Dynamic optical response of solids following 1-fs-scale photoinjection.

Photoinjection of charge carriers profoundly changes the properties of a solid. This manipulation enables ultrafast measurements, such as electric-field sampling1,2, advanced recently to petahertz frequencies3-7, and the real-time study of many-body physics8-13. Nonlinear photoexcitation by a few-cycle laser pulse can be confined to its strongest half-cycle14-16. Describing the associated subcycle optical response, vital for attosecond-scale optoelectronics, is elusive when studied with traditional pump-probe metrology as the dynamics distort any probing field on the timescale of the carrier, rather than that of the envelope. Here we apply field-resolved optical metrology to these dynamics and report the direct observation of the evolving optical properties of silicon and silica during the first few femtoseconds following a near-1-fs carrier injection. We observe that the Drude-Lorentz response forms within several femtoseconds-a time interval much shorter than the inverse plasma frequency. This is in contrast to previous measurements in the terahertz domain8,9 and central to the quest to speed up electron-based signal processing.

Ultra-broadband all-optical sampling of optical waveforms.

Optical-field sampling techniques provide direct access to the electric field of visible and near-infrared light. The existing methods achieve the necessary bandwidth using highly nonlinear light-matter interaction that involves ionization of atoms or generation of charge carriers in solids. We demonstrate an alternative, all-optical approach for measuring electric fields of broadband laser pulses, which offers an advantage in terms of sensitivity and signal-to-noise ratio and extends the detection bandwidth of optical methods to the petahertzdomain.

Electro-optic characterization of synthesized infrared-visible light fields.

The measurement and control of light field oscillations enable the study of ultrafast phenomena on sub-cycle time scales. Electro-optic sampling (EOS) is a powerful field characterization approach, in terms of both sensitivity and dynamic range, but it has not reached beyond infrared frequencies. Here, we show the synthesis of a sub-cycle infrared-visible pulse and subsequent complete electric field characterization using EOS. The sampled bandwidth spans from 700 nm to 2700 nm (428 to 110 THz). Tailored electric-field waveforms are generated with a two-channel field synthesizer in the infrared-visible range, with a full-width at half-maximum duration as short as 3.8 fs at a central wavelength of 1.7 µm (176 THz). EOS detection of the complete bandwidth of these waveforms extends it into the visible spectral range. To demonstrate the power of our approach, we use the sub-cycle transients to inject carriers in a thin quartz sample for nonlinear photoconductive field sampling with sub-femtosecond resolution.

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.

Optical Gain in Solids after Ultrafast Strong-Field Excitation.

Multiphoton excitation of a solid by a few-cycle, intense laser pulse forms a very nonequilibrium distribution of charge carriers, where occupation probabilities do not necessarily decrease with energy. Within a fraction of the pulse, significant population inversion can emerge between pairs of valence-band states with a dipole-allowed transition between them. This population inversion leads to stimulated emission in a laser-excited solid at frequencies where the unperturbed solid is transparent. We establish the optimal conditions for observing this kind of strong-field-induced optical gain.

Ni-Catalyzed Carboxylation of Aziridines en Route to ß-Amino Acids.

A Ni-catalyzed reductive carboxylation of N-substituted aziridines with CO2 at atmospheric pressure is disclosed. The protocol is characterized by its mild conditions, experimental ease, and exquisite chemo- and regioselectivity pattern, thus unlocking a new catalytic blueprint to access ß-amino acids, important building blocks with considerable potential as peptidomimetics.

Oxygen Atom Transfer as Key To Reverse Regioselectivity in the Gold(I)-Catalyzed Generation of Aminooxazoles from Ynamides.

We report on gold(I)-catalyzed oxidative annulation involving ynamides, nitriles, and 2,3-dichloropyridine N-oxide. The application of 2,3-dichloropyridine N-oxide as an oxygen atom transfer reagent reverses the regioselectivity to give 5-amino-1,3-oxazoles, in comparison with the previously reported syntheses of aminooxazoles based on gold-catalyzed nitrene transfers to ynamides to furnish 4-amino-1,3-oxazoles. The developed oxygen atom transfer approach allows the generation of 1,3-oxazoles containing a variety of sulfonyl-protected alkylamino groups in the fifth position of the oxazole ring (29 examples; up to 88% yields). In addition, the use of N-substituted nitriles, namely cyanamides, leads to the facile generation of difficult-to-obtain 2,5-diaminooxazoles. The process is feasible for wide ranges of ynamides or nitriles, and it can be conducted in gram scale.

Attosecond optoelectronic field measurement in solids.

The sub-cycle interaction of light and matter is one of the key frontiers of inquiry made accessible by attosecond science. Here, we show that when light excites a pair of charge carriers inside of a solid, the transition probability is strongly localized to instants slightly after the extrema of the electric field. The extreme temporal localization is utilized in a simple electronic circuit to record the waveforms of infrared to ultraviolet light fields. This form of petahertz-bandwidth field metrology gives access to both the modulated transition probability and its temporal offset from the laser field, providing sub-fs temporal precision in reconstructing the sub-cycle electronic response of a solid state structure.

Gold-Catalyzed Hydrohydrazidation of Terminal Alkynes.

Facile gold-catalyzed hydrohydrazidation of alkynes with various hydrazides R2CONHNH2 (R = Alk or Ar; including those with an additional nucleophilic moiety) in the presence of Ph3PAuNTf2 (6 mol %) leading to a wide range of substituted keto- N-acylhydrazones (18 examples) in excellent to good yields (99-66%) is reported. This novel metal-catalyzed coupling proceeds under mild conditions (chlorobenzene, 60 °C), exhibits high functional group tolerance, and is insensitive to the electronic and steric effects of the substituents in the reactants.