Near-IR Photoinduced Electrochemiluminescence Imaging with Structured Silicon Photoanodes.

Infrared (IR) imaging devices that convert IR irradiation (invisible to the human eye) to a visible signal are based on solid-state components. Here, we introduce an alternative concept based on light-addressable electrochemistry (i.e., electrochemistry spatially confined under the action of a light stimulus) that involves the use of a liquid electrolyte. In this method, the projection of a near-IR image (λexc = 850 or 840 nm) onto a photoactive Si-based photoanode, immersed into a liquid phase, triggers locally the photoinduced electrochemiluminescence (PECL) of the efficient [Ru(bpy)3]2+-TPrA system. This leads to the local conversion of near-IR light to visible (λPECL = 632 nm) light. We demonstrate that compared to planar Si photoanodes, the use of a micropillar Si array leads to a large enhancement of local light generation and considerably improves the resolution of the PECL image by preventing photogenerated minority carriers from diffusing laterally. These results are important for the design of original light conversion devices and can lead to important applications in photothermal imaging and analytical chemistry.

Off-Grid Electrogenerated Chemiluminescence with Customized p-i-n Photodiodes.

Electrochemiluminescence (ECL) is the generation of light induced by an electrochemical reaction, driven by electricity. Here, an all-optical ECL (AO-ECL) system is developped, which triggers ECL by the illumination of electrically autonomous "integrated" photoelectrochemical devices immersed in the electrolyte. Because these systems are made using small and cheap devices, they can be easily prepared and readily used by any laboratories. They are based on commercially available p-i-n Si photodiodes (≈1 € unit-1), coupled with well-established ECL-active and catalytic materials, directly coated onto the component leads by simple and fast wet processes. Here, a Pt coating (known for its high activity for reduction reactions) and carbon paint (known for its optimal ECL emission properties) are deposited at cathode and anode leads, respectively. In addition to its optimized light absorption properties, using the commercial p-i-n Si photodiode eliminates the need for a complicated manufacturing process. It is shown that the device can emit AO-ECL by illumination with polychromatic (simulated sunlight) or monochromatic (near IR) light sources to produce visible photons (425 nm) that can be easily observed by the naked eye or recorded with a smartphone camera. These low-cost off-grid AO-ECL devices open broad opportunities for remote photodetection and portable bioanalytical tools.

Local reactivity of metal-insulator-semiconductor photoanodes imaged by photoinduced electrochemiluminescence microscopy.

Localized photoinduced electrochemiluminescence (PECL) is studied on photoanodes composed of Ir microbands deposited on n-Si/SiOx. We demonstrate that PECL microscopy precisely imaged the hole-driven heterogeneous photoelectrochemical reactivity. The method is promising for elucidating the local activity of photoelectrodes that are employed in solar energy conversion.

Wireless Anti-Stokes Photoinduced Electrochemiluminescence at Closed Semiconducting Bipolar Electrodes.

Wireless electrochemical systems constitute a rapidly developing field. Herein, photoinduced electrochemiluminescence (PECL) is studied at Si-based closed bipolar electrodes (BPEs) for designing anti-Stokes systems that can convert IR into visible photons, without direct electrical contact. We show that protection of the anodic emitting pole of the BPE allows the triggering of bright and longstanding emission under the synergetic actions of an external bias and IR illumination. Photoactive n- and p-type Si BPEs are studied with front-side and back-side illumination, respectively, and nonphotoactive n+-Si BPEs are studied in the dark. Two electrochemiluminescent (ECL) systems ([Ru(bpy)3]2+/TPrA and L-012) are tested, and we show that the onset bias and the anti-Stokes shift can be controlled by the ECL system that is employed. These advances, rationalized by simulations, will be useful for the design of original PECL systems for chemical sensing or photodetection.

Anti-Stokes photoinduced electrochemiluminescence at a photocathode.

Anti-Stokes photoinduced electrochemiluminescence (PECL) converts infrared photons to visible photons and is usually triggered at a narrow band gap-protected photoanode. Here, we report the first example of PECL with the model [Ru(bpy)3]2+/benzoyl peroxide system at a bare p-type Si photocathode. The reported PECL system, which allows a notable decrease of the cathodic potential required for ECL generation, should open new opportunities for imaging and light-addressable devices.

Metal-Insulator-Semiconductor Anodes for Ultrastable and Site-Selective Upconversion Photoinduced Electrochemiluminescence.

Photoinduced electrochemiluminescence (PECL) allows the electrochemically assisted conversion of low-energy photons into high-energy photons at an electrode surface. This concept is expected to have important implications, however, it is dramatically limited by the stability of the surface, impeding future developments. Here, a series of metal-insulator-semiconductor (MIS) junctions, using photoactive n-type Si (n-Si) as a light absorber covered by a few-nanometer-thick protective SiOx /metal (SiOx /M, with M=Ru, Pt, and Ir) overlayers are investigated for upconversion PECL of the model co-reactant system involving the simultaneous oxidation of tris(bipyridine)ruthenium(II) and tri-n-propylamine. We show that n-Si/SiOx /Pt and n-Si/SiOx /Ir exhibit high photovoltages and record stabilities in operation (35 h for n-Si/SiOx /Ir) for the generation of intense PECL with an anti-Stokes shift of 218 nm. We also demonstrate that these surfaces can be employed for spatially localized PECL. These unprecedented performances are extremely promising for future applications of PECL.

Epitaxial III-V/Si Vertical Heterostructures with Hybrid 2D-Semimetal/Semiconductor Ambipolar and Photoactive Properties.

Hybrid materials taking advantage of the different physical properties of materials are highly attractive for numerous applications in today's science and technology. Here, it is demonstrated that epitaxial bi-domain III-V/Si are hybrid structures, composed of bulk photo-active semiconductors with 2D topological semi-metallic vertical inclusions, endowed with ambipolar properties. By combining structural, transport, and photoelectrochemical characterizations with first-principle calculations, it is shown that the bi-domain III-V/Si materials are able within the same layer to absorb light efficiently, separate laterally the photo-generated carriers, transfer them to semimetal singularities, and ease extraction of both electrons and holes vertically, leading to efficient carrier collection. Besides, the original topological properties of the 2D semi-metallic inclusions are also discussed. This comb-like heterostructure not only merges the superior optical properties of semiconductors with good transport properties of metallic materials, but also combines the high efficiency and tunability afforded by III-V inorganic bulk materials with the flexible management of nano-scale charge carriers usually offered by blends of organic materials. Physical properties of these novel hybrid heterostructures can be of great interest for energy harvesting, photonic, electronic or computing devices.

Strong Electron-Phonon Interaction in 2D Vertical Homovalent III-V Singularities.

Highly polar materials are usually preferred over weakly polar ones to study strong electron-phonon interactions and its fascinating properties. Here, we report on the achievement of simultaneous confinement of charge carriers and phonons at the vicinity of a 2D vertical homovalent singularity (antiphase boundary, APB) in an (In,Ga)P/SiGe/Si sample. The impact of the electron-phonon interaction on the photoluminescence processes is then clarified by combining transmission electron microscopy, X-ray diffraction, ab initio calculations, Raman spectroscopy, and photoluminescence experiments. 2D localization and layer group symmetry properties of homovalent electronic states and phonons are studied by first-principles methods, leading to the prediction of a type-II band alignment between the APB and the surrounding semiconductor matrix. A Huang-Rhys factor of 8 is finally experimentally determined for the APB emission line, underlining that a large and unusually strong electron-phonon coupling can be achieved by 2D vertical quantum confinement in an undoped III-V semiconductor. This work extends the concept of an electron-phonon interaction to 2D vertically buried III-V homovalent nano-objects and therefore provides different approaches for material designs, vertical carrier transport, heterostructure design on silicon, and device applications with weakly polar semiconductors.

Loss assessment in random crystal polarity gallium phosphide microdisks grown on silicon.

III-V semiconductors grown on silicon recently appeared as a promising platform to decrease the cost of photonic components and circuits. For nonlinear optics, specific features of the III-V crystal arising from the growth on the nonpolar Si substrate and called antiphase domains (APDs) offer a unique way to engineer the second-order properties of the semiconductor compound. Here we demonstrate the fabrication of microdisk resonators at the interface between a gallium-phosphide layer and its silicon substrate. The analysis of the whispering gallery mode quality factors in the devices allows the quantitative assessment of losses induced by a controlled distribution of APDs in the GaP layer and demonstrates the relevance of such a platform for the development of polarity-engineered III-V nonlinear photonic devices on silicon.

Cathodoluminescence hyperspectral analysis of whispering gallery modes in active semiconductor wedge resonators.

Whispering gallery mode resonators are key devices for integrated photonics. Despite their generalization in fundamental and applied science, information on spatial confinement of light in these structures is mostly retrieved from purely spectral analysis. In this work, we present a detailed spectral and spatial characterization of whispering gallery modes in active semiconductor microdisk resonators by use of hyperspectral cathodoluminescence. By comparing our experimental findings to finite element simulations, we demonstrate that the combination of spectral and spatial measurements enables unique identification of the modes and even reveals specific features of the microresonator geometry, such as a wedge profile.

Enhanced Second-Order Nonlinearity for THz Generation by Resonant Interaction of Exciton-Polariton Rabi Oscillations with Optical Phonons.

Semiconductor microcavities in the strong-coupling regime exhibit an energy scale in the terahertz (THz) frequency range, which is fixed by the Rabi splitting between the upper and lower exciton-polariton states. While this range can be tuned by several orders of magnitude using different excitonic media, the transition between both polaritonic states is dipole forbidden. In this work, we show that, in cadmium telluride microcavities, the Rabi-oscillation-driven THz radiation is actually active without the need for any change in the microcavity design. This feature results from the unique resonance condition which is achieved between the Rabi splitting and the phonon-polariton states and leads to a giant enhancement of the second-order nonlinearity.

Exciton-polariton gas as a nonequilibrium coolant.

Using angle-resolved Raman spectroscopy, we show that a resonantly excited ground-state exciton-polariton fluid behaves like a nonequilibrium coolant for its host solid-state semiconductor microcavity. With this optical technique, we obtain a detailed measurement of the thermal fluxes generated by the pumped polaritons. We thus find a maximum cooling power for a cryostat temperature of 50 K and below where optical cooling is usually suppressed, and we identify the participation of an ultrafast cooling mechanism. We also show that the nonequilibrium character of polaritons constitutes an unexpected resource: each scattering event can remove more heat from the solid than would be normally allowed using a thermal fluid with normal internal equilibration.