Fundamental Proximity Effects in Focused Electron Beam Induced Deposition

Fundamental proximity effects for electron beam induced deposition processes on nonflat surfaces were studied experimentally and <i>via</i> simulation. Two specific effects were elucidated and exploited to considerably increase the volumetric growth rate of this nanoscale direct write method: (1) increasing the scanning electron pitch to the scale of the lateral electron straggle increased the volumetric growth rate by 250% by enhancing the effective forward scattered, backscattered, and secondary electron coefficients as well as by strong recollection effects of adjacent features; and (2) strategic patterning sequences are introduced to reduce precursor depletion effects which increase volumetric growth rates by more than 90%, demonstrating the strong influence of patterning parameters on the final performance of this powerful direct write technique

The Nanoscale Implications of a Molecular Gas Beam during Electron Beam Induced Deposition

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

Focused Ion Beam vs Focused Electron Beam Deposition of Cobalt Silicide Nanostructures Using Single-Source Precursors: Implications for Nanoelectronic Gates, Interconnects, and Spintronics

Direct-write techniques for the fabrication of nanostructures are of specific interest due to their ability for a maskless fabrication of any arbitrary three-dimensional shape. To date, there is a very limited number of reports describing differences in the focused ion and electron beam induced deposition (FIBID/FEBID) for the same precursor species. This report contributes to filling this gap by testing two single-source precursors for the deposition of cobalt silicide in Ga-ion beam writing and reveals H2Si(Co(CO)4)2 to be a very suitable precursor for the technique retaining the 2:1 ratio of Co:Si in the deposit. Maximum metal/metalloid contents of up to 90 atom % are obtained in FIBID deposits, while FEBID with the same precursor provides material containing <60 atom % total metal/metalloid content. A dense deposit is obtained by using FEBID showing paramagnetic behavior and electric properties of a granular metal. In contrast, the FIBID material is porous and the expected ferromagnetic and temperature-dependent electric properties for dicobalt silicide have been observed. Further analysis enabled the proposition of different dominating material conversion channels based on the observed microstructural features including bubble formation in FIBID-derived material. The differences in materials properties depending on the deposition strategy can influence the cobalt silicide deposits’ applicability in nanoelectronics and spintronics

How Bound and Free Fatty Acids in Cellulose Films Impact Nonspecific Protein Adsorption

The effect of fatty acids and fatty acid esters to impair nonspecific protein adsorption on cellulose thin films is investigated. Thin films are prepared by blending trimethylsilyl cellulose solutions with either cellulose stearoyl ester or stearic acid at various ratios. After film formation by spin coating, the trimethylsilyl cellulose fraction of the films is converted to cellulose by exposure to HCl vapors. The morphologies and surface roughness of the blends were examined by atomic force microscopy revealing different feature shapes and sizes depending on the blend ratios. Nonspecific protein adsorption at the example of bovine serum albumin toward the blend thin films was tested by means of surface plasmon resonance spectroscopy in real-time. Incorporation of stearic acid into the cellulose leads to highly protein repellent surfaces regardless of the amount added. The stearic acid acts as a sacrificial compound that builds a complex with bovine serum albumin thereby inhibiting protein adsorption. For the blends where stearoyl ester is added to the cellulose films, the cellulose:cellulose stearoyl ester ratios of 3:1 and 1:1 lead to much lower nonspecific protein adsorption compared to pure cellulose, whereas for the other ratios, adsorption increases. Supplementary results were obtained from atomic force microscopy experiments performed in liquid during exposure to protein solution and surface free energy determinations

Toward Ultraflat Surface Morphologies During Focused Electron Beam Induced Nanosynthesis: Disruption Origins and Compensation

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

Electron-Beam-Assisted Oxygen Purification at Low Temperatures for Electron-Beam-Induced Pt Deposits: Towards Pure and High-Fidelity Nanostructures

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

Simulation-Guided 3D Nanomanufacturing <i>via</i> 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

Fundamental Resolution Limits during Electron-Induced Direct-Write Synthesis

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

Enhanced Performance of Germanium Halide Perovskite Solar Cells through Compositional Engineering

Germanium halide perovskites are an attractive alternative to lead perovskites because of their well-suited optical properties for photovoltaic applications. However, the power conversion efficiencies of solar cells based on germanium perovskites remained below 0.2% so far, and also, the device stability is an issue. Herein, we show that modifying the chemical composition of the germanium perovskite, i.e., introducing bromide ions into the methylammonium germanium iodide perovskite, leads to a significant improvement of the solar cell performance along with a slight enhancement of the stability of the germanium perovskite. With substitution of 10% of the iodide with bromide, power conversion efficiencies up to 0.57% were obtained in MAGeI_2.7Br_0.3 based solar cells with a planar p–i–n architecture using PEDOT:PSS as hole and PC₇₀BM as electron transport layer

Long-Chain Li and Na Alkyl Carbonates as Solid Electrolyte Interphase Components: Structure, Ion Transport, and Mechanical Properties

The solid electrolyte interphase (SEI) in Li and Na ion batteries forms when highly reducing or oxidizing electrode materials come into contact with a liquid organic electrolyte. Its ability to form a mechanically robust, ion-conducting, and electron-insulating layer critically determines performance, cycle life, and safety. Li or Na alkyl carbonates (LiAC and NaAC, respectively) are lead SEI components in state-of-the-art carbonate based electrolytes, and our fundamental understanding of their charge transport and mechanical properties may hold the key to designing electrolytes forming an improved SEI. We synthesized a homologous series of LiACs and NaACs from methyl to octyl analogues and characterized them with respect to structure, ionic conductivity, and stiffness. The compounds assume layered structures except for the lithium methyl carbonate. Room-temperature conductivities were found to be ∼10^–9 S cm^–1 for lithium methyl carbonate, <10^–12 S cm^–1 for the other LiACs, and <10^–12 S cm^–1 for the NaACs with ion transport mostly attributed to grain boundaries. While LiACs show stiffnesses of ∼1 GPa, NaACs become significantly softer with increasing chain lengths. These findings will help to more precisely interpret the complex results from charge transport and mechanical characterization of real SEIs and can give a rationale for influencing the SEI’s mechanical properties via the electrolyte