Transparent and Highly Responsive Phototransistors Based on a Solution-Processed, Nanometers-Thick Active Layer, Embedding a High-Mobility Electron-Transporting Polymer and a Hole-Trapping Molecule.

Organic materials are suitable for light sensing devices showing unique features such as low cost, large area, and flexibility. Moreover, transparent photodetectors are interesting for smart interfaces, windows, and display-integrated electronics. The ease of depositing ultrathin organic films with simple techniques enables low light absorbing active layers, resulting in the realization of transparent devices. Here, we demonstrate a strategy to obtain high efficiency organic photodetectors and phototransistors based on transparent active layers with a visible transmittance higher than 90%. The photoactive layer is composed of two phases, each a few nanometers thick. First, an acceptor polymer, which is a good electron-transporting material, on top of which a small molecule donor material is deposited, forming noncontinuous domains. The small molecule phase acts as a trap for holes, thus inducing a high photoconductive gain, resulting in a high photoresponsivity. The organic transparent detectors proposed here can reach very high external quantum efficiency and responsivity values, which in the case of the phototransistors can be as high as ∼74000% and 340 A W-1 at 570 nm respectively, despite an absorber total thickness below 10 nm. Moreover, frequency dependent 2D photocurrent mapping allows discrimination between the contribution of a fast but inefficient and highly spatially localized photoinduced injection mechanism at the electrodes, and the onset of a slower and spatially extended photoconductive process, leading to high responsivity.

Electronic transport regimes through an alkoxythiolated diphenyl-2,2'-bithiophene-based molecular junction diodes: critical assessment of the thermal dependence.

The detailed understanding of electronic transport through a single molecule or an ensemble of self-assembled molecules embedded between two metallic leads is still a matter of controversy. Multiple factors influence the charge transport in the molecular junction, with particular attention to be given to the band states of the electrodes, molecular orbital energies, bias potential and importantly molecule-electrode electronic coupling. Moreover it is not trivial to disentangle molecular contributions from other possible conduction pathways directly coupling the opposite electrodes. We here investigate the electronic transport properties of an ensemble molecular junction embedding an alkylthiol derivative of a diphenol substituted bithiophene (DPBT) by means of current vs. voltage and temperature dependent measurements. We explored different junction configurations using: micropores (Au//DPBT//Au and Au//DPBT-polymer conductor//Au) and conductive-atomic force microscopy (c-AFM). In all cases, we found a transition voltage V(T) of ∼0.35 V. The consistent presence of a similar V(T) in all the tested configurations is a strong, but not conclusive, indication of a molecular signature in the charge transport, which we assessed and confirmed by temperature dependent measurements. We found a transition from an incoherent resonant tunneling at low biases and close to room temperature, where transport is thermally activated with an activation energy of ∼85 meV, to a coherent tunneling at voltages higher than V(T). Unlike many other molecular junctions reported in the literature, resonant conditions commonly attributed to a hopping transport regime can be found already at room temperature and very low biases for a molecule only ∼1.5 nm long. This paper is the first report to clearly show temperature activated transport through a short and not fully conjugated molecule. Moreover, we could clearly identify a regime at low temperatures and low bias where the transport mechanism is controlled by the thermal conductivity of the metal electrodes rather than the molecule.

Photoactive molecular junctions based on self-assembled monolayers of indoline dyes.

We demonstrate the feasibility of a photodetector based on an ensemble molecular junction, where a self-assembled monolayer of an organic donor-acceptor dye is directly sandwiched between two electrodes. In such a device, upon photoexcitation and generation of a charge-transfer state on the molecule, charges are dissociated and directly collected at the electrodes without the need of transport through a bulk phase, as in usual photodetectors. We show that the device can work in photovoltaic regime and the spectral response can be tuned by varying the light absorbing dye. Therefore, the electro-optical properties of the downscaled device can be unambiguously related to the physical-chemical properties of the molecules, a commonly difficult point to demonstrate in a molecular junction device, because of the uncertainties of the interplay between molecules and electrodes. The proposed device, which relies on a simple self-assembly process, has a strong potentiality for fast responding, downscaled detectors, ultimately limited by charge dissociation dynamics, and can be considered also as a useful tool to investigate fundamental electro-optical processes in molecular monolayers.