Absence of photoemission from the Fermi level in potassium intercalated picene and coronene films: structure, polaron or correlation physics?

The electronic structure of potassium intercalated picene and coronene films has been studied using photoemission spectroscopy. Picene has additionally been intercalated using sodium. Upon alkali metal addition core level as well as valence band photoemission data signal a filling of previously unoccupied states of the two molecular materials due to charge transfer from potassium. In contrast to the observation of superconductivity in K_xpicene and K_xcoronene (x ~ 3), none of the films studied shows emission from the Fermi level, i.e. we find no indication for a metallic ground state. Several reasons for this observation are discussed.Comment: 15 pages, 6 figure

Elektronische Eigenschaften dotierter polyzyklischer aromatischer Kohlenwasserstoffe

In der vorliegenden Arbeit wurde die elektronische Struktur verschiedener undotierter und mit Alkalimetallen beziehungsweise 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethan (F 4 TCNQ) dotierter, polyzyklischer aromatischer Kohlenwasserstoffe (PAK) untersucht. Diese Untersuchungen waren motiviert durch verschiedene Veröffentlichungen in denen supraleitendes Verhalten an unterschiedlichen alkalimetalldotierten PAK beschrieben wurde. Erste Studien erfolgten an undotiertem 1,2:8,9-Dibenzopentacen (DBP) und Pentacen unter Nutzung von Photoelektronenspektroskopie (PES), Elektronenenergieverlustspektroskopie (EELS) und Dichtefunktionaltheorie (DFT). Die spektroskopischen Methoden zeigten für beide Materialien eine große Ähnlichkeit der elektronischen Zustände, vor allem im niederenergetischen Bereich, welche durch die theoretischen Ergebnisse bestätigt wurde. Die elektronische Ähnlichkeit beider Materialien ist im starken Gegensatz zu dem in der Literatur bei Dotierung beobachteten Verhalten, bei dem Pentacen zum Mott-Isolator wird, während DBP Supraleitung zeigt. Weitere Untersuchungen erfolgten an Picen und Coronen. Bandstrukturrechnungen zeigten, dass Picen vermutlich ein stark korreliertes Elektronensystem besitzt. Neben dem mit PES ermittelten Ionisationspotential und der Austrittsarbeit waren auch die mit EELS gemessenen optischen Bandlücken der beiden Materialien sehr ähnlich. Unterschiede zeigten sich hingegen vor allem in der Dichte der gemessenen Zustände von Picen und Coronen am Ferminiveau. Bei der Untersuchung der elektronischen Eigenschaften von mit Kalium-dotierten Picen und Coronen wurde trotz der erfolgreichen Dotierung in keinem der untersuchten Filme eine Zustandsdichte am Ferminiveau beobachtet somit wurde auch keiner der untersuchten Filme metallisch. Dasselbe Verhalten konnte auch für Natrium-dotierte Filme beobachtet werden. Eine Diskussion dieses Ergebnisses, welches im Gegensatz zu der von anderen Gruppen in dotierten Molekülen beobachteten Supraleitung steht, erfolgte im Hinblick auf die Bildung unterschiedlich dotierter Phasen, Elektron-Phonon-Kopplung, der Formierung von Bi-Polaronen und Korrelationseffekten. Für ein weitergehendes Verständnis der dotierungsinduzierten elektronischen Eigenschaften in den untersuchten Molekülen wurden diese nicht nur mit Alkalimetallen, sondern teilweise auch mit elektronenziehenden Molekülen wie F 4 TCNQ interkaliert. Dabei entstanden Kristalle verschiedener Ladungstransfersalze. Eine ausführliche Charakterisierung erfolgte für Picen/F 4 TCNQ-Kristalle, welche im Rahmen dieser Arbeit zum ersten Mal hergestellt und untersucht wurden. Dabei wurde zunächst deren Kristallstruktur mit Röntgendiffraktometrie (XRD) bestimmt. Eine Abschätzung der Größe des Ladungstransfers innerhalb der Molekülpaare aus Picen/ F 4 TCNQ erfolgte über Infrarot- und Bindungslängendaten, die auf diese Weise gefunden Werte wurden zusätzlich durch DFT-Rechnungen untermauert. Transportmessungen zeigten außerdem, dass die hergestellten Kristalle entlang ihrer Hauptwachstumsrichtung Isolatoren sind. Die Untersuchung der elektronischen Eigenschaften wurde mit EELS und PES an Picen/ F 4 TCNQ -Dünnfilmen durchgeführt, welche durch die Verdampfung der Einkristalle hergestellt wurden. Die Molekülpaare zeigen einen Ladungstransfer, der neue elektronische Anregungen im Niederenergiebereich der mit EELS gemessenen Verlustfunktion hervorruft. Im weiteren Verlauf der Arbeit erfolgte eine Diskussion bezüglich des Charakters und der Lokalisierung dieser neuen Anregungen. Bei den PES-Messungen zeigte sich der Ladungstransfer durch energetische Verschiebungen in den gemessen Rumpfniveauspektren sowie durch im Vergleich zu den reinen Materialien deutlich veränderte Ionisationspotentiale. Trotz des erfolgreichen Ladungstransfers und der damit verbundenen Füllung von unbesetzten Zuständen mit Elektronen in F 4 TCNQ wurde jedoch in den Valenzbandspektren keine Emission am Ferminiveau beobachtet. DFT-Rechnungen ermöglichten schließlich Aussagen über den Charakter des Ladunstransfers und die daraus resultierende, fehlende Zustandsdichte am Ferminiveau

Hyperspectral Imaging Tera Hertz System for Soil Analysis : Initial Results

Analyzing soils using conventional methods is often time consuming and costly due to their complexity. These methods require soil sampling (e.g., by augering), pretreatment of samples (e.g., sieving, extraction), and wet chemical analysis in the laboratory. Researchers are seeking alternative sensor-based methods that can provide immediate results with little or no excavation and pretreatment of samples. Currently, visible and infrared spectroscopy, electrical resistivity, gamma ray spectroscopy, and X-ray spectroscopy have been investigated extensively for their potential utility in soil sensing. Little research has been conducted on the application of THz (Tera Hertz) spectroscopy in soil science. The Tera Hertz band covers the frequency range between 100 GHz and 10 THz of the electromagnetic spectrum. One important feature of THz radiation is its correspondence with the particle size of the fine fraction of soil minerals (clay < 2 µm to sand < 2 mm). The particle size distribution is a fundamental soil property that governs soil water and nutrient content, among other characteristics. The interaction of THz radiation with soil particles creates detectable Mie scattering, which is the elastic scattering of electromagnetic waves by particles whose diameter corresponds approximately to the wavelength of the radiation. However, single-spot Mie scattering spectra are difficult to analyze and the understanding of interaction between THz radiation and soil material requires basic research. To improve the interpretation of THz spectra, a hyperspectral imaging system was developed. The addition of the spatial dimension to THz spectra helps to detect relevant features. Additionally, multiple samples can be scanned in parallel and measured under identical conditions, and the high number of data points within an image can improve the statistical accuracy. Technical details of the newly designed hyperspectral imaging THz system working from 250 to 370 GHz are provided. Results from measurements of different soil samples and buried objects in soil demonstrated its performance. The system achieved an optical resolution of about 2 mm. The sensitivity of signal damping to the changes in particle size of 100 µm is about 10 dB. Therefore, particle size variations in the µm range should be detectable. In conclusion, automated hyperspectral imaging reduced experimental effort and time consumption, and provided reliable results because of the measurement of hundreds of sample positions in one run. At this stage, the proposed setup cannot replace the current standard laboratory methods, but the present study represents the initial step to develop a new automated method for soil analysis and imaging

Terahertz spectroscopy for proximal soil sensing: An approach to particle size analysis

Spatially resolved soil parameters are some of the most important pieces of information for precision agriculture. These parameters, especially the particle size distribution (texture), are costly to measure by conventional laboratory methods, and thus, in situ assessment has become the focus of a new discipline called proximal soil sensing. Terahertz (THz) radiation is a promising method for nondestructive in situ measurements. The THz frequency range from 258 gigahertz (GHz) to 350 GHz provides a good compromise between soil penetration and the interaction of the electromagnetic waves with soil compounds. In particular, soil physical parameters influence THz measurements. This paper presents investigations of the spectral transmission signals from samples of different particle size fractions relevant for soil characterization. The sample thickness ranged from 5 to 17 mm. The transmission of THz waves was affected by the main mineral particle fractions, sand, silt and clay. The resulting signal changes systematically according to particle sizes larger than half the wavelength. It can be concluded that THz spectroscopic measurements provide information about soil texture and penetrate samples with thicknesses in the cm range

Electronic properties of molecular solids: the peculiar case of solid Picene

Recently, a new organic superconductor, K-intercalated Picene with high transition temperatures $T_c$ (up to 18\,K) has been discovered. We have investigated the electronic properties of the undoped relative, solid picene, using a combination of experimental and theoretical methods. Our results provide detailed insight into the occuopied and unoccupied electronic states

Hyperspectral Imaging Tera Hertz System for Soil Analysis: Initial Results

Analyzing soils using conventional methods is often time consuming and costly due to their complexity. These methods require soil sampling (e.g., by augering), pretreatment of samples (e.g., sieving, extraction), and wet chemical analysis in the laboratory. Researchers are seeking alternative sensor-based methods that can provide immediate results with little or no excavation and pretreatment of samples. Currently, visible and infrared spectroscopy, electrical resistivity, gamma ray spectroscopy, and X-ray spectroscopy have been investigated extensively for their potential utility in soil sensing. Little research has been conducted on the application of THz (Tera Hertz) spectroscopy in soil science. The Tera Hertz band covers the frequency range between 100 GHz and 10 THz of the electromagnetic spectrum. One important feature of THz radiation is its correspondence with the particle size of the fine fraction of soil minerals (clay < 2 µm to sand < 2 mm). The particle size distribution is a fundamental soil property that governs soil water and nutrient content, among other characteristics. The interaction of THz radiation with soil particles creates detectable Mie scattering, which is the elastic scattering of electromagnetic waves by particles whose diameter corresponds approximately to the wavelength of the radiation. However, single-spot Mie scattering spectra are difficult to analyze and the understanding of interaction between THz radiation and soil material requires basic research. To improve the interpretation of THz spectra, a hyperspectral imaging system was developed. The addition of the spatial dimension to THz spectra helps to detect relevant features. Additionally, multiple samples can be scanned in parallel and measured under identical conditions, and the high number of data points within an image can improve the statistical accuracy. Technical details of the newly designed hyperspectral imaging THz system working from 250 to 370 GHz are provided. Results from measurements of different soil samples and buried objects in soil demonstrated its performance. The system achieved an optical resolution of about 2 mm. The sensitivity of signal damping to the changes in particle size of 100 µm is about 10 dB. Therefore, particle size variations in the µm range should be detectable. In conclusion, automated hyperspectral imaging reduced experimental effort and time consumption, and provided reliable results because of the measurement of hundreds of sample positions in one run. At this stage, the proposed setup cannot replace the current standard laboratory methods, but the present study represents the initial step to develop a new automated method for soil analysis and imaging.BMBF, 031B0513A, BonaRes (Modul A, Phase 2): I4S - Integriertes System zum ortsspezifischen Management der Bodenfruchtbarkeit, Teilprojekt A: Projektkoordination sowie Entwicklung von Sensorplattformen, UV-, Vis-NIR- und THz-Sensore

IoT-Based Sensor Data Fusion for Determining Optimality Degrees of Microclimate Parameters in Commercial Greenhouse Production of Tomato

Optimum microclimate parameters, including air temperature (T), relative humidity (RH) and vapor pressure deficit (VPD) that are uniformly distributed inside greenhouse crop production systems are essential to prevent yield loss and fruit quality. The objective of this research was to determine the spatial and temporal variations in the microclimate data of a commercial greenhouse with tomato plants located in the mid-west of Iran. For this purpose, wireless sensor data fusion was incorporated with a membership function model called Optimality Degree (OptDeg) for real-time monitoring and dynamic assessment of T, RH and VPD in different light conditions and growth stages of tomato. This approach allows growers to have a simultaneous projection of raw data into a normalized index between 0 and 1. Custom-built hardware and software based on the concept of the Internet-of-Things, including Low-Power Wide-Area Network (LoRaWAN) transmitter nodes, a multi-channel LoRaWAN gateway and a web-based data monitoring dashboard were used for data collection, data processing and monitoring. The experimental approach consisted of the collection of meteorological data from the external environment by means of a weather station and via a grid of 20 wireless sensor nodes distributed in two horizontal planes at two different heights inside the greenhouse. Offline data processing for sensors calibration and model validation was carried in multiple MATLAB Simulink blocks. Preliminary results revealed a significant deviation of the microclimate parameters from optimal growth conditions for tomato cultivation due to the inaccurate timer-based heating and cooling control systems used in the greenhouse. The mean OptDeg of T, RH and VPD were 0.67, 0.94, 0.94 in January, 0.45, 0.36, 0.42 in June and 0.44, 0.0, 0.12 in July, respectively. An in-depth analysis of data revealed that averaged OptDeg values, as well as their spatial variations in the horizontal profile were closer to the plants’ comfort zone in the cold season as compared with those in the warm season. This was attributed to the use of heating systems in the cold season and the lack of automated cooling devices in the warm season. This study confirmed the applicability of using IoT sensors for real-time model-based assessment of greenhouse microclimate on a commercial scale. The presented IoT sensor node and the Simulink model provide growers with a better insight into interpreting crop growth environment. The outcome of this research contributes to the improvement of closed-field cultivation of tomato by providing an integrated decision-making framework that explores microclimate variation at different growth stages in the production season

Loss spectroscopy of molecular solids: Combining experiment and theory

The nature of the lowest-energy electronic excitations in prototypical molecular solids is studied here in detail by combining electron energy loss spectroscopy (EELS) experiments and state-of-the-art many-body calculations based on the Bethe–Salpeter equation. From a detailed comparison of the spectra in picene, coronene and tetracene we generally find a good agreement between theory and experiment, with an upshift of the main features of the calculated spectrum of 0.1–0.2 eV, which can be considered the error bar of the calculation. We focus on the anisotropy of the spectra, which illustrates the complexity of this class of materials, showing a high sensitivity with respect to the three-dimensional packing of the molecular units in the crystal. The differences between the measured and the calculated spectra are explained in terms of the small differences between the crystal structures of the measured samples and the structural model used in the calculations. Finally, we discuss the role played by the different electron–hole interactions in the spectra. We thus demonstrate that the combination of highly accurate experimental EELS and theoretical analysis is a powerful tool to elucidate and understand the electronic properties of molecular solids