Organic field-effect transistors and phototransistors based on amorphous materials

A comparison between the charge transport properties in low molecular amorphous thin films of spiro-linked compound and their corresponding parent compound has been demonstrated. The field-effect transistor method is used for extracting physical parameters such as field-effect mobility of charge carriers, ON/OFF ratios, and stability. In addition, phototransistors have been fabricated and demonstrated for the first time by using organic materials. In this case, asymmetrically spiro-linked compounds are used as active materials. The active materials used in this study can be divided into three classes, namely Spiro-linked compounds (symmetrically spiro-linked compounds), the corresponding parent-compounds, and photosensitive spiro-linked compounds (asymmetrically spiro-linked com-pounds). Some of symmetrically spiro-linked compounds used in this study were 2,2',7,7'-Tetrakis-(di-phenylamino)-9,9'-spirobifluorene (Spiro-TAD),2,2',7,7'-Tetrakis-(N,N'-di-p-methylphenylamino)-9,9'-spirobifluorene (Spiro-TTB), 2,2',7,7'-Tetra-(m-tolyl-phenylamino)-9,9'-spirobifluorene (Spiro-TPD), and 2,2Ž,7,7Ž-Tetra-(N-phenyl-1-naphtylamine)-9,9Ž-spirobifluorene (Spiro alpha-NPB). Related parent compounds of the symmetrically spiro-linked compound used in this study were N,N,N',N'-Tetraphenylbenzidine (TAD), N,N,N',N'-Tetrakis(4-methylphenyl)benzidine (TTB), N,N'-Bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), and N,N'-Diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (alpha-NPB). The photosensitive asymmetrically spiro-linked compounds used in this study were 2,7-bis-(N,N'-diphenylamino)-2',7'-bis(biphenyl-4-yl)-9,9'-spirobifluorene (Spiro-DPSP), and 2,7-bis-(N,N'-diphenylamino)-2',7'-bis(spirobifluorene-2-yl)-9,9'-spirobifluorene (Spiro-DPSP^2). It was found that the field-effect mobilities of charge carriers in thin films of symmetrically spiro-linked compounds and their corresponding parent compounds are in the same order of magnitude (~10^-5 cm^2/Vs). However, the thin films of the parent compounds were easily crystallized after the samples have been exposed in ambient atmosphere and at room temperature for three days. In contrast, the thin films and the transistor characteristics of symmetrically spiro-linked compound did not change significantly after the samples have been stored in ambient atmosphere and at room temperature for several months. Furthermore, temperature dependence of the mobility was analyzed in two models, namely the Arrhenius model and the Gaussian Disorder model. The Arrhenius model tends to give a high value of the prefactor mobility. However, it is difficult to distinguish whether the temperature behaviors of the material under consideration follows the Arrhenius model or the Gaussian Disorder model due to the narrow accessible range of the temperatures. For the first time, phototransistors have been fabricated and demonstrated by using organic materials. In this case, asymmetrically spiro-linked compounds are used as active materials. Intramolecular charge transfer between a bis(diphenylamino)biphenyl unit and a sexiphenyl unit leads to an increase in charge carrier density, providing the amplification effect. The operational responsivity of better than 1 A/W can be obtained for ultraviolet light at 370 nm, making the device interesting for sensor applications. This result offers a new potential application of organic thin film phototransistors as low-light level and low-cost visible blind ultraviolet photodetectors.

VUV-Laserablation von Spinnenseide

Spinnenseide gehört zu den stabilsten bekannten Polymerverbindungen. Spinnfäden können bis auf das Dreifache ihrer ursprünglichen Länge gedehnt werden, bevor sie reißen, und dabei mit rund 160 MJ/m³ mehr als dreimal soviel Energie absorbieren wie die stärkste synthetisch hergestellte Faser Kevlar (50 MJ/m³). Dabei weisen Spinnfäden mit 2 bis 5 Mikrometer nur ein Zehntel des Durchmessers eines menschlichen Haares auf. Das präzise, berührungslose Bearbeiten von Spinnenseide ist für verschiedene technische Anwendungen interessant, insbesondere wenn dabei ihre außergewöhnlichen Eigenschaften erhalten bleiben. Könnten die von Natur aus dünnen Seidenfäden gezielt in ihrem Durchmesser verringert werden, so wären sie unter anderem in der Mikroelektronik einzusetzen. Hier könnten sie als Trägermaterial für eine dünne, elektrisch leitfähige Schicht fungieren. Man erhielte Nanodrähte, die auch in mechanisch besonders belasteten Mikroelektronikbauteilen (MEMS) Verwendung finden könnten. In dieser Arbeit wird die Verwendung der laserinduzierten Ablation zur gezielten Bearbeitung von Haltefäden der Schwarzen Witwe (Latrodectus hesperus) beschrieben. Eingesetzt wurde ein VUV-Excimerlaser vom Typ LPF 205 (Lambda-Physik, Göttingen) mit einer Wellenlänge von 157 nm und einer Pulsdauer von 18 ns. Eine berührungslose Laserbearbeitung bei 157 nm erlaubt einen effizienten und präzisen Abtrag von Material durch Ablation aufgrund der geringen optischen Eindringtiefe von unter 100 nm oberhalb einer Schwellenfluenz (Energie/Fläche) von Φth=29 mJ/cm², ohne dabei das umgebende Material thermisch zu beeinträchtigen. Parallel zur Ablation setzt allerdings eine wellenförmige Oberflächenstrukturierung auf der Faseroberfläche ein, wodurch die mechanische Belastbarkeit der Faser entscheidend geschwächt wird. Die Ursache hierfür liegt im Abbau materialbedingter Spannungsfelder („stress release“) innerhalb einer durch das Laserlicht induzierten dünnen Schmelzschicht. Im Rahmen dieser Arbeit ist es nun gelungen, diese Strukturen durch einen anschließenden Glättungsprozeß zu entfernen. Dabei wird auf der bestrahlten Oberfläche mittels Laserlichts eine glatte Ablation erzielt. Mit feinerer Abstufung dieser Prozeßschritte konnte der Durchmesser des verwendeten Spinnenseidefadens zum Teil um 70 Prozent bis auf ca. 750 nm verringert werden. Durch Zugfestigkeitsexperimente wurde belegt, daß die mechanischen Eigenschaften der so bearbeiteten Spinnenseide weitgehend erhalten bleiben. Die im Rahmen dieser Arbeit angewandte Methode erlaubt somit eine präzise Laserablation von Spinnenseide und ähnlichen hochabsorbierenden Materialien, ohne deren Kernsubstanz in ihrer Beschaffenheit zu verändern.

Impact of sward type, cutting date and conditioning temperature on mass and energy flows in the integrated generation of solid fuel and biogas from semi-natural grassland

Energy production from biomass and the conservation of ecologically valuable grassland habitats are two important issues of agriculture today. The combination of a bioenergy production, which minimises environmental impacts and competition with food production for land with a conversion of semi-natural grasslands through new utilization alternatives for the biomass, led to the development of the IFBB process. Its basic principle is the separation of biomass into a liquid fraction (press fluid, PF) for the production of electric and thermal energy after anaerobic digestion to biogas and a solid fraction (press cake, PC) for the production of thermal energy through combustion. This study was undertaken to explore mass and energy flows as well as quality aspects of energy carriers within the IFBB process and determine their dependency on biomass-related and technical parameters. Two experiments were conducted, in which biomass from semi-natural grassland was conserved as silage and subjected to a hydrothermal conditioning and a subsequent mechanical dehydration with a screw press. Methane yield of the PF and the untreated silage was determined in anaerobic digestion experiments in batch fermenters at 37°C with a fermentation time of 13-15 and 27-35 days for the PF and the silage, respectively. Concentrations of dry matter (DM), ash, crude protein (CP), crude fibre (CF), ether extract (EE), neutral detergent fibre (NDF), acid detergent fibre (ADF), acid detergent ligning (ADL) and elements (K, Mg, Ca, Cl, N, S, P, C, H, N) were determined in the untreated biomass and the PC. Higher heating value (HHV) and ash softening temperature (AST) were calculated based on elemental concentration. Chemical composition of the PF and mass flows of all plant compounds into the PF were calculated. In the first experiment, biomass from five different semi-natural grassland swards (Arrhenaterion I and II, Caricion fuscae, Filipendulion ulmariae, Polygono-Trisetion) was harvested at one late sampling (19 July or 31 August) and ensiled. Each silage was subjected to three different temperature treatments (5°C, 60°C, 80°C) during hydrothermal conditioning. Based on observed methane yields and HHV as energy output parameters as well as literature-based and observed energy input parameters, energy and green house gas (GHG) balances were calculated for IFBB and two reference conversion processes, whole-crop digestion of untreated silage (WCD) and combustion of hay (CH). In the second experiment, biomass from one single semi-natural grassland sward (Arrhenaterion) was harvested at eight consecutive dates (27/04, 02/05, 09/05, 16/05, 24/05, 31/05, 11/06, 21/06) and ensiled. Each silage was subjected to six different treatments (no hydrothermal conditioning and hydrothermal conditioning at 10°C, 30°C, 50°C, 70°C, 90°C). Energy balance was calculated for IFBB and WCD. Multiple regression models were developed to predict mass flows, concentrations of elements in the PC, concentration of organic compounds in the PF and energy conversion efficiency of the IFBB process from temperature of hydrothermal conditioning as well as NDF and DM concentration in the silage. Results showed a relative reduction of ash and all elements detrimental for combustion in the PC compared to the untreated biomass of 20-90%. Reduction was highest for K and Cl and lowest for N. HHV of PC and untreated biomass were in a comparable range (17.8-19.5 MJ kg-1 DM), but AST of PC was higher (1156-1254°C). Methane yields of PF were higher compared to those of WCD when the biomass was harvested late (end of May and later) and in a comparable range when the biomass was harvested early and ranged from 332 to 458 LN kg-1 VS. Regarding energy and GHG balances, IFBB, with a net energy yield of 11.9-14.1 MWh ha-1, a conversion efficiency of 0.43-0.51, and GHG mitigation of 3.6-4.4 t CO2eq ha-1, performed better than WCD, but worse than CH. WCD produces thermal and electric energy with low efficiency, CH produces only thermal energy with a low quality solid fuel with high efficiency, IFBB produces thermal and electric energy with a solid fuel of high quality with medium efficiency. Regression models were able to predict target parameters with high accuracy (R2=0.70-0.99). The influence of increasing temperature of hydrothermal conditioning was an increase of mass flows, a decrease of element concentrations in the PC and a differing effect on energy conversion efficiency. The influence of increasing NDF concentration of the silage was a differing effect on mass flows, a decrease of element concentrations in the PC and an increase of energy conversion efficiency. The influence of increasing DM concentration of the silage was a decrease of mass flows, an increase of element concentrations in the PC and an increase of energy conversion efficiency. Based on the models an optimised IFBB process would be obtained with a medium temperature of hydrothermal conditioning (50°C), high NDF concentrations in the silage and medium DM concentrations of the silage.

Optimal control theory for a unitary operation under dissipative evolution

We show that optimizing a quantum gate for an open quantum system requires the time evolution of only three states irrespective of the dimension of Hilbert space. This represents a significant reduction in computational resources compared to the complete basis of Liouville space that is commonly believed necessary for this task. The reduction is based on two observations: the target is not a general dynamical map but a unitary operation; and the time evolution of two properly chosen states is sufficient to distinguish any two unitaries. We illustrate gate optimization employing a reduced set of states for a controlled phasegate with trapped atoms as qubit carriers and a iSWAP gate with superconducting qubits.

1.55 µm High-Speed QDs Lasers for Optical Telecommunication Applications

In this work investigation of the QDs formation and the fabrication of QD based semiconductor lasers for telecom applications are presented. InAs QDs grown on AlGaInAs lattice matched to InP substrates are used to fabricate lasers operating at 1.55 µm, which is the central wavelength for far distance data transmission. This wavelength is used due to its minimum attenuation in standard glass fibers. The incorporation of QDs in this material system is more complicated in comparison to InAs QDs in the GaAs system. Due to smaller lattice mismatch the formation of circular QDs, elongated QDs and quantum wires is possible. The influence of the different growth conditions, such as the growth temperature, beam equivalent pressure, amount of deposited material on the formation of the QDs is investigated. It was already demonstrated that the formation process of QDs can be changed by the arsenic species. The formation of more round shaped QDs was observed during the growth of QDs with As2, while for As4 dash-like QDs. In this work only As2 was used for the QD growth. Different growth parameters were investigated to optimize the optical properties, like photoluminescence linewidth, and to implement those QD ensembles into laser structures as active medium. By the implementation of those QDs into laser structures a full width at half maximum (FWHM) of 30 meV was achieved. Another part of the research includes the investigation of the influence of the layer design of lasers on its lasing properties. QD lasers were demonstrated with a modal gain of more than 10 cm-1 per QD layer. Another achievement is the large signal modulation with a maximum data rate of 15 Gbit/s. The implementation of optimized QDs in the laser structure allows to increase the modal gain up to 12 cm-1 per QD layer. A reduction of the waveguide layer thickness leads to a shorter transport time of the carriers into the active region and as a result a data rate up to 22 Gbit/s was achieved, which is so far the highest digital modulation rate obtained with any 1.55 µm QD laser. The implementation of etch stop layers into the laser structure provide the possibility to fabricate feedback gratings with well defined geometries for the realization of DFB lasers. These DFB lasers were fabricated by using a combination of dry and wet etching. Single mode operation at 1.55 µm with a high side mode suppression ratio of 50 dB was achieved.

Alley cropping of willows and grassland for bioenergy provision: productivity, tree-crop interactions and energy balance

The demand for biomass for bioenergy has increased rapidly in industrialized countries in the recent years. Biogenic energy carriers are known to reduce CO2 emissions. However, the resource-inefficient production of biomass often caused negative impacts on the environment, e.g. biodiversity losses, nitrate leaching, and erosion. The detrimental effects evolved mainly from annual crops. Therefore, the aim of modern bioenergy cropping systems is to combine yield stability and environmental benefits by the establishment of mixed-cropping systems. A particular emphasis is on perennial crops which are perceived as environmentally superior to annual crops. Agroforestry systems represent such mixed perennial cropping systems and consist of a mix of trees and arable crops or grassland within the same area of land. Agroforestry practices vary across the globe and alley cropping is a type of agroforestry system which is well adapted to the temperate zone, with a high degree of mechanization. Trees are planted in rows and crops are planted in the alleyways, which facilitates their management by machinery. This study was conducted to examine a young alley cropping system of willows and two grassland mixtures for bioenergy provision under temperate climate conditions. The first part of the thesis identified possible competition effects between willows and the two grassland mixtures. Since light seemed to be the factor most affecting the yield performance of the understory in temperate agroforestry systems, a biennial in situ artificial shade experiment was established over a separate clover-grass stand to quantify the effects of shade. Data to possible below- and aboveground interactions among willows and the two grassland mixtures and their effects on productivity, sward composition, and quality were monitored along a tree-grassland interface within the alleys. In the second part, productivity of the alley cropping system was examined on a triennial time frame and compared to separate grassland and willow stands as controls. Three different conversion technologies (combustion of hay, integrated generation of solid fuel and biogas from biomass, whole crop digestion) were applied to grassland biomass as feedstock and analyzed for its energetic potential. The energetic potential of willow wood chips was calculated by applying combustion as conversion technique. Net energy balances of separate grassland stands, agroforestry and pure willow stands evaluated their energy efficiency. Results of the biennial artificial shade experiment showed that severe shade (80 % light reduction) halved grassland productivity on average compared to a non-shaded control. White clover as heliophilous plant responded sensitively to limited radiation and its dry matter contribution in the sward decreased with increasing shade, whereas non-leguminous forbs (mainly segetal species) benefited. Changes in nutritive quality could not be confirmed by this experiment. Through the study on interactions within the alleys of the young agroforestry system it was possible to outline changes of incident light, soil temperature and sward composition of clover-grass along the tree-grassland interface. Nearly no effects of trees on precipitation, soil moisture and understory productivity occurred along the interface during the biennial experiment. Considering the results of the productivity and the net energy yield alley cropping system had lower than pure grassland stands, irrespective of the grassland seed mixture or fertilization, but was higher than that for pure willow stands. The comparison of three different energetic conversion techniques for the grassland biomass showed highest net energy yields for hay combustion, whereas the integrated generation of solid fuel and biogas from biomass (IFBB) and whole crop digestion performed similarly. However, due to the low fuel quality of hay, its direct combustion cannot be recommended as a viable conversion technique, whereas IFBB fuels were of a similar quality to wood chip from willow.