Summary Background: Focused electron beam induced deposition (FEBID) is a direct-writing technique with nanometer resolution, which has received strongly increasing attention within the last decade. In FEBID a precursor previously adsorbed on a substrate surface is dissociated in the focus of an electron beam. After 20 years of continuous development FEBID has reached a stage at which this technique is now particularly attractive for several areas in both, basic and applied research. The present topical review addresses selected examples that highlight this development in the areas of charge-transport regimes in nanogranular metals close to an insulator-to-metal transition, the use of these materials for strain- and magnetic-field sensing, and the prospect of extending FEBID to multicomponent systems, such as binary alloys and intermetallic compounds with cooperative ground states. Results: After a brief introduction to the technique, recent work concerning FEBID of Pt–Si alloys and (hard-magnetic) Co–Pt intermetallic compounds on the nanometer scale is reviewed. The growth process in the presence of two precursors, whose flux is independently controlled, is analyzed within a continuum model of FEBID that employs rate equations. Predictions are made for the tunability of the composition of the Co–Pt system by simply changing the dwell time of the electron beam during the writing process. The charge-transport regimes of nanogranular metals are reviewed next with a focus on recent theoretical advancements in the field. As a case study the transport properties of Pt–C nanogranular FEBID structures are discussed. It is shown that by means of a post-growth electron-irradiation treatment the electronic intergrain-coupling strength can be continuously tuned over a wide range. This provides unique access to the transport properties of this material close to the insulator-to-metal transition. In the last part of the review, recent developments in mechanical strain-sensing and the detection of small, inhomogeneous magnetic fields by employing nanogranular FEBID structures are highlighted. Conclusion: FEBID has now reached a state of maturity that allows a shift of the focus towards the development of new application fields, be it in basic research or applied. This is shown for selected examples in the present review. At the same time, when seen from a broader perspective, FEBID still has to live up to the original idea of providing a tool for electron-controlled chemistry on the nanometer scale. This has to be understood in the sense that, by providing a suitable environment during the FEBID process, the outcome of the electron-induced reactions can be steered in a controlled way towards yielding the desired composition of the products. The development of a FEBID-specialized surface chemistry is mostly still in its infancy. Next to application development, it is this aspect that will likely be a guiding light for the future development of the field of focused electron beam induced deposition.
In the majority of cases, nanostructures prepared by focused electron beam induced deposition employing an organometallic precursor contain predominantly carbon-based ligand dissociation products. This is unfortunate with regard to using this high-resolution direct-write approach for the preparation of nanostructures for various fields, such as mesoscopic physics, micromagnetism, metaoptical phenomena in the visible spectral range, or others. Following early attempts of postprocessing Pt-based structures prepared by focused electron beam induced deposition at several hundred degrees Celsius in a reactive gas atmosphere, recent work has focused on developing in situ purification processes by using a stationary O2 flux in combination with electron irradiation to oxidize the carbonaceous component of the deposits. Here we show that this purification process is driven by the catalytic activity of Pt and in fact does not rely on the parallel electron irradiation process to function, if the O2 exposure is done in a pulsed fashion. We suggest a multistep cleaning mechanism which results in pure, nanoporous Pt. By suitably chosen beam parameters, high-resolution Pt dot and line structures with dimensions below 10 nm can thus be conveniently obtained. In temperature-dependent resistance measurements, we find the typical metallic behavior of Pt. In low-temperature magnetoresistance measurements, we see clear evidence for weak antilocalization effects and deduce a dephasing length of 234 nm at 1.2 K. We consider this to be a promising starting point for developing this approach into a versatile preparation technique for Pt-based mesoscopic structures, in particular since the purification process can be run in parallel on different deposits. We furthermore anticipate that our results will spur further research on purification approaches for nanostructures prepared by focused electron beam induced deposition containing a catalytically active metal species such as Pd-, Fe-, or Co-based deposits.
Binary systems of Pt-Si are prepared by electron-beam-induced deposition using the two precursors, trimethyl(methylcyclopentadienyl)platinum(IV) (MeCpPt(Me)(3)) and neopentasilane (Si(SiH(3))(4)), simultaneously. By varying the relative flux of the two precursors during deposition, we are able to study composites containing platinum and silicon in different ratios by means of energy-dispersive X-ray spectroscopy, atomic force microscopy, electrical transport measurements, and transmission electron microscopy. The results show strong evidence for the formation of a binary, metastable Pt(2)Si(3) phase, leading to a maximum in the conductivity for a Si/Pt ratio of 3:2.
CoPt-C binary alloys have been fabricated by focused-electron-beam-induced deposition by the simultaneous use of Co₂(CO)₈ and (CH₃)₃CH₃C₅H₄Pt as precursor gases. The alloys are made of CoPt nanoparticles embedded in a carbonaceous matrix. TEM investigations show that as-grown samples are in an amorphous phase. By means of a room temperature low-energy electron irradiation treatment the CoPt nanoparticles transform into face-centered tetragonal L1₀ nanocrystallites. In parallel, the system undergoes a transition from a superparamagnetic to a ferromagnetic state at room temperature. By variation of the post-growth irradiation dose the electrical and magneto-transport properties of the alloy can be continuously tuned.
Air- and water-stable, π-conjugated [−donor–acceptor−] n oligomers containing thiophene fragments as donors and 9,10-dimesityl-9,10-dihydro-9,10-diboraanthracene (DBA(Mes)2) as acceptor units were prepared through Stille-type C–C-coupling protocols. The reaction between 2,6-dibromo-DBA(Mes)2 (1), 2,7-dibromo-DBA(Mes)2 (2), 2-bromo-6,7-dimethyl-DBA(Mes)2 (3), and 2,5-bis(trimethylstannyl)thiophene (7) furnished monodisperse, short-chain model systems 8 0 (2 × DBA(Mes)2, 1 × 2,5-thienylene) and 8 1 (3 × DBA(Mes)2, 2 × 2,5-thienylene) after GPC separation. In the absence of 3, the oligomerization of 1/2 with 7 provided analogous longer chain macromolecules 9 (MALDI–MS reveals up to 7 repeating units; GPC indicates also significantly longer chains). UV/vis absorption spectroscopy suggests that the obtained chain lengths of 9 are already sufficient to reach the maximum effective conjugation length (the lower limit of the HOMO–LUMO band gap corresponds to 2.3 eV). 9 gives rise to a dark orange fluorescence, both in C6H6 solution (ϕf = 47%) and as thin film (ϕf = 13%).
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