Núria Crivillers

Optically switchable transistor via energy-level phototuning in a bicomponent organic semiconductor

Organic semiconductors are suitable candidates for printable, flexible and large-area electronics. Alongside attaining an improved device performance, to confer a multifunctional nature to the employed materials is key for organic-based logic applications. Here we report on the engineering of an electronic structure in a semiconducting film by blending two molecular components, a photochromic diarylethene derivative and a poly(3-hexylthiophene) (P3HT) matrix, to attain phototunable and bistable energy levels for the P3HTs hole transport. As a proof-of-concept we exploited this blend as a semiconducting material in organic thin-film transistors. The device illumination at defined wavelengths enabled reversible tuning of the diarylethenes electronic states in the blend, which resulted in modulation of the output current. The device photoresponse was found to be in the microsecond range, and thus on a technologically relevant timescale. This modular blending approach allows for the convenient incorporation of various molecular components, which opens up perspectives on multifunctional devices and logic circuits.

A robust molecular platform for non-volatile memory devices with optical and magnetic responses

Bistable molecules that behave as switches in solution have long been known. Systems that can be reversibly converted between two stable states that differ in their physical properties are particularly attractive in the development of memory devices when immobilized in substrates. Here, we report a highly robust surface-confined switch based on an electroactive, persistent organic radical immobilized on indium tin oxide substrates that can be electrochemically and reversibly converted to the anion form. This molecular bistable system behaves as an extremely robust redox switch in which an electrical input is transduced into optical as well as magnetic outputs under ambient conditions. The fact that this molecular surface switch, operating at very low voltages, can be patterned and addressed locally, and also has exceptionally high long-term stability and excellent reversibility and reproducibility, makes it a very promising platform for non-volatile memory devices.

Single-crystal organic field-effect transistors based on dibenzo-tetrathiafulvalene

We report on the fabrication and characterization of field-effect transistors based on single crystals of the organic semiconductor dibenzo-tetrathiafulvalene (DB-TTF). We demonstrate that it is possible to prepare very-good-quality DB-TTF crystals from solution. These devices show high field-effect mobilities typically in the range 0.1–1?cm2/V?s. The temperature dependence was also studied revealing an initial increase of the mobility when lowering the temperature until it reached a maximum, after which the mobility decreased following a thermally activated behavior with activation energies between 50 and 60?meV. Calculations of the molecular reorganization energy and intermolecular transfer integrals for this material were also performed and are in agreement with the high mobility observed in this material.

Optical Modulation of the Charge Injection in an Organic Field-Effect Transistor Based on Photochromic Self-Assembled-Monolayer-Functionalized Electrodes

Source and drain functionalization with a light-responsive azobenzene-based self-assembled monolayer (SAM) is used to modulate the charge injection at the Au electrode–semiconductor interface of an organic field-effect transistor (OFET). This photochromic bistable SAM mediates the injection through the variation of the tunneling barrier across the SAM.

Attaching Persistent Organic Free Radicals to Surfaces: How and Why

Attaching Persistent Organic Free Radicals to Surfaces: How and Why Marta Mas-Torrent,* N uria Crivillers, Concepci o Rovira, and Jaume Veciana* Institut de Ci encia de Materials de Barcelona (ICMAB-CSIC), Campus UAB, 08193 Bellaterra, Spain Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN), ICMAB-CSIC, 08193 Bellaterra, Spain ISIS CNRS 7006, Universit e de Strasbourg, 8 all ee Gaspard Monge, 67000 Strasbourg, France

Large Work Function Shift of Gold Induced by a Novel Perfluorinated Azobenzene-Based Self-Assembled Monolayer

Tune it with light! Self-assembled monolayers on gold based on a chemisorbed novel azobenzene derivative with a perfluorinated terminal phenyl ring are prepared. The modified substrate shows a significant work function increase compared to the bare metal. The photo-conversion between trans and cis isomers chemisorbed on the surface shows great perspectives for being an accessible route to tune the gold properties by means of light.

Organic radicals on surfaces: towards molecular spintronics

The novel and exciting field of molecular spintronics has recently attracted a great deal of interest and promising results have already been reported. The utilisation of organic radicals that could favour spin polarisation and conservation during transport offers new possibilities; however, first a fundamental investigation of these materials, especially those deposited on surfaces, is required. Here we highlight our recent results regarding the functionalisation of surfaces with polychlorotriphenylmethyl (PTM) radicals following five different strategies in which interactions of different nature are involved (i.e. van der Waals, electrostatic, coordination bond and covalent bond). In all cases, it was proved that the magnetic character of the molecule persists on the surface.

Self-assembled monolayers of electroactive polychlorotriphenylmethyl radicals on Au(111).

Two new polychlorotriphenylmethyl (PTM) derivatives bearing a thioacetate and a disulfide group have been synthesized to anchor on gold substrate. On the basis of these molecules, three strategies were followed to prepare self-assembled monolayers (SAMs) of electroactive PTMs. The resulting SAMs were fully characterized by contact angle, atomic force microscopy (AFM), and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). The high coverage surface and stability of the SAMs were demonstrated by cyclic voltammetry. In addition, the electrochemical experiments proved that these SAMs are bistable since it is possible to reversibly switch between the PTM radical state to the corresponding anion. The magnetic response was investigated by electron paramagnetic resonance. We observed that when the PTM SAMs are in their radical form they confer magnetic functionality to the surface, whereas when they are in the anionic state, the surface is diamagnetic. Thus, the PTM-modified substrates are multifunctional surfaces since they combine magnetic and electroactive properties. The reported results show the high potential of these materials for the fabrication of surface molecular devices.

Optically switchable organic field-effect transistors based on photoresponsive gold nanoparticles blended with poly(3-hexylthiophene)

Interface tailoring represents a route for integrating complex functions in systems and materials. Although it is ubiquitous in biological systems—e.g., in membranes—synthetic attempts have not yet reached the same level of sophistication. Here, we report on the fabrication of an organic field-effect transistor featuring dual-gate response. Alongside the electric control through the gate electrode, we incorporated photoresponsive nanostructures in the polymeric semiconductor via blending, thereby providing optical switching ability to the device. In particular, we mixed poly(3-hexylthiophene) with gold nanoparticles (AuNP) coated with a chemisorbed azobenzene-based self-assembled monolayer, acting as traps for the charges in the device. The light-induced isomerization between the trans and cis states of the azobenzene molecules coating the AuNP induces a variation of the tunneling barrier, which controls the efficiency of the charge trapping/detrapping process within the semiconducting film. Our approach offers unique solutions to digital commuting between optical and electric signals.

Photoinduced work function changes by isomerization of a densely packed azobenzene-based SAM on Au: a joint experimental and theoretical study.

Responsive monolayers are key building blocks for future applications in organic and molecular electronics in particular because they hold potential for tuning the physico-chemical properties of interfaces, including their energetics. Here we study a photochromic SAM based on a conjugated azobenzene derivative and its influence on the gold work function (Φ(Au)) when chemisorbed on its surface. In particular we show that the Φ(Au) can be modulated with external stimuli by controlling the azobenzene trans/cis isomerization process. This phenomenon is characterized experimentally by four different techniques, kelvin probe, kelvin probe force microscopy, electroabsorption spectroscopy and ultraviolet photoelectron spectroscopy. The use of different techniques implies exposing the SAM to different measurement conditions and different preparation methods, which, remarkably, do not alter the observed work function change (Φ(trans)-Φ(cis)). Theoretical calculations provided a complementary insight crucial to attain a deeper knowledge on the origin of the work function photo-modulation.