Lars Gundlach

Sub-20 fs visible pulses with 750 nJ energy from a 100 kHz noncollinear optical parametric amplifier

We demonstrate the operation of a 100 kHz noncollinear optical parametric amplifier that is pumped by just a few microjoules of 800 nm pulses with 50 fs duration. The device delivers sub-20 fs pulses tunable from 460 nm to beyond 1 microm and pulse energies up to 750 nJ when it is pumped with 7 microJ of energy. The design of the single-stage amplifier has been carefully optimized, and the design considerations are discussed.

Femtosecond Kerr-gated wide-field fluorescence microscopy

We present a Kerr-gated microscope capable of collecting diffraction-limited 2D fluorescence images with sub-100 fs time resolution. The concept is based on the insertion of a solid-state optical Kerr gate into a wide-field microscope. In addition to the considerably improved temporal resolution, the wide-field design allows for simultaneous tracking of several objects and ultrafast fluorescence lifetime imaging of doped and heterogeneous surfaces. The ultrafast fluorescence dynamics of gold nanoparticles is presented as an example of the capabilities of the instrument.

Photoinduced Ultrafast Heterogeneous Electron Transfer at Molecule–Semiconductor Interfaces

This Perspective discusses recent developments in ultrafast electron transfer dynamics at interfaces between organic and inorganic materials. Heterogeneous electron transfer (HET) is a key process in important fields like catalysis and solar energy conversion. Furthermore, the solid state nature of the systems gives control over relevant parameters and allows for investigating excited state dynamics and electron transfer processes in unprecedented detail. Progress in synthesis, sample preparation, and instrumentation makes it possible to provide experimental proof of recent prediction from theory concerning the adiabaticity of the reaction and the influence of coherence. A short recapitulation of the field is followed by a discussion of recent experimental efforts that allowed for studying HET, particularly focusing on the influence of energetics and vibrational dynamics.

Excitons and excess electrons in nanometer size molecular polyoxotitanate clusters: electronic spectra, exciton dynamics, and surface states.

The behavior of excitons and excess electrons in the confined space of a molecular polyoxotitanate cluster Ti17(μ4-O)4(μ3-O)16(μ2-O)4(OPr(i))20 (in short Ti17) was studied using femtosecond pump-probe transient absorption, pulse radiolysis, and fluorescence spectroscopy. Due to pronounced quantum size effects, the electronic spectra of the exciton, Ti17*, and the excess electron carrying radical anion, Ti17(•-), are blue-shifted in comparison with bulk TiO2 and have maxima at 1.91 and 1.24 eV, respectively. The 0.7 eV difference in the position of the absorption maxima of Ti17* and Ti17(•-) indicates the presence of strong Coulomb interaction between the conduction band electron and the valence band hole in the ∼1 nm diameter cluster. Ground state Raman spectra and the vibronic structure of the fluorescence spectrum point to the importance of the interfacial ligand modes in the stabilization and localization of the fully relaxed exciton. Four pentacoordinate Ti sites near the surface of the cluster appear to play a special role in this regard. Solvent polarity has only a minor influence on the spectral behavior of Ti17*. Exciton recombination in Ti17 is faster than in anatase nanoparticles or mesoporous films. The kinetics exhibits three components, ranging from less than 1 ps to 100 ps, which are tentatively assigned to the geminate recombination within the core of the cluster and to the decay of the surface stabilized charge transfer exciton. A persistent long-lived component with τ > 300 ps may indicate the involvement of intraband dark states, i.e., triplet excitons (3)Ti17*.

Efficiency and temporal response of crystalline Kerr media in collinear optical Kerr gating

Optical Kerr gating is widely used in ultrafast measurements ranging from pulse characterization to spectroscopy and microscopy. We examined the efficiency and the temporal response of three cubic lattice Kerr media, YAG, GGG and BGO, and compared them with the well studied fused silica (fast response, low efficiency) and STO (high efficiency, slow response). YAG and GGG emerged as superior materials for ultrafast spectroscopy and microscopy applications thanks to their fast Kerr response and considerably higher gating efficiency than silica at low gating energies. Importantly, it was found that in collinear geometry all tested materials except STO are capable of reaching nearly 100% transmission.

Efficient Z-scheme charge separation in novel vertically aligned ZnO/CdSSe nanotrees

A new tree-like ZnO/CdSSe nanocomposite with CdSSe branches grown on ZnO nanowires prepared via a two-step chemical vapor deposition is presented. The nanotrees (NTs) are vertically aligned on a substrate. The CdSSe branches result in strong visible light absorption and form a type-II heterojunction with the ZnO stem that facilitates efficient electron transfer. A combination of photoluminescence spectroscopy and lifetime measurements indicates that the NTs are promising materials for applications that benefit from a Z-scheme charge transfer mechanism. Vertically aligned branched ZnO nanowires can provide direct electron transport pathways to substrates and allow for efficient charge separation. These advantages of nanoscale hierarchical heterostructures make ZnO/CdSSe NTs a promising semiconductor material for solar cells, and other opto-electronic devices.

Heterogeneous Electron-Transfer Dynamics through Dipole-Bridge Groups

Heterogeneous electron transfer (HET) between photoexcited molecules and colloidal TiO2 has been investigated for a set of Zn-porphyrin chromophores attached to the semiconductor via linkers that allow to change level alignment by 200 meV by reorientation of the dipole moment. These unique dye molecules have been studied by femtosecond transient absorption spectroscopy in solution and adsorbed on the TiO2 colloidal film in vacuum. In solution energy transfer from the excited chromophore to the dipole group has been identified as a slow relaxation pathway competing with S2-S1 internal conversion. On the film heterogeneous electron transfer occurred in 80 fs, much faster compared to all intramolecular pathways. Despite a difference of 200 meV in level alignment of the excited state with respect to the semiconductor conduction band, identical electron transfer times were measured for different linkers. The measurements are compared to a quantum-mechanical model that accounts for electronic-vibronic coupling and finite band width for the acceptor states. We conclude that HET occurs into a distribution of transition states that differs from regular surface states or bridge mediated states.

Ultrafast Photoinduced Electron Transfer at Electrodes: The General Case of a Heterogeneous Electron-Transfer Reaction

The general case of a heterogeneous electron-transfer reaction is realized by ultrafast electron transfer from a light-absorbing molecule to a wide continuum of electronic acceptor states, realizing the so-called wide band limit. Experimental data obtained for perylene dye/TiO(2) systems confirm the predictions of fully quantum mechanical model calculations of the dynamics. The energy distribution of the injected electron shows an energy loss due to excitations of high-energy (quantum) vibrational modes in the ionized perylene moiety. The electron-transfer mechanism is non-adiabatic and the reaction is ultrafast, for example, with a time constant of 9 fs for the COOH anchor-bridge group. The underlying strong coupling of the electronic states to high-energy vibrational modes is a characteristic feature of sensitizer molecules.

Growth and characterization of ErAs:GaBix As1−x

We explore the growth and characterization of ErAs:GaBiAs as a candidate material for terahertz generation and detection via photoconductive switches. Spectrophotometry shows that the incorporation of small amounts of bismuth causes a reduction in the band gap, making these materials compatible with fiber-coupled lasers. ErAs pins the Fermi level within the band gap, causing high dark resistance while maintaining high mobility, shown by Hall effect measurements. Finally, transient absorption (optical pump, optical probe) measurements show that the ErAs provides a carrier recombination pathway, causing short carrier lifetimes. These material properties make ErAs:GaBiAs an interesting choice for fiber-coupled photoconductive switches.

Ultraviolet femtosecond Kerr-gated wide-field fluorescence microscopy

A Kerr-gated microscope capable of imaging ultraviolet luminescence with femtosecond time resolution has been developed. The system allows the spatial, spectral, and temporal measurement of UV-emitting samples. The instrumentation was optimized for emission collection in the UV, resulting in sub 90 fs time resolution of gated signals. ZnO nanowires were used to demonstrate the performance of the instrument. The evolution of the emission from a single nanowire was tracked via ultrafast transient spectroscopy and through sequential imaging. Transient dynamics were extracted from a region of intense emission on a single ZnO nanowire. This technique is a powerful tool capable of contactless ultrafast measurements of charge carrier dynamics in single nanoparticles.