Epitaxial BiFeO3 nanostructures fabricated by differential etching of BiFeO3 films

We report on differential etching behavior of the different orientations of the polarization in BiFeO3 (BFO), similar to other ferroelectrics, such as LiNbO3. We show how this effect can be used to fabricate epitaxial BiFeO3 nanostructures. By means of piezoresponse force microscopy (PFM) domains of arbitrary shape and size can be poled in an epitaxial BiFeO3 film, which are then reproduced in the film morphology by differential etching. Structures with a lateral size smaller than 200 nm were fabricated and very good retention properties as well as a highly increased piezoelectric response were detected by PFM. (C) 2011 American Institute of Physics. [doi:10.1063/1.3630027]

Ordered arrays of multiferroic epitaxial nanostructures

Epitaxial heterostructures combining ferroelectric (FE) and ferromagnetic (FiM) oxides are a possible route to explore coupling mechanisms between the two independent order parameters, polarization and magnetization of the component phases. We report on the fabrication and properties of arrays of hybrid epitaxial nanostructures of FiM NiFe(2)O(4) (NFO) and FE PbZr(0.52)Ti(0.48)O(3) or PbZr(0.2)Ti(0.8)O(3), with large range order and lateral dimensions from 200 nm to 1 micron. METHODS: The structures were fabricated by pulsed-laser deposition. High resolution transmission electron microscopy and high angle annular dark-field scanning transmission electron microscopy were employed to investigate the microstructure and the epitaxial growth of the structures. Room temperature ferroelectric and ferrimagnetic domains of the heterostructures were imaged by piezoresponse force microscopy (PFM) and magnetic force microscopy (MFM), respectively. RESULTS: PFM and MFM investigations proved that the hybrid epitaxial nanostructures show ferroelectric and magnetic order at room temperature. Dielectric effects occurring after repeated switching of the polarization in large planar capacitors, comprising ferrimagnetic NiFe2O4 dots embedded in ferroelectric PbZr0.52Ti0.48O3 matrix, were studied. CONCLUSION: These hybrid multiferroic structures with clean and well defined epitaxial interfaces hold promise for reliable investigations of magnetoelectric coupling between the ferrimagnetic / magnetostrictive and ferroelectric / piezoelectric phases.

Relationship between biomedical catheter surface properties and lubricity as determined using textural analysis and multiple regression analysis

In this study, the surface properties of and work required to remove 12 commercially available and developmental catheters from a model biological medium (agar), a measure of catheter lubricity, were characterised and the relationships between these properties were examined using multiple regression and correlation analysis. The work required for removal of catheter sections (7 cm) from a model biological medium (1% w/w agar) were examined using tensile analysis. The water wettability of the catheters were characterised using dynamic contact angle analysis, whereas surface roughness was determined using atomic force microscopy. Significant differences in the ease of removal were observed between the various catheters, with the silicone-based materials generally exhibiting the greatest ease of removal. Similarly, the catheters exhibited a range of advancing and receding contact angles that were dependent on the chemical nature of each catheter. Finally, whilst the microrugosities of the various catheters differed, no specific relationship to the chemical nature of the biomaterial was apparent. Using multiple regression analysis, the relationship between ease of removal, receding contact angle and surface roughness was defined as: Work done (N mm) 17.18 + 0.055 Rugosity (nm)-0.52 Receding contact angle (degrees) (r = 0.49). Interestingly, whilst the relationship between ease of removal and surface roughness was significant (r = 0.48, p = 0.0005), in which catheter lubricity increased as the surface roughness decreased, this was not the case with the relationship between ease of removal and receding contact angle (r = -0.18, p > 0.05). This study has therefore uniquely defined the contributions of each of these surface properties to catheter lubricity. Accordingly, in the design of urethral catheters. it is recommended that due consideration should be directed towards biomaterial surface roughness to ensure maximal ease of catheter removal. Furthermore, using the method described in this study, differences in the lubricity of the various catheters were observed that may be apparent in their clinical use. (C) 2003 Elsevier Ltd. All rights reserved.

Measurement and interpretation of the mid-infrared properties of single crystal and polycrystalline gold

The contribution of electron-phonon scattering and grain boundary scattering to the mid-IR (lambda = 3.392 mum) properties of An has been assessed by examining both bulk, single crystal samples-Au(1 1 1) and Au(1 1 0)-and thin film, polycrystalline An samples at 300 K and 100 K by means of surface plasmon polariton excitation. The investigation constitutes a stringent test for the in-vacuo Otto-configuration prism coupler used to perform the measurements, illustrating its strengths and limitations. Analysis of the optical response is guided by a physically based interpretation of the Drude model. Relative to the reference case of single crystal Au at 100 K (epsilon = - 568 + i17.5), raising the temperature to 300 K causes increased electron-phonon scattering that accounts for a reduction of similar to40 nm in the electron mean free path. Comparison of a polycrystalline sample to the reference case determines a mean free path due to grain boundary scattering of similar to 17 nm, corresponding to about half the mean grain size as determined from atomic force microscopy and indicating a high reflectance coefficient for the An grain boundaries. An analysis combining consideration of grain boundary scattering and the inclusion of a small percentage of voids in the polycrystalline film by means of an effective medium model indicates a value for the grain boundary reflection coefficient in the range 0.55-0.71. (C) 2005 Elsevier B.V. All rights reserved.

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 similar to15 nm to similar to1 mum. 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 relative dielectric constant similar to40, and thickness of the order of tens of nanometers. For microstructures that were not purely columnar, models did not reproduce the observed dielectric behavior well. However, cross-sectional transmission electron microscopy indicated columnar microstructure, suggesting that grain boundary dead layers should be considered seriously in the overall dead-layer debate. (C) 2002 American Institute of Physics.

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.

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.

Plasma chloriding of thin-film silver - A novel process in silver-silver chloride reference electrode fabrication

Silver thin films were modified using a novel plasma modification process for the development of thin-film silver-silver chloride reference electrodes. The surface, physical, and electrochemical properties of these electrodes were investigated by atomic force microscopy, thickness and resistivity measurement techniques, as well as impedance spectroscopy and potentiometry. After plasma treatment, thin-film growth was observed and the electrodes, in general, exhibited low interface impedance and a roughened surface. Evidence of a complex surface reorganization was found. Correlating plasma conditions with film properties suggested that increasing pressure and exposure duration increased species availability, therefore governing the reaction rates, while input power appeared to influence the type of surface chemical reactions. Results also indicated that Ar/Cl-2 mixtures should be employed rather than pure chlorine plasmas. (C) 2002 The Electrochemical Society.

Self-affine crossover length in a layered silicate deposit

Self-affine dehydrated colloidal deposits on fresh mica surfaces of the synthetic layered silicate 2:1 smectite clay laponite have been studied by means of atomic force microscopy (AFM). AFM images of these prepared assemblies of sol and gel aggregates have been analyzed both by means of standard AFM Fourier software and a wavelet method. The deposited surfaces show a persistence to antipersistent crossover with a clay concentration dependent crossover length. It is concluded that the crossover length is associated with aggregate size, and further that the persistent roughness at small length scales signals near compact clusters of fractal dimension three, whereas the antipersistent roughness at large length scales signals a sedimentation process.

Domain Bundle Boundaries in Single Crystal BaTiO3 Lamellae: Searching for Naturally Forming Dipole Flux-Closure / Quadrupole Chains

Naturally occurring boundaries between bundles of 90o stripe domains, which form in BaTiO3 lamellae on cooling through the Curie Temperature, have been characterised using both piezoresponse force microscopy (PFM) and scanning transmission electron microscopy (STEM). Detailed interpretation of the dipole configurations present at these boundaries (using data taken from PFM) shows that, in the vast majority of cases, they are composed of simple zigzag 180° domain walls. Topological information from STEM shows that, occasionally, domain bundle boundaries can support chains of dipole flux closure and quadrupole nanostructures, but these kinds of boundaries are comparatively rare; when such chains do exist, it is notable that singularities at the cores of the dipole structures are avoided. The symmetry of the boundary shows that diads and centres of inversion exist at positions where core singularities should have been expected.

Scaling of Superdomain Bands in Ferroelectric Dots

Bundles of 90° stripe domains have been observed to form into distinct groups, or bands, in mesoscale BaTiO3 single crystal dots. Vector piezoresponse force microscopy (PFM) shows that each band region, when considered as a single entity, possesses a resolved polarization that lies approximately along the pseudocubic direction; antiparallel alignment of this resultant polarization in adjacent bands means that these regions can be considered as 180° “superdomains.” For dots with sidewall dimensions below ~2 microns, Landau–Kittel like scaling in the width of these superdomains was observed, strongly suggesting that they form in response to lateral depolarizing fields. In larger dot structures, scaling laws break down. We have rationalized these observations by considering changes in the driving force for the adoption of equilibrium superdomain periodicities implied by Landau–Kittel-free energy models; we conclude that the formation of ordered bands of superdomains is a uniquely meso/nanoscale phenomenon. We also note that the superdomain bands found by PFM imaging in air contrast with the quadrant arrangements seen previously by Schilling et al. (Nano Lett., 9, 3359 (2009)) through transmission electron microscopy imaging in vacuum. The importance of the exact nature of the boundary conditions in determining the domain patterns that spontaneously form in nanostructures is therefore clearly implied.

Mesoscale flux-closure domain formation in single-crystal BaTiO3

Over 60 years ago, Charles Kittel predicted that quadrant domains should spontaneously form in small ferromagnetic platelets. He expected that the direction of magnetization within each quadrant should lie parallel to the platelet surface, minimizing demagnetizing fields, and that magnetic moments should be configured into an overall closed loop, or flux-closure arrangement. Although now a ubiquitous observation in ferromagnets, obvious flux-closure patterns have been somewhat elusive in ferroelectric materials. This is despite the analogous behaviour between these two ferroic subgroups and the recent prediction of dipole closure states by atomistic simulations research. Here we show Piezoresponse Force Microscopy images of mesoscopic dipole closure patterns in free-standing, single-crystal lamellae of BaTiO3. Formation of these patterns is a dynamical process resulting from system relaxation after the BaTiO3 has been poled with a uniform electric field. The flux-closure states are composed of shape conserving 90° stripe domains which minimize disclination stresses.

Structural investigations and magnetic properties of sol-gel Ni0.5Zn0.5Fe2O4 thin films for microwave heating

Nanocrystalline Ni0.5Zn0.5Fe2O4 thin films have been synthesized with various grain sizes by a sol-gel method on polycrystalline silicon substrates. The morphology, magnetic, and microwave absorption properties of the films calcined in the 673-1073 K range were studied with x-ray diffraction, scanning electron microscopy, x-ray photoelectron spectroscopy, atomic force microscopy, vibrating sample magnetometry, and evanescent microwave microscopy. All films were uniform without microcracks. Increasing the calcination temperature from 873 to 1073 K and time from 1 to 3 h resulted in an increase of the grain size from 12 to 27 nm. The saturation and remnant magnetization increased with increasing the grain size, while the coercivity demonstrated a maximum near a critical grain size of 21 nm due to the transition from monodomain to multidomain behavior. The complex permittivity of the Ni-Zn ferrite films was measured in the frequency range of 2-15 GHz. The heating behavior was studied in a multimode microwave cavity at 2.4 GHz. The highest microwave heating rate in the temperature range of 315-355 K was observed in the film close to the critical grain size.

Domain Wall Propagation in Meso and Nanoscale Ferroelectrics

As part of an ongoing programme to evaluate the extent to which external morphology alters domain wall mobility in ferroelectrics, the electrical switching characteristics of single-crystal BaTiO3 nanorods and thin film plates have been measured and compared. It was found that ferroelectric nanorods were more readily switched than thin plates; increasing the shape constraint therefore appears to enhance switchability. This observation is broadly consistent with previous work, in which local notches patterned along the length of nanorods enhanced switching (McMillen et al 2010 Appl. Phys. Lett. 96 042904), while antinotches had the opposite effect (McQuaid et al 2010 Nano Lett. 10 3566). In this prior work, local enhancement and denudation of the electric field was expected at the notch and antinotch sites, respectively, and this was thought to be the reason for the differences in switching behaviour observed. However, for the simple nanorods and plates investigated here, no differences in the electric field distributions are expected. To rationalise the functional measurements, domain development during switching was imaged directly by piezoresponse force microscopy. A two-stage process was identified, in which narrow needle-like reverse domains initially form across the entire interelectrode gap and then subsequently coarsen through domain wall propagation perpendicular to the applied electric field. To be consistent with the electrical switching data, we suggest that the initial formation of needle domains occurs more readily in the nanorods than in the plates.

Domain annihilation due to temperature and thickness gradients in single-crystal BaTiO3

The manner in which 90? ferroelectric-ferroelastic domains respond to changes in temperature has been mapped in BaTiO3 single crystals using atomic force microscopy. Domain periodicity remains unaltered until approximately 2 ? C below the Curie temperature (TC ), whereupon domains coarsened dramatically. This behavior was successfully rationalized by considering the temperature dependence of the parameters associated with standard models of ferroelastic domain formation. However, while successful in describing the expected radical increase in equilibrium period with temperature, the model did not predict the unusual mechanism by which domain coarsening occurred; this was not continuous at a local level but instead involved discrete domain annihilation events. Subsequent insights from a combination of free energy analysis for the system and further experimental data from an analogous situation, in which domain period increases with increasing crystal thickness, suggested that domain annihilation is inevitable whenever a component of the relevant gradient that affects domain period is orientated parallel to the domain walls. Consistent with this thesis, we note that, for the observations presented herein, the thermal gradient possessed a significant component parallel to the domain walls. We suggest that domain annihilation is a general feature of domain structures in gradient fields.