Multidimensional Nano-Imaging of Structure, Coupling, and Disorder in Molecular Materials.

A hierarchy of intramolecular and intermolecular interactions controls the properties of biomedical, photophysical, and novel energy materials. However, multiscale heterogeneities often obfuscate the relationship between microscopic structure and emergent function, and they are generally difficult to access with conventional optical and electron microscopy techniques. Here, we combine vibrational exciton nanoimaging in variable-temperature near-field optical microscopy (IR s-SNOM) with four-dimensional scanning transmission electron microscopy (4D-STEM), and vibrational exciton modeling based on density functional theory (DFT), to link local microscopic molecular interactions to macroscopic three-dimensional order. In the application to poly(tetrafluoroethylene) (PTFE), large spatio-spectral heterogeneities with C-F vibrational energy shifts ranging from sub-cm-1 to ≳25 cm-1 serve as a molecular ruler of the degree of local crystallinity and disorder. Spatio-spectral-structural correlations reveal a previously invisible degree of highly variable local disorder in molecular coupling as the possible missing link between nanoscale morphology and associated electronic, photonic, and other functional properties of molecular materials.

Thin-disk laser system operating above 10 kW at near fundamental mode beam quality.

We report on a thin-disk laser system with more than 10 kW of output power and a beam quality of M2=1.76 at an overall optical-to-optical efficiency of 51%. The system consists of two thin-disk laser oscillators and a thin-disk multi-pass amplifier system. To reach high output powers while maintaining good beam quality, the output beams of two identical laser oscillators are polarization-combined. Subsequently, the beam is amplified in a multi-pass system. To the best of our knowledge, this is the highest output power achieved for a thin-disk laser system with a beam quality close to fundamental mode.

Purcell-Enhanced Spontaneous Emission of Molecular Vibrations.

Infrared (IR) spectroscopy of molecular vibrations provides insight into molecular structure, coupling, and dynamics. However, picosecond scale intermolecular and intramolecular many-body interactions, nonradiative relaxation, absorption, and thermalization typically dominate over IR spontaneous emission. We demonstrate how coupling to a resonant IR antenna can enhance spontaneous emission of molecular vibrations. Using time-domain nanoprobe spectroscopy we observe an up to 50% decrease in vibrational dephasing time T_{2,vib}, based on the coupling-induced population decay with T_{κ}≃550 fs and an associated Purcell factor of >10^{6}. This rate enhancement of the spontaneous emission of antenna-coupled molecular vibrations opens new avenues for IR coherent control, quantum information processing, and quantum chemistry.

Ultranarrow Second-Harmonic Resonances in Hybrid Plasmon-Fiber Cavities.

We demonstrate second-harmonic generation with ultranarrow resonances in hybrid plasmon-fiber cavities, formed by depositing single-crystalline gold nanorods onto the surface of tapered microfibers with diameters in the range of 1.7-1.8 µm. The localized surface plasmon mode of the single gold nanorod efficiently couples with a whispering gallery mode of the fiber, resulting in a very narrow hybrid plasmon-fiber resonance with a high quality factor Q of up to 250. When illuminated with a tunable 100 fs laser, a sharp SHG peak narrower than half of the spectral width of the impinging laser emerges, superimposed on a broad multiphoton photoluminescence background. The enhancement of the SHG peak of the hybrid system is typically 1000-fold when compared to that of a single gold nanorod alone. Tuning the laser over the hybrid resonance enables second-harmonic spectroscopy and yields an ultranarrow line width as small as 6.4 nm. We determine the second-harmonic signal to rise with the square of the laser power, while the multiphoton photoluminescence background rises with powers between 4 and 6, indicating a very efficient higher-order process. A coupled anharmonic oscillator model is able to describe the linear as well as second-harmonic resonances very well. Our work will open the door to the simultaneous utilization of narrow whispering gallery resonances together with high plasmonic near-field enhancement and should allow for nonlinear sensing and extremely efficient nonlinear light generation from ultrasmall volumes.

Probing the Near-Field of Second-Harmonic Light around Plasmonic Nanoantennas.

We introduce a new concept that enables subwavelength polarization-resolved probing of the second-harmonic near-field distribution of plasmonic nanostructures. As a local sensor, this method utilizes aluminum nanoantennas, which are resonant to the second-harmonic wavelength and which allow to efficiently scatter the local second-harmonic light to the far-field. We place these sensors into the second-harmonic near-field generated by plasmonic nanostructures and carefully vary their position and orientation. Observing the second-harmonic light resonantly scattered by the aluminum nanoantennas provides polarization-resolved information about the local second-harmonic near-field distribution. We then investigate the polarization-resolved second-harmonic near-field of inversion symmetric gold dipole nanoantennas. Interestingly, we find strong evidence that the second-harmonic dipole is predominantly oriented perpendicular to the gold nanoantenna long axis, although the excitation laser is polarized parallel to the nanoantennas. We believe that our investigations will help to disentangle the highly debated origin of the second-harmonic response of inversion symmetric plasmonic structures. Furthermore, we believe that our new method, which enables the measurement of local nonlinear electric fields, will find widespread implementation and applications in nonlinear near-field optical microscopy.

Single-step sub-200 fs mid-infrared generation from an optical parametric oscillator synchronously pumped by an erbium fiber laser.

We demonstrate the single-step generation of mid-infrared femtosecond laser pulses in a AgGaSe2 optical parametric oscillator that is synchronously pumped by a 100 MHz repetition rate sub-90 fs erbium fiber laser. The tuning range of the idler beam in principle covers ∼3.5 to 17 µm, only dependent on the choice of cavity and mirror design. As an example, we experimentally demonstrate idler pulse generation from 4.8 to 6.0 µm optimized for selective vibrational resonant molecular spectroscopy. We find an oscillation threshold as low as 150 mW of pump power. At 300 mW pump power and a central wavelength of ∼5.0 µm, we achieve an average infrared power of up to 17.5 mW, with a photon conversion efficiency of ∼18%. A pulse duration of ∼180 fs is determined from a nonlinear cross-correlation with residual pump light. The single-step nonlinear conversion leads to a high power stability with <1% average power drift at <0.5% rms noise over 1 h.

Nonlinear Refractory Plasmonics with Titanium Nitride Nanoantennas.

Titanium nitride (TiN) is a novel refractory plasmonic material which can sustain high temperatures and exhibits large optical nonlinearities, potentially opening the door for high-power nonlinear plasmonic applications. We fabricate TiN nanoantenna arrays with plasmonic resonances tunable in the range of about 950-1050 nm by changing the antenna length. We present second-harmonic (SH) spectroscopy of TiN nanoantenna arrays, which is analyzed using a nonlinear oscillator model with a wavelength-dependent second-order response from the material itself. Furthermore, characterization of the robustness upon strong laser illumination confirms that the TiN antennas are able to endure laser irradiation with high peak intensity up to 15 GW/cm(2) without changing their optical properties and their physical appearance. They outperform gold antennas by one order of magnitude regarding laser power sustainability. Thus, TiN nanoantennas could serve as promising candidates for high-power/high-temperature applications such as coherent nonlinear converters and local heat sources on the nanoscale.

Nonlinear Plasmonic Sensing.

We introduce the concept of nonlinear plasmonic sensing, relying on third harmonic generation from simple plasmonic nanoantennas. Because of the nonlinear conversion process we observe a larger sensitivity to a local change in the refractive index as compared to the commonly used linear localized surface plasmon resonance sensing. Refractive index changes as small as 10(-3) can be detected. In order to determine the spectral position of highest sensitivity, we perform linear and third harmonic spectroscopy on plasmonic nanoantenna arrays, which are the fundamental building blocks of our sensor. Furthermore, simultaneous detection of linear and nonlinear signals allows quantitative comparison of both methods, providing further insight into the working principle of our sensor. While the signal-to-noise ratio is comparable, nonlinear sensing gives about seven times higher relative signal changes.

Linear and nonlinear optical properties of hybrid metallic-dielectric plasmonic nanoantennas.

We study the linear and nonlinear optical properties of hybrid metallic-dielectric plasmonic gap nanoantennas. Using a two-step-aligned electron beam lithography process, we demonstrate the ability to selectively and reproducibly fill the gap region of nanoantennas with dielectric nanoparticles made of lithium niobate (LiNbO3) with high efficiency. The linear optical properties of the antennas are modified due to the large refractive index of the material. This leads to a change in the coupling strength as well as an increase of the effective refractive index of the surrounding. The combination of these two effects causes a red- or blue-shift of the plasmonic modes, respectively. We find that the nonlinear optical properties of the combined system are only modified in the range of one order of magnitude. The observed changes in our experiments in the nonlinear emission can be traced to the changed dielectric environment and thus the modified linear optical properties. The intrinsic nonlinearity of the dielectric used is in fact small when compared to the nonlinearity of the metallic part of the hybrid antennas. Thus, the nonlinear signals generated by the antenna itself are dominant in our experiments. We demonstrate that the well-known nonlinear response of bulk dielectric materials cannot always straightforwardly be used to boost the nonlinear response of nanoscale antenna systems. Our results significantly deepen the understanding of these interesting hybrid systems and offer important guidelines for the design of nanoscale, nonlinear light sources.

Strong Enhancement of Second Harmonic Emission by Plasmonic Resonances at the Second Harmonic Wavelength.

We perform second harmonic spectroscopy of aluminum nanoantenna arrays that exhibit plasmonic resonances at the second harmonic wavelength between 450 and 570 nm by focusing sub-30 fs laser pulses tunable from 900 to 1140 nm onto the nanoantenna arrays. We find that a plasmonic resonance at the second harmonic wavelength boosts the overall nonlinear process by more than an order of magnitude. In particular, in the measurement the resonant second harmonic polarization component is a factor of about 70 stronger when compared to the perpendicular off-resonant second harmonic polarization. Furthermore, the maximum of the second harmonic conversion efficiency is found to be slightly blue-shifted with respect to the peak of the linear optical far-field spectrum. This fact can be understood from a simple model that accounts for the almost off-resonant absorption at the fundamental wavelength and the resonant emission process at the second harmonic.

Third Harmonic Mechanism in Complex Plasmonic Fano Structures.

We perform third harmonic spectroscopy of dolmen-type nanostructures, which exhibit plasmonic Fano resonances in the near-infrared. Strong third harmonic emission is predominantly radiated close to the low energy peak of the Fano resonance. Furthermore, we find that the third harmonic polarization of the subradiant mode interferes destructively and diminishes the nonlinear signal in the far-field. By comparing the experimental third harmonic spectra with finite element simulations and an anharmonic oscillator model, we find strong indications that the source of the third harmonic is the optical nonlinearity of the bare gold enhanced by the resonant plasmonic polarization.

Doubling the efficiency of third harmonic generation by positioning ITO nanocrystals into the hot-spot of plasmonic gap-antennas.

We incorporate dielectric indium tin oxide nanocrystals into the hot-spot of gold nanogap-antennas and perform third harmonic spectroscopy on these hybrid nanostructure arrays. The combined system shows a 2-fold increase of the radiated third harmonic intensity when compared to bare gold antennas. In order to identify the origin of the enhanced nonlinear response we perform finite element simulations of the nanostructures, which are in excellent agreement with our measurements. We find that the third harmonic signal enhancement is mainly related to changes in the linear optical properties of the plasmonic antenna resonances when the ITO nanocrystals are incorporated. Furthermore, the dominant source of the third harmonic is found to be located in the gold volume of the plasmonic antennas.

Ultrabroadband chirped pulse second-harmonic spectroscopy: measuring the frequency-dependent second-order response of different metal films.

We introduce a spectroscopic method for measuring the frequency-dependent second-order response using ultrabroadband strongly chirped laser pulses. The dispersion suppresses nonlinear frequency mixing, hence the second-order response of a material can be unambiguously retrieved. We demonstrate this method by measuring the frequency-dependent second-harmonic (SH) response of the metals gold, aluminium, silver, and copper in the wavelength range of about 900-1150 nm and compare the results to classical SH spectroscopy. The SH spectra indicate that interband transitions in the metals influence the overall nonlinear optical response.

Interpreting chiral nanophotonic spectra: the plasmonic Born-Kuhn model.

One of the most intuitive ways to classically understand the generation of natural optical activity in chiral media is provided by the coupled oscillator model of Born and Kuhn consisting of two identical, vertically displaced, coupled oscillators. We experimentally realize and discuss its exact plasmonic analog in a system of corner-stacked gold nanorods. In particular, we analyze the arising circular dichroism and optical rotatory spectra in terms of hybridized electromagnetic modes and retardation. Specifically, we demonstrate how tuning the vertical distance between the nanorods can lead to a selective excitation of the occurring bonding and antibonding chiral plasmonic modes.

Plasmonic diastereomers: adding up chiral centers.

We construct chiral plasmonic molecules by assembling two individual chiral centers. Interestingly, depending on the exact arrangement of the centers, all combinations result in a chiral compound with a strong chiral optical response. Furthermore, we demonstrate that the overall circular dichrosim (CD) is determined by the response of the individual chiral centers. We find that the CD spectra of the composite molecules are then simply given as the sum of the CD spectra of the constituting building blocks. Interestingly, as soon as strong near-field coupling takes place between chiral centers, we find strong deviation from the simple additive chiral behavior. Most importantly, we demonstrate that the optical response of complex chiral plasmonic systems can be decomposed and understood in terms of fundamental building blocks, offering simple and straightforward design rules for future applications such as chiral optical elements and enantiomer sensors.

Third-harmonic spectroscopy and modeling of the nonlinear response of plasmonic nanoantennas.

We perform third-harmonic (TH) spectroscopy on rod-type gold nanoantenna arrays using widely tunable sub-30 fs laser pulses. We find the peak of the TH generation efficiency of the antenna arrays always slightly redshifted with respect to the peak of their linear extinction spectrum. We model the wavelength-dependent TH response quantitatively using a nonlinear harmonic oscillator model.

High-power widely tunable sub-20 fs Gaussian laser pulses for ultrafast nonlinear spectroscopy.

We demonstrate the generation of widely tunable sub-20 fs Gaussian-shaped laser pulses using a grating-based 4-f pulse shaper and a liquid crystal spatial light modulator. Our pump source is an Yb:KGW solitary mode-locked oscillator at 44 MHz repetition rate which is coupled into a large mode area microstructured fiber to generate a broad spectrum from below 900 nm to above 1150 nm. These pulses are precompressed by a prism sequence and subsequently sent into the pulse shaper. We use the multiphoton intrapulse interference phase scan (MIIPS) for phase shaping and iterative amplitude optimization to achieve Gaussian-like tunable sub-20 fs pulses with output powers of up to 142 mW as well as nontunable pulses with 310 mW output power as short as 11.5 fs.

Compact laser source for high-power white-light and widely tunable sub 65 fs laser pulses.

We demonstrate an Yb:KGW femtosecond solitary mode-locked laser oscillator, which is used as a pump source for tapered fibers to generate white-light laser pulses with an average output power of up to 2.5 W and a spectral bandwidth of over 1000 nm. By spectrally filtering these pulses and subsequent compression of the filtered pulses with a prism sequence, we are able to generate ultrashort laser pulses with durations between 26 and 65 fs that are tunable from 600 to 1450 nm and with tens to several hundreds of milliwatts of average power.