Michael G. Stanford

Simulation-Guided 3D Nanomanufacturing via Focused Electron Beam Induced Deposition

Focused electron beam induced deposition (FEBID) is one of the few techniques that enables direct-write synthesis of free-standing 3D nanostructures. While the fabrication of simple architectures such as vertical or curving nanowires has been achieved by simple trial and error, processing complex 3D structures is not tractable with this approach. In part, this is due to the dynamic interplay between electron-solid interactions and the transient spatial distribution of absorbed precursor molecules on the solid surface. Here, we demonstrate the ability to controllably deposit 3D lattice structures at the micro/nanoscale, which have received recent interest owing to superior mechanical and optical properties. A hybrid Monte Carlo-continuum simulation is briefly overviewed, and subsequently FEBID experiments and simulations are directly compared. Finally, a 3D computer-aided design (CAD) program is introduced, which generates the beam parameters necessary for FEBID by both simulation and experiment. Using this approach, we demonstrate the fabrication of various 3D lattice structures using Pt-, Au-, and W-based precursors.

Purification of nanoscale electron-beam-induced platinum deposits via a pulsed laser-induced oxidation reaction.

Platinum-carbon deposits made via electron-beam-induced deposition were purified via a pulsed laser-induced oxidation reaction and erosion of the amorphous carbon to form pure platinum. Purification proceeds from the top down and is likely catalytically facilitated via the evolving platinum layer. Thermal simulations suggest a temperature threshold of ∼485 K, and the purification rate is a function of the PtC5 thickness (80-360 nm) and laser pulse width (1-100 μs) in the ranges studied. The thickness dependence is attributed to the ∼235 nm penetration depth of the PtC5 composite at the laser wavelength, and the pulse-width dependence is attributed to the increased temperatures achieved at longer pulse widths. Remarkably fast purification is realized at cumulative laser exposure times of less than 1 s.

Focused helium-ion beam irradiation effects on electrical transport properties of few-layer WSe2: Enabling nanoscale direct write homo-junctions

Atomically thin transition metal dichalcogenides (TMDs) are currently receiving significant attention due to their promising opto-electronic properties. Tuning optical and electrical properties of mono and few-layer TMDs, such as tungsten diselenide (WSe2), by controlling the defects, is an intriguing opportunity to synthesize next generation two dimensional material opto-electronic devices. Here, we report the effects of focused helium ion beam irradiation on the structural, optical and electrical properties of few-layer WSe2, via high resolution scanning transmission electron microscopy, Raman spectroscopy, and electrical transport measurements. By controlling the ion irradiation dose, we selectively introduce precise defects in few-layer WSe2 thereby locally tuning the resistivity and transport properties of the material. Hole transport in the few layer WSe2 is degraded more severely relative to electron transport after helium ion irradiation. Furthermore, by selectively exposing material with the ion beam, we demonstrate a simple yet highly tunable method to create lateral homo-junctions in few layer WSe2 flakes, which constitutes an important advance towards two dimensional opto-electronic devices.

In Situ Mitigation of Subsurface and Peripheral Focused Ion Beam Damage via Simultaneous Pulsed Laser Heating.

Focused helium and neon ion (He(+)/Ne(+)) beam processing has recently been used to push resolution limits of direct-write nanoscale synthesis. The ubiquitous insertion of focused He(+)/Ne(+) beams as the next-generation nanofabrication tool-of-choice is currently limited by deleterious subsurface and peripheral damage induced by the energetic ions in the underlying substrate. The in situ mitigation of subsurface damage induced by He(+)/Ne(+) ion exposures in silicon via a synchronized infrared pulsed laser-assisted process is demonstrated. The pulsed laser assist provides highly localized in situ photothermal energy which reduces the implantation and defect concentration by greater than 90%. The laser-assisted exposure process is also shown to reduce peripheral defects in He(+) patterned graphene, which makes this process an attractive candidate for direct-write patterning of 2D materials. These results offer a necessary solution for the applicability of high-resolution direct-write nanoscale material processing via focused ion beams.

Nanoforging Single Layer MoSe2 Through Defect Engineering with Focused Helium Ion Beams.

Development of devices and structures based on the layered 2D materials critically hinges on the capability to induce, control, and tailor the electronic, transport, and optoelectronic properties via defect engineering, much like doping strategies have enabled semiconductor electronics and forging enabled introduction the of iron age. Here, we demonstrate the use of a scanning helium ion microscope (HIM) for tailoring the functionality of single layer MoSe2 locally, and decipher associated mechanisms at the atomic level. We demonstrate He+ beam bombardment that locally creates vacancies, shifts the Fermi energy landscape and increases the Young’s modulus of elasticity. Furthermore, we observe for the first time, an increase in the B-exciton photoluminescence signal from the nanoforged regions at the room temperature. The approach for precise defect engineering demonstrated here opens opportunities for creating functional 2D optoelectronic devices with a wide range of customizable properties that include operating in the visible region.

High Seebeck effects from conducting polymer: Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) based thin-film device with hybrid metal/polymer/metal architecture

Conductive polymers are of particular interest for thermoelectric applications due to their low thermal conductivity and relatively high electrical conductivity. In this study, commercially available conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) was used in a hybrid metal/polymer/metal thin film design in order to achieve a high Seebeck coefficient with the value of 252 μV/k on a relatively low temperature scale. Polymer film thickness was varied in order to investigate its influence on the Seebeck effect. The high Seebeck coefficient indicates that the metal/polymer/metal design can develop a large entropy difference in internal energy of charge carriers between high and low-temperature metal electrodes to develop electrical potential due to charge transport in conducting polymer film through metal/polymer interface. Therefore, the metal/polymer/metal structure presents a new design to combine inorganic metals and organic polymers in thin-film form to develop Seebeck devices.

Electron-stimulated purification of platinum nanostructures grown via focused electron beam induced deposition

Summary Platinum–carbon nanostructures deposited via electron beam induced deposition from MeCpPt(IV)Me3 are purified during a post-deposition electron exposure treatment in a localized oxygen ambient at room temperature. Time-dependent studies demonstrate that the process occurs from the top–down. Electron beam energy and current studies demonstrate that the process is controlled by a confluence of the electron energy loss and oxygen concentration. Furthermore, the experimental results are modeled as a 2nd order reaction which is dependent on both the electron energy loss density and the oxygen concentration. In addition to purification, the post-deposition electron stimulated oxygen purification process enhances the resolution of the EBID process due to the isotropic carbon removal from the as-deposited materials which produces high-fidelity shape retention.

High performance top-gated multilayer WSe2 field effect transistors

In this paper, high performance top-gated WSe2 field effect transistor (FET) devices are demonstrated via a two-step remote plasma assisted ALD process. High-quality, low-leakage aluminum oxide (Al2O3) gate dielectric layers are deposited onto the WSe2 channel using a remote plasma assisted ALD process with an ultrathin (∼1 nm) titanium buffer layer. The first few nanometers (∼2 nm) of the Al2O3 dielectric film is deposited at relatively low temperature (i.e. 50 °C) and remainder of the film is deposited at 150 °C to ensure the conformal coating of Al2O3 on the WSe2 surface. Additionally, an ultra-thin titanium buffer layer is introduced at the WSe2 channel surface prior to ALD process to mitigate oxygen plasma induced doping effects. Excellent device characteristics with current on-off ratio in excess of 106 and a field effect mobility as high as 70.1 cm2 V-1 s-1 are achieved in a few-layer WSe2 FET device with a 30 nm Al2O3 top-gate dielectric. With further investigation and careful optimization, this method can play an important role for the realization of high performance top gated FETs for future optoelectronic device applications.

Laser-assisted focused He+ ion beam induced etching with and without XeF2 gas assist

Focused helium ion (He+) milling has been demonstrated as a high-resolution nanopatterning technique; however, it can be limited by its low sputter yield as well as the introduction of undesired subsurface damage. Here, we introduce pulsed laser- and gas-assisted processes to enhance the material removal rate and patterning fidelity. A pulsed laser-assisted He+ milling process is shown to enable high-resolution milling of titanium while reducing subsurface damage in situ. Gas-assisted focused ion beam induced etching (FIBIE) of Ti is also demonstrated in which the XeF2 precursor provides a chemical assist for enhanced material removal rate. Finally, a pulsed laser-assisted and gas-assisted FIBIE process is shown to increase the etch yield by ∼9× relative to the pure He+ sputtering process. These He+ induced nanopatterning techniques improve material removal rate, in comparison to standard He+ sputtering, while simultaneously decreasing subsurface damage, thus extending the applicability of the He+ probe as a nanopattering tool.

Inert gas enhanced laser-assisted purification of platinum electron-beam-induced deposits

Electron-beam-induced deposition patterns, with composition of PtC5, were purified using a pulsed laser-induced purification reaction to erode the amorphous carbon matrix and form pure platinum deposits. Enhanced mobility of residual H2O molecules via a localized injection of inert Ar-H2 (4%) is attributed to be the reactive gas species for purification of the deposits. Surface purification of deposits was realized at laser exposure times as low as 0.1 s. The ex situ purification reaction in the deposit interior was shown to be rate-limited by reactive gas diffusion into the deposit, and deposit contraction associated with the purification process caused some loss of shape retention. To circumvent the intrinsic flaws of the ex situ anneal process, in situ deposition and purification techniques were explored that resemble a direct write atomic layer deposition (ALD) process. First, we explored a laser-assisted electron-beam-induced deposition (LAEBID) process augmented with reactive gas that resulted in a 75% carbon reduction compared to standard EBID. A sequential deposition plus purification process was also developed and resulted in deposition of pure platinum deposits with high fidelity and shape retention.