Photoinduced Force Mapping of Plasmonic Nanostructures.

The ability to image the optical near-fields of nanoscale structures, map their morphology, and concurrently obtain spectroscopic information, all with high spatiotemporal resolution, is a highly sought-after technique in nanophotonics. As a step toward this goal, we demonstrate the mapping of electromagnetic forces between a nanoscale tip and an optically excited sample consisting of plasmonic nanostructures with an imaging platform based on atomic force microscopy. We present the first detailed joint experimental-theoretical study of this type of photoinduced force microscopy. We show that the enhancement of near-field optical forces in gold disk dimers and nanorods follows the expected plasmonic field enhancements with strong polarization sensitivity. We then introduce a new way to evaluate optically induced tip-sample forces by simulating realistic geometries of the tip and sample. We decompose the calculated forces into in-plane and out-of-plane components and compare the calculated and measured force enhancements in the fabricated plasmonic structures. Finally, we show the usefulness of photoinduced force mapping for characterizing the heterogeneity of near-field enhancements in precisely e-beam fabricated nominally alike nanostructures - a capability of widespread interest for precise nanomanufacturing, SERS, and photocatalysis applications.

Direct Plasmon-Driven Photoelectrocatalysis.

Harnessing the energy from hot charge carriers is an emerging research area with the potential to improve energy conversion technologies.1-3 Here we present a novel plasmonic photoelectrode architecture carefully designed to drive photocatalytic reactions by efficient, nonradiative plasmon decay into hot carriers. In contrast to past work, our architecture does not utilize a Schottky junction, the commonly used building block to collect hot carriers. Instead, we observed large photocurrents from a Schottky-free junction due to direct hot electron injection from plasmonic gold nanoparticles into the reactant species upon plasmon decay. The key ingredients of our approach are (i) an architecture for increased light absorption inspired by optical impedance matching concepts,4 (ii) carrier separation by a selective transport layer, and (iii) efficient hot-carrier generation and injection from small plasmonic Au nanoparticles to adsorbed water molecules. We also investigated the quantum efficiency of hot electron injection for different particle diameters to elucidate potential quantum effects while keeping the plasmon resonance frequency unchanged. Interestingly, our studies did not reveal differences in the hot-electron generation and injection efficiencies for the investigated particle dimensions and plasmon resonances.

Light trapping for solar fuel generation with Mie resonances.

The implementation of solar fuel generation as a clean, terawatt-scale energy source is critically dependent on the development of high-performance, inexpensive photocatalysts. Many candidate materials, including for example α-Fe2O3 (hematite), suffer from very poor charge transport with minority carrier diffusion lengths that are significantly shorter (nanometer scale) than the absorption depth of light (micrometer scale near the band edge). As a result, most of the photoexcited carriers recombine rather than participate in water-splitting reactions. For this reason, there is a tremendous opportunity for photon management. Plasmon-resonant nanostructures have been employed to effectively enhance light absorption in the near-surface region of photocatalysts, but this approach suffers from intrinsic optical losses in the metal. Here, we circumvent this issue by driving optical resonances in the active photocatalyst material itself. We illustrate that judiciously nanopatterned photocatalysts support optical Mie and guided resonances capable of substantially enhancing the photocarrier generation rate within 10-20 nm from the water/photocatalyst interface.

Self-assembly based plasmonic arrays tuned by atomic layer deposition for extreme visible light absorption.

Achieving complete absorption of visible light with a minimal amount of material is highly desirable for many applications, including solar energy conversion to fuel and electricity, where benefits in conversion efficiency and economy can be obtained. On a fundamental level, it is of great interest to explore whether the ultimate limits in light absorption per unit volume can be achieved by capitalizing on the advances in metamaterial science and nanosynthesis. Here, we combine block copolymer lithography and atomic layer deposition to tune the effective optical properties of a plasmonic array at the atomic scale. Critical coupling to the resulting nanocomposite layer is accomplished through guidance by a simple analytical model and measurements by spectroscopic ellipsometry. Thereby, a maximized absorption of light exceeding 99% is accomplished, of which up to about 93% occurs in a volume-equivalent thickness of gold of only 1.6 nm. This corresponds to a record effective absorption coefficient of 1.7 × 10(7) cm(-1) in the visible region, far exceeding those of solid metals, graphene, dye monolayers, and thin film solar cell materials. It is more than a factor of 2 higher than that previously obtained using a critically coupled dye J-aggregate, with a peak width exceeding the latter by 1 order of magnitude. These results thereby substantially push the limits for light harvesting in ultrathin, nanoengineered systems.

Plasmon enhanced solar-to-fuel energy conversion.

Future generations of photoelectrodes for solar fuel generation must employ inexpensive, earth-abundant absorber materials in order to provide a large-scale source of clean energy. These materials tend to have poor electrical transport properties and exhibit carrier diffusion lengths which are significantly shorter than the absorption depth of light. As a result, many photoexcited carriers are generated too far from a reactive surface and recombine instead of participating in solar-to-fuel conversion. We demonstrate that plasmonic resonances in metallic nanostructures and multilayer interference effects can be engineered to strongly concentrate sunlight close to the electrode/liquid interface, precisely where the relevant reactions take place. On comparison of spectral features in the enhanced photocurrent spectra to full-field electromagnetic simulations, the contribution of surface plasmon excitations is verified. These results open the door to the optimization of a wide variety of photochemical processes by leveraging the rapid advances in the field of plasmonics.

Polarization-dependent scanning photoionization microscopy: ultrafast plasmon-mediated electron ejection dynamics in single Au nanorods.

This work investigates plasmon-enhanced multiphoton scanning photoelectron emission microscopy (SPIM) of single gold nanorods under vacuum conditions. Striking differences in their photoemission properties are observed for nanorods deposited either on 2 nm thick Pt films or 10 nm thick indium tin oxide (ITO) films. On a Pt support, the Au nanorods display fourth-order photoionization when excited at 800 nm, a wavelength corresponding to their plasmon resonance in aqueous solution. A cos(8)(θ) dependence of the photoelectron flux on laser polarization implies photoemission mediated by the dipolar plasmon; however, no plasmon resonance signature is exhibited over the 750-880 nm range. Electromagnetic simulations confirm that the resonance is severely broadened compared to aqueous solution, indicative of strong interactions between the Au nanorod and propagating surface plasmon modes in the Pt substrate. On ITO substrates, by way of contrast, sharp plasmon resonances in the photoemission from individual Au nanorods are observed, with widths limited only by fundamental internal electron collision processes. Furthermore, the ensemble-averaged plasmon resonance for Au nanorods on ITO is almost unshifted compared to its frequency in solution. Both findings suggest that plasmonic particle-substrate interactions are suppressed in the Au/ITO system. However, Au nanorods on ITO exhibit a surprising third-order photoemission (observed neither in Au nor ITO by itself), indicating that electrostatic interactions introduce a substantial shift in the work function for this fundamental nanoparticle-substrate system.

Direct measurement of the angular dependence of the single-photon ionization of aligned N2 and CO2.

By combining a state-of-the-art high-harmonic ultrafast soft X-ray source with field-free dynamic alignment, we map the angular dependence of molecular photoionization yields for the first time for a nondissociative molecule. The observed modulation in ion yield as a function of molecular alignment is attributed to the molecular frame transition dipole moment of single-photon ionization to the X, A and B states of N2(+) and CO2(+). Our data show that the transition dipoles for single-photon ionization of N2 and CO2 at 43 eV have larger perpendicular components than parallel ones. A direct comparison with published theoretical partial wave ionization cross-sections confirms these experimental observations, which are the first results to allow such comparison with theory for bound cation states. The results provide the first step toward a novel method for measuring molecular frame transition dipole matrix elements.

Long-term carrier-envelope phase stability from a grating-based, chirped pulse amplifier.

We demonstrate a carrier-envelope phase (CEP) stabilized, chirped pulse laser amplifier that exhibits greatly improved intrinsic long-term CEP stability compared with that of other amplifiers. This system employs a grating-based stretcher and compressor and a cryogenically cooled laser amplifier. Single-shot carrier envelope phase noise measurements are also presented that avoid underestimation of this parameter caused by fringe averaging and represent a rigorously accurate upper limit on CEP noise.

Broadband phase-coherent optical frequency synthesis with actively linked Ti:sapphire and Cr:forsterite femtosecond lasers.

We link the output spectra of a Ti:sapphire and a Cr:forsterite femtosecond laser phase coherently to form a continuous frequency comb with a wavelength coverage of 0.57-1.45 microm at power levels of 1 nW to 40 microW per frequency mode. To achieve this, the laser repetition rates and the carrier-envelope offset frequencies are phase locked to each other. The coherence time between the individual components of the two combs is 40 micros. The timing jitter between the lasers is 20 fs. The combined frequency comb is self-referenced for access to its overall offset frequency. We report the first demonstration to our knowledge of an extremely broadband and continuous, high-powered and phase-coherent frequency comb from two femtosecond lasers with different gain media.

Investigation of a grating-based stretcher/compressor for carrier-envelope phase stabilized fs pulses.

In this work, we experimentally investigate the effect of a grating based pulse stretcher/compressor on the carrier-envelope phase stability of femtosecond pulses. Grating based stretcher-compressor (SC) setups have been avoided in past demonstrations of chirped pulse amplification (CPA) of carrier envelope phase (CEP) stabilized femtosecond pulses, because they were expected to introduce significantly stronger CEP fluctuations than material-based SC systems. Using a microstructure fiber-based detection setup, we measure CEP fluctuations of PhiCE,SC = 340 milliradians rms for a frequency range from 63 mHz to 102 kHz for pulses propagating through the SC setup. When bypassing the beam path through the SC, we find CEP fluctuations of PhiCE,bypass = 250 milliradians rms. These values contain significant contributions from amplitude-to-phase conversion in our microstructure fiber-based detection setup for PhiCE. Hence, we do not unambiguously measure any added CEP noise intrinsic to the SC setup. To distinguish between intrinsic SC effects and amplitude-to-phase conversion, we introduce controlled beam pointing fluctuations alpha and again compare the phase noise introduced when passing through / bypassing the SC. Our measurements do not reveal any intrinsic effects of the SC system, but allow us to place an upper limit on the sensitivity of our SC system of PhiCEintrinsic,SC / alpha < 13000 rad/rad. Our results demonstrate experimentally that there is not a strong coupling mechanism between CEP and beam pointing through a stretcher/compressor , as well as measuring significantly smaller CEP fluctuations than experimental results reported previously.

Chromium-doped forsterite: dispersion measurement with white-light interferometry.

Using a Michelson white-light interferometer, we measure the group-delay dispersion and third-order dispersion coefficients, d2(phi)/d(omega)2 and d3(phi)/d(omega)3, of chromium-doped forsterite (Cr:Mg2SiO4) over wavelengths of 1050-1600 nm for light polarized along both the c and b crystal axes. In this interval, the second-order dispersion for the c axis ranges from 35 fs2/mm to -14 fs2/mm, and the third-order dispersion ranges from 36 fs3/mm to 142 fs3/mm. For the b axis the second-order dispersion ranges from 35 fs2/mm to -15 fs2/mm and the third-order from 73 fs3/mm to 185 fs3/mm. Our data are relevant for the development of optimized dispersion compensation tools for Cr:Mg2SiO4 femtosecond lasers. These measurements help to clarify previously published results and show some significant discrepancies that existed, especially in the third-order dispersion. Our results should furthermore be useful to build up an analytic expression for the index of refraction of chromium forsterite.