Light Conversion by Electrochemiluminescence at Semiconductor Surfaces.

ConspectusElectrochemiluminescence (ECL) is the electrochemical generation of light. It involves an interfacial charge transfer that produces the excited state of a luminophore at the electrode surface. ECL is a powerful readout method that is widely employed for immunoassays and clinical diagnostics and is progressively evolving into a microscopy technique. On the other hand, photoelectrochemistry at illuminated semiconductors is a field of research that deals with the transfer of photogenerated charge carriers at the solid-liquid interface. This concept offers several advantages such as a considerable lowering of the onset potential required for triggering an electrochemical reaction as well as light addressable chemistry, via the spatial confinement of redox reactions at locally illuminated semiconductor electrodes. The combination of ECL with photoelectrochemistry at illuminated semiconductors is termed photoinduced ECL (PECL). It deals with the triggering of an ECL reaction through the transfer of photogenerated minority charge carriers at the illuminated solid/liquid interface. PECL results in the conversion of incident photons (λexc), that are absorbed by the semiconductor photoelectrode to emitted photons (λPECL), produced by the ECL reaction. Although demonstrated in the 1970s by Bard et al. in ultradry organic solvents, PECL remained unexplored until the last five years. Nowadays, as a result of the considerable progress achieved in semiconductor photoelectrodes and ECL systems, a large variety of PECL systems can be designed by combining photoelectrode materials with ECL luminophores, making it a versatile tool for light conversion in aqueous media.In this Account, we introduce the fundamentals of ECL and photoelectrochemistry at illuminated semiconductors and review the recent developments in PECL. We discuss the two main PECL light conversion schemes: downconversion (where λexc < λPECL) and upconversion (where λexc > λPECL). Besides, PECL can be used to simplify considerably the common electrochemical setups employed for ECL. Indeed, by engineering the photoelectrode material and carefully considering the reactivity involved for ECL and its counter-reaction, PECL enables the ultimate concept of all-optical ECL (AO-ECL), i.e., ECL generation at an illuminated monolithic device immersed into the electrolyte solution. As discussed in this Account, AO-ECL is an important breakthrough that allows the simplest ECL experimental configuration ever reported, eliminating constraints such as an electrical power supply, wires, electrodes, connections, and specific electrochemical knowledge. As shown at the end of this Account, due to the robustness of recently manufactured PECL systems, several applications can already be envisioned for microscopy, elucidation of solar conversion mechanisms, near-infrared imaging, and bioanalysis.

Antiphase domain tailoring for combination of modal and 4¯ -quasi-phase matching in gallium phosphide microdisks.

We propose a novel phase-matching scheme in GaP whispering-gallery-mode microdisks grown on Si substrate combining modal and 4¯ -quasi-phase-matching for second-harmonic-generation. The technique consists in unlocking parity-forbidden processes by tailoring the antiphase domain distribution in the GaP layer. Our proposal can be used to overcome the limitations of form birefringence phase-matching and 4¯ -quasi-phase-matching using high order whispering-gallery-modes. The high frequency conversion efficiency of this new scheme demonstrates the competitiveness of nonlinear photonic devices monolithically integrated on silicon.

Hyperbolic spin vortices and textures in exciton-polariton condensates.

From cosmology to the microscopic scales of the quantum world, the study of topological excitations is essential for the understanding of phase conformation and phase transitions. Quantum fluids are convenient systems to investigate topological entities because well-established techniques are available for their preparation, control and measurement. Across a phase transition, a system dramatically changes its properties because of the spontaneous breaking of certain continuous symmetries, leading to generation of topological defects. In particular, attention is given to entities that involve both spin and phase topologies. Exciton-polariton condensates are quantum fluids combining coherence and spin properties that, thanks to their light-matter nature, bring the advantage of direct optical access to the condensate order parameter. Here we report on the spontaneous occurrence of hyperbolic spin vortices in polariton condensates, by directly imaging both their phase and spin structure, and observe the associated spatial polarization patterns, spin textures that arise in the condensate.

Ultrafast tristable spin memory of a coherent polariton gas.

Non-linear interactions in coherent gases are not only at the origin of bright and dark solitons and superfluids; they also give rise to phenomena such as multistability, which hold great promise for the development of advanced photonic and spintronic devices. In particular, spinor multistability in strongly coupled semiconductor microcavities shows that the spin of hundreds of exciton-polaritons can be coherently controlled, opening the route to spin-optronic devices such as ultrafast spin memories, gates or even neuronal communication schemes. Here we demonstrate that switching between the stable spin states of a driven polariton gas can be controlled by ultrafast optical pulses. Although such a long-lived spin memory necessarily relies on strong and anisotropic spinor interactions within the coherent polariton gas, we also highlight the crucial role of non-linear losses and formation of a non-radiative particle reservoir for ultrafast spin switching.

From single particle to superfluid excitations in a dissipative polariton gas.

Using an angle-resolved heterodyne four-wave-mixing technique, we probe the low momentum excitation spectrum of a coherent polariton gas. The experimental results are well captured by the Bogoliubov transformation which describes the transition from single particle excitations of a normal fluid to soundlike excitations of a superfluid. In a dense coherent polariton gas, we find all the characteristics of a Bogoliubov transformation, i.e., the positive and negative energy branch with respect to the polariton gas energy at rest, soundlike shapes for the excitations dispersion, intensity, and linewidth ratio between the two branches in agreement with the theory. The influence of the nonequilibrium character of the polariton gas is shown by a careful analysis of its dispersion.

Soliton instabilities and vortex street formation in a polariton quantum fluid.

Exciton polaritons have been shown to be an optimal system in order to investigate the properties of bosonic quantum fluids. We report here on the observation of dark solitons in the wake of engineered circular obstacles and their decay into streets of quantized vortices. Our experiments provide a time-resolved access to the polariton phase and density, which allows for a quantitative study of instabilities of freely evolving polaritons. The decay of solitons is quantified and identified as an effect of disorder-induced transverse perturbations in the dissipative polariton gas.

Multistability of a coherent spin ensemble in a semiconductor microcavity.

Coherent manipulation of spin ensembles is a key issue in the development of spintronics. In particular, multivalued spin switching may lead to new schemes of logic gating and memories. This phenomenon has been studied with atom vapours 30 years ago, but is still awaited in the solid state. Here, we demonstrate spin multistability with microcavity polaritons in a trap. Owing to the spinor nature of these light-matter quasiparticles and to the anisotropy of their interactions, we can optically control the spin state of a single confined level by tuning the excitation power, frequency and polarization. First, we realize high-efficiency power-dependent polarization switching. Then, at constant excitation power, we evidence polarization hysteresis and determine the conditions for realizing multivalued spin switching. Finally, we demonstrate an unexpected regime, where our system behaves as a high-contrast spin trigger. These results open new pathways to the development of advanced spintronics devices and to the realization of multivalued logic circuits.

Electrical control of a single Mn atom in a quantum dot.

We report on the reversible electrical control of the magnetic properties of a single Mn atom in an individual quantum dot. Our device permits us to prepare the dot in states with three different electric charges, 0, +1e, and -1e which result in dramatically different spin properties, as revealed by photoluminescence. Whereas in the neutral configuration the quantum dot is paramagnetic, the electron-doped dot spin states are spin rotationally invariant and the hole-doped dot spins states are quantized along the growth direction.

Geometrical effects on the optical properties of quantum dots doped with a single magnetic atom.

The emission spectra of individual self-assembled quantum dots containing a single magnetic Mn atom differ strongly from dot to dot. The differences are explained by the influence of the system geometry, specifically the in-plane asymmetry of the quantum dot and the position of the Mn atom. Depending on both these parameters, one has different characteristic emission features which either reveal or hide the spin state of the magnetic atom. The observed behavior in both zero field and under magnetic field can be explained quantitatively by the interplay between the exciton-manganese exchange interaction (dependent on the Mn position) and the anisotropic part of the electron-hole exchange interaction (related to the asymmetry of the quantum dot).

Probing the spin state of a single magnetic ion in an individual quantum dot.

The magnetic state of a single magnetic ion (Mn2+) embedded in an individual quantum dot is optically probed using microspectroscopy. The fine structure of a confined exciton in the exchange field of a single Mn2+ ion (S=5/2) is analyzed in detail. The exciton-Mn2+ exchange interaction shifts the energy of the exciton depending on the Mn2+ spin component and six emission lines are observed at zero magnetic field. Magneto-optic measurements reveal that the emission intensities in both circular polarizations are controlled by the Mn2+ spin distribution imposed by the exchange interaction with the exciton, the magnetic field, and an effective manganese temperature which depends on both the lattice temperature and the density of photocreated carriers. Under magnetic field, the electron-Mn interaction induces a mixing of the bright and dark exciton states.