Breaking Barriers in Ultrafast Spectroscopy and Imaging Using 100 kHz Amplified Yb-Laser Systems.

ConspectusUltrafast spectroscopy and imaging have become tools utilized by a broad range of scientists involved in materials, energy, biological, and chemical sciences. Commercialization of ultrafast spectrometers including transient absorption spectrometers, vibrational sum frequency generation spectrometers, and even multidimensional spectrometers have put these advanced spectroscopy measurements into the hands of practitioners originally outside the field of ultrafast spectroscopy. There is now a technology shift occurring in ultrafast spectroscopy, made possible by new Yb-based lasers, that is opening exciting new experiments in the chemical and physical sciences. Amplified Yb-based lasers are not only more compact and efficient than their predecessors but also, most importantly, operate at many times the repetition rate with improved noise characteristics in comparison to the previous generation of Ti:sapphire amplifier technologies. Taken together, these attributes are enabling new experiments, generating improvements to long-standing techniques, and affording the transformation of spectroscopies to microscopies. This Account aims to show that the shift to 100 kHz lasers is a transformative step in nonlinear spectroscopy and imaging, much like the dramatic expansion that occurred with the commercialization of Ti:sapphire laser systems in the 1990s. The impact of this technology will be felt across a great swath of scientific communities. We first describe the technology landscape of amplified Yb-based laser systems used in conjunction with 100 kHz spectrometers operating with shot-to-shot pulse shaping and detection. We also identify the range of different parametric conversion and supercontinuum techniques which now provide a path to making pulses of light optimal for ultrafast spectroscopy. Second, we describe specific instances from our laboratories of how the amplified Yb-based light sources and spectrometers are transformative. For multiple probe time-resolved infrared and transient 2D IR spectroscopy, the gain in temporal span and signal-to-noise enables dynamical spectroscopy measurements from femtoseconds to seconds. These gains widen the applicability of time-resolved infrared techniques across a range of topics in photochemistry, photocatalysis, and photobiology as well as lower the technical barriers to implementation in a laboratory. For 2D visible spectroscopy and microscopy with white light, as well as 2D IR imaging, the high repetition rates of these new Yb-based light sources allow one to spatially map 2D spectra while maintaining high signal-to-noise in the data. To illustrate the gains, we provide examples of imaging applications in the study of photovoltaic materials and spectroelectrochemistry.

Hot carrier extraction from 2D semiconductor photoelectrodes.

Hot carrier-based energy conversion systems could double the efficiency of conventional solar energy technology or drive photochemical reactions that would not be possible using fully thermalized, "cool" carriers, but current strategies require expensive multijunction architectures. Using an unprecedented combination of photoelectrochemical and in situ transient absorption spectroscopy measurements, we demonstrate ultrafast (<50 fs) hot exciton and free carrier extraction under applied bias in a proof-of-concept photoelectrochemical solar cell made from earth-abundant and potentially inexpensive monolayer (ML) MoS2. Our approach facilitates ultrathin 7 Å charge transport distances over 1 cm2 areas by intimately coupling ML-MoS2 to an electron-selective solid contact and a hole-selective electrolyte contact. Our theoretical investigations of the spatial distribution of exciton states suggest greater electronic coupling between hot exciton states located on peripheral S atoms and neighboring contacts likely facilitates ultrafast charge transfer. Our work delineates future two-dimensional (2D) semiconductor design strategies for practical implementation in ultrathin photovoltaic and solar fuel applications.

Dicyanamide Anion Reports on Water Induced Local Structural and Dynamic Heterogeneity in Ionic Liquid Mixtures.

The effects of limited amounts (under 21.6% χWater) of water on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) and 1-butyl-3-methylimidazolium dicyanamide (BmimDCA) room-temperature ionic liquid (RTIL) mixtures were characterized by tracking changes in the linear and two-dimensional infrared (2D IR) vibrational features of the dicyanamide anion (DCA). Peak shifts with increasing water suggest the formation of water-associated and nonwater-associated DCA populations. Further results showed clear differences in the dynamic behavior of these different populations of DCA at low (defined here as below 2.5% χWater), mid (defined here as between 2.5% χWater and 9.6% χWater), and high (defined here as between 11.6% χWater and 21.6% χWater) range water concentrations. Vibrational relaxation is accelerated with increasing water content for water-associated populations of DCA, indicating water facilitates population relaxation, possibly through the provision of additional bath modes. Conversely, spectral diffusion of water-associated populations slowed dramatically with increasing water, suggesting that water drives the formation of distinct and noninterchangeable or very slowly interchangeable local solvent environments.

Ultrafast vibrational dynamics of a trigonal planar anionic probe in ionic liquids (ILs): A two-dimensional infrared (2DIR) spectroscopic investigation.

A major impediment limiting the widespread application of ionic liquids (ILs) is their high shear viscosity. Incorporation of a tricyanomethanide (TCM-) anion in ILs leads to low shear viscosity and improvement of several characteristics suitable for large scale applications. However, properties including interactions of TCM- with the local environment and dynamics of TCM- have not been thoroughly investigated. Herein, we have studied the ultrafast dynamics of TCM- in several imidazolium ILs using linear IR and two-dimensional infrared spectroscopy techniques. The spectral diffusion dynamics of the CN stretching modes of TCM- in all ILs exhibit a nonexponential behavior with a short time component of ∼2 ps and a long time component spanning ∼9 ps to 14 ps. The TCM- vibrational probe reports a significantly faster relaxation of ILs compared to those observed previously using linear vibrational probes, such as thiocyanate and selenocyanate. Our results indicate a rapid relaxation of the local ion-cage structure embedding the vibrational probe in the ILs. The faster relaxation suggests that the lifetime of the local ion-cage structure decreases in the presence of TCM- in the ILs. Linear IR spectroscopic results show that the hydrogen-bonding interaction between TCM- and imidazolium cations in ILs is much weaker. Shorter ion-cage lifetimes together with weaker hydrogen-bonding interactions account for the low shear viscosity of TCM- based ILs compared to commonly used ILs. In addition, this study demonstrates that TCM- can be used as a potential vibrational reporter to study the structure and dynamics of ILs and other molecular systems.

0.85 PW laser operation at 3.3 Hz and high-contrast ultrahigh-intensity λ = 400 nm second-harmonic beamline.

We demonstrate the generation of 0.85 PW, 30 fs laser pulses at a repetition rate of 3.3 Hz with a record average power of 85 W from a Ti:sapphire laser. The system is pumped by high-energy Nd:glass slab amplifiers frequency doubled in LiB3O5 (LBO). Ultrahigh-contrast λ=400 nm femtosecond pulses were generated in KH2PO4 (KDP) with >40% efficiency. An intensity of 6.5×1021 W/cm2 was obtained by frequency doubling 80% of the available Ti:sapphire energy and focusing the doubled light with an f/2 parabola. This laser will enable highly relativistic plasma experiments to be conducted at high repetition rate.

High-Throughput Two-Dimensional Infrared (2D IR) Spectroscopy Achieved by Interfacing Microfluidic Technology with a High Repetition Rate 2D IR Spectrometer.

The precision control of microfluidic technology was successfully interfaced with a 100 kHz two-dimensional infrared (2D IR) spectrometer to observe the sensitivity of the anion cyanate (OCN-) to the surrounding solvent environment in a high-throughput manner. Producing high-throughput 2D IR spectroscopy measurements allows us to observe the vibrational response of cyanate in mixed solvent environments. Changes in solvation environment around the cyanate ion yield frequency shifts from 2150 to 2165 cm-1 when moving from a pure dimethylformamide solvent environment to a pure methanol environment. 2D IR spectra were captured laterally across microfluidic devices tailored to produce a tunable gradient to observe the OCN- vibrational response to mixed solvent environments. These experiments reveal that there is no preferential solvation of cyanate in this system; instead, a more complex local solvent environment is observed.

2D IR spectroscopy at 100 kHz utilizing a Mid-IR OPCPA laser source.

We present a 100 kHz 2D IR spectrometer. The system utilizes a ytterbium all normal dispersion fiber oscillator as a common source for the pump and seed beams of a MgO:PPLN OPCPA. The 1030 nm OPCPA pump is generated by amplification of the oscillator in cryocooled Yb:YAG amplifiers, while the 1.68 µm seed is generated in a OPO pumped by the oscillator. The OPCPA outputs are used in a ZGP DFG stage to generate 4.65 µm pulses. A mid-IR pulse shaper delivers pulse pairs to a 2D IR spectrometer allowing for data collection at 100 kHz.

Demonstration of a 100 Hz repetition rate gain-saturated diode-pumped table-top soft x-ray laser.

We demonstrate the operation of a gain-saturated table-top soft x-ray laser at 100 Hz repetition rate. The laser generates an average power of 0.15 mW at λ=18.9 nm, the highest laser power reported to date from a sub-20-nm wavelength compact source. Picosecond laser pulses of 1.5 µJ energy were produced at λ=18.9 nm by amplification in a Mo plasma created by tailoring the temporal intensity profile of single pump pulses with 1 J energy produced by a diode-pumped chirped pulse amplification Yb:YAG laser. Lasing was also obtained in the 13.9 nm line of Ni-like Ag. These results increase by an order of magnitude the repetition rate of plasma-based soft x-ray lasers opening the path to milliwatt average power table-top lasers at sub-20 nm wavelengths.

Demonstration of an all-diode-pumped soft x-ray laser.

We have demonstrated an 18.9 nm Ni-like molybdenum soft x-ray laser, pumped by a compact all-diode-pumped Yb:YAG laser. The solid-state pump laser produces 8.5 ps pulses with up to 1 J energy at 10 Hz repetition rate. This diode-pumped laser has the potential to greatly increase the repetition rate and the average power of soft x-ray lasers on a significantly smaller footprint.