Exploring the fabrication and transfer mechanism of metallic nanostructures on carbon nanomembranes via focused electron beam induced processing.
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ABSTRACT: Focused electron beam-induced processing is a versatile method for the fabrication of metallic nanostructures with arbitrary shape, in particular, on top of two-dimensional (2D) organic materials, such as self-assembled monolayers (SAMs). Two methods, namely electron beam-induced deposition (EBID) and electron beam-induced surface activation (EBISA) are studied with the precursors Fe(CO)5 and Co(CO)3NO on SAMs of 1,1',4',1''-terphenyl-4-thiol (TPT). For Co(CO)3NO only EBID leads to deposits consisting of cobalt oxide. In the case of Fe(CO)5 EBID and EBISA yield deposits consisting of iron nanocrystals with high purity. Remarkably, the EBISA process exhibits a strong time dependence, which is analyzed in detail for different electron doses. This time dependence is a new phenomenon, which, to the best of our knowledge, was not reported before. The electron-induced cross-linking of the SAM caused by the cleavage of C-H bonds and the subsequent formation of new C-C bonds between neighboring molecules also seems to play a crucial role in the EBISA process. Previous studies showed that iron nanostructures fabricated on top of a cross-linked SAM on Au/mica can be transferred to solid substrates and grids without any changes, aside from oxidation. Here we demonstrate that iron as well as cobalt oxide structures on top of a cross-linked SAM on Ag/mica do change more significantly. The Fe(NO3)3 solution used for etching of the Ag layer also dissolves the cobalt oxide structures and causes dissolution and reduction of the iron structures. These results demonstrate that the fabrication of hybrids of metallic nanostructures onto organic 2D materials is an intrinsically complex procedure. The interactions among the metallic deposits, the substrate for the growth of the SAM, and the associated etching/dissolving agent need to be considered and further studied.
Project description:Photonic nanostructures such as gratings and ring resonators have become ubiquitous building blocks in Photonics. For example, they are used in filters, they resonantly enhance signals and act as grating couplers. Much research effort is invested in using such structures to create novel functionalities, which often employs electron-beam lithography. An intrinsic issue in this field is the ability to accurately achieve a specific operating wavelength, especially for resonant systems, because nanometer-scale variations in feature size may easily detune the device. Here, we examine some of the key fabrication steps and show how to improve the reproducibility of fabricating wavelength scale photonic nanostructures. We use guided mode resonance grating sensors as our exemplar and find that the exposure condition and the development process significantly affect the consistency of the resonance wavelength, amplitude, and sensitivity of the sensor. By having careful control over these factors, we can achieve consistent performance for all the sensors studied, with less than 10% variation in their resonance behaviors. These investigations provide useful guidelines for fabricating nanostructures more reliably and to achieve a higher success rate in exploratory experiments.
Project description:Performing reliable preparation of transmission electron microscopy (TEM) samples is the necessary basis for a meaningful investigation by ex situ and even more so by in situ TEM techniques, but it is challenging using materials that are sensitive to electron beam irradiation. Focused ion beam is currently the most commonly employed technique for a targeted preparation, but the structural modifications induced during focused ion beam preparation are not fully understood for a number of materials. Here, we have investigated the impact of both the electron and the Ga+ ion beam on insulating solid-state electrolytes (lithium phosphorus oxynitride, Na-β"-alumina solid electrolyte and Na3.4Si2.4Zr2P0.6O12 (NaSICON)) and observed significant lithium/sodium whisker growth induced by both the electron and ion beam already at fairly low dose, leading to a significant change in the chemical composition. The metal whisker growth is presumably mainly due to surface charging, which can be reduced by coating with a gold layer or preparation under cryogenic conditions as efficient approaches to stabilize the solid electrolyte for scanning electron microscopy imaging and TEM sample preparation. Details on the different preparation approaches, the acceleration voltage dependence and the induced chemical and morphological changes are reported.
Project description:In many areas of science and technology, patterned films and surfaces play a key role in engineering and development of advanced materials. Here, we introduce a new generic technique for the fabrication of polysaccharide nano-structures via focused electron beam induced conversion (FEBIC). For the proof of principle, organosoluble trimethylsilyl-cellulose (TMSC) thin films have been deposited by spin coating on SiO2 / Si and exposed to a nano-sized electron beam. It turns out that in the exposed areas an electron induced desilylation reaction takes place converting soluble TMSC to rather insoluble cellulose. After removal of the unexposed TMSC areas, structured cellulose patterns remain on the surface with FWHM line widths down to 70 nm. Systematic FEBIC parameter sweeps reveal a generally electron dose dependent behavior with three working regimes: incomplete conversion, ideal doses and over exposure. Direct (FT-IR) and indirect chemical analyses (enzymatic degradation) confirmed the cellulosic character of ideally converted areas. These investigations are complemented by a theoretical model which suggests a two-step reaction process by means of TMSC → cellulose and cellulose → non-cellulose material conversion in excellent agreement with experimental data. The extracted, individual reaction rates allowed the derivation of design rules for FEBIC parameters towards highest conversion efficiencies and highest lateral resolution.
Project description:Nanofabrication techniques are essential for exploring nanoscience and many closely related research fields such as materials, electronics, optics and photonics. Recently, three-dimensional (3D) nanofabrication techniques have been actively investigated through many different ways, however, it is still challenging to make elaborate and complex 3D nanostructures that many researchers want to realize for further interesting physics studies and device applications. Electron beam lithography, one of the two-dimensional (2D) nanofabrication techniques, is also feasible to realize elaborate 3D nanostructures by stacking each 2D nanostructures. However, alignment errors among the individual 2D nanostructures have been difficult to control due to some practical issues. In this work, we introduce a straightforward approach to drastically increase the overlay accuracy of sub-20 nm based on carefully designed alignmarks and calibrators. Three different types of 3D nanostructures whose designs are motivated from metamaterials and plasmonic structures have been demonstrated to verify the feasibility of the method, and the desired result has been achieved. We believe our work can provide a useful approach for building more advanced and complex 3D nanostructures.
Project description:This communication describes the fabrication of gold structures (for example, rings) with wall thickness of 40 nm, and with high aspect ratios up to 25. This technique combines thin-film deposition of metal on a topographically patterned epoxy substrate, with nanometer-scale sectioning using a microtome in a plane parallel to the patterned substrate. The dimensions of the metal structures are determined by the thickness of the metal film and the thickness of the epoxy sections. The shape of the resulting nanostructure is defined by the cross section of the original template.
Project description:The ability of electrons and atomic hydrogen (AH) to remove residual chlorine from PtCl2 deposits created from cis-Pt(CO)2Cl2 by focused electron beam induced deposition (FEBID) is evaluated. Auger electron spectroscopy (AES) and energy-dispersive X-ray spectroscopy (EDS) measurements as well as thermodynamics calculations support the idea that electrons can remove chlorine from PtCl2 structures via an electron-stimulated desorption (ESD) process. It was found that the effectiveness of electrons to purify deposits greater than a few nanometers in height is compromised by the limited escape depth of the chloride ions generated in the purification step. In contrast, chlorine atoms can be efficiently and completely removed from PtCl2 deposits using AH, regardless of the thickness of the deposit. Although AH was found to be extremely effective at chemically purifying PtCl2 deposits, its viability as a FEBID purification strategy is compromised by the mobility of transient Pt-H species formed during the purification process. Scanning electron microscopy data show that this results in the formation of porous structures and can even cause the deposit to lose structural integrity. However, this phenomenon suggests that the use of AH may be a useful strategy to create high surface area Pt catalysts and may reverse the effects of sintering. In marked contrast to the effect observed with AH, densification of the structure was observed during the postdeposition purification of PtC x deposits created from MeCpPtMe3 using atomic oxygen (AO), although the limited penetration depth of AO restricts its effectiveness as a purification strategy to relatively small nanostructures.
Project description:Simple high-performance, two-stage hybrid technique was developed for fabrication of different plasmonic nanostructures, including nanorods, nanorings, as well as more complex structures on glass substrates. In this technique, a thin noble-metal film on a dielectric substrate is irradiated by a single tightly focused nanosecond laser pulse and then the modified region is slowly polished by an accelerated argon ion (Ar(+)) beam. As a result, each nanosecond laser pulse locally modifies the initial metal film through initiation of fast melting and subsequent hydrodynamic processes, while the following Ar(+)-ion polishing removes the rest of the film, revealing the hidden topography features and fabricating separate plasmonic structures on the glass substrate. We demonstrate that the shape and lateral size of the resulting functional plasmonic nanostructures depend on the laser pulse energy and metal film thickness, while subsequent Ar(+)-ion polishing enables to vary height of the resulting nanostructures. Plasmonic properties of the fabricated nanostructures were characterized by dark-field micro-spectroscopy, Raman and photoluminescence measurements performed on single nanofeatures, as well as by supporting numerical calculations of the related electromagnetic near-fields and Purcell factors. The developed simple two-stage technique represents a new step towards direct large-scale laser-induced fabrication of highly ordered arrays of complex plasmonic nanostructures.
Project description:Solid-state nanopores (ssNPs) are extremely versatile single-molecule sensors and their potential have been established in numerous biomedical applications. However, the fabrication of ssNPs remains the main bottleneck to their widespread use. Herein, we introduce a rapid and localizable ssNPs fabrication method based on feedback-controlled optical etching. We show that a focused blue laser beam irreversibly etches silicon nitride (SiNx) membranes in solution. Furthermore, photoluminescence (PL) emitted from the SiNx is used to monitor the etching process in real-time, hence permitting rate adjustment. Transmission electron microscopy (TEM) images of the etched area reveal an inverted Gaussian thickness profile, corresponding to the intensity point spread function of the laser beam. Continued laser exposure leads to the opening of a nanopore, which can be controlled to reproducibly fabricate nanopores of different sizes. The optically-formed ssNPs exhibit electrical noise on par with TEM-drilled pores, and translocate DNA and proteins readily. Notably, due to the localized thinning, the laser-drilled ssNPs exhibit highly suppressed background PL and improved spatial resolution. Given the total control over the nanopore position, this easily implemented method is ideally suited for electro-optical sensing and opens up the possibility of fabricating large nanopore arrays in situ.
Project description:The fabrication of nanoscale patterns over a large area has been considered important but difficult, because there are few ways to satisfy both conditions. Previously, visually tolerable tiling (VTT) for fabricating nanopatterns for optical applications has been reported as a candidate for large area fabrication. The essence of VTT is the inevitable stitching of the nanoscale optical component, which is not seen by the naked eye if the boundary is very narrow while the tiles are overlapped. However, it had been difficult to control the shape of the spread of liquid prepolymers in the previous work, and there was room for the development of tiling. Here, we propose a method for transferring various shapes of tiles, which can be defined with a shadow mask. The method of using a transparent shadow mask can provide a wide process window, because it allows the spreading of a liquid prepolymer to be more easily controlled. We optimize the coating condition of a liquid prepolymer and the ultraviolet (UV) exposure time. Using this method, we can attach tiles of various shapes without a significant visible trace in the overlapped region.
Project description:Focused electron beam induced deposition (FEBID) is a flexible direct-write method to obtain defined structures with a high lateral resolution. In order to use this technique in application fields such as plasmonics, suitable precursors which allow the deposition of desired materials have to be identified. Well known for its plasmonic properties, silver represents an interesting candidate for FEBID. For this purpose the carboxylate complex silver(I) pentafluoropropionate (AgO2CC2F5) was used for the first time in FEBID and resulted in deposits with high silver content of up to 76 atom %. As verified by TEM investigations, the deposited material is composed of pure silver crystallites in a carbon matrix. It showed good electrical properties and a strong Raman signal enhancement. Interestingly, silver crystal growth presents a strong dependency on electron dose and precursor refreshment.