Enrico Bandiello

Efficient vacuum deposited p-i-n and n-i-p perovskite solar cells employing doped charge transport layers

Methylammonium lead halide perovskites have emerged as high performance photovoltaic materials. Most of these solar cells are prepared via solution-processing and record efficiencies (>20%) have been obtained employing perovskites with mixed halides and organic cations on (mesoscopic) metal oxides. Here, we demonstrate fully vacuum deposited planar perovskite solar cells by depositing methylammonium lead iodide in between intrinsic and doped organic charge transport molecules. Two configurations, one inverted with respect to the other, p-i-n and n-i-p, are prepared and optimized leading to planar solar cells without hysteresis and very high efficiencies, 16.5% and 20%, respectively. It is the first time that a direct comparison between these two opposite device configurations has been reported. These fully vacuum deposited solar cells, employing doped organic charge transport layers, validate for the first time vacuum based processing as a real alternative for perovskite solar cell preparation.

Efficient methylammonium lead iodide perovskite solar cells with active layers from 300 to 900 nm

Efficient methylammonium lead iodide perovskite-based solar cells have been prepared in which the perovskite layer is sandwiched in between two organic charge transporting layers that block holes and electrons, respectively. This configuration leads to stable and reproducible devices that do not suffer from strong hysteresis effects and when optimized lead to efficiencies close to 15%. The perovskite layer is formed by using a dual-source thermal evaporation method, whereas the organic layers are processed from solution. The dual-source thermal evaporation method leads to smooth films and allows for high precision thickness variations. Devices were prepared with perovskite layer thicknesses ranging from 160 to 900 nm. The short-circuit current observed for these devices increased with increasing perovskite layer thickness. The main parameter that decreases with increasing perovskite layer thickness is the fill factor and as a result optimum device performance is obtained for perovskite layer thickness aro...

Ion-selective organic electrochemical transistors.

Ion-selective organic electrochemical transistors with sensitivity to potassium approaching 50 μA dec(-1) are demonstrated. The remarkable sensitivity arises from the use of high transconductance devices, where the conducting polymer is in direct contact with a reference gel electrolyte and integrated with an ion-selective membrane.

Effects of high-pressure on the structural, vibrational, and electronic properties of monazite-type PbCrO4

We have performed an experimental study of the crystal structure, lattice dynamics, and optical properties of PbCrO4 (the mineral crocoite) at ambient and high pressures. In particular, the crystal structure, Raman-active phonons, and electronic band gap have been accurately determined. X-ray-diffraction, Raman, and optical absorption experiments have allowed us also to completely characterize two pressure-induced structural phase transitions. The first transition is from a monoclinic structure to another monoclinic structure. It maintains the symmetry of the crystal but has important consequences in the physical properties; among others, a band-gap collapse is induced. The second one involves an increase of the symmetry of the crystal, a volume collapse, and probably the metallization of PbCrO4. The results are discussed in comparison with related compounds, and the effects of pressure in the electronic structure are explained. Finally, the room-temperature equation of state of the low-pressure phases is also obtained.

Controlling the mode of operation of organic transistors through side-chain engineering

Significance Side-chain engineering is a versatile tool to modify the processability, as well as the physical, electrical, and optical properties, of conjugated polymers. This approach is used to tailor the operating mechanism of electrolyte-gated organic transistors, allowing for facile bulk doping and therefore efficient modulation of transistor channel conductance. Such transistors combine fast response with high current-to-voltage signal transduction necessary for active sensing and low-power circuit applications. Electrolyte-gated organic transistors offer low bias operation facilitated by direct contact of the transistor channel with an electrolyte. Their operation mode is generally defined by the dimensionality of charge transport, where a field-effect transistor allows for electrostatic charge accumulation at the electrolyte/semiconductor interface, whereas an organic electrochemical transistor (OECT) facilitates penetration of ions into the bulk of the channel, considered a slow process, leading to volumetric doping and electronic transport. Conducting polymer OECTs allow for fast switching and high currents through incorporation of excess, hygroscopic ionic phases, but operate in depletion mode. Here, we show that the use of glycolated side chains on a thiophene backbone can result in accumulation mode OECTs with high currents, transconductance, and sharp subthreshold switching, while maintaining fast switching speeds. Compared with alkylated analogs of the same backbone, the triethylene glycol side chains shift the mode of operation of aqueous electrolyte-gated transistors from interfacial to bulk doping/transport and show complete and reversible electrochromism and high volumetric capacitance at low operating biases. We propose that the glycol side chains facilitate hydration and ion penetration, without compromising electronic mobility, and suggest that this synthetic approach can be used to guide the design of organic mixed conductors.

Molecular Design of Semiconducting Polymers for High-Performance Organic Electrochemical Transistors

The organic electrochemical transistor (OECT), capable of transducing small ionic fluxes into electronic signals in an aqueous environment, is an ideal device to utilize in bioelectronic applications. Currently, most OECTs are fabricated with commercially available conducting poly(3,4-ethylenedioxythiophene) (PEDOT)-based suspensions and are therefore operated in depletion mode. Here, we present a series of semiconducting polymers designed to elucidate important structure–property guidelines required for accumulation mode OECT operation. We discuss key aspects relating to OECT performance such as ion and hole transport, electrochromic properties, operational voltage, and stability. The demonstration of our molecular design strategy is the fabrication of accumulation mode OECTs that clearly outperform state-of-the-art PEDOT-based devices, and show stability under aqueous operation without the need for formulation additives and cross-linkers.

Operational Mechanism of Conjugated Polyelectrolytes

Conjugated polyelectrolytes (CPEs) are versatile materials used in a range of organic optoelectronic applications. Because of their ionic/electronic nature, characterizing these materials is nontrivial, and their operational mechanism is not fully understood. In this work we use a methodology that combines constant-voltage-driven current-density transient measurements with fast current vs voltage scans to allow decoupling of ionic and electronic phenomena. This technique is applied to diodes prepared with cationic CPEs having different charge-compensating anions. Our results indicate that the operational mechanism of these devices is governed by electrochemical doping of the CPE. On the basis of the notion that the saturated depletion layer for the anions consists of the same π-conjugated backbone material, we discern how the extent and speed of formation of the doped region depend on the anion structure. Apart from addressing fundamental transport questions, this work provides a tool for future characterization of different CPEs and other similar systems.

Lithium salt additives and the influence of their counterion on the performances of light-emitting electrochemical cells

In this work we study the effect of the addition of lithium salts to light-emitting electrochemical cells (LECs), and in particular the effect of the lithium counterion. We found that the chosen lithium salts can substantially improve the device turn-on time as well as the overall lifetime, with respect to reference LECs using the pure emitter. A correlation between the lithium counterion and the corresponding device performance is established, and efficient LECs with lifetimes approaching 2000 hours are presented.

Aqueous electrolyte-gated ZnO transistors for environmental and biological sensing

Electrolyte-gated transistors (EGTs) based on ZnO thin films, obtained by solution processing of suspensions of nanoparticles, have a low turn-on voltage (<0.5 V), a high on/off ratio and transconductance exceeding 0.2 mS. Importantly, the ZnO surface can be functionalized with a large variety of molecular recognition elements, making these devices ideal transducers in physiological and environmental monitoring. We present simple glucose-sensing and ion-selective EGTs, demonstrating the versatility of such devices in biosensing.

Influence of mobile ions on the electroluminescence characteristics of methylammonium lead iodide perovskite diodes

In this work, we study the effect of voltage bias on the optoelectronic behavior of methylammonium lead iodide planar diodes. Upon biasing the diodes with a positive voltage, the turn-on voltage of the electroluminescence diminishes and its intensity substantially increases. This behavior is reminiscent of that observed in light-emitting electrochemical cells (LECs), single-layer electroluminescent devices in which the charge injection is assisted by the accumulation of ions at the electrode interface. Because of this mechanism, performances are largely independent from the work function of the electrodes. The similarities observed between planar perovskite diodes and LECs suggest that mobile ions in the perovskite do play an important role in device operation. Besides enhanced electroluminescence, biasing these devices can also result in improved photovoltaic performance.