Dorian Dupont

Efficient exciton concentrators built from colloidal core/crown CdSe/CdS semiconductor nanoplatelets.

We present the synthesis and the optical properties of a new type of two-dimensional heterostructure: core/crown CdSe/CdS nanoplatelets. They consist of CdSe nanoplatelets that are extended laterally with CdS. Both the CdSe core and the CdS crown dimensions can be controlled. Their thickness is controlled at the monolayer level. These novel nanoplatelet-based heterostructures have spectroscopic properties that can be similar to nanoplatelets or closer to quantum dots, depending on the CdSe core lateral size.

Aminophosphines: A Double Role in the Synthesis of Colloidal Indium Phosphide Quantum Dots.

Aminophosphines have recently emerged as economical, easy-to-implement precursors for making InP nanocrystals, which stand out as alternative Cd-free quantum dots for optoelectronic applications. Here, we present a complete investigation of the chemical reactions leading to InP formation starting from InCl3 and tris(dialkylamino)phosphines. Using nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction, we demonstrate that injection of the aminophosphine in the reaction mixture is followed by a transamination with oleylamine, the solvent of the reaction. In addition, mass spectrometry and NMR indicate that the formation of InP concurs with that of tetra(oleylamino)phosphonium chloride. The chemical yield of the InP formation agrees with this 4 P(+III) → P(-III) + 3 P(+V) disproportionation reaction occurring, since full conversion of the In precursor was only attained for a 4:1 P/In ratio. Hence it underlines the double role of the aminophosphine as both precursor and reducing agent. These new insights will guide further optimization of high quality InP quantum dots and might lead to the extension of synthetic protocols toward other pnictide nanocrystals.

Band-Edge Exciton Fine Structure and Recombination Dynamics in InP/ZnS Colloidal Nanocrystals

We report on a temperature-, time-, and spectrally resolved study of the photoluminescence of type-I InP/ZnS colloidal nanocrystals with varying core size. By studying the exciton recombination dynamics we assess the exciton fine structure in these systems. In addition to the typical bright-dark doublet, the photoluminescence stems from an upper bright state in spite of its large energy splitting (∼100 meV). This striking observation results from dramatically lengthened thermalization processes among the fine structure levels and points to optical-phonon bottleneck effects in InP/ZnS nanocrystals. Furthermore, our data show that the radiative recombination of the dark exciton scales linearly with the bright-dark energy splitting for CdSe and InP nanocrystals. This finding strongly suggests a universal dangling bonds-assisted recombination of the dark exciton in colloidal nanostructures.

Indium Phosphide‐Based Quantum Dots with Shell‐Enhanced Absorption for Luminescent Down‐Conversion

It is shown that admixing small amounts of cadmium into the shell of InP/ZnSe core/shell quantum dots results in an increased absorption of blue light and a limited redshift of the band-edge emission. These effects reflect the reduced bandgap of (Zn,Cd)Se alloys and their smaller conduction-band offset with InP. Nevertheless, adjusting the InP core size enables InP/ZnSe and InP/(Zn,Cd)Se quantum dots with identical emission characteristics to be made. Processing both materials into remote phosphor disks, it is demonstrated that the shell-enhanced absorbance of InP/(Zn,Cd)Se has the double benefit of suppressing self-absorption and reducing the amount of quantum dots by weight needed to attain a given blue-to-red color conversion.

InAs Colloidal Quantum Dots Synthesis via Aminopnictogen Precursor Chemistry

Despite their various potential applications, InAs colloidal quantum dots have attracted considerably less attention than more classical II-VI materials because of their complex syntheses that require hazardous precursors. Recently, aminophosphine has been introduced as a cheap, easy-to-use and efficient phosphorus precursor to synthesize InP quantum dots. Here, we use aminopnictogen precursors to implement a similar approach for synthesizing InAs quantum dots. We develop a two-step method based on the combination of aminoarsine as the arsenic precursor and aminophosphine as the reducing agent. This results in state-of-the-art InAs quantum dots with respect to the size dispersion and band gap range. Moreover, we present shell coating procedures that lead to InAs/ZnS(e) core/shell quantum dots that emit in the infrared region. This innovative synthesis approach can greatly facilitate the research on InAs quantum dots and may lead to synthesis protocols for a wide range of III-V quantum dots.

Exciton Fine Structure and Lattice Dynamics in InP/ZnSe Core/Shell Quantum Dots

Nanocrystalline InP quantum dots (QDs) hold promise for heavy-metal-free optoelectronic applications due to their bright and size-tunable emission in the visible range. Photochemical stability and high photoluminescence (PL) quantum yield are obtained by a diversity of epitaxial shells around the InP core. To understand and optimize the emission line shapes, the exciton fine structure of InP core/shell QD systems needs be investigated. Here, we study the exciton fine structure of InP/ZnSe core/shell QDs with core diameters ranging from 2.9 to 3.6 nm (PL peak from 2.3 to 1.95 eV at 4 K). PL decay measurements as a function of temperature in the 10 mK to 300 K range show that the lowest exciton fine structure state is a dark state, from which radiative recombination is assisted by coupling to confined acoustic phonons with energies ranging from 4 to 7 meV, depending on the core diameter. Circularly polarized fluorescence line-narrowing (FLN) spectroscopy at 4 K under high magnetic fields (up to 30 T) demonstrates that radiative recombination from the dark F = ±2 state involves acoustic and optical phonons, from both the InP core and the ZnSe shell. Our data indicate that the highest intensity FLN peak is an acoustic phonon replica rather than a zero-phonon line, implying that the energy separation observed between the F = ±1 state and the highest intensity peak in the FLN spectra (6 to 16 meV, depending on the InP core size) is larger than the splitting between the dark and bright fine structure exciton states.

Searching for the optimal synthesis parameters of InP/Cd x Zn 1-x Se quantum dots when combined with a broad band phosphor to optimize color rendering and efficacy of a hybrid remote phosphor white LED

Combining traditional phosphors with a broad emission spectrum and non-scattering quantum dots with a narrow emission spectrum can have multiple advantages for white LEDs. It allows to reduce the amount of scattering in the wavelength conversion element, increasing the efficiency of the complete system. Furthermore, the unique possibility to tune the emission spectrum of quantum dots allows to optimize the resulting LED spectrum in order to achieve optimal color rendering properties for the light source. However, finding the optimal quantum dot properties to achieve optimal efficacy and color rendering is a non-trivial task. Instead of simply summing up the emission spectra of the blue LED, phosphor and quantum dots, we propose a complete simulation tool that allows an accurate analysis of the final performance for a range of different quantum dot synthesis parameters. The recycling of the reflected light from the wavelength conversion element by the LED package is taken into account, as well as the re-absorption and the associated red-shift. This simulation tool is used to vary two synthesis parameters (core size and cadmium fraction) of InP/CdxZn1-xSe quantum dots. We find general trends for the ideal quantum dot that should be combined with a specific YAG:Ce broad band phosphor to obtain optimal efficiency and color rendering for a white LED with a specific pumping LED and recycling cavity, with a desired CCT of 3500K.