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The quantification of the electronic transport energy gap of a molecular semiconductor is essential for pursuing any challenge in molecular optoelectronics. However, this remains largely elusive because of the difficulties in its determination by conventional spectroscopic methods. This communication presents an in-device molecular spectroscopy (i-MOS) technique, which permits measuring this gap seamlessly, in real device operative conditions, at room temperature and without any previous knowledge of the material's parameters. This result is achieved by determining the occupied and unoccupied molecular orbitals of an organic semiconductor thin-film by using a single three terminal solid-state device., Materials horizons;2019, 6, 1663--166

A spin-valve solar cell Electronic spin currents can be measured with a spin valve—a device that injects charge carriers from one ferromagnetic electrode to another through a semiconductor layer. Some organic semiconductors can have long spin-carrier lifetimes and can also generate charge carriers through the photovoltaic effect. Sun et al. fabricated a spin valve based on C 60 and showed that the spin current could be modulated by the photocurrent. At certain light intensities, the sign of the photocurrent could be changed using an applied magnetic field, an effect that could potentially be harnessed for sensing applications. Science , this issue p. 677

An approach for the synthesis of pyrene-fused acenes that allows the introduction of electron-withdrawing cyano groups in key positions that simultaneously (i) induce twists in the aromatic framework and (ii) stabilize the LUMO level is reported. This combination of steric and electronic features provide a twisted, stable, and n-type tetrabenzoheptacene as confirmed by a combination of theoretical calculations and optical, electrochemical, thermal, and electrical characterization.

Flexible and wearable devices are among the upcoming trends in the opto-electronics market. Nevertheless, bendable devices should ensure the same efficiency and stability as their rigid analogs. It is well-known that the energy barriers between the metal Fermi energy and the molecular levels of organic semiconductors devoted to charge transport are key parameters in the performance of organic-based electronic devices. Therefore, it is paramount to understand how the energy barriers at metal/organic semiconductor interfaces change with bending. In this work, we experimentally measure the interface energy barriers between a metallic contact and small semiconducting molecules. The measurements are performed in operative conditions, while the samples are bent by a controlled applied mechanical strain. We determine that energy barriers are not sensitive to bending of the sample, but we observe that the hopping transport of the charges in flat molecules can be tuned by mechanical strain. The theoretical model developed for this work confirms our experimental observations.

Long distance spin transport and photoresponse are demonstrated in a single F16 CuPc spin valve. By introducing a low-temperature strategy for controlling the morphology of the organic layer during the fabrication of a molecular spin valve, a large spin-diffusion length up to 180 nm is achieved at room temperature. Magnetoresistive and photoresponsive signals are simultaneously observed even in an air atmosphere.

Molecules are proposed to be an efficient medium to host spin-polarized carriers, due to their weak spin relaxation mechanisms. While relatively long spin lifetimes are measured in molecular devices, the most promising route toward device functionalization is to use the chemical versatility of molecules to achieve a deterministic control and manipulation of the electron spin. Here, by combining magnetotransport experiments with element-specific X-ray absorption spectroscopy, this study shows the ability of molecules to modify spin-dependent properties at the interface level via metal–molecule hybridization pathways. In particular, it is described how the formation of hybrid states determines the spin polarization at the relevant spin valve interfaces, allowing the control of macroscopic device parameters such as the sign and magnitude of the magnetoresistance. These results consolidate the application of the spinterface concept in a fully functional device platform.

A pyrene-fused phenazinothiadiazole that shows electron mobilities (μe= 0.016 cm2V−1s−1) two orders of magnitude higher than those reported for pyrene-fused pyrazaacenes is described.

Organic field-effect transistors (OFETs) are fundamental building blocks for plastic electronics such as organic photovoltaics or bendable displays with organic light emitting diodes, and radio-frequency identification (RFID) tags. A key part in the performance of OFET is the organic material constituting the channel. OFETs based on solution-processed polymers represent a new class of organic electronic devices. Recent developments in upscale solution-processed polymers have advanced towards high throughput, low-cost, and environmentally friendly materials for high-performance applications. Together with the integration of high performance materials, another enduring challenge in OFET development is the improvement and control of the injection of charge carriers. Graphene, a two-dimensional layer of covalently bonded carbon atoms, is steadily making progress into applications relying on van der Waals heterointerfaces with organic semiconductors. Here, we demonstrate the versatile operation of solution-processed organic transistors both in lateral and vertical geometries by exploiting the weak-screening effect and work function modulation properties of graphene electrodes. Our results demonstrate a general strategy for overcoming traditional noble metal electrodes and to integrate graphene with solution-processed Polyera ActiveInk™ N2200 polymer transistors for high-performance devices suitable for future plastic electronics.

Enhanced light-matter interactions are the basis of surface-enhanced infrared absorption (SEIRA) spectroscopy, and conventionally rely on plasmonic materials and their capability to focus light to nanoscale spot sizes. Phonon polariton nanoresonators made of polar crystals could represent an interesting alternative, since they exhibit large quality factors, which go far beyond those of their plasmonic counterparts. The recent emergence of van der Waals crystals enables the fabrication of high-quality nanophotonic resonators based on phonon polaritons, as reported for the prototypical infrared-phononic material hexagonal boron nitride (h-BN). In this work we use, for the first time, phonon-polariton-resonant h-BN ribbons for SEIRA spectroscopy of small amounts of organic molecules in Fourier transform infrared spectroscopy. Strikingly, the interaction between phonon polaritons and molecular vibrations reaches experimentally the onset of the strong coupling regime, while numerical simulations predict that vibrational strong coupling can be fully achieved. Phonon polariton nanoresonators thus could become a viable platform for sensing, local control of chemical reactivity and infrared quantum cavity optics experiments., We also acknowledge support from the European Commission under the Graphene Flagship (GrapheneCore1, Grant no. 696656), the Marie SklodowskaCurie individual fellowship (SGPCM-705960), the Spanish Ministry of Economy and Competitiveness (Maria de Maetzu Units of Excellence Programme MDM-2016-0618 and national projects FIS2014-60195-JIN, MAT2014-53432- C5-4-R, MAT2015-65525-R, MAT2015-65159-R, FIS2016-80174-P, MAT2017- 88358-C3-3-R), the Basque government (PhD fellowship PRE-2016-1-0150, PRE-2016-2-0025), the Department of Industry of the Basque Government (ELKARTEK project MICRO4FA), the Regional Council of Gipuzkoa (project no. 100/16) and the ERC starting grant 715496, 2DNANOPTICA.

Molecular spins have become key enablers for exploring magnetic interactions, quantum information processes and many-body effects in metals. Metal-organic molecules, in particular, let the spin state of the core metal ion to be modified according to its organic environment, allowing localized magnetic moments to emerge as functional entities with radically different properties from its simple atomic counterparts. Here, using and preserving the integrity of transition metal phthalocyanine high-spin complexes, we demonstrate the magnetic doping of gold thin films, effectively creating a new ground state. We demonstrate it by electrical transport measurements that are sensitive to the scattering of itinerant electrons with magnetic impurities, such as Kondo effect and weak antilocalization. Our work expands in a simple and powerful way the classes of materials that can be used as magnetic dopants, opening a new channel to couple the wide range of molecular properties with spin phenomena at a functional scale., Molecular magnets are molecules with an inherent non-zero spin that can exhibit magnetic ordering. Here, the authors show that such molecules can change the many-body ground state of nonmagnetic metals at a functional scale with magnetic phthalocyanines.

The synthesis and properties of two highly stable K-conjugated dibenzoazahexacenes are reported. Single-crystal X-ray, optoelectronic, and electrochemical characterization combined with theoretical studies show a favorable molecular packing and an optimal energy alignment of their frontier orbitals for charge transport. Electrical characterization illustrates that the preferential transport of holes or electrons depends on the number of N atoms in the aromatic framework.

The synthesis and characterisation of a pyrene-fused tetraazaheptacene that is constituted of two terminal pyrene units and a central tetraazaanthracene core are reported. The optoelectronic properties (experimental and calculated) of this heptacene derivative are discussed together with its charge transport properties in thin films.

We show the operation of a Cu/Al_2O_3/Cu/n-Si hot-electron transistor for the straightforward determination of a metal/semiconductor energy barrier height even at temperatures below carrier-freeze out in the semiconductor. The hot-electron spectroscopy measurements return a fairly temperature independent value for the Cu/n-Si barrier of 0.66 $\pm$ 0.04 eV at temperatures below 180 K, in substantial accordance with mainstream methods based on complex fittings of either current-voltage (I-V) and capacitance-voltage (C-V) measurements. The Cu/n-Si hot-electron transistors exhibit an OFF current of ~2 * 10^-13 A, an ON/OFF ratio of ~10^5 and an equivalent subtreshold swing of ~96 mV/dec at low temperatures, which are suitable values for potential high frequency devices., Comment: 15 pages, 3 figures, accepted in Appl. Phys. Lett. 2015

Energy barriers between the metal Fermi energy and the molecular levels of organic semiconductor devoted to charge transport play a fundamental role in the performance of organic electronic devices. Typically, techniques such as electron photoemission spectroscopy, Kelvin probe measurements, and in-device hot-electron spectroscopy have been applied to study these interfacial energy barriers. However, so far there has not been any direct method available for the determination of energy barriers at metal interfaces with n-type polymeric semiconductors. This study measures and compares metal/solution-processed electron-transporting polymer interface energy barriers by in-device hot-electron spectroscopy and ultraviolet photoemission spectroscopy. It not only demonstrates in-device hot-electron spectroscopy as a direct and reliable technique for these studies but also brings it closer to technological applications by working ex situ under ambient conditions. Moreover, this study determines that the contamination layer coming from air exposure does not play any significant role on the energy barrier alignment for charge transport. The theoretical model developed for this work confirms all the experimental observations.

The energetics of metal/molecular semiconductor interfaces plays a fundamental role in organic electronics, determining the performance of very diverse devices. So far, information about the energy level alignment has been most commonly gained by spectroscopy techniques that typically require experimental conditions far from the real device operation. Here we demonstrate that a simple three-terminal device allows the acquisition of spectroscopic information about the metal/molecule energy alignment in real operative condition. As a proof of principle, we employ the proposed device to measure the energy barrier height between different clean metals and C60 molecules and we recover typical results from photoemission spectroscopy. The device is designed to inject a hot electron current directly into the molecular level devoted to charge transport, disentangling the contributions of both the interface and the bulk to the device total resistance, with important implications for spintronics and low-temperature physics. Fil: Gobbi, M.. CIC nanoGUNE; España. Université de Strasbourg; Francia Fil: Pietrobon, L.. CIC nanoGUNE; España Fil: Atxabal, A.. CIC nanoGUNE; España Fil: Bedoya Pinto, A.. CIC nanoGUNE; España Fil: Sun, X.. CIC nanoGUNE; España Fil: Golmar, Federico. CIC nanoGUNE; España. Instituto Nacional de Tecnología Industrial; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Llopis, R.. CIC nanoGUNE; España Fil: Casanova, F.. CIC nanoGUNE; España. Fundación Vasca para la Ciencia; España Fil: Hueso, L. E.. CIC nanoGUNE; España. Fundación Vasca para la Ciencia; España

Marcus’s theory of electron transfer, initially formulated six decades ago for redox reactions in solution, is now of great importance for very diverse scientific communities. The molecular scale tunability of electronic properties renders organic semiconductor materials in principle an ideal platform to test this theory. However, the demonstration of charge transfer in different Marcus regions requires a precise control over the driving force acting on the charge carriers. Here, we make use of a three-terminal hot-electron molecular transistor, which lets us access unconventional transport regimes. Thanks to the control of the injection energy of hot carriers in the molecular thin film we induce an effective negative differential resistance state that is a direct consequence of the Marcus Inverted Region., To demonstrate charge transfer in different Marcus regimes in an organic semiconductor, precise tuning of the material’s electronic properties is required. Here, the authors use a three-terminal hot-electron technique to access the Marcus regimes for electronic transport in organic thin films.

Phonon-polaritons, mixed excitations of light coupled to lattice vibrations (phonons), are emerging as a powerful platform for nanophotonic applications. This is because of their ability to concentrate light into extreme sub-wavelength scales and because of their longer phonon lifetimes compared to their plasmonic counterparts. In this work, the infrared properties of phonon-polaritonic nanoresonators made of monoisotopic 10B hexagonal boron nitride (h-BN) are explored, a material with increased phonon-polariton lifetimes compared to naturally abundant h-BN due to reduced photon scattering from randomly distributed isotopes. An average relative improvement of 50% of the quality factor of monoisotopic h-BN nanoresonators is obtained with respect to nanoresonators made of naturally abundant h-BN, allowing for the sensing of nanometric-thick films of molecules through both surface-enhanced absorption spectroscopy and refractive index sensing. Further, even strong coupling between molecular vibrations and the phonon-polariton resonance in monoisotopic h-BN ribbons can be achieved., The authors acknowledge funding from the Graphene Flagship (Core2 and Core3), the Spanish Ministry of Science and Innovation (projects MDM-2016-0618 of the Maria de Maeztu Units of Excellence Programme and national projects (RTI2018-094830-B-100, RTI2018-094861-B-100, and PID2019-107432GB-I00)), and the Basque Government (project GIU18/202, Ekartek project KK-2018/00001, IT1164-19, and PhD fellowships PRE_2018_2_0253 and PRE_2017_2_0052). The h-BN crystal growth was supported by the National Science Foundation, grant CMMI 1538127 and the II-VI Foundation.