Ultrafast and Low-Threshold THz Mode Switching of Two-Dimensional Nonlinear Metamaterials.

Judiciously designed two-dimensional THz metamaterials consisting of resonant metallic structures embedded in a dielectric environment locally enhance the electromagnetic field of an incident THz pulse to values sufficiently high to cause nonlinear responses of the environment. In semiconductors, the response is attributed to nonlinear transport phenomena via intervalley scattering, impact ionization, or interband tunneling and can affect the resonant behavior of the metallic structure, which results, for instance, in mode switching. However, details of mode switching, especially time scales, are still debated. By using metallic split-ring resonators with nm-size gaps on intrinsic semiconductors with different bandgaps, we identify the most relevant carrier generation processes. In addition, by combining nonlinear THz time-domain spectroscopy with simulations, we establish the fastest time constant for mode switching to around hundred femtoseconds. Our results not only elucidate dominant carrier generation mechanisms and dynamics but also pave the route toward optically driven modulators with THz bandwidth.

Merging of Azulene and Perylene Diimide for Optical pH Sensors.

Polycyclic aromatic hydrocarbons (PAHs) have emerged as promising materials for organic electronics, including organic photovoltaics (OPVs), organic field-effect transistors (OFETs), and organic light-emitting diodes (OLEDs). Particularly, non-hexagonal ring-fused PAHs are highly desirable due to their unique optoelectronic properties. Herein, a new redox-active azulene-perylene diimide triad 1 and its ring-fused counterpart, diazulenocoronene diimide 2, were synthesized and fully characterized by a combination of NMR, cyclic voltammetry, and UV-visible absorption spectroscopy. Direct comparison of their electronic properties leads us to the conclusion that a significant change in the localization of HOMO and LUMO occurs upon the fusion of azulene and perylene diimide in 2, leading to the lack of intramolecular charge-transfer character for transitions in the visible spectral region. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed to gain further insight into various electronic transitions. Moreover, we found that the adaptive response to acids and bases manifests itself in a reversible two-color change that can be attributed to changes in the chemical structures. Our findings pave the way for manipulating the relative HOMO and LUMO energy levels of organic chromophores by fusing non-alternant azulenes to an otherwise flat PAH, which could possibly lead to applications in organic electronics and optical sensors.

Structure, Organization, and Heterogeneity of Water-Containing Deep Eutectic Solvents.

The spectroscopy and structural dynamics of a deep eutectic mixture (KSCN/acetamide) with varying water content is investigated from 2D IR (with the C-N stretch vibration of the SCN- anions as the reporter) and THz spectroscopy. Molecular dynamics simulations correctly describe the nontrivial dependence of both spectroscopic signatures depending on water content. For the 2D IR spectra, the MD simulations relate the steep increase in the cross-relaxation rate at high water content to the parallel alignment of packed SCN- anions. Conversely, the nonlinear increase of the THz absorption with increasing water content is mainly attributed to the formation of larger water clusters. The results demonstrate that a combination of structure-sensitive spectroscopies and molecular dynamics simulations provides molecular-level insights into the emergence of heterogeneity of such mixtures by modulating their composition.

3D-printed THz wave- and phaseplates.

Three-dimensional printing based on fused deposition modeling has been shown to provide a cost-efficient and time-saving tool for fabricating a variety of THz optics for a frequency range of <0.2 THz. By using a broadband THz source, with a useful spectral range from 0.08 THz to 1.5 THz, we show that 3D-printed waveplates operate well up to 0.6 THz and have bandwidths similar to commercial products. Specifically, we investigate quarter- and half-waveplates, q-plates, and spiral phaseplates. We demonstrate a route to achieve broadband performance, so that 3D-printed waveplates can also be used with broadband, few-cycle THz pulses, for instance, in nonlinear THz spectroscopy or other THz high field applications.

Optically Controlled Electron Transfer in a ReI Complex.

Ultrafast optical control of intramolecular charge flow was demonstrated, which paves the way for photocurrent modulation and switching with a highly wavelength-selective ON/OFF ratio. The system that was explored is a fac-[Re(CO)3 (TTF-DPPZ)Cl] complex, where TTF-DPPZ=4',5'-bis(propylthio)tetrathiafulvenyl[i]dipyrido[3,2-a:2',3'-c]phenazine. DFT calculations and AC-Stark spectroscopy confirmed the presence of two distinct optically active charge-transfer processes, namely a metal-to-ligand charge transfer (MLCT) and an intra-ligand charge transfer (ILCT). Ultrafast transient absorption measurements showed that the ILCT state decays in the ps regime. Upon excitation to the MLCT state, only a long-lived 3 MLCT state was observed after 80 ps. Remarkably, however, the bleaching of the ILCT absorption band remained as a result of the effective inhibition of the HOMO-LUMO transition.

Temporal fine structure of all-normal dispersion fiber supercontinuum pulses caused by non-ideal pump pulse shapes.

We experimentally investigate the spectro-temporal characteristics of coherent supercontinuum (SC) pulses generated in several implementations of silica and soft-glass all-normal dispersion (ANDi) photonic crystal fibers optimized for pumping with Erbium (Er):fiber femtosecond laser technology. We characterize the resulting SC using time-domain ptychography, which is especially suitable for the measurement of complex, spectrally broadband ultrashort pulses. The measurements of the ANDi SC pulses reveal intricate pulse shapes, considerable temporal fine structure, and oscillations on time scales of < 25 femtoseconds, which differ from the smoothness and simplicity of temporal profiles obtained in numerical simulations and observed in previous experiments. We link the measured complex features to temporal sub-structures of the pump pulse, such as pre- and post-pulses and low-level pedestals, which are common in high pulse energy ultrafast Er:fiber systems. We also observe spectro-temporal structures consistent with incoherent noise amplification in weakly birefringent fiber samples. Our results highlight the importance of the pump source and polarization-maintaining (PM) fibers for high-quality SC generation and have practical relevance for many ultrafast photonics applications employing ANDi fiber-based SC sources.

High-resolution phase-sensitive sum frequency generation spectroscopy by time-domain ptychography.

We demonstrate that time-domain ptychography, when applied to a set of broadband vibrational sum frequency spectra, reconstructs amplitude and phase of the vibrational free induction decay from an interfacial sample with a resolution that is independent of up-converting pulse bandwidth and spectrometer resolution. These important improvements require no modifications to most standard homodyne setups, and the method is applicable to other coherent homodyne spectroscopies such as coherent anti-Stokes Raman spectroscopy and transient grating spectroscopy.

DNA-organized artificial LHCs - testing the limits of chromophore segmentation.

DNA-organized multi-chromophoric systems containing phenanthrene and pyrene derivatives exhibit a highly efficient excitation energy transfer from phenanthrene (donor) to pyrene (acceptor). The energy transfer also occurs if the phenanthrene antenna is interrupted by intervening DNA base pairs. Artificial light-harvesting complexes composed of up to five phenanthrene-DNA alternations with fluorescence quantum yields as high as 68% are described.

Anti-Kasha Conformational Photoisomerization of a Heteroleptic Dithiolene Metal Complex Revealed by Ultrafast Spectroscopy.

We investigated the anti-Kasha photochemistry and anti-Kasha emission of d8-metal donor-acceptor dithiolene with femtosecond UV-vis transient absorption spectroscopy and molecular modeling. Experimentally, we found a lifetime of 1.4 ps for higher excited states, which is exceptionally long when compared to typical values for internal conversion (IC) (10 s of fs or less). Consequently, a substantial emission originates from the second excited state. Molecular modeling suggests this to be a consequence of the spatially separated molecular orbitals of the first and second excited states, which gives a charge transfer character to the IC. More surprisingly, we found that the inherent flexibility of the molecule allows the metal complex to access different configurations depending on the photoexcited state. We believe that this unique manifestation of anti-Kasha photoinduced conformational isomerization is facilitated by the exceptionally long lifetime of the second excited state.

Ultra low-noise coherent supercontinuum amplification and compression below 100 fs in an all-fiber polarization-maintaining thulium fiber amplifier.

We report an ultra-low noise, polarization-maintaining, ultrafast Thulium-doped all-fiber chirped pulse amplifier, seeded by a polarized all-normal dispersion (ANDi) supercontinuum (SC) driven by an ultrafast Erbium-fiber laser. The system comprises only polarization-maintaining fibers and delivers 96 fs pulses with 350 mW output power at 100 MHz, centered at 1900 nm. The integrated relative intensity noise (RIN) in the range of 10 Hz - 10 MHz is only 0.047% at the amplifier output, which is virtually identical to the RIN of the Erbium-fiber laser driving the SC. Therefore, neither the SC generation nor the amplification process introduce significant excess noise. The RIN of our system is an order of magnitude lower than similar systems previously seeded with Raman solitons. This highlights the superior noise properties of ANDi SC and their potential as ultra-low noise seed sources for broadband, high power ultrafast fiber amplifiers and frequency combs.

Terahertz ptychography.

We realized a phase retrieval technique using terahertz (THz) radiation as an alternative to THz digital holography, named THz ptychography. Ptychography has been used in x-ray imaging as a groundbreaking improvement of conventional coherent diffraction imaging. Here we show that ptychography can be performed at THz frequencies too. We reconstructed an amplitude and a phase object with both simulated and real data. Lateral resolution accounts to <2λ, while depth variations as low as λ/30 can be assessed.

Single-graded CIGS with narrow bandgap for tandem solar cells.

Multi-junction solar cells show the highest photovoltaic energy conversion efficiencies, but the current technologies based on wafers and epitaxial growth of multiple layers are very costly. Therefore, there is a high interest in realizing multi-junction tandem devices based on cost-effective thin film technologies. While the efficiency of such devices has been limited so far because of the rather low efficiency of semitransparent wide bandgap top cells, the recent rise of wide bandgap perovskite solar cells has inspired the development of new thin film tandem solar devices. In order to realize monolithic, and therefore current-matched thin film tandem solar cells, a bottom cell with narrow bandgap (~1 eV) and high efficiency is necessary. In this work, we present Cu(In,Ga)Se2 with a bandgap of 1.00 eV and a maximum power conversion efficiency of 16.1%. This is achieved by implementing a gallium grading towards the back contact into a CuInSe2 base material. We show that this modification significantly improves the open circuit voltage but does not reduce the spectral response range of these devices. Therefore, efficient cells with narrow bandgap absorbers are obtained, yielding the high current density necessary for thin film multi-junction solar cells.

Refractive indices of layers and optical simulations of Cu(In,Ga)Se2 solar cells.

Cu(In,Ga)Se2 based solar cells have reached efficiencies close to 23%. Further knowledge-driven improvements require accurate determination of the material properties. Here, we present refractive indices for all layers in Cu(In,Ga)Se2 solar cells with high efficiency. The optical bandgap of Cu(In,Ga)Se2 does not depend on the Cu content in the explored composition range, while the absorption coefficient value is primarily determined by the Cu content. An expression for the absorption spectrum is proposed, with Ga and Cu compositions as parameters. This set of parameters allows accurate device simulations to understand remaining absorption and carrier collection losses and develop strategies to improve performances.

Surface Passivation for Reliable Measurement of Bulk Electronic Properties of Heterojunction Devices.

Quantum efficiency measurements of state of the art Cu(In,Ga)Se2 (CIGS) thin film solar cells reveal current losses in the near infrared spectral region. These losses can be ascribed to inadequate optical absorption or poor collection of photogenerated charge carriers. Insight on the limiting mechanism is crucial for the development of more efficient devices. The electron beam induced current measurement technique applied on device cross-sections promises an experimental access to depth resolved information about the charge carrier collection probability. Here, this technique is used to show that charge carrier collection in CIGS deposited by multistage co-evaporation at low temperature is efficient over the optically active region and collection losses are minor as compared to the optical ones. Implications on the favorable absorber design are discussed. Furthermore, it is observed that the measurement is strongly affected by cross-section surface recombination and an accurate determination of the collection efficiency is not possible. Therefore it is proposed and shown that the use of an Al2 O3 layer deposited onto the cleaved cross-section significantly improves the accuracy of the measurement by reducing the surface recombination. A model for the passivation mechanism is presented and the passivation concept is extended to other solar cell technologies such as CdTe and Cu2 (Zn,Sn)(S,Se)4 .

Solvation-driven charge transfer and localization in metal complexes.

In any physicochemical process in liquids, the dynamical response of the solvent to the solutes out of equilibrium plays a crucial role in the rates and products: the solvent molecules react to the changes in volume and electron density of the solutes to minimize the free energy of the solution, thus modulating the activation barriers and stabilizing (or destabilizing) intermediate states. In charge transfer (CT) processes in polar solvents, the response of the solvent always assists the formation of charge separation states by stabilizing the energy of the localized charges. A deep understanding of the solvation mechanisms and time scales is therefore essential for a correct description of any photochemical process in dense phase and for designing molecular devices based on photosensitizers with CT excited states. In the last two decades, with the advent of ultrafast time-resolved spectroscopies, microscopic models describing the relevant case of polar solvation (where both the solvent and the solute molecules have a permanent electric dipole and the mutual interaction is mainly dipole-dipole) have dramatically progressed. Regardless of the details of each model, they all assume that the effect of the electrostatic fields of the solvent molecules on the internal electronic dynamics of the solute are perturbative and that the solvent-solute coupling is mainly an electrostatic interaction between the constant permanent dipoles of the solute and the solvent molecules. This well-established picture has proven to quantitatively rationalize spectroscopic effects of environmental and electric dynamics (time-resolved Stokes shifts, inhomogeneous broadening, etc.). However, recent computational and experimental studies, including ours, have shown that further improvement is required. Indeed, in the last years we investigated several molecular complexes exhibiting photoexcited CT states, and we found that the current description of the formation and stabilization of CT states in an important group of molecules such as transition metal complexes is inaccurate. In particular, we proved that the solvent molecules are not just spectators of intramolecular electron density redistribution but significantly modulate it. Our results solicit further development of quantum mechanics computational methods to treat the solute and (at least) the closest solvent molecules including the nonperturbative treatment of the effects of local electrostatics and direct solvent-solute interactions to describe the dynamical changes of the solute excited states during the solvent response.

THz near-field enhancement by means of isolated dipolar antennas: the effect of finite sample size.

Generation of high intensity terahertz radiation in the low frequency region (f < 5 THz) is still a challenging task and only few experimental demonstrations exceeding 1 MV/cm have been reported so far. One viable option is the use of resonant metallic structures which act as amplifiers for the impinging radiation. Here with the aid of finite difference time domain simulations, we design and realize a set of isolated resonant elements which allow us to reach a 28-fold enhancement of freely propagating THz radiation at f ≈ 1 THz. These elements are deposited on a GaP sample allowing the direct measurement of the field enhancement using electro-optical sampling. Interestingly, we experimentally show strong modifications of the antennas resonance which is interpreted in terms of interference effects. These are particularly important in samples thinner than half the spatial pulse length.

Improved retrieval of complex supercontinuum pulses from XFROG traces using a ptychographic algorithm.

We demonstrate that time-domain ptychography, a recently introduced iterative ultrafast pulse retrieval algorithm, has properties well suited for the reconstruction of complex light pulses with large time-bandwidth products from a cross-correlation frequency-resolved optical gating (XFROG) measurement. It achieves temporal resolution on the scale of a single optical cycle using long probe pulses and low sampling rates. In comparison to existing algorithms, ptychography minimizes the data to be recorded and processed, and significantly reduces the computational time of the reconstruction. Experimentally, we measure the temporal waveform of an octave-spanning, 3.5 ps long, supercontinuum pulse generated in photonic crystal fiber, resolving features as short as 5.7 fs with sub-fs resolution and 30 dB dynamic range using 100 fs probe pulses and similarly large delay steps.

All-optical implementation of a time-domain ptychographic pulse reconstruction setup.

An all-optical implementation of pulse reconstruction using time-domain ptychography has been demonstrated showing excellent results. The implementation was easy to set up and eliminated a number of drawbacks found in other second-order techniques, such as the beam splitter modifying the pulse under consideration, the time ambiguity, or the strict correspondence between time delay increment and temporal resolution. Ptychography generally offers superior performance compared to algorithms based on general projections, requires considerably less computational effort, and is much less susceptible to noise.

All-optical implementation of a time-domain ptychographic pulse reconstruction setup: publisher's note.

This note reports author corrections that were omitted from Appl. Opt.55, 5008 (2016) 10.1364/AO.55.005008 in error during production. The article was corrected online 23 June 2016.

Pulse-shaping assisted multidimensional coherent electronic spectroscopy.

Understanding nuclear and electronic dynamics of molecular systems has advanced considerably by probing their nonlinear responses with a suitable sequence of pulses. Moreover, the ability to control crucial parameters of the excitation pulses, such as duration, sequence, frequency, polarization, slowly varying envelope, or carrier phase, has led to a variety of advanced time-resolved spectroscopic methodologies. Recently, two-dimensional electronic spectroscopy with ultrashort pulses has become a more and more popular tool since it allows to obtain information on energy and coherence transfer phenomena, line broadening mechanisms, or the presence of quantum coherences in molecular complexes. Here, we present a high fidelity two-dimensional electronic spectroscopy setup designed for molecular systems in solution. It incorporates the versatility of pulse-shaping methods to achieve full control on the amplitude and phase of the individual exciting and probing pulses. Selective and precise amplitude- and phase-modulation is shown and applied to investigate electronic dynamics in several reference molecular systems.