Resonant Electron Tunneling Induces Isomerization of π-Expanded Oligothiophene Macrocycles in a 2D Crystal

Macrocyclic oligothiophenes and their π-expanded derivatives constitute versatile building blocks for the design of (supra)molecularly engineered active interfaces, owing to their structural, chemical, and optoelectronic properties. Here, it is demonstrated how resonant tunneling effect induces single molecular isomerization in a 2D crystal, self-assembled at solid–liquid interfaces under ambient conditions. Monolayers of a series of four π-expanded oligothiophene macrocycles are investigated by means of scanning tunneling microscopy and scanning tunneling spectroscopy (STS) at the interface between their octanoic acid solutions and the basal plane of highly oriented pyrolytic graphite. Current–voltage characteristics confirm the donor-type character of the macrocycles, with the highest occupied molecular orbital and the lowest unoccupied molecular orbital (LUMO) positions consistent with time-dependent density functional theory calculations. Cyclic STS measurements show the redox isomerization from Z,Z-8T6A to its isomer E,E-8T6A occurring in the 2D crystal, due to the formation of a negatively charged species when the tunneling current is in resonance with the LUMO of the macrocycle.Peer Reviewe

Nanostructured solid-state hybrid photovoltaic cells fabricated by electrostatic layer-by-layer deposition

We report on the fabrication of hybrid organic/inorganic photovoltaic cells utilizing layer-by-layer deposition of water-soluble polyions and nanocrystals. A bulk heterojunction structure was created consisting of alternating layers of the p-conductive polythiophene derivative poly[2-(3-thienyl)-ethoxy-4-butylsulfonate] and n-conductive TiO2nanoparticles. We fabricated working devices with the heterostructure sandwiched between suitable charge carrier blocking layers and conducting oxide and metal electrodes, respectively. We analyzed the influence of the thickness and nanostructure of the active layer on the cell performance and characterized the devices in terms of static and transient current response with respect to illumination and voltage conditions. We observed reproducible and stable photovoltaic behavior with photovoltages of up to 0.9 V

Hydration effects turn a highly stretched polymer from an entropic into an energetic spring

Polyethylene glycol (PEG) is a structurally simple and nontoxic water-soluble polymer that is widely used in medical and pharmaceutical applications as molecular linker and spacer. In such applications, PEG’s elastic response against conformational deformations is key to its function. According to text-book knowledge, a polymer reacts to the stretching of its end-to-end separation by a decrease in entropy that is due to the reduction of available conformations, which is why polymers are commonly called entropic springs. By a combination of single-molecule force spectroscopy experiments with molecular dynamics simulations in explicit water, we show that entropic hydration effects almost exactly compensate the chain conformational entropy loss at high stretching. Our simulations reveal that this entropic compensation is due to the stretching-induced release of water molecules that in the relaxed state form double hydrogen bonds with PEG. As a consequence, the stretching response of PEG is predominantly of energetic, not of entropic, origin at high forces and caused by hydration effects, while PEG backbone deformations only play a minor role. These findings demonstrate the importance of hydration for the mechanics of macromolecules and constitute a case example that sheds light on the antagonistic interplay of conformational and hydration degrees of freedom

Shaping surfaces and interfaces of 2D materials on mica with intercalating water and ethanol

Interfaces between mica and graphene, as well as the transition metal dichalcogenides (TMDCs) MoS2 and WS2, were wetted with water and ethanol, and investigated employing scanning force microscopy and molecular dynamics (MD) simulations. Below 25% RH, water wets the graphene-mica interface with labyrinthine structures, exhibiting branch widths of about 50 nm for single layers of graphene, increasing to almost an order of magnitude more for four graphene layers. At mica-TMDC interfaces, water films exhibit a transition from labyrinthine to compact morphology upon going from single- to multi-layers of the TMDCs. Ethanol films show a compact morphology at all the interfaces, regardless of the number of 2D material layers on top. The film morphologies are attributed to an equilibrium between electrostatic repulsion of preferentially oriented molecular dipoles, and the line tension of the wetted areas, which is dominated by the deformation of the 2D materials at the edges of the wet areas. The compact front of the water wetting film under multilayers of TMDCs is attributed to a much larger bending stiffness of these materials than of graphene multilayers. The thickness dependent stiffness of the 2D materials may be employed to shape their surfaces from the nano- to the micrometer scale.Peer Reviewe

Resonance Energy Transfer from Monolayer WS2 to Organic Dye Molecules: Conversion of Faint Visible-Red into Bright Near-Infrared Luminescence

The synergetic combination of transition metal dichalcogenides (TMDCs) with organic dye molecules in functional heterostructures is promising for various optoelectronic applications. Here resonance energy transfer (RET) from a red‐emitting WS2 monolayer (1L‐WS2) to a layer of near‐infrared (NIR) emitting organic dye molecules is demonstrated. It is found that the total photoluminescence (PL) yield of the heterostructures is up to a factor of eight higher as compared to the PL yield of pristine 1L‐WS2. This is attributed to the efficient conversion of the mostly non‐radiative excitons in 1L‐WS2 into radiative excitons in the dye layer. A type‐I energy level alignment of the 1L‐WS2/dye interface assures the emission of bright PL. From excitation density‐dependent PL experiments, it is concluded that RET prevails against defect‐assisted non‐radiative recombination as well as Auger‐type exciton‐exciton annihilation in 1L‐WS2. The work paves the way for employing organic dye molecules in heterostructures with TMDCs in nanoscale light‐emitting devices with improved efficiency and tunable color.Peer Reviewe