Nitrile IR intensities characterize electric fields and hydrogen bonding in protic, aprotic, and protein environments

Nitriles are widely used as vibrational probes; however, the interpretation of their IR frequencies is complicated by hydrogen bonding (H-bonding) in protic environments. We report a new vibrational Stark effect (VSE) that correlates the electric field projected on the nitrile bond to the transition dipole moment and, by extension, the nitrile peak area or integrated intensity. This linear VSE applies to both H-bonding and non-H-bonding interactions. It can therefore be generally applied to determine electric fields in all environments. Additionally, it allows for semi-empirical extraction of the H-bonding contribution to the blueshift of the nitrile frequency. Nitriles were incorporated at H-bonding and non-H-bonding protein sites using amber suppression, and each nitrile variant was structurally characterized at high resolution. We exploited the combined information now available from variations in frequency and integrated intensity and demonstrate that nitriles are a generally useful probe for electric fields.

Ultrafast imaging of terahertz electric waveforms using quantum dots

Microscopic electric fields govern the majority of elementary excitations in condensed matter and drive electronics at frequencies approaching the Terahertz (THz) regime. However, only few imaging schemes are able to resolve sub-wavelength fields in the THz range, such as scanning-probe techniques, electro-optic sampling, and ultrafast electron microscopy. Still, intrinsic constraints on sample geometry, acquisition speed and field strength limit their applicability. Here, we harness the quantum-confined Stark-effect to encode ultrafast electric near-fields into colloidal quantum dot luminescence. Our approach, termed Quantum-probe Field Microscopy (QFIM), combines far-field imaging of visible photons with phase-resolved sampling of electric waveforms. By capturing ultrafast movies, we spatio-temporally resolve a Terahertz resonance inside a bowtie antenna and unveil the propagation of a Terahertz waveguide excitation deeply in the sub-wavelength regime. The demonstrated QFIM approach is compatible with strong-field excitation and sub-micrometer resolution—introducing a direct route towards ultrafast field imaging of complex nanodevices in-operando.

Спектральный отклик микрорезонатора с двумя квантовыми точками, обусловленный взаимодействием между локализованными электронами

A theoretical model of a semiconductor nanostructure consisting of a single-mode microresonator containing two quantum dots is considered. It is shown that the Coulomb interaction between electrons localized in the quantum dots modifies a spectral response of the system to an external laser field. The possibility of its use for detecting an elementary charge in the third (optically inactive) quantum dot is discussed. The influence of both diagonal (Stark effect) and non-diagonal (Förster effect) Coulomb matrix elements of the Hamiltonian on the detection accuracy is studied. The dependences of a measuring contrast on the parameters of the resonator and the quantum dots are calculated. The existence of such structural configurations for which the contrast retains an optimal value even at large distances to the measured dot is established.

Optical detected magnetic resonance of nitrogen-vacancy centers in vertical diamond Schottky diode

Diamond solid-state devices are very attractive to electrically control the charge state of Nitrogen-Vacancy (NV) centers. In this work, Vertical p-type Diamond Schottky Diode (VDSDs) is introduced as a platform to electrically control the interconversion between the neutral charge NV (NV0) and negatively charged NV (NV-) centers. The photoluminescence (PL) of NV centers generated by ion-implantation in VDSDs shows the increase of NV- Zero Phonon Line (ZPL) and phonon sideband (PBS) intensities with the reverse voltage, whereas the NV0 ZPL intensity decreases. Thus, NV centers embedded into VDSDs are converted into NV- under reverse bias voltage. Moreover, the optically detected magnetic resonance (ODMR) of NV- exhibits an increase in the ODMR contrast with the reverse bias voltage and splitting of the resonance dips. Since no magnetic is applied, such a dip splitting in ODMR spectrum is ascribed the Stark effect induced by the interaction of NV- with the electric field existing within the depletion region of VDSDs.

Observation of the ponderomotive effect in non-valence bound states of polyatomic molecular anions

The ponderomotive force on molecular systems has rarely been observed hitherto, despite potentially being extremely useful for the manipulation of the molecular properties. Here, the ponderomotive effect in the non-valence bound states has been experimentally demonstrated, for the first time to the best of our knowledge, giving great promise for the manipulation of polyatomic molecules by the dynamic Stark effect. Entire quantum levels of the dipole-bound state (DBS) and quadrupole-bound state (QBS) of the phenoxide (or 4-bromophenoxide) and 4-cyanophenoxide anions, respectively, show clear-cut ponderomotive blue-shifts in the presence of the spatiotemporally overlapped non-resonant picosecond control laser pulse. The quasi-free electron in the QBS is found to be more vulnerable to the external oscillating electromagnetic field compared to that in the DBS, suggesting that the non-valence orbital of the former is more diffusive and thus more polarizable compared to that of the latter.

Enhanced Optoelectronic Performance of Yellow Light-Emitting Diodes Grown on InGaN/GaN Pre-Well Structure

InGaN-based long-wavelength light-emitting diodes (LEDs) are indispensable components for the next-generation solid-state lighting industry. In this work, we introduce additional InGaN/GaN pre-wells in LED structure and investigate the influence on optoelectronic properties of yellow (~575 nm) LEDs. It is found that yellow LED with pre-wells exhibits a smaller blue shift, and a 2.2-fold increase in light output power and stronger photoluminescence (PL) intensity compared to yellow LED without pre-wells. The underlying mechanism is revealed by using Raman spectra, temperature-dependent PL, and X-ray diffraction. Benefiting from the pre-well structure, in-plane compressive stress is reduced, which effectively suppresses the quantum confined stark effect. Furthermore, the increased quantum efficiency is also related to deeper localized states with reduced non-radiative centers forming in multiple quantum wells grown on pre-wells. Our work demonstrates a comprehensive understanding of a pre-well structure for obtaining efficient LEDs towards long wavelengths.

Interlayer exciton mediated second harmonic generation in bilayer MoS2

Second-harmonic generation (SHG) is a non-linear optical process, where two photons coherently combine into one photon of twice their energy. Efficient SHG occurs for crystals with broken inversion symmetry, such as transition metal dichalcogenide monolayers. Here we show tuning of non-linear optical processes in an inversion symmetric crystal. This tunability is based on the unique properties of bilayer MoS2, that shows strong optical oscillator strength for the intra- but also interlayer exciton resonances. As we tune the SHG signal onto these resonances by varying the laser energy, the SHG amplitude is enhanced by several orders of magnitude. In the resonant case the bilayer SHG signal reaches amplitudes comparable to the off-resonant signal from a monolayer. In applied electric fields the interlayer exciton energies can be tuned due to their in-built electric dipole via the Stark effect. As a result the interlayer exciton degeneracy is lifted and the bilayer SHG response is further enhanced by an additional two orders of magnitude, well reproduced by our model calculations. Since interlayer exciton transitions are highly tunable also by choosing twist angle and material combination our results open up new approaches for designing the SHG response of layered materials.