Electronic Structure of Lithium Tetraborate

Due to interest as neutron detection material, an investigation of Li2B4O7(110) and Li2B4O7(100) was undertaken, utilizing photoemission and inverse photoemission spectroscopic techniques. The measured band gap depended on crystallographic direction with the band gaps ranging from 8.9±0.5 eV to 10.1±0.5 eV. The measurement yielded a density of states that qualitatively agreed with the theoretical results from model bulk band structure calculations for Li2B4O7; albeit with a larger band gap than predicted, but consistent with the known deficiencies of LDA and DFT calculations. The occupied states of both surfaces were extremely flat; to the degree that resolving periodic dispersion of the occupied states was inconclusive, within the resolution of the system. However, both surfaces demonstrated clear periodic dispersion within the empty states very close to theoretical Brillouin zone values. These attributes also translated to a lighter charge carrier effective mass in the unoccupied states. Li2B4O7(110) yielded the more consistent values in orthogonal directions for energy states. The presence of a bulk band gap surface state and image potential state in Li2B4O7(110) was indicative of a defect-free surface. The absence of both in the more polar, more dielectric Li2B4O7(100) was attributed to the presence of defects determined to be O vacancies. The results from Li2B4O7(110) were indicative of a more stable surface than Li2B4O7(100). In addition, Li 1s bulk and surface core level components were determined at the binding energies of -56.5+0.4 and -53.7+0.5 eV. Resonance features were observed along the [001] direction and were attributed to a Coster-Kronig process. The pyroelectric and piezoelectric character of Li2B4O7 was explored more deeply and a non-zero, off-axis pyroelectric coefficient for the Li2B4O7(110) direction was discovered

Charge transfer at organic heterojunctions: electronic structure and molecular assembly

Ziel dieser Arbeit war es, den grundlegenden Mechanismus des Ladungstransfers bei molekularer Dotierung an organisch-organischen Grenzflächen besser zu verstehen. Es wurde eine Vielfalt modernster spektroskopischer Methoden eingesetzt, um die elektronische Struktur und neue dotierungsinduzierte CT-Übergänge zu ergründen. Dazu gehören UPS und XPS für Valenzsignaturen und Kernniveauzustände. Absorptionsspektroskopie im UV-vis-NIR und Röntgenbereich wurde zur Bestimmung der Übergangsenergien eingesetzt. Schwingungsspektroskopie wurde eingesetzt, um den CT-Grad in DA-Systemen für gestapelte und gemischte Heteroübergänge zu quantifizieren. Strom-Spannungs-Messungen wurden zur Bestimmung der elektrischen Leitfähigkeit und Rasterkraftmikroskopie zur Charakterisierung der Oberflächenmorphologie eingesetzt. Die in dieser Arbeit behandelten Themen sind: (1) Planare Heteroübergänge aus DIP und F6TCNNQ wurden hergestellt. Sie wurden im Hinblick auf CT-Komplexbildung, Grenzflächendotierung und Exzitonenbindungsenergien an der D|A-Grenzfläche untersucht. (2) DBTTF wurde mit TCNNQ und F6TCNNQ in Lösung und in dünnen Filmen gemischt. Daraus wurde der Zusammenhang zwischen Dotierungsmechanismen, CTC- und IPA-Bildung, mit dem Aggregatzustand hergeleitet. (3.1) Rubren-Einkristalle wurden mit Mo(tfd)3 und CoCp2 p- und n-dotiert. Nach der Dotierung verschiebt sich die Banddispersion entsprechend, wohingegen die effektive Masse der Löcher konstant bleibt. (3.2) DBTTF-Einkristalle wurden mit TCNNQ, F6TCNNQ und Mo(tfd)3 dotiert. Aus den Änderungen der elektronischen Struktur wurden der CT über die D|A-Grenzfläche sowie die Dichte der Oberflächenzustände quantifiziert. (4) Von drei DA-Systemen mit unterschiedlicher GS-Wechselwirkungsstärke, DIP:C60, DIP:PDIR-CN2 und DIP|F6TCNNQ, wurden die Grenzflächenexzitonen charakterisiert. Ein Vergleich verschiedener Modelle, die die optische CTC Absorption aus dem DA-Energieniveauoffset beschreiben und abschätzen können, rundet die Ergebnisse ab.The aim of this thesis was to enhance the understanding of the charge transfer mechanism during molecular doping at organic-organic interfaces. A wide range of state-of-the-art spectroscopic methods was employed to unravel the electronic structure and new CT transitions resulting from doping. This includes UPS and XPS for valence signatures and core level states. Absorption spectroscopies in the UV-vis-NIR and X-ray regions were used to determine transition energies. Vibrational spectroscopy was employed to quantify the CT degree in DA systems for stacked and mixed heterojunctions. Current-voltage measurements were used for the determination of electrical conductivities and scanning force microscopy for surface morphology characterization. The topics covered in this thesis are: (1) Planar heterojunctions of DIP and F6TCNNQ were fabricated. They were studied with regard to CT complex formation, interface doping and exciton binding energies at the D|A interface. (2) DBTTF was blended with TCNNQ and F6TCNNQ in solution and in thin films. From this, the connection of the two doping mechanisms, CTC and IPA formation, to the state of matter was derived. (3.1) Rubrene single crystals were p- and n-doped with Mo(tfd)3 and CoCp2. After doping, the band dispersion shifts accordingly, while the hole effective mass stays constant. (3.2) DBTTF single crystals were doped with TCNNQ, F6TCNNQ and Mo(tfd)3. From changes in the electronic structure, the CT across the D|A interface as well as the density of surface states were quantified. (4) From three DA systems with varying GS interaction strength, DIP:C60, DIP:PDIR–CN2 and DIP|F6TCNNQ, the interfacial excitons were characterized. A comparison of different models, which describe and allow to estimate the optical absorption in CTCs from the DA energy level offset, concludes the results

Optimizing Organic Solar Cells: Transparent Electron Transport Materials for Improving the Device Performance

This thesis deals with the characterization and implementation of transparent electron transport materials (ETM) in vacuum deposited p-i-n type organic solar cells (OSC) for substituting the parasitically absorbing standard ETM composed of n-doped C60. In addition to transparency in the visible range of the sun spectrum, the desired material properties include high electron mobility and conductivity, thermal and morphological stability, as well as good energy level alignment relative to the adjacent acceptor layer which is commonly composed of intrinsic C60. In this work, representatives of three different material classes are evaluated with regard to the above mentioned criteria. HATCN (hexaazatriphenylene hexacarbonitrile) is a small discoid molecule with six electron withdrawing nitrile groups at its periphery. It forms smooth thin films with an optical energy gap of 3.3eV, thus being transparent in the visible range of the sun spectrum. Doping with either 5wt% of the cationic n-dopant AOB or 7wt% of the proprietary material NDN1 effectively increases the conductivity to 7.6*10^-6 S/cm or 2.2*10^-4 S/cm, respectively. However, the fabrication of efficient OSC is impeded by the exceptionally high electron affinity (EA ) of approximately 4.8eV that causes the formation of an electron injection barrier between n-HATCN and intrinsic C60 (EA=4.0eV). This work presents a strategy to remove the barrier by introducing doped and undoped C60 intermediate layers, thus demonstrating the importance of energy level matching in a multi-layer structure and the advantages of Fermi level control by doping. Next, a series of six Bis-Fl-NTCDI (N,N-bis(fluorene-2-yl)-naphthalenetetracarboxylic diimide) compounds, which only differ by the length of the alkyl chains attached to the C9 positions of the fluorene side groups, is examined. When increasing the chain length from 0 to 6 carbon atoms, the energy levels remain nearly unchanged: We find EA=3.5eV as estimated from cyclic voltammetry, an ionization potential (IP ) in the range between 6.45eV and 6.63eV, and Eg,opt=3.1eV which means that all compounds form transparent thin films. Concerning thin film morphology, the addition of side chains results in the formation of amorphous layers with a surface roughness <1nm on room temperature glass substrates, and (1.5+/-0.5)nm for deposition onto glass substrates heated to 100°C. In contrast, films composed of the side chain free compound Bis-HFl-NTCDI exhibit a larger surface roughness of (2.5+/-0.5)nm and 9nm, respectively, and are nanocrystalline already at room temperature. Moreover, the conductivity achievable by n-doping is very sensitive to the side chain length: Whereas doping of Bis-HFl-NTCDI with 7wt% NDN1 results in a conductivity in the range of 10^-4 S/cm, the attachment of alkyl chains causes a conductivity which is more than three orders of magnitude smaller despite equal or slightly higher doping concentrations. The insufficient transport properties of the alkylated derivatives lead to the formation of pronounced s-kinks in the jV -characteristics of p-i-n type OSC while the use of n-Bis-HFl-NTCDI results in well performing devices. The last material, HATNA-Cl6 (2,3,8,9,14,15- hexachloro-5,6,11,12,17,18-hexaazatrinaphthylene), exhibits Eg,opt=2.7eV and is therefore not completely transparent in the visible range of the sun spectrum. However, its energy level positions of EA=4.1eV and IP=7.3eV are well suited for the application as ETM in combination with i-C60 as acceptor. The compound is dopable with all available n-dopants, resulting in maximum conductivities of sigma=1.6*10^-6, 3.5*10^-3, and 7.5*10^-3 S/cm at 7.5wt% AOB, Cr2(hpp)4, and NDN1, respectively. Applying n-HATNA-Cl6 instead of the reference ETM n-C60 results in a comparable or improved photocurrent density at an ETM thickness d(ETM)=40nm or 120nm, respectively. At d(ETM)=120nm, the efficiency eta is more than doubled as it increases from eta(n-C60)=0.4% to eta(n-HATNA-Cl6)=0.9% . Optical simulations show that the replacement of n-C60 by n-Bis-HFl-NTCDI, n-HATNA-Cl6, or the previously studied n-NTCDA (naphthalenetretracarboxylic dianhydride) in p-i-n or n-i-p type device architectures is expected to result in an increased photocurrent due to reduced parasitic absorption. For quantifying the gain, the performance of p-i-n type OSC with varying ETM type and thickness is evaluated. Special care has to be taken when analyzing devices comprising the reference ETM n-C60 as its conductivity is sufficiently large to extend the area of the aluminum cathode and thus the effective device area which may lead to distorted results. Overall, the experiment is able to confirm the trends predicted by the optical simulation. At large ETM thickness in the range between 60 and 120nm, the window layer effect of the ETM is most pronounced. For instance, at d(ETM)=120nm, eta(C60) is more than doubled using n-HATNA-Cl6 and even more than tripled using n-Bis-HFl-NTCDI or n-NTCDA. At optimized device geometry the photocurrent gain is slightly less than expected but nonetheless, the efficiency is improved from eta(max)=2.1% for n-C60 and n-HATNA-Cl6 solar cells to eta(max)=2.3, and 2.4% for n-Bis-HFl-NTCDI and n-NTCDA devices, respectively. This development is supported by generally higher Voc and FF in solar cells with transparent ETM. Finally, p-i-n type solar cells with varying ETM are aged at a temperature of 50°C and an illumination intensity of approximately 2 suns. Having extrapolated lifetimes t(80) of 36, 500, and 14000h and nearly unchanged jV-characteristics after 2000h, n-C60 and n-Bis-HFl-NTCDI devices exhibit the best stability. In contrast, n-NTCDA devices suffer from a constant decrease in Isc while n-HATNA-Cl6 solar cells show a rapid dscegradation of both Isc and FF associated with a decomposition of the material or a complete de-doping of the ETM. Here, lifetimes of only 4500h and 445hare achieved

Theoretical description of electronic excitations in extended systems: beyond the static material model

The theoretical description of bistable materials requires dealing with the interplay of various phenomena, like temperature, environmental effects and electron correlation. We developed a procedure to combine the benefits of the molecular dynamics techniques with the accuracy of the ab initio wave function based methods including various models for the surroundings. The combination of these computational methods involved the making of specific software tools. The proposed procedure has been applied successfully, obtaining good agreements with experimental data, on organic molecules in solvent (cytosine tautomers in water), crystalline materials (NiO, LaMnO3 and TTTA) and inorganic spin-crossover compounds (FeII(bpy)3). We achieved a significant improvement in the description of their absorption spectra: including ligand-to-metal and metal-to-metal charge transfer processes, formally dipole forbidden transitions and the broadening of the spectral bands. Moreover, we observe dramatic changes on the electronic structure by incorporating the environmental effects on the theoretical model.La descripció teòrica de materials biestables requereix el tractament de diversos fenòmens interactuants, com la temperatura, els efectes del medi i la correlació electrònica. S'ha desenvolupat un procediment que combina els beneficis de la dinàmica molecular amb la precisió dels mètodes ab initio basats en la funció d'ona incloent diferents models de l'entorn. La combinació d'aquests mètodes computacionals ha involucrat la creació de programari específic. El procediment proposat ha estat aplicat amb èxit, obtenint bona concordança amb els experiments, a molècules orgàniques en solvent (citosina en aigua), materials cristal•lins (NiO, LaMnO3 i TTTA) i compostos spin-crossover inorgànics (FeII(bpy)3). S'ha assolit una millora significativa en la descripció del seus espectres d'absorció: incloent la transferència de càrrega lligand-metall i metall-metall, les transicions formalment prohibides per dipol i l'eixamplament de les bandes espectrals. A més, s'observen canvis importants en l'estructura electrònica al incorporar els efectes de l'entorn en el model teòric

Tunneling spectroscopy of highly ordered organic thin films

In this work, a Au(100) single crystal was used as substrate for organic molecular beam epitaxy. Highly ordered organic thin films of the molecules 3,4,9,10-perylenetetracarboxylic-3,4,9,10-dianhydrid (PTCDA) and hexa-peri-hexabenzo-coronene (HBC) as well as organic-organic heterostructures on reconstructed Au(100) were prepared. The molecular arrangement was characterized in Scanning Tunneling Microscopy and Low Energy Electron Diffraction investigations. Scanning Tunneling Spectroscopy data were recorded on monolayer and submonolayer PTCDA films. Measurements on closed PTCDA layers at different fixed tip sample separations revealed a peak +0.95V. Other measurements performed consecutively on a PTCDA island and on uncovered Au(100) areas showed that this peak is indeed caused by the PTCDA molecules. Another set of consecutive measurements on herringbone and square phase PTCDA islands indicates that in the normalized differential conductivity the peak shape and peak position depend on the molecular arrangement. The STS data are compared to UPS and IPES results, already published. In the case of highly ordered films of HBC on Au(100) it was possible to derive the energetic positions of the HBC frontier orbitals and the energies of the molecular states next to these frontier orbitals from Tunneling Spectroscopy measurements. These measurements were performed using two different tip materials. The results are compared to UPS measurements, to theoretical calculations of the electronic conductance based on a combination of the Landauer transport formalism with a density-functional-parametrized tight-binding scheme within the Local Density Approximation (LDA) as well as semiempirical quantum chemistry calculations.Für die hier dargestelleten Arbeiten wurde ein Au(100) Einkristall als Substrat für die organische Molekularstrahlepitaxie verwendet. Hochgeordnete organische Dünnschichten der Moleküle 3,4,9,10-Perylen-tetracarbonsäure-3,4,9,10-dianhydrid (PTCDA) und Hexa-peri-hexabenzo-coronen (HBC) sowie organisch-organische Heteroschichten wurden auf der Au(100) Oberfläche abgeschieden. Die Struktur der Schichten wurde mittels Rastertunnelmikroskopie (STM) und Niederenergetischer Elektronenbeugung (LEED) untersucht. Tunnelspektroskopiedaten wurden für Monolagen sowie Submonolagen von PTCDA aufgenommen. Messungen an geschlossenen PTCDA Filmen zeigen für verschiedene Probe-Spitze-Abstände ein Maximum in der normierten differentiellen Leitfähigkeit bei +0.95V. Aufeinanderfolgende Messungen auf PTCDA-Inseln und unbedeckten Gebieten der Au(100) Oberfläche zeigen eindeutig, dass dieses Maximum auf die PTCDA Moleküle zurückzuführen ist. Weitere Messungen an PTCDA Inseln unterschiedlicher Struktur (Fischgrätenstruktur bzw. quadratische Struktur) belegen einen Zusammenhang zwischen der Anordnung der Moleküle und der Peakposition bzw. Peakform in der normierten differentiellen Leitfähigkeit. Die STS Daten werden mit UPS und IPES Ergebnissen aus der Literatur verglichen. Im Falle hochgeordneter HBC Schichten auf Au(100) war es möglich, neben dem höchsten besetzten und niedrigsten unbesetzten Molekülorbital auch die energetische Position der jeweils nächsten Orbitale zu bestimmen. Diese Messungen wurden mit zwei unterschiedlichen Spitzenmaterialien durchgeführt. Die Ergebnisse für HBC auf Au(100) werden mit UPS Daten sowie mit theoretischen Rechnungen verglichen

Jordbrukarnas uppfattningar om effektiviteten hos push pullteknik för att kontrollera majsstamborare (Chilo Partellus) i Gatsibo distriktet Rwanda

This case study investigated the perceptions of farmers and the historical effectiveness of push-pull technology to control the maize stem borer (Chilo Partellus) in Nyagihanga sector of Gatsibo District (Rwanda). The investigation was done in collaboration with Food for the Hungry/Rwanda, an organization operating in the mentioned region. Historical data from the region show that the push pull technology can significantly increase maize yield while decreasing damages by the maize stem borer. The agronomist and livelihood officer at Food for the Hungry/Rwanda and 27 farmers participated in the study. Semi-structured interviews were conducted in February 2019. The material was analyzed using a framework (thematic) analysis of farmers ‘narratives about the push pull technology. Maize harvest during three consecutive growing seasons (2016A, 2017A and 2018A) showed a remarkable and continuous increase of yield in push pull plots, in comparison with a maize monoculture. Farmers appreciated the technology, mentioning a range of benefits during the interviews but they stressed the challenging side of it. The most-mentioned benefits of the method were stem borer control, maize yield increase and fodder for animals. On the other hand, the mostmentioned limitations were the increase of labor cost (for the very first installation), the necessity of a new crop rotation and the difficulty to access high quality desmodium seeds. The results of the study show that push pull technology is beneficial, as many other previous researchers have proven, especially for maize stem borer control. Nevertheless, the working environment, consisting of the agriculture policy and regulations, the food needs and the income state of smallholders, and many other external factors can have a detrimental impact on it as a farming system. Because the current agricultural policy is not actively supporting the adoption of the push pull technology, the development of a strong collaboration between all the stakeholders is essential to establish a strong maize production system

Bioactive extracts from persimmon waste: influence of extraction conditions and ripeness

In this work, a bioactive persimmon extract was produced from discarded fruits. A central composite design was used to evaluate the effect of different extraction parameters and ripeness stages of persimmon fruits on the total phenolic content and antioxidant activity of the resulting extracts. Significantly greater phenolic contents were obtained from immature persimmon (IP) fruits. The optimum IP extract with the conditions set by the experimental design was industrially up-scaled and its composition and functional properties were evaluated and compared with those obtained under lab-scale conditions. Both extracts contained significant protein (>20%) and phenolic contents (similar to 11-27 mg GA/g dry extract) and displayed significant antiviral activity against murine norovirus and hepatitis A virus. Moreover, the extract showed no toxicity and significantly reduced the fat content and the cellular ageing of Caenorhabditis elegans (C. elegans) without affecting the worm development. These effects were mediated by down-regulation of fat-7, suggesting an anti-lipogenic activity of this extract