M Munde

Nanoscale transformations in metastable, amorphous, silicon-rich silica

Electrically biasing thin films of amorphous, substoichiometric silicon oxide drives surprisingly large structural changes, apparent as density variations, oxygen movement, and ultimately, emission of superoxide ions. Results from this fundamental study are directly relevant to materials that are increasingly used in a range of technologies, and demonstrate a surprising level of field-driven local reordering of a random oxide network.

Intrinsic Resistance Switching in Amorphous Silicon Suboxides: The Role of Columnar Microstructure

We studied intrinsic resistance switching behaviour in sputter-deposited amorphous silicon suboxide (a-SiOx) films with varying degrees of roughness at the oxide-electrode interface. By combining electrical probing measurements, atomic force microscopy (AFM), and scanning transmission electron microscopy (STEM), we observe that devices with rougher oxide-electrode interfaces exhibit lower electroforming voltages and more reliable switching behaviour. We show that rougher interfaces are consistent with enhanced columnar microstructure in the oxide layer. Our results suggest that columnar microstructure in the oxide will be a key factor to consider for the optimization of future SiOx-based resistance random access memory.

Diffusion and aggregation of oxygen vacancies in amorphous silica

Using density functional theory (DFT) calculations, we investigated oxygen vacancy diffusion and aggregation in relation to dielectric breakdown in amorphous silicon dioxide (a-SiO2). Our calculations indicate the existence of favourable sites for the formation of vacancy dimers and trimers in the amorphous network with maximum binding energies of approximately 0.13 eV and 0.18 eV, respectively. However, an average energy barrier height for neutral vacancy diffusion is found to be about 4.6 eV, rendering this process unfeasible. At Fermi level positions above 6.4 eV with respect to the top of the valence band, oxygen vacancies can trap up to two extra electrons. Average barriers for the diffusion of negative and double negatively charged vacancies are found to be 2.7 eV and 2.0 eV, respectively. These barriers are higher than or comparable to thermal ionization energies of extra electrons from oxygen vacancies into the conduction band of a-SiO2. In addition, we discuss the competing pathways for electron trapping in oxygen deficient a-SiO2 caused by the existence of intrinsic electron traps and oxygen vacancies. These results provide new insights into the role of oxygen vacancies in degradation and dielectric breakdown in amorphous silicon oxides.

In situ transmission electron microscopy of resistive switching in thin silicon oxide layers

Silicon oxide-based resistive switching devices show great potential for applications in nonvolatile random access memories. We expose a device to voltages above hard breakdown and show that hard oxide breakdown results in mixing of the SiOx layer and the TiN lower contact layers. We switch a similar device at sub-breakdown fields in situ in the transmission electron microscope (TEM) using a movable probe and study the diffusion mechanism that leads to resistance switching. By recording bright-field (BF) TEM movies while switching the device, we observe the creation of a filament that is correlated with a change in conductivity of the SiOx layer. We also examine a device prepared on a microfabricated chip and show that variations in electrostatic potential in the SiOx layer can be recorded using off-axis electron holography as the sample is switched in situ in the TEM. Taken together, the visualization of compositional changes in ex situ stressed samples and the simultaneous observation of BF TEM contrast...

The interplay between structure and function in redox-based resistance switching

We report a study of the relationship between oxide microstructure at the scale of tens of nanometres and resistance switching behaviour in silicon oxide. In the case of sputtered amorphous oxides, the presence of columnar structure enables efficient resistance switching by providing an initial structured distribution of defects that can act as precursors for the formation of chains of conductive oxygen vacancies under the application of appropriate electrical bias. Increasing electrode interface roughness decreases electroforming voltages and reduces the distribution of switching voltages. Any contribution to these effects from field enhancement at rough interfaces is secondary to changes in oxide microstructure templated by interface structure.

Electrospun fabrication of one-dimensional composite nanofibres using colloidal gold/polymer aqueous blends

We successfully demonstrate the facile fabrication of composite polymer/gold nanofibres using the electrospinning technique and show their physical characterization. Scanning Electron Microscopy (SEM) revealed the consistent structural fabrication of uniform nanofibres, and high-resolution Scanning Transmission Electron Microscopy (HR-STEM) images, in both bright field (BF-STEM) and dark field (DF-STEM) modes exposed nanoparticle dispersions in the polymer matrix. There is a critical need for establishing processing methods that are effective on the nanoscale yet are applicable to macroscopic processing; the findings presented here demonstrate that the electrospinning process provides a straightforward technique to fabricate arrays of nanoparticles and potentially functional nanoassemblies for future nanodevices.