Tunable magnetic exchange interactions in manganese-doped inverted core/shell ZnSe/CdSe nanocrystals

Magnetic doping of semiconductor nanostructures is actively pursued for applications in magnetic memory and spin-based electronics. Central to these efforts is a drive to control the interaction strength between carriers (electrons and holes) and the embedded magnetic atoms. In this respect, colloidal nanocrystal heterostructures provide great flexibility via growth-controlled `engineering' of electron and hole wavefunctions within individual nanocrystals. Here we demonstrate a widely tunable magnetic sp-d exchange interaction between electron-hole excitations (excitons) and paramagnetic manganese ions using `inverted' core-shell nanocrystals composed of Mn-doped ZnSe cores overcoated with undoped shells of narrower-gap CdSe. Magnetic circular dichroism studies reveal giant Zeeman spin splittings of the band-edge exciton that, surprisingly, are tunable in both magnitude and sign. Effective exciton g-factors are controllably tuned from -200 to +30 solely by increasing the CdSe shell thickness, demonstrating that strong quantum confinement and wavefunction engineering in heterostructured nanocrystal materials can be utilized to manipulate carrier-Mn wavefunction overlap and the sp-d exchange parameters themselves.Comment: To appear in Nature Materials; 18 pages, 4 figures + Supp. Inf

Microwave-assisted synthesis of water-dispersed CdTe/CdSe core/shell type II quantum dots

A facile synthesis of mercaptanacid-capped CdTe/CdSe (core/shell) type II quantum dots in aqueous solution by means of a microwave-assisted approach is reported. The results of X-ray diffraction and high-resolution transmission electron microscopy revealed that the as-prepared CdTe/CdSe quantum dots had a core/shell structure with high crystallinity. The core/shell quantum dots exhibit tunable fluorescence emissions by controlling the thickness of the CdSe shell. The photoluminescent properties were dramatically improved through UV-illuminated treatment, and the time-resolved fluorescence spectra showed that there is a gradual increase of decay lifetime with the thickness of CdSe shell

Nano-engineered electron–hole exchange interaction controls exciton dynamics in core–shell semiconductor nanocrystals

A strong electron–hole exchange interaction (EI) in semiconductor nanocrystals (NCs) gives rise to a large (up to tens of meV) splitting between optically active ('bright') and optically passive ('dark') excitons. This dark–bright splitting has a significant effect on the optical properties of band-edge excitons and leads to a pronounced temperature and magnetic field dependence of radiative decay. Here we demonstrate a nanoengineering-based approach that provides control over EI while maintaining nearly constant emission energy. We show that the dark–bright splitting can be widely tuned by controlling the electron–hole spatial overlap in core–shell CdSe/CdS NCs with a variable shell width. In thick-shell samples, the EI energy reduces to <250 μeV, which yields a material that emits with a nearly constant rate over temperatures from 1.5 to 300 K and magnetic fields up to 7 T. The EI-manipulation strategies demonstrated here are general and can be applied to other nanostructures with variable electron–hole overlap

Electrical injection of a photonic crystal nanocavity

The possibility of electrical pumping of a single QD and the integration of such a device in an opto-electronic circuit would be a fundamental step towards achieving an on demand single photon source. In this paper we describe the fabrication process and preliminary results of a Light Emitting Diode (LED) integrated with a photonic crystal (PhC) nanocavity on a GaAs membrane. We demonstrate effective electric pumping of the QDs embedded into the membrane by contacting the doped layers (p and n) of the thin membrane, and the excitation of cavity modes of the PhC nanocavity fabricated on it at telecom wavelength

Tuning optical modes in slab photonic crystal by atomic layer deposition and laser-assisted oxidation

The authors experimentally investigate the effects of atomic layer deposition (ALD) and laser-assisted oxidation on the optical modes in GaAs L3 photonic crystal air-bridge cavities, using layers of InAs quantum dots as internal light source. Four distinct optical mode peaks are observed in the photonic bandgap and they show different wavelength-redshifts (0–6.5 nm) as the photonic crystal surface is coated with an Al2O3 layer (0–5.4 nm thick). Numerical finite-difference time-domain (FDTD) simulations can well-reproduce the experimental result and give insight into the origin of the shifts of modes with different spatial profiles. By combining the ALD coating with in situ laser-assisted oxidation, we are able to both redshift and blueshift the optical modes and we attribute the blueshift to the formation of a GaAs-oxide at the expense of GaAs at the interface between GaAs and the Al2O3 layer. This result can be quantitatively reproduced by including a GaAs-oxide layer into the FDTD model. Selective etching experiments, confirm that this GaAs-oxide layer is mainly at the interface between GaAs and Al2O3 layers

Nanofluidic control of coupled photonic crystal resonators

A fine control of a photonic molecule is obtained by nanofluidic techniques. The coupling condition between the modes of two photonic crystal nanocavities is modified by spectrally tuning each single resonator. Clear mode anticrossing and transition from localized to delocalized states are observed. The detuning induced by disorder, always present in real device, is experimentally compensated by locally modifying the photonic environment of the cavity

Post-fabrication control of evanescent tunnelling in photonic crystal molecules

The post-fabrication control of evanescent tunnelling in photonic crystal molecules is demonstrated through the combination of selective infiltration and oxidation. By laser non thermal oxidation, we reduce the photonic coupling by more than 30% while by means of water micro-infiltration, we increase it by 28%. Fine-tuning of the photonic coupling is achieved by low-power laser oxidation and forced evaporation, opening the route to post-fabrication control of array of coupled cavities

Mode tuning of photonic crystal nanocavities by photoinduced non-thermal oxidation

A method to achieve photoinduced tuning of PhC nanocavity modes is discussed and implemented. It is based on light induced oxidation in air atmosphere with very low thermal budget which produces a local reduction of the GaAs membrane effective thickness and a large blueshift of the nanocavity modes. It is also shown that green light is much more efficient in inducing the micro-oxidation with respect to near infrared light. The observed behaviour is attributed to oxide growth promoted by photoenhanced reactivity

Continuous injection synthesis of indium arsenide quantum dots emissive in the short-wavelength infrared

With the emergence of applications based on short-wavelength infrared light, indium arsenide quantum dots are promising candidates to address existing shortcomings of other infrared-emissive nanomaterials. However, III–V quantum dots have historically struggled to match the high-quality optical properties of II–VI quantum dots. Here we present an extensive investigation of the kinetics that govern indium arsenide nanocrystal growth. Based on these insights, we design a synthesis of large indium arsenide quantum dots with narrow emission linewidths. We further synthesize indium arsenide-based core-shell-shell nanocrystals with quantum yields up to 82% and improved photo- and long-term storage stability. We then demonstrate non-invasive through-skull fluorescence imaging of the brain vasculature of murine models, and show that our probes exhibit 2–3 orders of magnitude higher quantum yields than commonly employed infrared emitters across the entire infrared camera sensitivity range. We anticipate that these probes will not only enable new biomedical imaging applications, but also improved infrared nanocrystal-LEDs and photon-upconversion technology.National Science Foundation (U.S.) (EECS-1449291)National Institutes of Health (U.S.) (Massachusetts Institute of Technology. Laser Biomedical Research Center. 9-P41-EB015871-26A1)Massachusetts Institute of Technology. Institute for Soldier Nanotechnologies (W911NF-13-D-0001)Boehringer Ingelheim FondsEuropean Molecular Biology Organization (Long-term Fellowship)National Science Foundation (U.S.). Graduate Research Fellowship ProgramAmerican Society for Engineering Education. National Defense Science and Engineering Graduate FellowshipUnited States. Dept. of Energy. Center for Excitonics (DE- SC0001088)