Emanuele Orgiu

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.

25th Anniversary Article: Organic Electronics Marries Photochromism: Generation of Multifunctional Interfaces, Materials, and Devices

Organic semiconductors have garnered significant interest as key components for flexible, low-cost, and large-area electronics. Hitherto, both materials and processing thereof seems to head towards a mature technology which shall ultimately meet expectations and efforts built up over the past years. However, by its own organic electronics cannot compete or complement the silicon-based electronics in integrating multiple functions in a small area unless novel solutions are brought into play. Photochromic molecules are small organic molecules able to undergo reversible photochemical isomerization between (at least) two (meta)stable states which exhibit markedly different properties. They can be embedded as additional component in organic-based materials ready to be exploited in devices such as OLEDs, OFETs, and OLETs. The structurally controlled incorporation of photochromic molecules can be done at various interfaces of a device, including the electrode/semiconductor or dielectric/semiconductor interface, or even as a binary mixture in the active layer, in order to impart a light responsive nature to the device. This can be accomplished by modulating via a light stimulus fundamental physico-chemical properties such as charge injection and transport in the device.

Local Current Mapping and Patterning of Reduced Graphene Oxide

Conductive atomic force microscopy (C-AFM) has been used to correlate the detailed structural and electrical characteristics of graphene derived from graphene oxide. Uniform large currents were measured over areas exceeding tens of micrometers in few-layer films, supporting the use of graphene as a transparent electrode material. Moreover, defects such as electrical discontinuities were easily detected. Multilayer films were found to have a higher conductivity per layer than single layers. It is also shown that a local AFM-tip-induced electrochemical reduction process can be used to pattern conductive pathways on otherwise-insulating graphene oxide. Transistors with micrometer-scale tip-reduced graphene channels that featured ambipolar transport and an 8 order of magnitude increase in current density upon reduction were successfully fabricated.

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.

Conductivity in organic semiconductors hybridized with the vacuum field.

Much effort over the past decades has been focused on improving carrier mobility in organic thin-film transistors by optimizing the organization of the material or the device architecture. Here we take a different path to solving this problem, by injecting carriers into states that are hybridized to the vacuum electromagnetic field. To test this idea, organic semiconductors were strongly coupled to plasmonic modes to form coherent states that can extend over as many as 10(5) molecules and should thereby favour conductivity. Experiments show that indeed the current does increase by an order of magnitude at resonance in the coupled state, reflecting mostly a change in field-effect mobility. A theoretical quantum model confirms the delocalization of the wavefunctions of the hybridized states and its effect on the conductivity. Our findings illustrate the potential of engineering the vacuum electromagnetic environment to modify and to improve properties of materials.

Degradation of Methylammonium Lead Iodide Perovskite Structures through Light and Electron Beam Driven Ion Migration

Organometal halide perovskites show promising features for cost-effective application in photovoltaics. The material instability remains a major obstacle to broad application because of the poorly understood degradation pathways. Here, we apply simultaneous luminescence and electron microscopy on perovskites for the first time, allowing us to monitor in situ morphology evolution and optical properties upon perovskite degradation. Interestingly, morphology, photoluminescence (PL), and cathodoluminescence of perovskite samples evolve differently upon degradation driven by electron beam (e-beam) or by light. A transversal electric current generated by a scanning electron beam leads to dramatic changes in PL and tunes the energy band gaps continuously alongside film thinning. In contrast, light-induced degradation results in material decomposition to scattered particles and shows little PL spectral shifts. The differences in degradation can be ascribed to different electric currents that drive ion migration. Moreover, solution-processed perovskite cuboids show heterogeneity in stability which is likely related to crystallinity and morphology. Our results reveal the essential role of ion migration in perovskite degradation and provide potential avenues to rationally enhance the stability of perovskite materials by reducing ion migration while improving morphology and crystallinity. It is worth noting that even moderate e-beam currents (86 pA) and acceleration voltages (10 kV) readily induce significant perovskite degradation and alter their optical properties. Therefore, attention has to be paid while characterizing such materials using scanning electron microscopy or transmission electron microscopy techniques.

Optically switchable transistors by simple incorporation of photochromic systems into small-molecule semiconducting matrices

The fabrication of multifunctional high-performance organic thin-film transistors as key elements in future logic circuits is a major research challenge. Here we demonstrate that a photoresponsive bi-functional field-effect transistor with carrier mobilities exceeding 0.2 cm(2) V(-1) s(-1) can be developed by incorporating photochromic molecules into an organic semiconductor matrix via a single-step solution processing deposition of a two components blend. Tuning the interactions between the photochromic diarylethene system and the organic semiconductor is achieved via ad-hoc side functionalization of the diarylethene. Thereby, a large-scale phase-segregation can be avoided and superior miscibility is provided, while retaining optimal π-π stacking to warrant efficient charge transport and to attenuate the effect of photoinduced switching on the extent of current modulation. This leads to enhanced electrical performance of transistors incorporating small conjugated molecules as compared with polymeric semiconductors. These findings are of interest for the development of high-performing optically gated electronic devices.

Harnessing the Liquid‐Phase Exfoliation of Graphene Using Aliphatic Compounds: A Supramolecular Approach

The technological exploitation of the extraordinary properties of graphene relies on the ability to achieve full control over the production of a high-quality material and its processing by up-scalable approaches in order to fabricate large-area films with single-layer or a few atomic-layer thickness, which might be integrated in working devices. A simple method is reported for producing homogenous dispersions of unfunctionalized and non-oxidized graphene nanosheets in N-methyl-2-pyrrolidone (NMP) by using simple molecular modules, which act as dispersion-stabilizing compounds during the liquid-phase exfoliation (LPE) process, leading to an increase in the concentration of graphene in dispersions. The LPE-processed graphene dispersion was shown to be a conductive ink. This approach opens up new avenues for the technological applications of this graphene ink as low-cost electrodes and conducting nanocomposite for electronics.

Flexible non-volatile optical memory thin-film transistor device with over 256 distinct levels based on an organic bicomponent blend

Organic nanomaterials are attracting a great deal of interest for use in flexible electronic applications such as logic circuits, displays and solar cells. These technologies have already demonstrated good performances, but flexible organic memories are yet to deliver on all their promise in terms of volatility, operational voltage, write/erase speed, as well as the number of distinct attainable levels. Here, we report a multilevel non-volatile flexible optical memory thin-film transistor based on a blend of a reference polymer semiconductor, namely poly(3-hexylthiophene), and a photochromic diarylethene, switched with ultraviolet and green light irradiation. A three-terminal device featuring over 256 (8 bit storage) distinct current levels was fabricated, the memory states of which could be switched with 3 ns laser pulses. We also report robustness over 70 write-erase cycles and non-volatility exceeding 500 days. The device was implemented on a flexible polyethylene terephthalate substrate, validating the concept for integration into wearable electronics and smart nanodevices.

Graphene nanoribbon blends with P3HT for organic electronics.

In organic field-effect transistors (OFETs) the electrical characteristics of polymeric semiconducting materials suffer from the presence of structural/morphological defects and grain boundaries as well as amorphous domains within the film, hindering an efficient transport of charges. To improve the percolation of charges we blend a regioregular poly(3-hexylthiophene) (P3HT) with newly designed N = 18 armchair graphene nanoribbons (GNRs). The latter, prepared by a bottom-up solution synthesis, are expected to form solid aggregates which cannot be easily interfaced with metallic electrodes, limiting charge injection at metal-semiconductor interfaces, and are characterized by a finite size, thus by grain boundaries, which negatively affect the charge transport within the film. Both P3HT and GNRs are soluble/dispersible in organic solvents, enabling the use of a single step co-deposition process. The resulting OFETs show a three-fold increase in the charge carrier mobilities in blend films, when compared to pure P3HT devices. This behavior can be ascribed to GNRs, and aggregates thereof, facilitating the transport of the charges within the conduction channel by connecting the domains of the semiconductor film. The electronic characteristics of the devices such as the Ion/Ioff ratio are not affected by the addition of GNRs at different loads. Studies of the electrical characteristics under illumination for potential use of our blend films as organic phototransistors (OPTs) reveal a tunable photoresponse. Therefore, our strategy offers a new method towards the enhancement of the performance of OFETs, and holds potential for technological applications in (opto)electronics.