Coherent Multidimensional Off-resonant THz Spectroscopy on Semiconductors

Zum ersten Mal konnte die kohärente Erzeugung von ultrakurzen Pulsen mit Feld stärken im MV/cm Bereich mit einem Spektralbereich von 0.1-30 THz im organischen Kristall DSTMS. Kohärente mehrdimensionale Terahertzspektroskopie (CMTS) hat sich zu einer wichtigen Methode zur Untersuchung der niederenergetischen Anregungen von Halbleitern and deren kohärenter Dynamik entwickelt. Eine neuartige CMTS Methode mit drei phasenstarren, zueinander zeitverzögerten Terahertzpulsen wurde entwickelt. Sie beruht auf der kollinearen Wechselwirkung der Pulse mit der Probe, sodass verschiedene Ordnungen des nichtlinearen Signals in gleicher Richtung emittiert werden und deshalb gleichzeitig gemessen werden können. Amplitude und Phase des nichtlinearen Signals können durch elektro-optisches Abtasten vermessen werden, wodurch die zeitliche Entwicklung der kohärenten Wechselwirkungen in Echtzeit untersucht werden kann. CMTS erlaubt zusätzlich die eindeutige Zerlegung des nichtlinearen Signals in die verschiedenen nichtlinearen Ordnungen in der jeweiligen mehrdimensionalen Frequenzdomäne. Die nichtlineare, nicht-resonante Antwort zweier undotierter Halbleiter, des Ferroelektrikums Lithiumniobat (LiNbO3) und Indiumantimonids (InSb) kann mit dieser neuartigen Methode untersucht werden. In LiNbO3 wird das nichtlineare Signal durch einen Femtosekunden nichtlinearen Verschiebestrom (SC) hervorgerufen. SC wird durch die gebrochene Inversionssymmetrie des Kristalls in Verbindung mit einer ultraschnellen Dephasierung der feldinduzierten, kohärenten interband-Polarisation hervorgerufen. Die Dephasierung der interband-Polarisation erlaubt das Tunneln von Elektronen vom Valenzband in das Leitungsband. In InSb wird das kohärente Signal durch sowohl zwei-Phonen als auch zwei-Photonen interband-Anregungen erzeugt. Die impulsive Anregung einer kohärenten zwei-Phononen Polarisation wird durch das große Übergangsdipolmoment von InSb verstärkt, was zu deutlich größeren Amplituden der Polarisation als im linearem Regime führt.For the first time, the coherent generation of ultrashort MV/cm field pulses with a spectrum covering the frequency range 0.1-30 THz is demonstrated in the organic crystal DSTMS. Coherent multidimensional terahertz spectroscopy (CMTS) has become a prominent technique for, e.g., driving low-energy excitations in semiconductors and monitoring their coherent dynamics. A novel CMTS technique using three phase-locked inter-delayed THz pulses is implemented. It relies on a collinear interaction of the pulses with a sample, so that different contributions to the nonlinear signal are emitted in the same direction, and thus can be measured all at once. Phase-resolved detection by electro-optic sampling allows for measuring amplitude and absolute phase of the nonlinear signal, thereby enabling to investigate the evolution of coherent interactions between quantum excitations in real time. In CMTS, the nonlinear signal is dissected into the distinct nonlinear contributions in the corresponding multidimensional frequency domain. This novel technique is applied to study the nonlinear off-resonant response of two undoped bulk semiconductors, the wide-bandgap ferroelectric lithium niobate (LiNbO3) and the narrow-bandgap indium antimonide (InSb). In LiNbO3, the nonlinear signal is generated by a femtosecond nonlinear shift current (SC), a distinctive characteristic of the bulk photovoltaic effect. The SC stems from the lack of inversion symmetry and the ultrafast dephasing of the field-induced interband coherent polarization due to a sufficiently high decoherence rate, which enables tunneling of electrons from the valence to the conduction band. In InSb, the nonlinear signal is caused by the coherent response on both the two-phonon and two-photon interband excitations. The impulsive generation of the two-phonon coherent polarization is enhanced by the large interband transition dipole of InSb, resulting in much larger polarization amplitudes than in the regime of linear response

Nonlinear optical characterisation of organic chromophores and aspects of molecular aggregation

The work presented in this thesis describes an investigation into the properties and behaviour of a new class of nonlinear optical organic chromophores. This study contributes to the optimisation of nonlinear optical molecules through an improved understanding of the relationships between the molecular nonlinear optical properties and the measured macroscopic quantities. A series of highly dipolar non-linear optical chromophores with absorption typically in the range of 350-500 nm have been synthesised by the reactions of amines with tetracyanoquinodimethane (TCNQ). One of the advantages of these materials is the large molecular figure of merit (μβ where μ is the molecular dipole moment and P is the second order polarisability), which theoretically allows large nonlinear optical coefficients to be obtained. The molecular dipole moments of these chromophores were determined both experimentally and theoretically, and were found to agree. The nonlinear optical properties of these compounds in solution were studied using an electric field induced second harmonic generation (EFISH) technique. The measurements of μβ at 1064 nm and 1907 nm in chloroform and acetone are presented. Moderate μβ values were obtained but β is found to be unexpectedly small in chloroform and shows unusual dispersion characteristics in this solvent compared to acetone. Further concentration investigations revealed features that suggest the presence of aggregates within solution. Optical spectroscopy measurements provide evidence of new species whose presence and conformation were found to be solvent-dependent. The results of this work highlight the need for an entire concentration range to be studied if accurate determination of molecular properties of highly dipolar molecules is required. Guest-host polymer films of these materials have been corona poled using a constant current corona triode. Detailed characterisation studies of the second order nonlinearities using second harmonic generation (SHG) were compared to a less dipolar molecule. These investigations showed that the highly dipolar TCNQ derivatives show severe aggregation within the polymer films. The magnitude of the SHG that can be obtained from such systems is therefore limited by this aggregation