicknesses of similar to 5-10 nm have been fabricated and structurally, crystallographically, and chemically characterized using an analytical transmission electron microscope. Ring fabrication involved conformal solution deposition of a thin layer of PZT on the inside of a thin film of anodized aluminum oxide nanopores, and subsequent sectioning of the coated pores perpendicular to their cylinder axes. Although the starting solution used for the solution deposition was made from morphotropic phase boundary PZT, the nanorings were found to be on the zirconium-rich side of the PZT phase diagram. Nevertheless, coatings were found to be of perovskite crystallography. The dimensions of these nanorings are such that they have the potential to demonstrate polarization vortices, as modeled by Naumov [Nature (London) 432, 737 (2004)], and moreover represent the perfect morphology to allow vortex alignment and the creation of the ferroelectric "solenoid" as modeled by Gorbatsevich and Kopaev [Ferroelectrics 161, 321 (1994)].

Three-dimensional photonic crystals based on macroporous silicon with modulated pore diameter

We report on the fabrication and optical characterization of a three-dimensional (3D) photonic crystal on the basis of macroporous silicon. The structure consists of a 2D array of air pores in silicon whose diameter is varied (modulated) periodically with depth. The bandstructure of the resulting 3D hexagonal photonic crystal is calculated and compared with transmission measurements. The described structure allows to adjust the dispersion relation along the pore axis almost independently from the dispersion relation in the plane perpendicular to the pore axis.

Optical bistability in nonlinear surface-plasmon polaritonic crystals

Nonlinear optical transmission through periodically nanostructured metal films (surface-plasmon polaritonic crystals) has been studied. The surface polaritonic crystals have been coated with a nonlinear polymer. The optical transmission of such nanostructures has been shown to depend on the control-light illumination conditions. The resonant transmission exhibits bistable behavior with the control-light intensity. The bistability is different at different resonant signal wavelengths and for different wavelengths of the control light. The effect is explained by the strong sensitivity of the surface-plasmon mode resonances at the signal wavelength to the surrounding dielectric environment and the electromagnetic field enhancement due to plasmonic excitations at the controlled light wavelengths.

Ferroelectricity and isotope effects in hydrogen-bonded KDP crystals

Based on an accurate first principles description of the energetics in H-bonded potassium-dihydrogen-phosphate crystals, we conduct a first study of nuclear quantum effects and of the changes brought about by deuteration. Tunneling is allowed only for clusters involving correlated protons and heavy ion displacements, the main effect of deuteration being a depletion of the proton probability density at the O-H-O bridge center, which in turn weakens its proton-mediated covalent bonding. The ensuing lattice expansion couples self-consistently with the proton off-centering, thus explaining both the giant isotope effect and its close connection with geometrical effects.

Toward Self-Assembled Ferroelectric Random Access Memories: Hard-Wired Switching Capacitor Arrays with Almost Tb/in.2 Densities

We report on the successful fabrication of arrays of switchable nanocapacitors made by harnessing the self-assembly of materials. The structures are composed of arrays of 20-40 nm diameter Pt nanowires, spaced 50-100 nm apart, electrodeposited through nanoporous alumina onto a thin film lower electrode on a silicon wafer. A thin film ferroelectric (both barium titanate (BTO) and lead zirconium titanate (PZT)) has been deposited on top of the nanowire array, followed by the deposition of thin film upper electrodes. The PZT nanocapacitors exhibit hysteresis loops with substantial remnant polarizations, while although the switching performance was inferior, the low-field characteristics of the BTO nanocapacitors show dielectric behavior comparable to conventional thin film heterostructures. While registration is not sufficient for commercial RAM production, this is nevertheless an embryonic form of the highest density hard-wired FRAM capacitor array reported to date and compares favorably with atomic force microscopy read-write densities.