Mark McMillen

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 bulklike, demonstrating a sharp Curie anomaly, as well as Curie–Weiss behavior. In addition, the sudden change in the remanent polarization 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 Saad et al. [J. Phys.: Condens. Matter 16, L451 (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 deposit...

Increasing recoverable energy storage in electroceramic capacitors using “dead-layer” engineering

The manner in which ultrathin films of alumina, deposited at the dielectric-electrode interface, affect the recoverable energy density associated with (BiFeO3)0.6–(SrTiO3)0.4 (BFST) thin film capacitors has been characterised. Approximately 6 nm of alumina on 400 nm of BFST increases the maximum recoverable energy of the system by around 30% from ∼13 Jcc−1 to ∼17 Jcc−1. Essentially, the alumina acts in the same way as a naturally present parasitic “dead-layer,” distorting the polarisation-field response such that the ultimate polarisation associated with the BFST is pushed to higher values of electric field. The work acts as a proof-of-principle to illustrate how the design of artificial interfacial dielectric “dead-layers” can increase energy densities in simple dielectric capacitors, allowing them to compete more generally with other energy storage technologies.

Application of AAO Matrix in Aligned Gold Nanorod Array Substrates for Surface-Enhanced Fluorescence and Raman Scattering

In this paper, we probed surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) from probe molecule Rhodamine 6G (R6G) on self-standing Au nanorod array substrates made using a combination of anodization and potentiostatic electrodeposition. The initial substrates were embedded within a porous alumina template (AAO). By controlling the thickness of the AAO matrix, SEF and SERS were observed exhibiting an inverse relationship. SERS and SEF showed a non-linear response to the removal of AAO matrix due to an inhomogeneous plasmon activity across the nanorod which was supported by FDTD calculations. We showed that by optimizing the level of AAO thickness, we could obtain either maximized SERS, SEF or simultaneously observe both SERS and SEF together.

The influence of point defects and inhomogeneous strain on the functional behavior 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.

Tuneable magneto-optical metamaterials based on photonic resonances in nickel nanorod arrays

We investigate the magneto-optical properties of a nanostructured metamaterial comprised of arrays of nickel nanorods embedded in an anodized aluminum oxide template. The rods are grown using a self-assembly bottom-up technique that provides a uniform, quasi-hexagonal array over a large area, quickly and at low cost. The tuneability of the magneto-optic response of the material is investigated by varying the nanorod dimensions: diameter, length and inter-rod spacing as well as the overall thickness of the template. It is demonstrated that the system acts as a sub-wavelength light trap with enhanced magneto-optical properties occurring at reflectivity minima corresponding to photonic resonances of the metamaterial. Changes in dimensions of the nickel rods on the order of tens of nanometers cause a spectral blue-shift in the peak magneto-optical response of 270 nm in the visible range. A plasmonic enhancement is also observed at lower wavelengths, which becomes increasingly damped with larger diameters and increased volume fraction of nickel inclusions. This type of structure has potential applications in high density magneto-optical data storage (up to 1011–12 rods per square inch), ultrafast magneto-plasmonic switching and optical components for telecommunications.

The influence of notches on domain dynamics in ferroelectric nanowires

The extent to which notches inhibit axial switching of polarization in ferroelectric nanowires was investigated by monitoring the switching behavior of single crystal BaTiO3 wires before and after patterning triangular notches along their lengths. Static zero-field domain patterns suggested a strong domain-notch interaction, implying that notches should act as pinning sites for domain wall propagation. Surprisingly though, notches appeared to assist, rather than inhibit, polar switching. The origin of this effect was rationalized using finite element modeling of the electric field distribution along the notched wire; it was found that the air gap associated with the notch acted to enhance the local field, both in the air, and in the adjacent region of the ferroelectric. It seems that this local field enhancement outweighs any pinning interactions.

Control over plasmon enhanced Raman and fluorescence from quasi free-standing Au nanorod arrays

Nanoscale structures made from coinage metals such as gold or silver possess localized surface plasmon-polariton (LSP) excitations when the material interacts with light of the correct frequency and polarization. LSPs generated from freestanding 2D nanorod arrays have been applied to enable surface-enhanced Raman scattering (SERS) and surface enhanced fluorescence (SEF) spectra from Rhodamine 6G molecules adsorbed on the surface of the arrays. We study the conditions that optimize SERS and SEF from self-standing Au nanorod arrays by studying the effect of changing the surrounding environment using Al2O3 as a dielectric spacer layer.

Effect of matrix on Raman scattering and luminescence in 2D gold nanorod arrays

In this paper we probe the surface enhanced fluorescence (SEF) and Raman scattering (SERS) from arrays of selfstanding Au nanorod arrays embedded within a porous alumina template (AAO). By controlling the thickness of the AAO matrix both SEF and SERS are observed exhibiting an inverse relationship. SERS and SEF show a nonlinear response to the removal of AAO matrix due to an inhomogeneous plasmon activity across the nanorod. Optimization of the level of alumina matrix thickness optimizes conditions for obtaining either maximized SERS, SEF or for simultaneously observing both SERS and SEF together.