Steven Randolph

Electron postgrowth irradiation of platinum-containing nanostructures grown by electron-beam-induced deposition from Pt(PF3)4

The material grown in a scanning electron microscope by electron beam-induced deposition (EBID) using Pt(PF3)4 precursor is shown to be electron beam sensitive. The effects of deposition time and postgrowth electron irradiation on the microstructure and resistivity of the deposits were assessed by transmission electron microscopy, selected area diffraction, and four-point probe resistivity measurements. The microstructure, notably the platinum nanocrystallite grain size, is shown to evolve with electron fluence in a controllable manner. The resistivity was observed to decrease as a result of postgrowth electron irradiation, with the lowest observed value of 215±15????cm. The authors demonstrate that electron beam-induced changes in microstructure can be caused using electron fluences similar to those used during the course of EBID and suggest that the observed effects can be used to tailor the microstructure and functionality of deposits grown by EBID in situ without breaking vacuum.

Liquid Phase Electron-Beam-Induced Deposition on Bulk Substrates Using Environmental Scanning Electron Microscopy

The introduction of gases, such as water vapor, into an environmental scanning electron microscope is common practice to assist in the imaging of insulating or biological materials. However, this capability may also be exploited to introduce, or form, liquid phase precursors for electron-beam-induced deposition. In this work, the authors report the deposition of silver (Ag) and copper (Cu) structures using two different cell-less in situ deposition methods--the first involving the in situ hydration of solid precursors and the second involving the insertion of liquid droplets using a capillary style liquid injection system. Critically, the inclusion of surfactants is shown to drastically improve pattern replication without diminishing the purity of the metal deposits. Surfactants are estimated to reduce the droplet contact angle to below ~10°.

Kinetics of gas mediated electron beam induced etching

Electron beam induced etching (EBIE) is a high resolution, direct write, chemical dry etch process in which surface-adsorbed precursor molecules are activated by an electron beam. We show that nanoscale EBIE is rate limited through at least two mechanisms ascribed to adsorbate depletion and the transport of gaseous precursor molecules into an etch pit during etching, respectively. The latter has, to date, not been accounted for in models of EBIE and is needed to reproduce etch kinetics which govern the time-evolution of etch pits, EBIE throughput, and spatial resolution.

Maskless milling of diamond by a focused oxygen ion beam

Recent advances in focused ion beam technology have enabled high-resolution, maskless nanofabrication using light ions. Studies with light ions to date have, however, focused on milling of materials where sub-surface ion beam damage does not inhibit device performance. Here we report on maskless milling of single crystal diamond using a focused beam of oxygen ions. Material quality is assessed by Raman and luminescence analysis, and reveals that the damage layer generated by oxygen ions can be removed by non-intrusive post-processing methods such as localised electron beam induced chemical etching.

Capsule-free fluid delivery and beam-induced electrodeposition in a scanning electron microscope

Gold coated borosilicate nanocapillaries are used to locally deliver aqueous, electrolytic CuSO4 solution into the low vacuum chamber of an environmental scanning electron microscope (ESEM). Capillary flow of the liquid is induced by bringing a nanocapillary into contact with a substrate. A microscopic droplet is stabilized by controlling the droplet evaporation rate with the substrate temperature and the pressure of H2O vapor injected into the vacuum chamber. An electron beam is admitted to the droplet through a pressure limiting aperture. Electrochemical reduction of aqueous Cu2+ to solid, high purity, deposited Cu is achieved by biasing the nanocapillary and supplying current by the beam which acts as a virtual cathode and enables electrodeposition on both conductive and insulating substrates. Delivery of liquids into vacuum enables localized, capsule-free beam induced electrochemistry, opening new pathways for direct-write nano and micro-lithography via beam induced electrodeposition.

Robust, directed assembly of fluorescent nanodiamonds

Arrays of fluorescent nanoparticles are highly sought after for applications in sensing, nanophotonics and quantum communications. Here we present a simple and robust method of assembling fluorescent nanodiamonds into macroscopic arrays. Remarkably, the yield of this directed assembly process is greater than 90% and the assembled patterns withstand ultra-sonication for more than three hours. The assembly process is based on covalent bonding of carboxyl to amine functional carbon seeds and is applicable to any material, and to non-planar surfaces. Our results pave the way to directed assembly of sensors and nanophotonics devices.

Radiation-Induced Damage and Recovery of Ultra-Nanocrystalline Diamond: Toward Applications in Harsh Environments

Ultra-nanocrystalline diamond (UNCD) is increasingly being used in the fabrication of devices and coatings due to its excellent tribological properties, corrosion resistance, and biocompatibility. Here, we study its response to irradiation with kiloelectronvolt electrons as a controlled model for extreme ionizing environments. Real time Raman spectroscopy reveals that the radiation-damage mechanism entails dehydrogenation of UNCD grain boundaries, and we show that the damage can be recovered by annealing at 883 K. Our results have significant practical implications for the implementation of UNCD in extreme environment applications, and indicate that the films can be used as radiation sensors.