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We demonstrate direct-write patterning of single and multilayer MoS 2 via a focused electron beam-induced etching (FEBIE) process mediated with the XeF 2 precursor. MoS 2 etching is performed at various currents, areal doses, on different substrates, and characterized using scanning electron and atomic force microscopies as well as Raman and photoluminescence spectroscopies. Scanning transmission electron microscopy reveals a sub-40 nm etching resolution and the progression of point defects and lateral etching of the consequent unsaturated bonds. The results confirm that the electron beam-induced etching process is minimally invasive to the underlying material in comparison to ion beam techniques, which damage the subsurface material. Single-layer MoS 2 field-effect transistors are fabricated, and device characteristics are compared for channels that are edited via the selected area etching process. The source-drain current at constant gate and source-drain voltage scale linearly with the edited channel width. Moreover, the mobility of the narrowest channel width decreases, suggesting that backscattered and secondary electrons collaterally affect the periphery of the removed area. Focused electron beam doses on single-layer transistors below the etching threshold were also explored as a means to modify/thin the channel layer. The FEBIE exposures showed demonstrative effects via the transistor transfer characteristics, photoluminescence spectroscopy, and Raman spectroscopy. While strategies to minimize backscattered and secondary electron interactions outside of the scanned regions require further investigation, here, we show that FEBIE is a viable approach for selective nanoscale editing of MoS 2 devices.

The chemical composition and morphology of Au x Co 1- x thin films and nanoparticles are controlled via a combination of cosputtering, pulsed laser-induced dewetting (PLiD), and annealing, leading to tunable magnetic and optical properties. Regardless of chemical composition, the as-deposited thin films and as-PLiD nanoparticles are found to possess a face-centered cubic (FCC) Au x Co 1- x solid-solution crystal structure. Annealing results in large phase-separated grains of Au and Co in both the thin films and nanostructures for all chemical compositions. The magnetic and optical properties are characterized via vibrating sample magnetometry (VSM), ellipsometry, optical transmission spectroscopy, and electron energy loss spectroscopy (EELS). Despite the exceptionally high magnetic anisotropy inherent to Co, the presence of sufficient Au (72 atom %) in the Au x Co 1- x solid solution results in superparamagnetic thin films. Among the as-PLiD nanoparticle samples, an increased Co composition leads to a departure from traditional ferromagnetism in favor of wasp-waisted hysteresis caused by magnetic vortices. Phase separation resulting from annealing leads to ferromagnetism for all compositions in both the thin films and nanoparticles. The optical properties of Au x Co 1- x nanostructures are also largely influenced by the chemical morphology, where the Au x Co 1- x intermixed solid solution has significantly damped plasmonic performance relative to pure Au and comparable to pure Co. Phase separation greatly enhances the quality factor, optical absorption, and electron energy loss spectroscopy (EELS) signatures. The enhancement of the localized surface plasmon resonances (LSPRs) scales with the reduction in Co composition, despite EELS evidence that excitation of the Co portions of a nanoparticle can provide a similar, and in some instances enhanced, LSPR resonance compared to Au. This behavior, however, is seemingly limited to the LSPR dipole mode, while higher-order modes are greatly damped by a Co aloof position. This observed magneto-plasmonic functionality and tunability could be applicable in biomedicine, namely, cancer therapeutics.

Laser-induced graphene (LIG) is a multifunctional graphene foam that is commonly direct-written with an infrared laser into a carbon-based precursor material. Here, a visible 405 nm laser is used to directly convert polyimide into LIG. This enabled the formation of LIG with a spatial resolution of ∼12 μm and a thickness of <5 μm. The spatial resolution enabled by the relatively smaller focused spot size of the 405 nm laser represents a >60% reduction in LIG feature sizes reported in prior publications. This process occurs in situ in an SEM chamber, thus allowing direct observation of LIG formation. The reduced size of the LIG features enables the direct-write formation of flexible electronics that are not visible to the unaided eye. A humidity sensor is demonstrated which could detect human breath with a response time of 250 ms. With the growing interest in LIG for flexible electronics and sensors, finer features can greatly expand its utility.

Controlled O 2 /Ar plasma exposure and subsequent low temperature inert atmosphere annealing of chemical vapor deposition (CVD) grown PdSe 2 flakes etch PdSe 2 layer-by-layer in an atomic layer etching-like (ALE) process. X-ray photoelectron spectroscopy (XPS) shows that exposure to a remote inductively coupled plasma (ICP) oxygen plasma oxidizes the top layer of the PdSe 2 to form PdO 2 and SeO 2 . After an in situ annealing, XPS shows no trace of PdO 2 or SeO 2 , suggesting the byproducts are volatile at low temperature. Atomic force microscopy of PdSe 2 exposed to various O 2 + Ar plasmas (O 2 = 25-100%) demonstrates a clear trend between the oxygen concentration and the number of layers etched per cycle. PdSe 2 field effect transistors (FETs) were characterized at various stages of two ALE-like cycles, and the electrical properties are correlated to the oxidation and byproduct desorption and layer reduction.

Ionic liquids (ILs) have been investigated extensively because of their unique ability to form the electric double layer (EDL), which induces high electrical field. For certain materials, low-temperature IL charging is needed to limit the electrochemical etching. Here, we report our investigation of the low-temperature charging dynamics in two widely used ILs-DEME-TF 2 N and C 4 mim-TF 2 N. Results show that the formation of the EDL at ∼220 K requires several hours relative to milliseconds at room temperature, and an equivalent voltage V e is introduced as a measure of the EDL formation during the biasing process. The experimental observation is supported by molecular dynamics simulation, which shows that the dynamics are logically a function of gate voltage, time, and temperature. To demonstrate the importance of understanding the charging dynamics, a 140 nm thick FeSe 0.5 Te 0.5 film was biased using the DEME IL, showing a tunable T c between 18 and 35 K. Notably, this is the first observation of the tunability of the T c in thick film FeSe 0.5 Te 0.5 superconductors.

Most studies of ionic liquid (IL)-gated field effect transistors (FETs) focus on the extremely large electric field and capacitance induced in liquid/solid interfaces and correspondingly the significantly enhanced carrier density in semiconductors, which can appreciably improve the gating performance. However, how to boost the switching speed, another key property of gating performance of FETs, has been rarely explored. In this work, the gating performance of molybdenum disulfide (MoS 2 ) FETs, gated by the mixtures of IL/organic solvent (1-butyl-3-methylimidazolium tetrafluoroborate/acetonitrile, [Bmim][BF 4 ]/ACN) at different ion concentrations, is investigated for both dynamic and static properties by a combination of molecular dynamics simulation and resistance network analysis. Results reveal that organic solvent can speed up the IL response time by a factor of about 40 times at the optimal ion concentration of 1.94 M, which is mainly attributed to the increased ionic conductivity of IL via the addition of organic solvent. Meanwhile, the surface charge distribution of MoS 2 becomes more homogenous after the addition of organic solvent, which increases the conductivity of MoS 2 by up to 2.4 times. Surprisingly, the optimal ion concentration for increased switching speed is nearly the same as that for achieving the highest MoS 2 conductivity. Thus, our findings provide a strategy to simultaneously improve the dynamic and static gating performance of IL-gated FETs as well as a modeling technique to screen out the ideal ion concentration.

In electric double-layer transistors (EDLTs), it is well known that the EDL formed by ionic liquids (ILs) can induce an ultrahigh carrier density at the semiconductor surface, compared to solid dielectric. However, the mechanism of device performance is still not fully understood, especially at a molecular level. Here, we evaluate the gating performance of amorphous indium gallium zinc oxide (a-IGZO) transistor coupled with a series of imidazolium-based ILs, using an approach combining of molecular dynamics simulation and finite element modeling. Results reveal that the EDL with different ion structures could produce inhomogeneous electric fields at the solid-electrolyte interface, and the heterogeneity of electric field-induced charge distributions at semiconductor surface could reduce the electrical conductance of a-IGZO during gating process. Meanwhile, a resistance network analysis was adopted to bridge the nanoscopic data with the macroscopic transfer characteristics of IL-gated transistor, and showed that our theoretical results could well estimate the gating performance of practical devices. Thereby, our findings could provide both new concepts and modeling techniques for IL-gated transistors.

Atmospheric and long-term aging effects on electrical properties of WSe 2 transistors with various thicknesses are examined. Although countless published studies report electrical properties of transition-metal dichalcogenide materials, many are not attentive to testing environment or to age of samples, which we have found significantly impacts results. Our as-fabricated exfoliated WSe 2 pristine devices are predominantly n-type, which is attributed to selenium vacancies. Transfer characteristics of as-fabricated devices measured in air then vacuum reveal physisorbed atmospheric molecules significantly reduced n-type conduction in air. First-principles calculations suggest this short-term reversible atmospheric effect can be attributed primarily to physisorbed H 2 O on pristine WSe 2 , which is easily removed from the pristine surface in vacuum due to the low adsorption energy. Devices aged in air for over 300 h demonstrate irreversibly increased p-type conduction and decreased n-type conduction. Additionally, they develop an extended time constant for recovery of the atmospheric adsorbents effect. Short-term atmospheric aging (up to approximately 900 h) is attributed to O 2 and H 2 O molecules physisorbed to selenium vacancies where electron transfer from the bulk and adsorbed binding energies are higher than the H 2 O-pristine WSe 2 . The residual/permanent aging component is attributed to electron trapping molecular O 2 and isoelectronic O chemisorption at selenium vacancies, which also passivates the near-conduction band gap state, p-doping the material, with very high binding energy. All effects demonstrated have the expected thickness dependence, namely, thinner devices are more sensitive to atmospheric and long-term aging effects.

The formation of an electric double layer in ionic liquid (IL) can electrostatically induce charge carriers and/or intercalate ions in and out of the lattice which can trigger a large change of the electronic, optical, and magnetic properties of materials and even modify the crystal structure. We present a systematic study of ionic liquid gating of exfoliated 2D molybdenum trioxide (MoO 3 ) devices and correlate the resultant electrical properties to the electrochemical doping via ion migration during the IL biasing process. A nearly 9 orders of magnitude modulation of the MoO 3 conductivity is obtained for the two types of ionic liquids that are investigated. In addition, notably rapid on/off switching was realized through a lithium-containing ionic liquid whereas much slower modulation was induced via oxygen extraction/intercalation. Time of flight-secondary ion mass spectrometry confirms the Li intercalation. Density functional theory (DFT) calculations have been carried out to examine the underlying metallization mechanism. Results of short-pulse tests show the potential of these MoO 3 devices as neuromorphic computing elements due to their synaptic plasticity.

Ionic liquid gating of transition metal oxides has enabled new states (magnetic, electronic, metal-insulator), providing fundamental insights into the physics of strongly correlated oxides. However, despite much research activity, little is known about the correlation of the structure of the liquids in contact with the transition metal oxide surface, its evolution with the applied electric potential, and its correlation with the measured electronic properties of the oxide. Here, we investigate the structure of an ionic liquid at a semiconducting oxide interface during the operation of a thin film transistor where the electrical double layer gates the device using experiment and theory. We show that the transition between the ON and OFF states of the amorphous indium gallium zinc oxide transistor is accompanied by a densification and preferential spatial orientation of counterions at the oxide channel surface. This process occurs in three distinct steps, corresponding to ion orientations, and consequently, regimes of different electrical conductivity. The reason for this can be found in the surface charge densities on the oxide surface when different ion arrangements are present. Overall, the field-effect gating process is elucidated in terms of the interfacial ionic liquid structure, and this provides unprecedented insight into the working of a liquid gated transistor linking the nanoscopic structure to the functional properties. This knowledge will enable both new ionic liquid design as well as advanced device concepts.

Amorphous indium gallium zinc oxide (a-IGZO) is a transparent semiconductor which has demonstrated excellent electrical performance as thin-film transistors (TFTs). However, a high-temperature activation process is generally required which is incompatible for next-generation flexible electronic applications. In this work, He + irradiation is demonstrated as an athermal activation process for a-IGZO TFTs. Controlling the He + dose enables the tuning of charge density, and a dose of 1 × 10 14 He + /cm 2 induces a change in charge density of 2.3 × 10 12 cm -2 . Time-dependent transport measurements and time-of-flight secondary ion mass spectroscopy (ToF-SIMS) indicate that the He + -induced trapped charge is introduced because of preferential oxygen-vacancy generation. Scanning microwave impedance microscopy confirms that He + irradiation improves the conductivity of the a-IGZO. For realization of a permanent activation, IGZO was exposed with a He + dose of 5 × 10 14 He + /cm 2 and then aged 24 h to allow decay of the trapped oxide charge originating for electron-hole pair generation. The resultant shift in the charge density is primarily attributed to oxygen vacancies generated by He + sputtering in the near-surface region.

During the past decade, significant progress has been made in the field of resonant optics ranging from fundamental aspects to concrete applications. While several techniques have been introduced for the fabrication of highly defined metallic nanostructures, the synthesis of complex, free-standing three-dimensional (3D) structures is still an intriguing, but so far intractable, challenge. In this study, we demonstrate a 3D direct-write synthesis approach that addresses this challenge. Specifically, we succeeded in the direct-write fabrication of 3D nanoarchitectures via electron-stimulated reactions, which are applicable on virtually any material and surface morphology. By that, complex 3D nanostructures composed of highly compact, pure gold can be fabricated, which reveal strong plasmonic activity and pave the way for a new generation of 3D nanoplasmonic architectures that can be printed on-demand.

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 XeF 2 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.

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.

Emerging applications for nanoscale materials demand precise deposit shape retention from design to deposition. This study investigates the effects that disrupt high-fidelity shapes during focused electron beam induced nanosynthesis. It is shown that process parameters, patterning strategies and deposit topography can impose lateral precursor coverage gradients during growth resulting in unwanted topographic artifacts. The study classifies the evolving surface shapes into four general types and explains the formation and transition from a fundamental point of view. Continuum model calculations and simulations expand the experimental results to provide a comprehensive insight into understand the disruption mechanism. The findings demonstrate that the well-established concept of growth regimes has to be expanded by its lateral gradients as they strongly influence final shape fidelities. Finally, the study is complemented by a compensation strategy that improves the edge fidelity on the lower nanoscale to further push this technique toward the intrinsic limitations.

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.

In this study, we focus on the resolution limits for quasi 2-D single lines synthesized via focused electron-beam-induced direct-write deposition at 5 and 30 keV in a scanning electron microscope. To understand the relevant proximal broadening effects, the substrates were thicker than the beam penetration depth and we used the MeCpPt(IV)Me3 precursor under standard gas injection system conditions. It is shown by experiment and simulation how backscatter electron yields increase during the initial growth stages which broaden the single lines consistent with the backscatter range of the deposited material. By this it is shown that the beam diameter together with the evolving backscatter radius of the deposit material determines the achievable line widths even for ultrathin deposit heights in the sub-5-nm regime.

Directed assembly of nanomaterials is a promising route for the synthesis of nanoscale materials. In this paper, we demonstrate the directed-assembly of highly ordered two-dimensional arrays of hierarchical nanostructures with tunable size, spacing and composition. The directed assembly is achieved on lithographically patterned metal films that are subsequently pulse-laser melted; during the brief liquid lifetime, the pattened nanostructures assemble into highly ordered primary and secondary nanoparticles, with sizes below that which was originally patterned. Complementary fluid-dynamics simulations emulate the resultant patterns and show how the competition of capillary forces and liquid metal-solid substrate interaction potential drives the directed assembly. As an example of the enhanced functionality, a full-wave electromagnetic analysis has been performed to identify the nature of the supported plasmonic resonances.

The gas flux direction in focused electron beam induced processes can strongly destabilize the morphology on the nanometer scale. We demonstrate how pattern parameters such as position relative to the gas nozzle, axial rotation, scanning direction, and patterning sequence result in different growth modes for identical structures. This is mainly caused by nanoscale geometric shadowing, particularly when shadowing distances are comparable to surface diffusion lengths of (CH3)3-Pt-CpCH3 adsorbates. Furthermore, two different adsorbate replenishment mechanisms exist and are governed by either surface diffusion or directional gas flux adsorption. The experimental study is complemented by calculations and dynamic growth simulations which successfully emulate the observed morphology instabilities and support the proposed growth model.

Nanoscale metal deposits written directly by electron-beam-induced deposition, or EBID, are typically contaminated because of the incomplete removal of the original organometallic precursor. This has greatly limited the applicability of EBID materials synthesis, constraining the otherwise powerful direct-write synthesis paradigm. We demonstrate a low-temperature purification method in which platinum-carbon nanostructures deposited from MeCpPtIVMe3 are purified by the presence of oxygen gas during a post-electron exposure treatment. Deposit thickness, oxygen pressure, and oxygen temperature studies suggest that the dominant mechanism is the electron-stimulated reaction of oxygen molecules adsorbed at the defective deposit surface. Notably, pure platinum deposits with low resistivity and retain the original deposit fidelity were accomplished at an oxygen temperature of only 50 °C.

The directed assembly of arrayed nanoparticles is demonstrated by dictating the flow of a liquid phase filament on the nanosecond time scale. Results for the assembly of Ni nanoparticles on SiO2 are presented. Previously, we have implemented a sinusoidal perturbation on the edge of a solid phase Ni, thin film strip to tailor nanoparticle assembly. Here, a nonlinear square waveform is explored. This waveform made it possible to expand the range of nanoparticle spacing-radius combinations attainable, which is otherwise limited by the underlying Rayleigh-Plateau type of instability. Simulations of full Navier-Stokes equations based on volume of fluid method were implemented to gain further insight regarding the nature of instability mechanism leading to particle formation in experiments.