"SAMs meet MEMS": surface modification with self-assembled monolayers for the dry-demolding of photoplastic MEMS/NEMS

In this contribution we demonstrate the use of self-assembled monolayers (SAMs) as anti-adhesion coating to assist the removal of photoplastic MEMS/NEMS with a patterned metal layer from the surface without wet chemical sacrificial layer etching, so-called 'dry-demolding'. The SAMs functionality here is to reduce the stiction between the surface and a thin evaporated metal film. The double-layer SAM/metal provides enough stability to support subsequent micromachining step

Functionalized Polyelectrolytes for Bioengineered Interfaces and Biosensing Applications

The possibility of tuning the chemical moieties and their density plays a fundamental role in targeting surface-confined molecular structures and their functionalities at macro and nanoscale levels. Such interfacial control is crucial for engineered coating formation and biorecognition purposes, where the type and density of ligands/receptors at the surface affect the overall binding affinities and the device performance. Together with the well-established self-assembled monolayers, a surface modification approach based on polyelectrolytes (PEs) has gained importance to provide desired characteristics at the substrate interface. This review presents the innovations of functional PEs, modified in a preceding synthetic step, and their wide applicability in functional (a)biotic substrates. Examples of 2D and 3D architectures made by modified PEs are reviewed in relation with the reactive groups grafted to the PE backbones. The main focus lies on the strategy to use modified PEs to form bioengineered coatings for orthogonally anchoring biological entities, manufacturing biocidal/antifouling films, and their combinations in functional biosensing applications

Multi-silicon ridge nanofabrication by repeated edge lithography

We present a multi-Si nanoridge fabrication scheme and its application in nanoimprint\ud lithography (NIL). Triple Si nanoridges approximately 120 nm high and 40 nm wide separated\ud by 40 nm spacing are fabricated and successfully applied as a stamp in nanoimprint lithography.\ud The fabrication scheme, using a full-wet etching procedure in combination with repeated edge\ud lithography, consists of hot H3PO4 acid SiNx retraction etching, 20% KOH Si etching, 50% HF\ud SiNx retraction etching and LOCal Oxidation of Silicon (LOCOS). Si nanoridges with smooth\ud vertical sidewalls are fabricated by using Si 110 substrates and KOH etching. The presented\ud technology utilizes a conventional photolithography technique, and the fabrication of multi-Si\ud nanoridges on a full wafer scale has been demonstrated

Size-controlled and redox-responsive supramolecular nanoparticles

Control over the assembly and disassembly of nanoparticles is pivotal for their use as drug delivery vehicles. Here, we aim to form supramolecular nanoparticles (SNPs) by combining advantages of the reversible assembly properties of SNPs using host–guest interactions and of a stimulus-responsive moiety. The SNPs are composed of a core of positively charged poly(ethylene imine) grafted with β-cyclodextrin (CD) and a positively charged ferrocene (Fc)-terminated poly(amidoamine) dendrimer, with a monovalent stabilizer at the surface. Fc was chosen for its loss of CD-binding properties when oxidizing it to the ferrocenium cation. The ionic strength was shown to play an important role in controlling the aggregate growth. The attractive supramolecular and repulsive electrostatic interactions constitute a balance of forces in this system at low ionic strengths. At higher ionic strengths, the increased charge screening led to a loss of electrostatic repulsion and therefore to faster aggregate growth. A Job plot showed that a 1:1 stoichiometry of host and guest moieties gave the most efficient aggregate growth. Different stabilizers were used to find the optimal stopper to limit the growth. A weaker guest moiety was shown to be less efficient in stabilizing the SNPs. Also steric repulsion is important for achieving SNP stability. SNPs of controlled particle size and good stability (up to seven days) were prepared by fine-tuning the ratio of multivalent and monovalent interactions. Finally, reversibility of the SNPs was confirmed by oxidizing the Fc guest moieties in the core of the SNPs

Reactivity mapping: electrochemical gradients for monitoring reactivity at surfaces in space and time

Studying and controlling reactions at surfaces is of great fundamental and applied interest in, among others, biology, electronics and catalysis. Because reaction kinetics is different at surfaces compared with solution, frequently, solution-characterization techniques cannot be used. Here we report solution gradients, prepared by electrochemical means, for controlling and monitoring reactivity at surfaces in space and time. As a proof of principle, electrochemically derived gradients of a reaction parameter (pH) and of a catalyst (Cu(I)) have been employed to make surface gradients on the micron scale and to study the kinetics of the (surface-confined) imine hydrolysis and the copper(I)-catalysed azide-alkyne 1,3-dipolar cycloaddition, respectively. For both systems, the kinetic data were spatially visualized in a two-dimensional reactivity map. In the case of the copper(I)-catalysed azide-alkyne 1,3-dipolar cycloaddition, the reaction order (2) was deduced from it

Erratum:Influenza as a molecular walker (Chemical Science (2020) 11 (27–36) DOI: 10.1039/c9sc05149j)

The authors regret that incorrect details were given for ref. 70 in the original article. The correct version of ref. 70 is given below as ref. 1. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.</p

Controlled Doping Methods for Radial p/n Junctions in Silicon

P/n and n/p junctions with depths of 200 nm to several micrometers have been created in flat silicon substrates as well as on 3D microstructures by means of a variety of methods, including solid source dotation (SSD), low-pressure chemical vapor deposition (LPCVD), atmospheric pressure chemical vapor deposition, and plasma-enhanced chemical vapor deposition. Radial junctions in Si micropillars are inspected by optical and scanning electron micro­scopies, using a CrO3-based staining solution, which enables visualization of the junction depth. When applying identical-doping parameters to flat substrates, ball grooving, followed by staining and optical microscopy, yields similar junction depth values as high-resolution scanning electron microscopy imaging on stained cross-sections and secondary ion mass spectrometry depth profilometry. For the investigated 3D microstructures, doping based on SSD and LPCVD give uniform and conformal junctions. Junctions made with SSD-boron doping and CVD-phosphorus doping could be accurately predicted with a model based on Fick's diffusion law. 3D-microstructured silicon pillar arrays show an increased efficiency for sunlight capturing. The functionality of micropillar arrays with radial junctions is evidenced by improved short-circuit current densities and photovoltaic efficiencies compared with flat surfaces, for both n- and p-type wafers (average pillar arrays efficiencies of 9.4% and 11%, respectively, compared with 8.3% and 6.4% for the flat samples)

Strongly inhibited spontaneous emission of PbS quantum dots inside 3D silicon photonic crystals

We present an optical study of the spontaneous emission of lead sulfide (PbS) nanocrystal quantum dots in 3D photonic band gap crystals made from silicon. The nanocrystals are covalently bonded to polymer brush layers that are grafted from the Si-air interfaces inside the 3D nanostructure using surface-initiated atom transfer radical polymerization (SI-ATRP). The presence and position of the quantum dots was previously characterized by X-ray fluorescence tomography. We report both continuous wave emission spectra and time-resolved time-correlated single photon counting of the quantum dots. In time-resolved measurements, we observe that the total emission rate greatly increases when the quantum dots are transferred from suspension to the silicon nanostructures, likely due to quenching that is tentatively attributed to the presence of Cu-catalyst during synthesis. In this regime, continuous wave (cw) emission spectra are known to be proportional to the radiative rate, hence to the local density of states. In spectra normalized to those taken on flat Si, we observe a broad and deep stop band that we attribute to a 3D photonic band gap with a relative bandwidth up to 26%. The observed inhibition is 5 to 30 times enhanced, similar to previously reported band gap inhibitions, but for completely coincidental reasons. Our results are relevant to applications in photochemistry, sensing, photovoltaics, and to efficient miniature light sources

Coupled molecular switching processes in ordered mono- and multilayers of stimuli-sesponsive rotaxanes on gold surfaces

Interfaces provide the structural basis for function as, for example, encountered in nature in the membrane-embedded photosystem or in technology in solar cells. Synthetic functional multilayers of molecules cooperating in a coupled manner can be fabricated on surfaces through layer-by-layer self-assembly. Ordered arrays of stimulus-responsive rotaxanes undergoing well-controlled axle shuttling are excellent candidates for coupled mechanical motion. Such stimulus-responsive surfaces may help integrate synthetic molecular machines in larger systems exhibiting even macroscopic effects or generating mechanical work from chemical energy through cooperative action. The present work demonstrates the successful deposition of ordered mono- and multilayers of chemically switchable rotaxanes on gold surfaces. Rotaxane mono- and multilayers are shown to reversibly switch in a coupled manner between two ordered states as revealed by linear dichroism effects in angle-resolved NEXAFS spectra. Such a concerted switching process is observed only when the surfaces are well packed, while less densely packed surfaces lacking lateral order do not exhibit such effect

Nanoscale work function contrast induced by decanethiol self-assembled monolayers on Au(111)

In this paper, we obtain maps of the spatial tunnel barrier variations in self-assembled monolayers of organosulfurs on Au(111). Maps down to the sub-nanometer scale are obtained by combining topographic scanning tunneling microscopy images with dI/dz spectroscopy. The square root of the tunnel barrier height is directly proportional to the local work function and the dI/dz signal. We use ratios of the tunnel barriers to study the work function contrast in various decanethiol phases: the lying-down striped β phase, the dense standing-up φ phase, and the oxidized decanesulfonate λ phase. We compare the induced work function variations too: the work function contrast induced by a lying-down striped phase in comparison to the modulation induced by the standing-up φ phase, as well as the oxidized λ phase. By performing these comparisons, we can account for the similarities and differences in the effects of the mechanisms acting on the surface and extract valuable insights into molecular binding to the substrate. The pillow effect, governing the lowering of the work function due to lying-down molecular tails in the striped low density phases, seems to have quite a similar contribution as the surface dipole effect emerging in the dense standing-up decanethiol phases. The dI/dz spectroscopy map of the nonoxidized β phase compared to the map of the oxidized λ phase indicates that the strong binding of molecules to the substrate is no longer present in the latter.Fil: Tsvetanova, Martina. University of Twente; Países BajosFil: Oldenkotte, Valent J. S.. University of Twente; Países BajosFil: Bertolino, María Candelaria. University of Twente; Países Bajos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Gao, Yuqiang. University of Twente; Países BajosFil: Siekman, Martin H.. University of Twente; Países BajosFil: Huskens, Jurriaan. University of Twente; Países BajosFil: Zandvliet, Harold J. W.. University of Twente; Países BajosFil: Sotthewes, Kai. University of Twente; Países Bajo