External Control of GaN Band Bending Using Phosphonate Self-Assembled Monolayers.

We report on the optoelectronic properties of GaN(0001) and (11̅00) surfaces after their functionalization with phosphonic acid derivatives. To analyze the possible correlation between the acid's electronegativity and the GaN surface band bending, two types of phosphonic acids, n-octylphosphonic acid (OPA) and 1H,1H,2H,2H-perfluorooctanephosphonic acid (PFOPA), are grafted on oxidized GaN(0001) and GaN(11̅00) layers as well as on GaN nanowires. The resulting hybrid inorganic/organic heterostructures are investigated by X-ray photoemission and photoluminescence spectroscopy. The GaN work function is changed significantly by the grafting of phosphonic acids, evidencing the formation of dense self-assembled monolayers. Regardless of the GaN surface orientation, both types of phosphonic acids significantly impact the GaN surface band bending. A dependence on the acids' electronegativity is, however, only observed for the oxidized GaN(11̅00) surface, indicating a relatively low density of surface states and a favorable band alignment between the surface oxide and acids' electronic states. Regarding the optical properties, the covalent bonding of PFOPA and OPA on oxidized GaN layers and nanowires significantly affects their internal quantum efficiency, especially in the nanowire case due to the large surface-to-volume ratio. The variation in the internal quantum efficiency is related to the modification of both the internal electric fields and surface states. These results demonstrate the potential of phosphonate chemistry for the surface functionalization of GaN, which could be exploited for selective sensing applications.

Excitonic Aharonov-Bohm Oscillations in Core-Shell Nanowires.

Phase coherence in nanostructures is at the heart of a wide range of quantum effects such as Josephson oscillations between exciton-polariton condensates in microcavities, conductance quantization in 1D ballistic transport, or the optical (excitonic) Aharonov-Bohm effect in semiconductor quantum rings. These effects only occur in structures of the highest perfection. The 2D semiconductor heterostructures required for the observation of Aharonov-Bohm oscillations have proved to be particularly demanding, since interface roughness or alloy fluctuations cause a loss of the spatial phase coherence of excitons, and ultimately induce exciton localization. Experimental work in this field has so far relied on either self-assembled ring structures with very limited control of shape and dimension or on lithographically defined nanorings that suffer from the detrimental effects of free surfaces. Here, it is demonstrated that nanowires are an ideal platform for studies of the Aharonov-Bohm effect of neutral and charged excitons, as they facilitate the controlled fabrication of nearly ideal quantum rings by combining all-binary radial heterostructures with axial crystal-phase quantum structures. Thanks to the atomically flat interfaces and the absence of alloy disorder, excitonic phase coherence is preserved even in rings with circumferences as large as 200 nm.

Tailoring the exciton fine structure of cadmium selenide nanocrystals with shape anisotropy and magnetic field.

We use nominally spheroidal CdSe nanocrystals with a zinc blende crystal structure to study how shape perturbations lift the energy degeneracies of the band-edge exciton. Nanocrystals with a low degree of symmetry exhibit splitting of both upper and lower bright state degeneracies due to valence band mixing combined with the isotropic exchange interaction, allowing active control of the level splitting with a magnetic field. Asymmetry-induced splitting of the bright states is used to reveal the entire 8-state band-edge fine structure, enabling complete comparison with band-edge exciton models.

State selective pumping reveals spin-relaxation pathways in CdSe quantum dots.

The band-edge exciton in elongated CdSe nanocrystals is composed of an upper and lower manifold associated with heavy and light holes in which the energy separation is sensitive to the nanocrystal shape. Using resonant photoluminescence excitation, we probe the upper heavy hole exciton manifold and find rapid relaxation to the lower light hole manifold on a 5 ps time scale. State selective excitation allows the preparation of single quantum states in this system. We used this to map the hole spin relaxation pathways between the fine structure sublevels, which have energy splittings incommensurate with either optical or acoustic phonon energies. This reveals a hitherto unexpected hole spin-relaxation channel in these materials.

The optical phonon spectrum of CdSe colloidal quantum dots.

The direct coupling of excited electronic states to optical phonons in single CdSe colloidal quantum dots is explored using both photoluminescence emission and excitation spectroscopies. We find a broad optical phonon spectrum associated with a single fine structure state. Multiple peaks in the optical phonon sideband are ascribed to different optical phonon types emanating from both the core and shell layers. A mixed emission process that involves the simultaneous generation of two different types of optical phonon is also observed. In general, rather than a single mode, each designated phonon type is associated with a dispersed family of modes. Narrow optical phonon sidebands, consistent with the dominant LO mode, are observed in some nanocrystals. A linewidth analysis indicates that optical phonon lifetimes are in the 10 picosecond range. We demonstrate the ability to selectively excite a specific band-edge state by directly exciting its LO phonon sideband.

The ultimate limit to the emission linewidth of single nanocrystals.

Measurements of the emission linewidth of single nanocrystals are usually limited by spectral diffusion. At cryogenic temperatures, the origin of this instability was revealed to be photo-induced, suggesting that the spectral peak position may be stable in the limit of vanishing optical excitation. Here we test this stability using resonant photoluminescence excitation and find there is persistent spectral broadening, which ultimately limits the emission linewidth in these materials. The spectral broadening is shown to be consistent with spontaneous fluctuations of the local electrostatic field within the disordered environment surrounding the nanocrystal.

Magneto-optical properties of trions in non-blinking charged nanocrystals reveal an acoustic phonon bottleneck.

Charged quantum dots provide an important platform for a range of emerging quantum technologies. Colloidal quantum dots in particular offer unique advantages for such applications (facile synthesis, manipulation and compatibility with a wide range of environments), especially if stable charged states can be harnessed in these materials. Here we engineer the CdSe nanocrystal core and shell structure to efficiently ionize at cryogenic temperatures, resulting in trion emission with a single sharp zero-phonon line and a mono exponential decay. Magneto-optical spectroscopy enables direct determination of electron and hole g-factors. Spin relaxation is observed in high fields, enabling unambiguous identification of the trion charge. Importantly, we show that spin flips are completely inhibited for Zeeman splittings below the low-energy bound for confined acoustic phonons. This reveals a characteristic unique to colloidal quantum dots that will promote the use of these versatile materials in challenging quantum technological applications.