Hybrid organic-inorganic perovskites emerged as a new generation of absorber materials for high-efficiency low-cost solar cells in 2009. Very recently, fully inorganic perovskite quantum dots also led to promising efficiencies, making them a potentially stable and efficient alternative to their hybrid cousins. Currently, the record efficiency is obtained with CsPbI, whose crystallographical characterization is still limited. Here, we show through high-resolution in situ synchrotron XRD measurements that CsPbI can be undercooled below its transition temperature and temporarily maintained in its perovskite structure down to room temperature, stabilizing a metastable perovskite polytype (black γ-phase) crucial for photovoltaic applications. Our analysis of the structural phase transitions reveals a highly anisotropic evolution of the individual lattice parameters versus temperature. Structural, vibrational, and electronic properties of all the experimentally observed black phases are further inspected based on several theoretical approaches. Whereas the black γ-phase is shown to behave harmonically around equilibrium, for the tetragonal phase, density functional theory reveals the same anharmonic behavior, with a Brillouin zone-centered double-well instability, as for the cubic phase. Using total energy and vibrational entropy calculations, we highlight the competition between all the low-temperature phases of CsPbI (γ, δ, β) and show that avoiding the order-disorder entropy term arising from double-well instabilities is key to preventing the formation of the yellow perovskitoid phase. A symmetry-based tight-binding model, validated by self-consistent GW calculations including spin-orbit coupling, affords further insight into their electronic properties, with evidence of Rashba effect for both cubic and tetragonal phases when using the symmetry-breaking structures obtained through frozen phonon calculations.

Hybrid perovskites have emerged over the past five years as absorber layers for novel high-efficiency low-cost solar cells combining the advantages of organic and inorganic semiconductors. Unfortunately, electrical transport in these materials is still poorly understood. Employing the linear response approach of density functional theory, we reveal strong anharmonic effects and a double-well phonon instability at the center of the Brillouin zone for both cubic and orthorhombic phases of inorganic CsPbI. Previously reported soft phonon modes are stabilized at the actual lower-symmetry equilibrium structure, which occurs in a very flat energy landscape, highlighting the strong competition between the different phases of CsPbI. Factoring these low-energy phonons into electron-phonon interactions and band gap calculations could help better understand the electrical transport properties in these materials. Furthermore, the perovskite oscillations through the corresponding energy barrier could explain the underlying ferroelectricity and the dynamical Rashba effect predicted in halide perovskites for photovoltaics.

In recent decades, the development of organic−inorganic hybrid perovskite solar cells (PSCs) has been increasing very quickly due to their high initial efficiency and low-cost process. However, key points such as crystal growth mechanisms, current−voltage hysteresis, and instability remain still unexplained or misunderstood. Among several possibilities, ionic migration in PSCs has been suggested to explain the hysteresis effect. However, direct experimental evidence of ionic migration under operation or measurement conditions of PSCs is still missing. This work shows directly the ionic migration of halogen components (I − and Cl − ) of a CH 3 NH 3 PbI 3−x Cl x perovskite film under an applied bias using glow discharge optical emission spectrometry (GD-OES). Furthermore, no migration of lead and nitrogen ions is observed on a polarization time scale less than 2 min. The ratio of fixed to mobile iodide ions is deduced from the evolution of the GD-OES profile lines as a function of the applied bias. The average length of iodide and chloride ion migration is deduced from the experimental results.

This roadmap includes the perspectives and visions of leading researchers in the key areas of flexible and printable electronics. The covered topics are broadly organized by the device technologies (sections 1-9), fabrication techniques (sections 10-12), and design and modeling

In bottom‐contact organic field‐effect transistors (OFETs), the functionalization of source/drain electrodes leads to a tailored surface chemistry for film growth and controlled interface energetics for charge injection. This report describes a comprehensive investigation into separating and correlating the energetic and morphological effects of a self‐assembled monolayers (SAMs) treatment on Au, Ag, and Cu electrodes. Fluorinated 5,11‐bis(triethylsilylethynyl) anthradithiophene (diF‐TES‐ADT) and pentafluorobenzenethiol (PFBT) are employed as a soluble small‐molecule semiconductor and a SAM material, respectively. Upon SAM modification, the Cu electrode devices benefit from a particularly dramatic performance improvement, closely approaching the performance of OFETs with PFBT‐Au and PFBT‐Ag. Ultraviolet photoemission spectroscopy, polarized optical microscopy, grazing‐incidence wide‐angle X‐ray scattering elucidate the metal work function change and templated crystal growth with high crystallinity resulting from SAMs. The transmission‐line method separates the channel and contact properties from the measured OFET current–voltage data, which conclusively describes the impact of the SAMs on charge injection and transport behavior.

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International audienceWe propose a theoretical description of the charge distribution and the contact resistance in coplanar organic field-effect transistors (OFETs). Based on the concept that the current in organic semiconductors is only carried by injected carriers from the electrodes, an analytical formulation for the charge distribution inside the organic layer was derived. We found that the contact resistance in coplanar OFETs arises from a sharp low-carrier-density zone at the source/channel edge because the gate-induced channel carrier density is orders of magnitude higher than the source carrier density. This image is totally different from the contact resistance in staggered OFETs, in which the contact resistance mainly originates from the resistance through the semiconductor bulk. The contact resistance was calculated through charge-distribution functions, and the model could explain the effect of the gate voltage and injection barrier on the contact resistance. Experimental data on pentacene OFETs were analyzed using the transmission-line method. We finally noticed that the gate-voltage-dependent mobility is a critical factor for proper understanding of the contact resistance in real devices

In order to build upon the exceptional interest for flexible sensors based on carbon nanotube networks (CNNs), the field requires high device-to-device reproducibility. Inkjet printing has provided outstanding results for flexible ohmic sensors in terms of reproducibility of their resistance. However, the reproducibility of the sensitivity, the most critical parameter for sensing application, has been only marginally assessed. In the present paper, CNN based resistive strain sensors fabricated by inkjet-printing on flexible Ethylene Tetrafluoroethylene (EFTE) sheets are presented. The variability on the device initial resistance is studied for 5 different batches of sensors from 3 to 72 devices each. The variability ranges between 8.4% and 43% depending on the size of the batches, with a 20% average. An 8-device batch with 15% variability on initial resistance is further studied for variability on the strain and thermal sensitivity. Standard deviation values are found to be as low as 16% on the strain sensitivity and 8% on the temperature sensitivity. Moreover, the devices are hysteresis free, a rare achievement for CNT strain sensors on plastics