Far-Field Petahertz Sampling of Plasmonic Fields.

The response of metal nanostructures to optical excitation leads to localized surface plasmon (LSP) generation with nanoscale field confinement driving applications in, for example, quantum optics and nanophotonics. Field sampling in the terahertz domain has had a tremendous impact on the ability to trace such collective excitations. Here, we extend such capabilities and introduce direct sampling of LSPs in a more relevant petahertz domain. The method allows to measure the LSP field in arbitrary nanostructures with subcycle precision. We demonstrate the technique for colloidal nanoparticles and compare the results to finite-difference time-domain calculations, which show that the build-up and dephasing of the plasmonic excitation can be resolved. Furthermore, we observe a reshaping of the spectral phase of the few-cycle pulse, and we demonstrate ad-hoc pulse shaping by tailoring the plasmonic sample. The methodology can be extended to single nanosystems and applied in exploring subcycle, attosecond phenomena.

The emergence of macroscopic currents in photoconductive sampling of optical fields.

Photoconductive field sampling enables petahertz-domain optoelectronic applications that advance our understanding of light-matter interaction. Despite the growing importance of ultrafast photoconductive measurements, a rigorous model for connecting the microscopic electron dynamics to the macroscopic external signal is lacking. This has caused conflicting interpretations about the origin of macroscopic currents. Here, we present systematic experimental studies on the signal formation in gas-phase photoconductive sampling. Our theoretical model, based on the Ramo-Shockley-theorem, overcomes the previously introduced artificial separation into dipole and current contributions. Extensive numerical particle-in-cell-type simulations permit a quantitative comparison with experimental results and help to identify the roles of electron-neutral scattering and mean-field charge interactions. The results show that the heuristic models utilized so far are valid only in a limited range and are affected by macroscopic effects. Our approach can aid in the design of more sensitive and more efficient photoconductive devices.

Breast-cancer detection using blood-based infrared molecular fingerprints.

BACKGROUND: Breast cancer screening is currently predominantly based on mammography, tainted with the occurrence of both false positivity and false negativity, urging for innovative strategies, as effective detection of early-stage breast cancer bears the potential to reduce mortality. Here we report the results of a prospective pilot study on breast cancer detection using blood plasma analyzed by Fourier-transform infrared (FTIR) spectroscopy - a rapid, cost-effective technique with minimal sample volume requirements and potential to aid biomedical diagnostics. FTIR has the capacity to probe health phenotypes via the investigation of the full repertoire of molecular species within a sample at once, within a single measurement in a high-throughput manner. In this study, we take advantage of cross-molecular fingerprinting to probe for breast cancer detection. METHODS: We compare two groups: 26 patients diagnosed with breast cancer to a same-sized group of age-matched healthy, asymptomatic female participants. Training with support-vector machines (SVM), we derive classification models that we test in a repeated 10-fold cross-validation over 10 times. In addition, we investigate spectral information responsible for BC identification using statistical significance testing. RESULTS: Our models to detect breast cancer achieve an average overall performance of 0.79 in terms of area under the curve (AUC) of the receiver operating characteristic (ROC). In addition, we uncover a relationship between the effect size of the measured infrared fingerprints and the tumor progression. CONCLUSION: This pilot study provides the foundation for further extending and evaluating blood-based infrared probing approach as a possible cross-molecular fingerprinting modality to tackle breast cancer detection and thus possibly contribute to the future of cancer screening.

Multi-octave, CEP-stable source for high-energy field synthesis.

The development of high-energy, high-power, multi-octave light transients is currently the subject of intense research driven by emerging applications in attosecond spectroscopy and coherent control. We report on a phase-stable, multi-octave source based on a Yb:YAG amplifier for light transient generation. We demonstrate the amplification of a two-octave spectrum to 25 µJ of energy in two broadband amplification channels and their temporal compression to 6 and 18 fs at 1 and 2 µm, respectively. In this scheme, due to the intrinsic temporal synchronization between the pump and seed pulses, the temporal jitter is restricted to long-term drift. We show that the intrinsic stability of the synthesizer allows subcycle detection of an electric field at 0.15 PHz. The complex electric field of the 0.15-PHz pulses and their free induction decay after interaction with water molecules are resolved by electro-optic sampling over 2 ps. The scheme is scalable in peak and average power.

Field-resolved infrared spectroscopy of biological systems.

The proper functioning of living systems and physiological phenotypes depends on molecular composition. Yet simultaneous quantitative detection of a wide variety of molecules remains a challenge1-8. Here we show how broadband optical coherence opens up opportunities for fingerprinting complex molecular ensembles in their natural environment. Vibrationally excited molecules emit a coherent electric field following few-cycle infrared laser excitation9-12, and this field is specific to the sample's molecular composition. Employing electro-optic sampling10,12-15, we directly measure this global molecular fingerprint down to field strengths 107 times weaker than that of the excitation. This enables transillumination of intact living systems with thicknesses of the order of 0.1 millimetres, permitting broadband infrared spectroscopic probing of human cells and plant leaves. In a proof-of-concept analysis of human blood serum, temporal isolation of the infrared electric-field fingerprint from its excitation along with its sampling with attosecond timing precision results in detection sensitivity of submicrograms per millilitre of blood serum and a detectable dynamic range of molecular concentration exceeding 105. This technique promises improved molecular sensitivity and molecular coverage for probing complex, real-world biological and medical settings.

Near-PHz-bandwidth, phase-stable continua generated from a Yb:YAG thin-disk amplifier.

We report on the generation of a multi-octave, phase-stable continuum from the output of a Yb:YAG regenerative amplifier delivering 1-ps pulses with randomly varying carrier-envelope phase (CEP). The intrinsically CEP-stable spectral continuum spans from 450 nm to beyond 2500 nm, covering a spectral range of about 0.6 PHz. The generated coherent broadband light carries an energy of 4 µJ, which can be scaled to higher values if required. The system has been designed and is ideally suited for seeding broadband parametric amplifiers and multichannel synthesizers pumped by picosecond Yb:YAG amplifiers, obviating the need for active timing synchronization required in previous approaches. The presented concept paves the way to cost-effective, reliable all-Yb:YAG single-cycle sources with terawatt peak-power and tens-of-Watts average power.

Visualization of bond rearrangements in acetylene using near single-cycle laser pulses.

The migration of hydrogen atoms resulting in the isomerization of hydrocarbons is an important process which can occur on ultrafast timescales. Here, we visualize the light-induced hydrogen migration of acetylene to vinylidene in an ionic state using two synchronized 4 fs intense laser pulses. The first pulse induces hydrogen migration, and the second is used for monitoring transient structural changes via Coulomb explosion imaging. Varying the time delay between the pulses reveals the migration dynamics with a time constant of 54 ± 4 fs as observed in the H+ + H+ + CC+ channel. Due to the high temporal resolution, vibrational wave-packet motions along the CC- and CH-bonds are observed. Even though a maximum in isomerization yield for kinetic energy releases above 16 eV is measured, we find no indication for a backwards isomerization - in contrast to previous measurements. Here, we propose an alternative explanation for the maximum in isomerization yield, namely the surpassing of the transition state to the vinylidene configuration within the excited dication state.

Attosecond photoelectron streaking with enhanced energy resolution for small-bandgap materials.

Attosecond photoelectron streaking spectroscopy allows time-resolved electron dynamics with a temporal resolution approaching the atomic unit of time. Studies have been performed in numerous systems, including atoms, molecules, and surfaces, and the quest for ever higher temporal resolution called for ever wider spectral extent of the attosecond pulses. For typical experiments relying on attosecond pulses with a duration of 200 as, the time-bandwidth limitation for a Gaussian pulse implies a minimal spectral bandwidth larger than 9 eV translating to a corresponding spread of the detected photoelectron kinetic energies. Here, by utilizing a specially tailored narrowband reflective XUV multilayer mirror, we explore experimentally the minimal spectral width compatible with attosecond time-resolved photoelectron spectroscopy while obtaining the highest possible spectral resolution. The validity of the concept is proven by recording attosecond electron streaking traces from the direct semiconductor gallium arsenide (GaAs), with a nominal bandgap of 1.42 eV at room temperature, proving the potential of the approach for tracking charge dynamics also in these technologically highly relevant materials that previously have been inaccessible to attosecond science.

High-power, 1-ps, all-Yb:YAG thin-disk regenerative amplifier.

We report a 100 W, 20 mJ, 1-ps, all-Yb:YAG thin-disk regenerative amplifier seeded by a microjoule-level Yb:YAG thin-disk Kerr-lens mode-locked oscillator. The regenerative amplifier is implemented in a chirped pulse amplification system and operates at an ambient temperature in air, delivering ultrastable output pulses at a 5 kHz repetition rate and with a root mean square power noise value of less than 0.5%. Second harmonic generation of the amplifier's output in a 1.5 mm-thick BBO crystal results in more than 70 W at 515 nm, making the system an attractive source for pumping optical parametric chirped pulse amplifiers in the visible and near-infrared spectral ranges.

Influence of surface coating on structural and photoluminescent properties of CaMoO4:Pr nanoparticles.

CaMoO4:Pr(core), CaMoO4:Pr@CaMoO4 (core/shell) and CaMoO4:Pr@CaMoO4@SiO2 (core/shell/shell) nanoparticles were synthesized using polyol method. X-ray diffraction (XRD), thermogravimatric analysis (TGA), UV-vis absorption, optical band gap energy analysis, Fourier transform infrared (FTIR), FT-Raman and photoluminescence (PL) spectroscopy were employed to investigate the structural and optical properties of the synthesized core and core/shell nanoparticles. The results of the XRD indicate that the obtained core, core/shell and core/shell/shell nanoparticles crystallized well at ~150 °C in ethylene glycol (EG) under urea hydrolysis. The growth of the CaMoO4 and SiO2 shell (~12 nm) around the CaMoO4:Pr core nanoparticles resulted in an increase of the average size of the nanopaticles as well as in a broadening of their size distribution. These nanoparticles can be well-dispersed in distilled water to form clear colloidal solutions. The photoluminescence spectra of core, core/shell and core/shell/shell nanoparticles show the characteristic charge transfer emission band of MoO4 (2-) (533 nm) and Pr(3+) 4f(2) → 4f(2), with multiple strong (3)H4 → (3)P2, (1)D2 → (3)H4 and (3)P0 → (3) F2 transitions located at ~490, 605 and 652 nm, respectively. The emission intensity of the CaMoO4:Pr@CaMoO4 core/shell and CaMoO4:Pr@CaMoO4@SiO2 core/shell/shell nanoparticles increased ~4.5 and 1.7 times,respectively, with respect to those of CaMoO4:Pr core nanoparticles. This indicates that a significant amount of nonradiative centers existing on the surface of CaMoO4:Pr@CaMoO4 core/shell nanoparticles can be eliminated by the shielding effect of CaMoO4 shells.

Effect of surface coating on optical properties of Eu(3+)-doped CaMoO4 nanoparticles.

A simple polyol method has been used for the synthesis of CaMoO4:Eu (core), CaMoO4:Eu@CaMoO4 (core/shell) and their silica coated CaMoO4:Eu@CaMoO4 (core/shell/shell) nanoparticles. X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR), UV/Vis absorption and photoluminescence (PL) spectroscopies techniques has been employed for their characterization. XRD patterns and FT-Raman spectra showed that these nanoparticles have a scheelite-type tetragonal structure without the presence of deleterious phases. These nanoparticles were easily dispersed in water, producing a transparent colloidal solution. The optical energy band-gap decreases after core/shell formation due to increase the crystalline size. The photoluminescence (PL) spectra of the as-synthesized core, core/shell and core/shell/shell nanoparticles measured with an excitation source wavelength of 325nm showed that the emission intensity was increases after shell formation around the surface of core nanoparticles.

Real-time observation of valence electron motion.

The superposition of quantum states drives motion on the atomic and subatomic scales, with the energy spacing of the states dictating the speed of the motion. In the case of electrons residing in the outer (valence) shells of atoms and molecules which are separated by electronvolt energies, this means that valence electron motion occurs on a subfemtosecond to few-femtosecond timescale (1 fs = 10(-15) s). In the absence of complete measurements, the motion can be characterized in terms of a complex quantity, the density matrix. Here we report an attosecond pump-probe measurement of the density matrix of valence electrons in atomic krypton ions. We generate the ions with a controlled few-cycle laser field and then probe them through the spectrally resolved absorption of an attosecond extreme-ultraviolet pulse, which allows us to observe in real time the subfemtosecond motion of valence electrons over a multifemtosecond time span. We are able to completely characterize the quantum mechanical electron motion and determine its degree of coherence in the specimen of the ensemble. Although the present study uses a simple, prototypical open system, attosecond transient absorption spectroscopy should be applicable to molecules and solid-state materials to reveal the elementary electron motions that control physical, chemical and biological properties and processes.

Generation of sub-3 fs pulses in the deep ultraviolet.

We demonstrate generation and measurement of intense deep-ultraviolet light pulses with a duration of approximately 2.8 fs (FWHM of the intensity envelope) and a wavelength distribution between 230 and 290 nm. They emerge via direct frequency upconversion of sub-4 fs laser pulses of a carrier wavelength of approximately 750 nm focused into an Ne-filled, quasi-static gas cell. Dispersion-free, third-order autocorrelation measurements provide access to their temporal intensity profile.

Power scaling of a high-repetition-rate enhancement cavity.

A passive optical resonator is used to enhance the power of a pulsed 78 MHz repetition rate Yb laser providing 200 fs pulses. We find limitations relating to the achievable time-averaged and peak power, which we distinguish by varying the duration of the input pulses. An intracavity average power of 18 kW is generated with close to Fourier-limited pulses of 10 W average power. Beyond this power level, intensity-related effects lead to resonator instabilities, which can be removed by chirping the seed laser pulses. By extending the pulse duration in this way to 2 ps, we could obtain 72 kW of intracavity circulating power with 50 W of input power.