Optically active quantum dots in bottom-up nanowires

This thesis is dedicated to the discovery and progressive study of quantum emitters embedded in the shell of coaxial gallium arsenide/ aluminum gallium arsenide nanowires. The bottom-up core/shell nanowires were grown in a molecular beam epitaxy machine. During the shell growth, diffusion-driven phenomena lead to segregation effects. Gallium-rich regions are formed at the nanoscopic scale. The observation has been made that the reduced dimensionality of these regions provides true tridimensional confinement for the carriers. The recombination spectra of the electrons with the holes in what was coined shell quantum dots (shell-QDs) thus appear as sets of narrow, intense peaks. The formation of shell quantum dots is taking place on a large range of growth temperatures and nominal alloy fractions, giving freedom to engineer the growth process. The shell thickness plays an important role in the quantum dot density and total ensemble spectrum. In addition, the adjunction of an aluminum arsenide predeposition layer increasing the local curvature has been seen to foster the quantum dots formation. Single emitter spectroscopy reveals the few-particles electronic structure of quantum dots, with systematic signatures for the different degrees of occupation of the quantum dot. The shape anisotropy of the quantum dots leads to observable spin-spin interactions, which lift the degeneracy of the exciton level (one hole and one electron). Generally undesirable, this effect allows here to find that the orientation of the quantum dots in the nanowire is not hard-wired to the growth direction or to the nanowire long axis. This observation is confirmed by magneto-photoluminescence experiments. The energetic splitting and shift of the spin sublevels when an external magnetic field is applied also confirms the small size of the quantum dots. It is found that for GaAs in the strong confinement regime, the Landé coefficients of the electron and hole take opposite signs and are dependent on the angle at which the field is applied. These effects allow to tune the exciton composite Landé coefficient and could be used to reduce the splitting between the exciton spin sublevels or create optically degenerate coupled systems. Finally, the sub-nanosecond dynamics happening in the quantum dots are probed with time-correlated photon counting. It is shown that the carriers in the shell are quickly captured by the quantum dots. In addition, it is proposed that the electron population is reduced due to diffusion-assisted mechanisms or through electron-donor recombination.

Integrated photonics enables continuous-beam electron phase modulation

Guanhao Huang, Tobias Kippenberg, Junqiu Liu, Jiahe Pan, Arslan Sajid Raja, Rui Ning Wang, Yujia Yang

Integrated photonics facilitates extensive control over fundamental light-matter interactions in manifold quantum systems including atoms(1), trapped ions(2,3), quantum dots(4) and defect centres(5). Ultrafast electron microscopy has recently made free-electron beams the subject of laser-based quantum manipulation and characterization(6-11), enabling the observation of free-electron quantum walks(12-14), attosecond electron pulses(10,15-17) and holographic electromagnetic imaging(18). Chip-based photonics(19,20) promises unique applications in nanoscale quantum control and sensing but remains to be realized in electron microscopy. Here we merge integrated photonics with electron microscopy, demonstrating coherent phase modulation of a continuous electron beam using a silicon nitride microresonator. The high-finesse (Q(0) approximate to 10(6)) cavity enhancement and a waveguide designed for phase matching lead to efficient electron-light scattering at extremely low, continuous-wave optical powers. Specifically, we fully deplete the initial electron state at a cavity-coupled power of only 5.35 microwatts and generate >500 electron energy sidebands for several milliwatts. Moreover, we probe unidirectional intracavity fields with microelectronvolt resolution in electron-energy-gain spectroscopy(21). The fibre-coupled photonic structures feature single-optical-mode electron-light interaction with full control over the input and output light. This approach establishes a versatile and highly efficient framework for enhanced electron beam control in the context of laser phase plates(22), beam modulators and continuous-wave attosecond pulse trains(23), resonantly enhanced spectroscopy(24-26) and dielectric laser acceleration(19,20,27). Our work introduces a universal platform for exploring free-electron quantum optics(28-31), with potential future developments in strong coupling, local quantum probing and electron-photon entanglement.

NATURE PORTFOLIO2021

Nanoparticle sensitisation of solid-state nanocrystalline solar cell

Robert Plass

Over the past fifteen years dye-sensitised nanocrystalline solar cells have been the subject of intense research and development efforts. These systems provide a technically and economically credible alternative to classical p-n junction solar cells, reaching over 10 % certified efficiency under standard solar illumination conditions (AM 1.5, 1000 W/m2). Recently, the liquid electrolyte, commonly used in these dye-sensitised solar cells, could successfully be replaced by a novel solid hole-conducting material (spiro-OMeTAD). The absence of volatile solvents and corrosive components like iodine presents a clear advantage of these solid-state devices over their photoelectrochemical counterparts. Yet, their maximum overall efficiency of about 3 % clearly lacks behind the performance features of classical dye-sensitized solar cells. The objective of this work is the replacement of the usually used sensitiser (transition metal complexes and organic dyes) by quantum-dots. It was motivated by the possibility to achieve panchromatic light absorption due to the size-dependent properties of the quantum-dots. Some studies have been published using quantum-dots of inorganic low-bandgap semiconductors as sensitisers for mesoporous wide bandgap semiconductor electrodes in conjunction with liquid electrolytes. These systems often suffer from corrosion and photo-corrosion mainly due to the aggressive nature of the electrolyte employed. Solid-state organic-inorganic heterojunctions might provide the desired environment for quantum-dot sensitisation, as the environment is much less aggressive. A large variety of inorganic quantum-dot materials like PbS, CdS, PbSe and CdSe were scrutinized for their use as sensitisers. All particles were synthesised in situ on the TiO2 surface using two different techniques: dip-coating and chemical bath deposition. Lead sulphide was the most investigated due to its superior photovoltaic characteristics. High Resolution Transmission Electron Microscopy (HRTEM) of PbS sensitised TiO2 electrodes fabricated via dip-coating clearly showed the distinct particles on the surface of the semiconductor. The electron transfer dynamics following optical excitation of quantum-dot sensitized TiO2/spiro-OMeTAD heterojunctions were thoroughly studied. Fluorescence spectroscopy was used to prove the possible electron injection from the PbS into the TiO2. Nanosecond laser spectroscopy was applied to monitor the interfacial recombination of the injected electron and the oxidised hole-conductor. Femtosecond laser spectroscopy allowed measuring the ultra-fast kinetics in the system, including electron trapping, exciton recombination and PbS regeneration. An overall efficiency of 0.5 % at 0.1 sun (AM 1.5) has been reached with such systems. Chemical bath deposition (CBD) of PbS leads to the formation of a layer rather than distinct particles on the TiO2. Solar cells fabricated via CBD exhibited open-circuit voltages which were generally 100 mV higher then those of comparable devices made via dip-coating. The PbS layer acts as blocking layer, hindering the contact between TiO2 and the hole-conductor. This technique allowed achieving devices highly linear with respect to the illumination power. Different strategies were pursued to impede interfacial recombination, among which the introduction of self-assembled monolayers at the interface between the organic and inorganic phases was proven to be the most efficient. Nanosecond laser spectroscopy showed a strong decrease of the interfacial recombination kinetic rates in the presence of hexadecylmalonic acid or decylphosphonic acid monolayers. Short-circuit currents could be raised by a factor two to four using such type of molecules. The overall efficiency of the device could be strongly increased, reaching 1 % at 0.1 Sun (AM 1.5). CBD was also used to deposit PbSe and CdSe layers at the surface of TiO2. Fluorescence spectroscopy was used to probe electron injection from CdSe quantum dots to TiO2. Generally it was observed that metal sulfides were more efficient in sensitizing TiO2/OMeTAD heterojunctions then the respective selenides.

EPFL2004

Synthesis and properties of heterostructures in nanowires and 2-D materials

Akshay Balgarkashi

Modern solid-state devices were made possible by the discovery of semiconductor heterostructures. Heterostructures offer the ability to fabricate low-dimensional nanostructures such as quantum dots which can restrain carriers in all three-directions. Quantum dots as single photon sources can be used as building blocks in quantum photonics and information processing applications. In this thesis, we explore heterostructures in nanowires and 2-D materials towards fabrication of quantum dots. In the first part, we show how facet-driven nanostructure self-assembly can be used to grow axial and radial QDs in lattice-mismatched NW heterostructures. We investigate the growth of InAs/GaAs nanowire heterostructure arrays on Si substrates using the Ga-catalyzed method. We show how the nanowire tip morphology affects the formation of axial In(Ga)As clusters. The occurrence of In-rich clusters on the nanowires is elucidated by electron microscopy. We also show how the In(Ga)As cluster formation on the nanowire sidewalls is driven by the convex nature of the {11-2} corner facets. Cathodoluminescence and photoluminescence maps close to the NW tip evidence the presence of optically active emission centers along the NW sidewalls. The second part is dedicated to heterostructures using monolayer 2-D transition-metal dichalcogenides. Firstly, we study the heterojunction between monolayer MoS2 and gold. We provide a detailed understanding of the microscopic origins behind Raman mode splitting in monolayer MoS2 exfoliated on gold substrates. We show that splitting in the Raman modes is a convolution of two effects: structural perturbations in MoS2 due to the Au-S interaction and breaking of symmetry rules by the metallic plasmons. We confirm the proposed hypothesis by using Al as the metal which does not show any peak splitting. In the last part, we successfully combine monolayer MoS2 with a GaAs NW array as a first step towards integrating monolayer 2-D materials with III-V nanowire arrays. Using detailed structural investigation, we show three different configurations of the MoS2 monolayer on NWs. Through confocal Raman and photoluminescence mapping, we show variations in the properties of the monolayer due to nanowires. We show how the vibrational properties are mainly affected by strain and charge transfer due to the nanowires. A blueshift in the luminescence attributing to an enhanced dielectric screening due to GaAs nanowires is observed. We show how III-V nanowires can be used to engineer the properties and enhance light extraction from monolayer 2-D materials.

EPFL2022