Continuous advancement in nonvolatile and morphotropic beyond-Moore electronic devices requires integration of ferroelectric and semiconductor materials. The emergence of hafnium oxide (HfO ₂ )–based ferroelectrics that are compatible with atomic-layer deposition has opened interesting and promising avenues of research. However, the origins of ferroelectricity and pathways to controlling it in HfO ₂ are still mysterious. We demonstrate that local helium (He) implantation can activate ferroelectricity in these materials. The possible competing mechanisms, including He ion–induced molar volume changes, vacancy redistribution, vacancy generation, and activation of vacancy mobility, are analyzed. These findings both reveal the origins of ferroelectricity in this system and open pathways for nanoengineered binary ferroelectrics.

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°.

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.

Selected area deposition of high purity gold films onto nanoscale 3D architectures is highly desirable as gold is conductive, inert, plasmonically active, and can be functionalized with thiol chemistries, which are useful in many biological applications. Here, we show that high-purity gold coatings can be selectively grown with the Me₂Au (acac) precursor onto nanoscale 3D architectures via a pulsed laser pyrolytic chemical vapor deposition process. The selected area of deposition is achieved due to the high thermal resistance of the nanoscale geometries. Focused electron beam induced deposits (FEBID) and carbon nanofibers are functionalized with gold coatings, and we demonstrate the effects that laser irradiance, pulse width, and precursor pressure have on the growth rate. Furthermore, we demonstrate selected area deposition with a feature-targeting resolutions of ~100 and 5 µm, using diode lasers coupled to a multimode (915 nm) and single mode (785 nm) fiber optic, respectively. The experimental results are rationalized via finite element thermal modeling.

Focused electron beam induced etching (FEBIE) of Nb films produced a maximum etching yield of 3 Nb atoms/e⁻ while varying beam energy, beam current, dwell time, and XeF₂ precursor working pressure. An optimized etch resolution of 17 nm was achieved.