RESUMEN
Electron irradiation of self-assembled monolayers (SAMs) is a versatile tool for lithographic methods and the formation of new 2D materials such as carbon nanomembranes (CNMs). While the interaction between the electron beam and standard thiolate SAMs has been well studied, the effect of electron irradiation for chemically and thermally ultrastable N-heterocyclic carbenes (NHCs) remains unknown. Here we analyze electron irradiation of NHC SAMs featuring different numbers of benzene moieties and different sizes of the nitrogen side groups to modify their structure. Our results provide design rules to optimize NHC SAMs for effective electron-beam modification that includes the formation of sulfur-free CNMs, which are more suitable for ultrafiltration applications. Considering that NHC monolayers exhibit up to 100 times higher stability of their bonding with the metal substrate toward electron-irradiation compared to standard SAMs, they offer a new alternative for chemical lithography where structural modification of SAMs should be limited to the functional group.
RESUMEN
The chemistry and physics of macropolyhedral B18H22 clusters have attracted significant attention due to the interesting photophysical properties of anti-B18H22 (blue emission, laser properties) and related potential applications. We have focused our attention on the "forgotten" syn-B18H22 isomer, which has received very little attention since its discovery compared to its anti-B18H22 isomer, presumably because numerous studies have reported this isomer as nonluminescent. In our study, we show that in crystalline form, syn-B18H22 exhibits blue fluorescence and becomes phosphorescent when substituted at various positions on the cluster, associated with peculiar microstructural-dependent effects. This work is a combined theoretical and experimental investigation that includes the synthesis, separation, structural characterization, and first elucidation of the photophysical properties of three different monothiol-substituted cluster isomers, [1-HS-syn-B18H21] 1, [3-HS-syn-B18H21] 3, and [4-HS-syn-B18H21] 4, of which isomers 1 and 4 have been proved to exist in two different polymorphic forms. All of these newly substituted macropolyhedral cluster derivatives (1, 3, and 4) have been fully characterized by NMR spectroscopy, mass spectrometry, single-crystal X-ray diffraction, IR spectroscopy, and luminescence spectroscopy. This study also presents the first report on the mechanochromic shift in the luminescence of a borane cluster and generally enriches the area of rather rare boron-based luminescent materials. In addition, we present the first results proving that they are useful constituents of carbon-free self-assembled monolayers.
RESUMEN
A critical point drying (CPD) technique is reported with supercritical CO2 as a cleaning step for graphene field-effect transistors (GFETs) microfabricated on oxidized Si wafers, which results in an increase of the field-effect mobility and a decrease of the impurity doping. It is shown that the polymeric residues remaining on graphene after the transfer process and device microfabrication are significantly reduced after the CPD treatment. Moreover, the CPD effectively removes ambient adsorbates such as water therewith reducing the undesirable p-type doping of the GFETs. It is proposed that CPD of electronic, optoelectronic, and photonic devices based on 2D materials as a promising technique to recover their intrinsic properties after the microfabrication in a cleanroom and after storage at ambient conditions.
RESUMEN
The electron-irradiation-induced synthesis of carbon nanomembranes (CNMs) from aromatic thiol-based self-assembled monolayers (SAMs) on gold substrate is a well-established method to form molecular thin nanosheets. These molecular two-dimensional materials can be prepared with tunable properties; therefore, they find a variety of applications in nanotechnology ranging from ultrafiltration to nanobiosensors. However, no chemically inert CNM was fabricated up to now, as the reactive thiol group is present on the membrane surface even after transferring it to other substrates. Here, we study the electron irradiation of carboxylic acid-based SAMs on a silver substrate as an alternative route for CNM formation. Our analysis, based on a combination of X-ray photoelectron spectroscopy and scanning electron microscopy demonstrates that for this type of SAMs, purely carbonaceous CNMs with tunable porosity can be obtained.