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.

Theoretical study of the physicochemical properties of the light transactinides

A theoretical study of the physicochemical properties of elements 104, 105, and 106 and their compounds in the gas phase and aqueous solutions has been undertaken using relativistic atomic and molecular codes. Trends in properties such as bonding, ionization potentials, electron affinities, energies of electronic transitions, stabilities of oxidation states etc. have been defined within the corresponding chemical groups and within the transactinides. These trends are shown to be determined by increasing relativistic effects within the groups. The behaviour of some gas phase compounds and complexes in solutions is predicted for the gas chromatography and solvent extraction experiments. Redox potentials in aqueous solutions of these elements are estimated.

Time-resolved studies of neutral and ionized Na_n clusters with femtosecond light pulses

The real-time dynamics of Na_n (n=3-21) cluster multiphoton ionization and fragmentation has been studied in beam experiments applying femtosecond pump-probe techniques in combination with ion and electron spectroscopy. Three dimensional wave packet motions in the trimer Na_3 ground state X and excited state B have been observed. We report the first study of cluster properties (energy, bandwidth and lifetime of intermediate resonances Na_n^*) with femtosecond laser pulses. The observation of four absorption resonances for the cluster Na_8 with different energy widths and different decay patterns is more difficult to interpret by surface plasmon like resonances than by molecular structure and dynamics. Timeresolved fragmentation of cluster ions Na_n^+ indicates that direct photo-induced fragmentation processes are more important at short times than the statistical unimolecular decay.

Analytical Study of Light Propagation in Highly Nonlinear Media

The present dissertation is devoted to the construction of exact and approximate analytical solutions of the problem of light propagation in highly nonlinear media. It is demonstrated that for many experimental conditions, the problem can be studied under the geometrical optics approximation with a sufficient accuracy. Based on the renormalization group symmetry analysis, exact analytical solutions of the eikonal equations with a higher order refractive index are constructed. A new analytical approach to the construction of approximate solutions is suggested. Based on it, approximate solutions for various boundary conditions, nonlinear refractive indices and dimensions are constructed. Exact analytical expressions for the nonlinear self-focusing positions are deduced. On the basis of the obtained solutions a general rule for the single filament intensity is derived; it is demonstrated that the scaling law (the functional dependence of the self-focusing position on the peak beam intensity) is defined by a form of the nonlinear refractive index but not the beam shape at the boundary. Comparisons of the obtained solutions with results of experiments and numerical simulations are discussed.

Synthesis and Characterization of Novel Spiro-Starburst-Structures as Blue Light Emitters and Zeolites

Spiro-starburst-structures with symmetric globular structures in forms of first and second generations that readily form stable amorphous glasses have been synthesized and then characterised in this work. During the synthesis of these materials, possibilities of the extension of the chains of the phenyl rings in 2,2’,7 and 7’-positions of the central core of the spirobifluorene as well as the 2’,7 and 7’-positions of the terminal spirobifluorene units of the spiro-starburst-structures have been investigated so that solubilities and morphologies of the compounds are not negatively influenced. Their morphological properties have been explored by recording their decomposition temperature and glass transition temperature. These compounds possessing two perpendicular arrangement of the two molecular halves show high glass transition temperature (Tg), which is one of the most important parameter indicating the stability of the amorphous state of the material for optoelectronic devices like organic light emitting diodes. Within the species of second generation compounds, for example, 4-spiro3 shows the highest Tg (330 °C) and the highest branching degree. When one [4B(SBF)SBF-SBF 84] or two [4SBFSBF-SBF 79] terminal spirobifluorene units are removed, the Tg decreases to 318 °C and 307 °C respectively. Photo absorption and fluorescence spectra and cyclic voltammetry measurements are taken in account to characterize the optoelectronic properties of the compounds. Spiro-starburst-structures emit radiation in the blue region of the visible spectrum. The peak maxima of absorption and emission spectra are observed to be at higher wavelength in the molecules with longer chromophore chains than in the molecules with shorter chromophore chains. Excitation spectra are monitored with their emission peak maxima. The increasing absorbing species in molecule leads to increasing molar extinction coefficient. In the case of 4B(TP)SBF-SBF 53 and 4B(SBF)SBF-SBF 84, the greater values of the molar extinction coefficients (43*104 and 44*104 L mol-1 cm-1 respectively) are the evidences of the presence of four times octiphenyl conjugation rings and eight times terminal fluorene units respectively. The optical properties of solid states of these compounds in the form of thin film indicate that the intermolecular interaction and aggregation of individual molecules in neat amorphous films are effectively hindered by their sterically demanding structures. Accordingly, in solid state, they behave like isolated molecules in highly dilute solution. Cyclic voltammetry measurements of these compounds show electrochemically reversibility and stability. Furthermore, the zeolitic nature (host-guest) of the molecular sieve of the synthesized spiro-starburst-structures has been analysed by thermogravimetric analysis method.

Asymptotic model for shape resonance control of diatomics by intense non-resonant light

We derive a universal model for atom pairs interacting with non-resonant light via the polarizability anisotropy, based on the long range properties of the scattering. The corresponding dynamics can be obtained using a nodal line technique to solve the asymptotic Schrödinger equation. It consists of imposing physical boundary conditions at long range and vanishing the wavefunction at a position separating the inner zone and the asymptotic region. We show that nodal lines which depend on the intensity of the non-resonant light can satisfactorily account for the effect of the polarizability at short range. The approach allows to determine the resonance structure, energy, width, channel mixing and hybridization even for narrow resonances.

Asymptotic model for shape resonance control of diatomics by intense non-resonant light: universality in the single-channel approximation

Non-resonant light interacting with diatomics via the polarizability anisotropy couples different rotational states and may lead to strong hybridization of the motion. The modification of shape resonances and low-energy scattering states due to this interaction can be fully captured by an asymptotic model, based on the long-range properties of the scattering (Crubellier et al 2015 New J. Phys. 17 045020). Remarkably, the properties of the field-dressed shape resonances in this asymptotic multi-channel description are found to be approximately linear in the field intensity up to fairly large intensity. This suggests a perturbative single-channel approach to be sufficient to study the control of such resonances by the non-resonant field. The multi-channel results furthermore indicate the dependence on field intensity to present, at least approximately, universal characteristics. Here we combine the nodal line technique to solve the asymptotic Schrödinger equation with perturbation theory. Comparing our single channel results to those obtained with the full interaction potential, we find nodal lines depending only on the field-free scattering length of the diatom to yield an approximate but universal description of the field-dressed molecule, confirming universal behavior.