Simone Fabiano

From Monolayer to Multilayer N-Channel Polymeric Field-Effect Transistors with Precise Conformational Order

Monolayer field-effect transistors based on a high-mobility n-type polymer are demonstrated. The accurate control of the long-range order by Langmuir-Schäfer (LS) deposition yields dense polymer packing exhibiting good injection properties, relevant current on/off ratio and carrier mobility in a staggered configuration. Layer-by-layer LS film transistors of increasing thickness are fabricated and their performance compared to those of spin-coated films.

Experimental evidence that short-range intermolecular aggregation is sufficient for efficient charge transport in conjugated polymers

Significance Understanding the nature of charge transport and its limitations has guided the rational design of organic semiconductors. Research has mainly focused on increasing the crystallinity of conjugated polymers as a strategy to improve the long-range charge transport properties. Here, we demonstrate that local aggregation over very few chains is a sufficient mesoscopic structure to ensure high mobility, with charge transport mainly occurring along the polymer backbones, and that extended crystallinity is not necessary. These results provide an explanation for the high mobilities observed in seemingly disordered polymers and set molecular-design guidelines for next-generation conjugated polymers. Efficiency, current throughput, and speed of electronic devices are to a great extent dictated by charge carrier mobility. The classic approach to impart high carrier mobility to polymeric semiconductors has often relied on the assumption that extensive order and crystallinity are needed. Recently, however, this assumption has been challenged, because high mobility has been reported for semiconducting polymers that exhibit a surprisingly low degree of order. Here, we show that semiconducting polymers can be confined into weakly ordered fibers within an inert polymer matrix without affecting their charge transport properties. In these conditions, the semiconducting polymer chains are inhibited from attaining long-range order in the π-stacking or alkyl-stacking directions, as demonstrated from the absence of significant X-ray diffraction intensity corresponding to these crystallographic directions, yet still remain extended along the backbone direction and aggregate on a local length scale. As a result, the polymer films maintain high mobility even at very low concentrations. Our findings provide a simple picture that clarifies the role of local order and connectivity of domains.

Organoboron Polymers for Photovoltaic Bulk Heterojunctions

We report on the application of three-coordinate organoboron polymers, inherently strong electron acceptors, in flexible photovoltaic (PV) cells. Poly[(1,4-divinylenephenylene)(2,4,6-triisopropylphenylborane)] (PDB) has been blended with poly(3-hexylthiophene-2,5-diyl) (P3HT) to form a thin film bulk heterojunction (BHJ) on PET/ITO substrates. Morphology may be modulated to give a high percentage of domains (10-20 nm in size) allowing exciton separation. The photoelectric properties of the BHJs in devices with aluminium back electrodes were imaged by light beam induced current (LBIC) and light beam induced voltage (LBIV) techniques. Open circuit voltages, short circuit currents and overall external quantum efficiencies obtained are among the highest reported for all-polymer PV cells.

Poly(ethylene imine) impurities induce n-doping reaction in organic (semi)conductors

Volatile impurities contained in polyethyleneimine (PEI), and identified as ethyleneimine dimers and trimers, are reported. These N-based molecules show a strong reducing character, as demonstrated by the change in electrical conductivity of organic (semi)conductors exposed to the PEI vapor. The results prove that electron transfer rather than a dipole effect at the electrode interface is the origin of the work-function modification by the PEI-based layers.

Selective Remanent Ambipolar Charge Transport in Polymeric Field‐Effect Transistors For High‐Performance Logic Circuits Fabricated in Ambient

Ambipolar polymeric field-effect transistors can be programmed into a p- or n-type mode by using the remanent polarization of a ferroelectric gate insulator. Due to the remanent polarity, the device architecture is suited as a building block in complementary logic circuits and in CMOS-compatible memory cells for non-destructive read-out operations.

Ferroelectric Polarization Induces Electric Double Layer Bistability in Electrolyte-Gated Field-Effect Transistors

The dense surface charges expressed by a ferroelectric polymeric thin film induce ion displacement within a polyelectrolyte layer and vice versa. This is because the density of dipoles along the surface of the ferroelectric thin film and its polarization switching time matches that of the (Helmholtz) electric double layers formed at the ferroelectric/polyelectrolyte and polyelectrolyte/semiconductor interfaces. This combination of materials allows for introducing hysteresis effects in the capacitance of an electric double layer capacitor. The latter is advantageously used to control the charge accumulation in the semiconductor channel of an organic field-effect transistor. The resulting memory transistors can be written at a gate voltage of around 7 V and read out at a drain voltage as low as 50 mV. The technological implication of this large difference between write and read-out voltages lies in the non-destructive reading of this ferroelectric memory.

Ionic thermoelectric gating organic transistors

Temperature is one of the most important environmental stimuli to record and amplify. While traditional thermoelectric materials are attractive for temperature/heat flow sensing applications, their sensitivity is limited by their low Seebeck coefficient (∼100 μV K−1). Here we take advantage of the large ionic thermoelectric Seebeck coefficient found in polymer electrolytes (∼10,000 μV K−1) to introduce the concept of ionic thermoelectric gating a low-voltage organic transistor. The temperature sensing amplification of such ionic thermoelectric-gated devices is thousands of times superior to that of a single thermoelectric leg in traditional thermopiles. This suggests that ionic thermoelectric sensors offer a way to go beyond the limitations of traditional thermopiles and pyroelectric detectors. These findings pave the way for new infrared-gated electronic circuits with potential applications in photonics, thermography and electronic-skins.

Naphthalenediimide Polymers with Finely Tuned In-Chain π-Conjugation: Electronic Structure, Film Microstructure, and Charge Transport Properties

Naphthalenediimide-based random copolymers (PNDI-TVTx) with different π-conjugated dithienylvinylene (TVT) versus π-nonconjugated dithienylethane (TET) unit ratios (x = 100→0%) are investigated. The PNDI-TVTx-transistor electron/hole mobilities are affected differently, a result rationalized by molecular orbital topologies and energies, with hole mobility vanishing but electron mobility decreasing only by ≈2.5 times when going from x = 100% to 40%.

Selecting speed-dependent pathways for a programmable nanoscale texture by wet interfaces

The realization of well-defined and ordered structures on the nanoscale is a main issue in nanoscience and nanotechnology, biotechnology and other related fields like plastic or organic electronics. Among the bottom-up approaches, to date, self-assembly (equilibrium aggregates) received a major attention. In spite of this, far from equilibrium conditions allow for the generation of a wider landscape of organized systems depending on the set of control parameters employed. Under an adaptation vision of the structures, here we report some case studies showing how it is possible to programme and control the nanoscale features of ordered super- or supra-aggregates at wet interfaces by modulating the dynamic parameters. In particular, speed is foreseen as a threshold factor for changing the aggregation mechanism along with the shape and degree of order of the structures as well as, within a specific aggregation path, their size and defectivity.

Bias stress effect in polyelectrolyte-gated organic field-effect transistors

A main factor contributing to bias stress instability in organic transistors is charge trapping of mobile carriers near the gate insulator-semiconductor interface into localized electronic states. In this paper, we study the bias stress behavior in low-voltage (p-type) polyelectrolyte-gated organic field effect transistors (EGOFETs) at various temperatures. Stressing and recovery in these EGOFETs are found to occur six orders of magntiude faster than typical bias stress/recovery reported for dielectric-gated OFETs. The mechanism proposed for EGOFETs involves an electron transfer reaction between water and the charged semiconductor channel that promotes the creation of extra protons diffusing into the polyelectrolyte.