The effects of pillar height and junction depth on solar cell characteristics are investigated to provide design rules for arrays of such pillars in solar energy applications. Radially doped silicon pillar arrays are fabricated by deep reactive ion etching of silicon substrates followed by the introduction of dopant atoms by diffusion from a phosphorus oxide layer conformally deposited by low-pressure chemical vapor deposition. Increasing the height of the pillars has led to doubling of the efficiency from 6% for flat substrates to 12% for 40 μm high pillars with a 900 nm junction depth because of an increase in the total junction area and lower optical reflection. For higher pillars, the current density and efficiency is decreased, which is attributed to the increasing presence of defect states at the surface introduced during the etching process. This effect can be counteracted by an Al₂O₃ passivation layer on the pillar surface. An optimum efficiency of 13% is found for a junction depth of 790 nm for 40 μm pillar height. At increased junction depths, the efficiency is decreased due to the ever thinner undoped core of the pillars, causing pillars with a large junction depth to become less efficient than flat silicon substrates.

The modulation of the hierarchical nucleated self-assembly of tri-β³-peptides has been studied. β³-Tyrosine provided a handle to control the assembly process through host-guest interactions with CB[7] and CB[8]. By varying the cavity size from CB[7] to CB[8] distinct phases of assembling tri-β³-peptides were arrested. Given the limited size of the CB[7] cavity, only one aromatic β³-tyrosine can be simultaneously hosted and, hence, CB[7] was primarily acting as an inhibitor of self-assembly. In strong contrast, the larger CB[8] can form a ternary complex with two aromatic amino acids and hence CB[8] was acting primarily as cross-linker of multiple fibers and promoting the formation of larger aggregates. General insights on modulating supramolecular assembly can lead to new ways to introduce functionality in supramolecular polymers.

Silicon is one of the main components of commercial solar cells and is used in many other solar-light-harvesting devices. The overall efficiency of these devices can be increased by the use of structured surfaces that contain nanometer- to micrometer-sized pillars with radial p/n junctions. High densities of such structures greatly enhance the light-absorbing properties of the device, whereas the 3D p/n junction geometry shortens the diffusion length of minority carriers and diminishes recombination. Due to the vast silicon nano- and microfabrication toolbox that exists nowadays, many versatile methods for the preparation of such highly structured samples are available. Furthermore, the formation of p/n junctions on structured surfaces is possible by a variety of doping techniques, in large part transferred from microelectronic circuit technology. The right choice of doping method, to achieve good control of junction depth and doping level, can contribute to an improvement of the overall efficiency that can be obtained in devices for energy applications. A review of the state-of-the-art of the fabrication and doping of silicon micro and nanopillars is presented here, as well as of the analysis of the properties and geometry of thus-formed 3D-structured p/n junctions.

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).

Control over particle size and composition are pivotal to tune the properties of metal organic frameworks (MOFs), for example, for biomedical applications. Particle-size control and functionalization of MIL-88A were achieved by using stoichiometric replacement of a small fraction of the divalent fumarate by monovalent capping ligands. A fluorine-capping ligand was used to quantify the surface coverage of capping ligand at the surface of MIL-88A. Size control at the nanoscale was achieved by using a monovalent carboxylic acid-functionalized poly(ethylene glycol) (PEG-COOH) ligand at different concentrations. Finally, a biotin–carboxylic acid capping ligand was used to functionalize MIL-88A to bind fluorescently labeled streptavidin as an example towards bioapplications.

Self-assembly to create molecular and nanostructures is typically performed at the thermodynamic minimum. To achieve dynamic functionalities, such as adaptability, internal feedback, and self-replication, there is a growing focus on out-of-equilibrium systems. This report presents the dynamic self-assembly of an artificial host–guest system at an interface, under control by a dissipative electrochemical process using (electrical) energy, resulting in an out-of-equilibrium system exhibiting a supramolecular surface gradient. The gradient, its steepness, rate of formation, and complex surface composition after backfilling, as well as the surface compositions after switching between the different states of the system, are assessed and supported by modelling. Our method shows for the first time an artificial surface-confined out-of-equilibrium system. The electrochemical process parameters provide not only control over the system in time, but also in space.

Tuneable and stable surface-chemical gradients in supported lipid bilayers (SLBs) hold great promise for a range of applications in biological sensing and screening. Yet, until now, no method has been reported that provides temporal control of SLB gradients. Herein we report on the development of locked-in SLB gradients that can be tuned in space, time and density by applying a process to control lipid phase behaviour, electric field and temperature. Stable gradients of charged Texas-Red-, serine- or biotin-terminated lipids have been prepared. For example, the Texas-Red surface density was varied from 0 to 2 mol %, while the length was varied between several tens to several hundreds of microns. At room temperature the gradients are shown to be stable up to 24 h, while at 60 °C the gradients could be erased in 30 min. Covalent and non-covalent chemical modification of the gradients is demonstrated, for example, by FITC, hexahistidine-tagged proteins, and SAv/biotin. The amenability to various (bio)chemistries paves the way for novel SLB-based gradients, useful in sensing, high-throughput screening and for understanding dynamic biological processes.

Supramolecular nanoparticles (SNPs) encompass multiple copies of different building blocks brought together by specific noncovalent interactions. The inherently multivalent nature of these systems allows control of their size as well as their assembly and disassembly, thus promising potential as biomedical delivery vehicles. Here, dual responsive SNPs have been based on the ternary host–guest complexation between cucurbit[8]uril (CB[8]), a methyl viologen (MV) polymer, and mono- and multivalent azobenzene (Azo) functionalized molecules. UV switching of the Azo groups led to fast disruption of the ternary complexes, but to a relatively slow disintegration of the SNPs. Alternating UV and Vis photoisomerization of the Azo groups led to fully reversible SNP disassembly and reassembly. SNPs were only formed with the Azo moieties in the trans and the MV units in the oxidized states, respectively, thus constituting a supramolecular AND logic gate.

This review surveys recent developments in the field of electrochemically generated gradients. The gradual variation of properties, which is a key characteristic of gradients, is of eminent importance in technology, for example, directional wetting, as well as biology, for example, chemotaxis. Electrochemical techniques offer many benefits, such as the generation of dynamic solution and surface gradients, integration with electronics, and compatibility with automation. An overview is given of newly developed methods, from purely electrochemical techniques to the combination of electrochemistry with other methods. Electrochemically fabricated gradients are employed extensively for biological and technological applications, such as high-throughput screening, high-throughput deposition, and device development, all of which are covered herein. Especially promising are developments towards the study and control of dynamic phenomena, such as the directional motion of molecules, droplets, and cells.

Supramolecular nanoparticles (SNPs) encompass multiple copies of different building blocks brought together by specific noncovalent interactions. The inherently multivalent nature of these systems allows control of their size as well as their assembly and disassembly, thus promising potential as biomedical delivery vehicles. Here, dual responsive SNPs have been based on the ternary host–guest complexation between cucurbit[8]uril (CB[8]), a methyl viologen (MV) polymer, and mono- and multivalent azobenzene (Azo) functionalized molecules. UV switching of the Azo groups led to fast disruption of the ternary complexes, but to a relatively slow disintegration of the SNPs. Alternating UV and Vis photoisomerization of the Azo groups led to fully reversible SNP disassembly and reassembly. SNPs were only formed with the Azo moieties in the trans and the MV units in the oxidized states, respectively, thus constituting a supramolecular AND logic gate.

Gegenstand dieses Aufsatz ist die aktuellen Entwicklung auf dem Gebiet von elektrochemisch erzeugten Gradienten. Eine graduelle Änderung von Merkmalen, die das Charakteristikum von Gradienten ist, hat für Technologie und Biologie eine große Bedeutung, wie das “directional wetting” bzw. die Chemotaxis zeigen. Elektrochemische Techniken bieten viele Vorteile, darunter die Erzeugung von dynamischen Lösungs- und Oberflächengradienten, die Integration von elektronischen Bauteilen und die Automatisierung. Hier werden neue Methoden vorgestellt, von rein elektrochemischen Techniken bis hin zur Kombination von Elektrochemie mit anderen Verfahren. Elektrochemisch erzeugte Gradienten werden in biologischem und technologischem Kontext eingesetzt. Beispiele sind Hochdurchsatzscreening und -galvanisierung sowie elektronische Bauelemente. Besonders vielversprechend sind Entwicklungen, die sich mit der Untersuchung und gezielten Beeinflussung von dynamischen Phänomenen befassen, etwa mit der gerichteten Bewegung von Molekülen, Tröpfchen und Zellen.

A method is described for fabricating and electrically characterizing large-area (100–400 μm²) metal-molecular monolayer-metal junctions with a relatively high overall yield of ≈45%. The measurement geometry consists of ultra-smooth (template-stripped) patterned Au bottom electrodes, combined with ultra-smooth top Au electrodes deposited using wedging transfer. The fabrication method is applied to the electrical characterization of Au-alkanethiol self-assembled monolayer-Au junctions. An exponential decay of the current density is found for increasing the chain length of the alkanethiols, in agreement with earlier studies. The symmetric device geometry, and flexibility for contacting monolayers with various end groups are important advantages compared to existing techniques for electrically characterizing molecular monolayers.

The functionalization of nanoporous zeolite L crystals with β-cyclodextrin (CD) has been demonstrated. The zeolite surface was first modified with amino groups by using two different aminoalkoxysilanes. Then, 1,4-phenylene diisothiocyanate was reacted with the amino monolayer and used to bind CD heptamine by using its remaining isothiocyanate groups. The use of the different aminoalkoxysilanes, 3-aminopropyl dimethylethoxysilane (APDMES) and 3-aminopropyl triethoxysilane (APTES), led to drastic differences in uptake and release properties. Thionine was found to be absorbed and released from amino- and CD-functionalized zeolites when APDMES was used, whereas functionalization by APTES led to complete blockage of the zeolite channels. Fluorescence microscopy showed that the CD groups covalently attached to the zeolite crystals could bind adamantyl-modified dyes in a specific and reversible manner. This strategy allowed the specific immobilization of His-tagged proteins by using combined host–guest and His-tag-Ni-nitrilotriacetic acid (NTA) coordination chemistry. Such multifunctional systems have the potential for encapsulation of drug molecules inside the zeolite pores and non-covalent attachment of other (for example, targeting) ligand molecules on its surface.

In this report, the development of conventional, mass-printing strategies into high-resolution, alternative patterning techniques is reviewed with the focus on large-area patterning of flexible thin-film transistors (TFTs) for display applications. In the first part, conventional and digital printing techniques are introduced and categorized as far as their development is relevant for this application area. The limitations of conventional printing guides the reader to the second part of the progress report: alternative-lithographic patterning on low-cost flexible foils for the fabrication of flexible TFTs. Soft and nanoimprint lithography-based patterning techniques and their limitations are surveyed with respect to patterning on low-cost flexible foils. These show a shift from fabricating simple microlense structures to more complicated, high-resolution electronic devices. The development of alternative, low-temperature processable materials and the introduction of high-resolution patterning strategies will lead to the low-cost, self-aligned fabrication of flexible displays and solar cells from cheaper but better performing organic materials.

Functional polymer brush nanostructures are obtained by combining step-and-flash imprint lithography (SFIL) with controlled, surface-initiated polymerization (CSIP). Patterning is achieved at length scales such that the smallest elements have dimensions in the sub-100 nm range. The patterns exhibit different shapes, including lines and pillars, over large surface areas. The platforms obtained are used to selectively immobilize functional biomacromolecules. Acrylate-based polymer resist films patterned by SFIL are first used for the selective immobilization of ATRP silane-based initiators, which are coupled to unprotected domains of silicon substrates. These selectively deposited initiators are then utilized in the controlled radical SIP of poly(ethylene glycol)methacrylates (PEGMA). Nanostructured brush surfaces are then obtained by removal of the resist material. The areas previously protected by the SFIL resist are passivated by inert, PEG-based silane monolayers following resist removal. PEGMA brush nanostructures are finally functionalized with biotin units in order to provide selective attachment points for streptavidin proteins. Atomic force microscopy and fluorescence spectroscopy confirm the successful immobilization of streptavidin molecules on the polymer grafts. Finally, it is demontrated that this fabrication method allows the immobilization of a few tens of protein chains attached selectively to brush nanostructures, which are surrounded by nonfouling PEG-functionalized areas.

A novel nanopatterning process was developed by combining capillary force lithography (CFL) and microcontact printing (µCP). Flat polydimethylsiloxane (PDMS) was used as the substrate in CFL, and after chemical functionalization, as the stamp in µCP, which increased the resolution of both methods. The polymer patterns, produced by CFL on a thin polymer film on the flat PDMS substrate, acted as a mask to oxidize the uncovered regions of the PDMS. The chemical patterns were subsequently formed by gas phase evaporation of a fluorinated silane. After removal of the polymer, these stamps were used to transfer thiol inks to a gold substrate by µCP. Gold patterns at a scale of less than 100 nm were successfully replicated by these chemically patterned flat PDMS stamps.

Within the past years there has been much effort in developing and improving new techniques for the nanoscale patterning of functional materials used in promising applications like nano(opto)electronics. Here a high-resolution soft lithography technique—nanomolding in capillaries (NAMIC)—is demonstrated. Composite PDMS stamps with sub-100 nm features are fabricated by nanoimprint lithography to yield nanomolds for NAMIC. NAMIC is used to pattern different functional materials such as fluorescent dyes, proteins, nanoparticles, thermoplastic polymers, and conductive polymers at the nanometer scale over large areas. These results show that NAMIC is a simple, versatile, low-cost, and high-throughput nanopatterning tool.

Microcontact printing is a heavily used surface modification method in materials and life science applications. This concept article focuses on the development of versatile stamps for microcontact printing that can be used to bind and release inks through molecular recognition or through an ink reservoir, the latter being used for the transfer of heavy inks, such as biomolecules and particles. Conceptually, such stamp properties can be introduced at the stamp surface or by changing the bulk stamp material; both lines of research will be reviewed here. Examples include supramolecular stamps with affinity properties, polymer-layer-grafted PDMS stamps, and porous multilayer-grafted PDMS stamps for the first case, and hydrogel stamps and porous stamps made by phase-separation micromolding for the second. Potential directions for future advancement of this field are also discussed.

Microcontact printing (µCP) offers a simple and low-cost surface patterning methodology with high versatility and sub-micrometer accuracy. The process has undergone a spectacular evolution since its invention, improving its capability to form sub-100 nm SAM patterns of various polar and apolar materials and biomolecules over macroscopic areas. Diverse development lines of µCP are discussed in this work detailing various printing strategies. New printing schemes with improved stamp materials render µCP a reproducible surface-patterning technique with an increased pattern resolution. New stamp materials and PDMS surface-treatment methods allow the use of polar molecules as inks. Flat elastomeric surfaces and low-diffusive inks push the feature sizes to the nanometer range. Chemical and supramolecular interactions between the ink and the substrate increase the applicability of the µCP process.

β-Cyclodextrin (β-CD) monolayers have been immobilized in microchannels. The host–guest interactions on the β-CD monolayers inside the channels were comparable to the interactions on β-CD monolayers on planar surfaces, and a divalent fluorescent guest attached with a comparable binding strength. Proteins were attached to these monolayers inside microchannels in a selective manner by employing a strategy that uses streptavidin and orthogonal linker molecules. The design of the chip, which involved a large channel that splits into four smaller channels, allowed the channels to be addressed separately and led to the selective immobilization of antibodies. Experiments with labeled antibodies showed the selective immobilization of these antibodies in the separate channels.