R. M. Bowman

Dielectric enhancement and Maxwell–Wagner effects in ferroelectric superlattice structures

In an attempt to reproduce the functional properties associated with relaxor electroceramics, pulsed laser deposition has been used to fabricate thin-film capacitor structures in which the dielectric layer is composed of a superlattice of Ba0.8Sr0.2TiO3 and Ba0.2Sr0.8TiO3. The properties of the capacitors were investigated as a function of superlattice periodicity. The dielectric constant was significantly enhanced at stacking periodicities of a few unit cells, consistent with relaxor behavior. However, enhancement in dielectric constant was generally associated with high dielectric loss. Analysis of the imaginary permittivity as a function of frequency shows that fine-scale superlattices conform to Maxwell–Wagner behavior. This suggests that the observed enhancement of the real part of the dielectric constant is an artifact produced by carrier migration to interfaces within the dielectric. A comparison of this data with that already published on dielectric superlattices suggests that previous claims of a...

Relaxor features in ferroelectric superlattices: A Maxwell–Wagner approach

A Maxwell–Wagner series capacitor model is proposed to explain anomalous dielectric properties of ferroelectric superlattices. The results of the model show that a superlattice consisting of normal ferroelectric layers separated by low-resistivity interfacial regions can account for most experimental results reported to date, namely: dielectric enhancement for certain stacking periodicities, giant permittivities, and temperature migration of dielectric maxima as a function of frequency. The predictions of the model are discussed and compared to our own experimental results from thin film superlattice capacitors made by pulsed-laser deposition.

Investigation of dead-layer thickness in SrRuO3/Ba0.5Sr0.5TiO3/Au thin-film capacitors

Thin-film capacitors, with barium strontium titanate (BST) dielectric layers between 7.5 and 950 nm in thickness, were fabricated by pulsed-laser deposition. Both crystallography and cation chemistry were consistent with successful growth of the BST perovskite. At room temperature, all capacitors displayed frequency dispersion such that e100 kHz/e100 Hz was greater than 0.75. The dielectric constant as a function of thickness was fitted, using the series capacitor model, for BST thicknesses greater than 70 nm. This yielded a large interfacial di/ei ratio of 0.40±0.05 nm, implying a highly visible parasitic dead layer within the capacitor structure. Modeled consideration of the dielectric behavior for BST films, whose total thickness was below that of the dead layer, predicted anomalies in the plots of d/e against d at the dead-layer thickness. In the capacitors studied here, no anomaly was observed. Hence, either (i) 7.5 nm is an upper limit for the total dead-layer thickness in the SRO/BST/Au system, or ...

Exploring grain size as a cause for “dead-layer” effects in thin film capacitors

Pulsed laser deposition was used to make a series of Au/Ba0.5Sr0.5TiO3 (BST)/SrRuO3/MgO thin film capacitors with dielectric thickness ranging from ∼15 nm to ∼1 μm. Surface grain size of the dielectric was monitored as a function of thickness using both atomic force microscopy and transmission electron microscopy. Grain size data were considered in conjunction with low field dielectric constant measurements. It was observed that the grain size decreased with decreasing thickness in a manner similar to the dielectric constant. Simple models were developed in which a functionally inferior layer at the grain boundary was considered as responsible for the observed dielectric behavior. If a purely columnar microstructure was assumed, then constant thickness grain-boundary dead layers could indeed reproduce the series capacitor dielectric response observed, even though such layers would contribute electrically in parallel with unaffected bulk-like BST. Best fits indicated that the dead layers would have a relat...

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 Tm (the temperature at which the maximum dielectric constant was observed) and Tc* (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 thi...

High-field conduction in barium titanate

We present current–voltage studies of very thin (∼77nm) barium titanate single crystals up to 1.3GV∕m applied field. These show that the mechanism of leakage current at high fields is that of space charge limited conduction (SCLC) in a regime with a continuous distribution of traps, according to the original model of Rose [Phys. Rev. 97, 1538 (1955)]. This study represents a factor of ×5 in field compared with the early studies of BaTiO3 conduction [A. Branwood et al., Proc. Phys. Soc. London 79, 1161 (1962)]. Comparison is also given with ceramic multilayer barium titanate capacitors, and with variable range hopping [B. I. Shklovskii, Sov. Phys. Semicond. 6, 1964 (1973)], reported in SrTiO3 films [D. Fuchs, M. Adam, and R. Schneider, J. Phys. IV France 11, 71 (2001)].

Dielectric and electromechanical properties of Pb(Mg1/3,Nb2/3)O3–PbTiO3 thin films grown by pulsed laser deposition

Pulsed laser deposition was used to grow thin films of several compositions from the Pb(Mg1/3,Nb2/3)O3–PbTiO3 (PMN–PT) solid solution as dielectric layers in thin film capacitor structures. They were found to display functional behavior characteristic of relaxors, with the only significant difference between thin film and bulk being a severely reduced dielectric permittivity. Room temperature polarization loops showed a general increase in both the remanent polarization and absolute magnitude of the polarization for a given field with PT content. The electric field-induced strain was primarily examined by in situ x-ray diffraction and although fields greater than 20 MV m−1 were applied to the films, the maximum observed strain was only ∼0.3%, considerably less than the 1.4% seen in single crystal samples. Piezo-response atomic force microscopy studies were consistent in that the macroscopic effective piezoelectric coefficient d33, was found to differ from single crystal measurements by an order of magnitu...

Thickness-induced stabilization of ferroelectricity in SrRuO3/Ba0.5Sr0.5TiO3/Au thin film capacitors

Pulsed-laser deposition has been used to fabricate Au/Ba0.5Sr0.5TiO3/SrRuO3/MgO thin film capacitor structures. Crystallographic and microstructural investigations indicated that the Ba0.5Sr0.5TiO3 (BST) had grown epitaxially onto the SrRuO3 lower electrode, inducing in-plane compressive and out-of-plane tensile strain in the BST. The magnitude of strain developed increased systematically as film thickness decreased. At room temperature this composition of BST is paraelectric in bulk. However, polarization measurements suggested that strain had stabilized the ferroelectric state, and that the decrease in film thickness caused an increase in remanent polarization. An increase in the paraelectric–ferroelectric transition temperature upon a decrease in thickness was confirmed by dielectric measurements. Polarization loops were fitted to Landau–Ginzburg–Devonshire (LGD) polynomial expansion, from which a second order paraelectric–ferroelectric transition in the films was suggested at a thickness of ∼500 nm. F...

Enhancement of dielectric constant and associated coupling of polarization behavior in thin film relaxor superlattices

Thin film capacitor structures in which the dielectric is composed of superlattices of the relaxors [0.2Pb(Zn1/3Nb2/3)O3–0.8BaTiO3] and Pb(Mg1/3Nb2/3)O3 have been fabricated by pulsed laser deposition. Superlattice wavelength (Λ) was varied between ∼3 and ∼600 nm, and dielectric properties were investigated as a function of Λ. Progressive enhancement of the dielectric constant was observed on decreasing Λ, and, in contrast to previous work, this was not associated with the onset of Maxwell–Wagner behavior. Polarization measurements as a function of temperature suggested that the observed enhancement in dielectric constant was associated with the onset of a coupled response. The superlattice wavelength (Λ=20 nm) at which coupled functional behavior became apparent is comparable to that found in literature for the onset of coupled structural behavior (between Λ=5 nm and Λ=10 nm).

Strategies for gallium removal after focused ion beam patterning of ferroelectric oxide nanostructures.

As part of a study into the properties of ferroelectric single crystals at nanoscale dimensions, the effects that focused ion beam (FIB) processing can have, in terms of structural damage and ion implantation, on perovskite oxide materials has been examined, and a post-processing procedure developed to remove such effects. Single crystal material of the perovskite ferroelectric barium titanate (BaTiO(3)) has been patterned into thin film lamellae structures using a FIB microscope. Previous work had shown that FIB patterning induced gallium impregnation and associated creation of amorphous layers in a surface region of the single crystal material some 20 nm thick, but that both recrystallization and expulsion of gallium could be achieved through thermal annealing in air. Here we confirm this observation, but find that thermally induced gallium expulsion is associated with the formation of gallium-rich platelets on the surface of the annealed material. These platelets are thought to be gallium oxide. Etching using nitric and hydrochloric acids had no effect on the gallium-rich platelets. Effective platelet removal involved thermal annealing at 700 degrees C for 1 h in a vacuum followed by 1 h in oxygen, and then a post-annealing low-power plasma clean in an Ar/O atmosphere. Similar processing is likely to be necessary for the full recovery of post FIB-milled nanostructures in oxide ceramic systems in general.