Evolutionary optimization of optical antennas

The design of nano-antennas is so far mainly inspired by radio-frequency technology. However, material properties and experimental settings need to be reconsidered at optical frequencies, which entails the need for alternative optimal antenna designs. Here a checkerboard-type, initially random array of gold cubes is subjected to evolutionary optimization. To illustrate the power of the approach we demonstrate that by optimizing the near-field intensity enhancement the evolutionary algorithm finds a new antenna geometry, essentially a split-ring/two-wire antenna hybrid which surpasses by far the performance of a conventional gap antenna by shifting the n=1 split-ring resonance into the optical regime.Comment: Also see Supplementary material, as attached to the main pape

Mode-selective vibrational control of charge transport in ππ-conjugated molecular materials

The soft character of organic materials leads to strong coupling between molecular nuclear and electronic dynamics. This coupling opens the way to control charge transport in organic electronic devices by inducing molecular vibrational motions. However, despite encouraging theoretical predictions, experimental realization of such control has remained elusive. Here we demonstrate experimentally that photoconductivity in a model organic optoelectronic device can be controlled by the selective excitation of molecular vibrations. Using an ultrafast infrared laser source to create a coherent superposition of vibrational motions in a pentacene/C60 photoresistor, we observe that excitation of certain modes in the 1500-1700 cm$^{-1}$ region leads to photocurrent enhancement. Excited vibrations affect predominantly trapped carriers. The effect depends on the nature of the vibration and its mode-specific character can be well described by the vibrational modulation of intermolecular electronic couplings. Vibrational control thus presents a new tool for studying electron-phonon coupling and charge dynamics in (bio)molecular materials.This work was supported by the Netherlands Organization for Scientific Research (NWO) through the ‘Stichting voor Fundamenteel Onderzoek der Materie’ (FOM) research programme. A.A.B. also acknowledges a VENI grant from the NWO. A.A.B. is currently a Royal Society University Research Fellow. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No 639750). R.L. acknowledges a Marie Curie IE Fellowship from the EU, held at the Weizmann Institute (FP7-PEOPLE-2011-IEF no. 29866). X.Y. thanks the Council for Higher Education (Israel) for a PBC programme postdoctoral research fellowship. V.C. thanks support from the Office of Naval Research and MURI Center on Advanced Molecular Photovoltaics, award No. N00014-14-1-0580. J.L.B. acknowledges support by competitive research funding from King Abdullah University of Science and Technology (KAUST) and by ONR Global, Grant N62909-15-1-2003. D.C. thanks the Israel Science Foundation Centre of Excellence program, the Grand Centre for Sensors and Security and the Schmidt Minerva Centre for Supramolecular Architecture for partial support. D.C. holds the Sylvia and Rowland Schaefer Chair in Energy Research.This is the final published version. It first appeared at http://dx.doi.org/10.1038/ncomms888

Time-domain observation of interlayer exciton formation and thermalization in a MoSe2/WSe2 heterostructure

: Vertical heterostructures of transition metal dichalcogenides (TMDs) host interlayer excitons with electrons and holes residing in different layers. With respect to their intralayer counterparts, interlayer excitons feature longer lifetimes and diffusion lengths, paving the way for room temperature excitonic optoelectronic devices. The interlayer exciton formation process and its underlying physical mechanisms are largely unexplored. Here we use ultrafast transient absorption spectroscopy with a broadband white-light probe to simultaneously resolve interlayer charge transfer and interlayer exciton formation dynamics in a MoSe2/WSe2 heterostructure. We observe an interlayer exciton formation timescale nearly an order of magnitude (~1 ps) longer than the interlayer charge transfer time (~100 fs). Microscopic calculations attribute this relative delay to an interplay of a phonon-assisted interlayer exciton cascade and thermalization, and excitonic wave-function overlap. Our results may explain the efficient photocurrent generation observed in optoelectronic devices based on TMD heterostructures, as the interlayer excitons are able to dissociate during thermalization

Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites.

The introduction of a mobile and polarized organic moiety as a cation in 3D lead-iodide perovskites brings fascinating optoelectronic properties to these materials. The extent and the time scales of the orientational mobility of the organic cation and the molecular mechanism behind its motion remain unclear, with different experimental and computational approaches providing very different qualitative and quantitative description of the molecular dynamics. Here we use ultrafast 2D vibrational spectroscopy of methylammonium (MA) lead iodide to directly resolve the rotation of the organic cations within the MAPbI3 lattice. Our results reveal two characteristic time constants of motion. Using ab initio molecular dynamics simulations, we identify these as a fast (∼300 fs) "wobbling-in-a-cone" motion around the crystal axis and a relatively slow (∼3 ps) jump-like reorientation of the molecular dipole with respect to the iodide lattice. The observed dynamics are essential for understanding the electronic properties of perovskite materials.This work was supported by The Netherlands Organization for Scientific Research (NWO) through the “Stichting voor Fundamenteel Onderzoek der Materie” (FOM) research program. A.A.B. also acknowledges a VENI grant from the NWO. A.A.B. is currently a Royal Society University Research Fellow. Z.S. and Z.C. acknowledge the ANR-2011-JS09-004-01-PvCoNano project and the EU Marie Curie Career Integration Grant (303824). A.A.B., Z.S., and Z.C. thank Dutch-French Academy for the support through van Gogh grant.This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jpclett.5b0155

Temperature-Induced Collapse of Elastin-like Peptides Studied by 2DIR Spectroscopy

Elastin-like peptides are hydrophobic biopolymers that exhibit a reversible coacervation transition when the temperature is raised above a critical point. Here, we use a combination of linear infrared spectroscopy, two-dimensional infrared spectroscopy, and molecular dynamics simulations to study the structural dynamics of two elastin-like peptides. Specifically, we investigate the effect of the solvent environment and temperature on the structural dynamics of a short (5-residue) elastin-like peptide and of a long (450-residue) elastin-like peptide. We identify two vibrational energy transfer processes that take place within the amide I' band of both peptides. We observe that the rate constant of one of the exchange processes is strongly dependent on the solvent environment and argue that the coacervation transition is accompanied by a desolvation of the peptide backbone where up to 75% of the water molecules are displaced. We also study the spectral diffusion dynamics of the valine(1) residue that is present in both peptides. We find that these dynamics are relatively slow and indicative of an amide group that is shielded from the solvent. We conclude that the coacervation transition of elastin-like peptides is probably not associated with a conformational change involving this residue

Temperature-induced collapse of elastin-like peptides studied by 2DIR spectroscopy

\u3cp\u3eElastin-like peptides are hydrophobic biopolymers that exhibit a reversible coacervation transition when the temperature is raised above a critical point. Here, we use a combination of linear infrared spectroscopy, two-dimensional infrared spectroscopy, and molecular dynamics simulations to study the structural dynamics of two elastin-like peptides. Specifically, we investigate the effect of the solvent environment and temperature on the structural dynamics of a short (5-residue) elastin-like peptide and of a long (450-residue) elastin-like peptide. We identify two vibrational energy transfer processes that take place within the amide I′ band of both peptides. We observe that the rate constant of one of the exchange processes is strongly dependent on the solvent environment and argue that the coacervation transition is accompanied by a desolvation of the peptide backbone where up to 75% of the water molecules are displaced. We also study the spectral diffusion dynamics of the valine(1) residue that is present in both peptides. We find that these dynamics are relatively slow and indicative of an amide group that is shielded from the solvent. We conclude that the coacervation transition of elastin-like peptides is probably not associated with a conformational change involving this residue.\u3c/p\u3

Development and characterization of the superconducting integrated receiver channel of the TELIS atmospheric sounder

The balloon-borne instrument TELIS (TErahertz and submillimetre LImb Sounder) is a three-channel superconducting heterodyne spectrometer for atmospheric research use. It detects spectral emission lines of stratospheric trace gases that have their rotational transitions at THz frequencies. One of the channels is based on the superconducting integrated receiver (SIR) technology. We demonstrate for the first time the capabilities of the SIR technology for heterodyne spectroscopy in general, and atmospheric limb sounding in particular. We also show that the application of SIR technology is not limited to laboratory environments, but that it is well suited for remote operation under harsh environmental conditions. Within a SIR the main components needed for a superconducting heterodyne receiver such as a superconductor-insulator-superconductor (SIS) mixer with a quasi-optical antenna, a flux-flow oscillator (FFO) as the local oscillator, and a harmonic mixer to phase lock the FFO are integrated on a single chip. Light weight and low power consumption combined with broadband operation and nearly quantum limited sensitivity make the SIR a perfect candidate for use in future airborne and space-borne missions. The noise temperature of the SIR was measured to be as low as 120 K, with an intermediate frequency band of 4-8 GHz in double-sideband operation. The spectral resolution is well below 1 MHz, confirmed by our measurements. Remote control of the SIR under flight conditions has been demonstrated in a successful balloon flight in Kiruna, Sweden. The sensor and instrument design are presented, as well as the preliminary science results from the first flight