Colloidal synthesis and optical properties of type-II CdSe-CdTe and inverted CdTe-CdSe core-wing heteronanoplatelets

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.We developed colloidal synthesis to investigate the structural and electronic properties of CdSe-CdTe and inverted CdTe-CdSe heteronanoplatelets and experimentally demonstrate that the overgrowth of cadmium selenide or cadmium telluride core nanoplatelets with counterpartner chalcogenide wings leads to type-II heteronanoplatelets with emission energies defined by the bandgaps of the CdSe and CdTe platelets and the characteristic band offsets. The observed conduction and valence band offsets of 0.36 eV and 0.56 eV are in line with theoretical predictions. The presented type-II heteronanoplatelets exhibit efficient spatially indirect radiative exciton recombination with a quantum yield as high as 23%. While the exciton lifetime is strongly prolonged in the investigated type-II 2D systems with respect to 2D type-I systems, the occurring 2D giant oscillator strength (GOST) effect still leads to a fast and efficient exciton recombination. This makes type-II heteronanoplatelets interesting candidates for low threshold lasing applications and photovoltaics

Temperature dependent radiative and non-radiative recombination dynamics in CdSe-CdTe and CdTe-CdSe type II hetero nanoplatelets

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.We investigate the temperature-dependent decay kinetics of type II CdSe-CdTe and CdTe-CdSe core-lateral shell nanoplatelets. From a kinetic analysis of the photoluminescence (PL) decay and a measurement of the temperature dependent quantum yield we deduce the temperature dependence of the non-radiative and radiative lifetimes of hetero nanoplates. In line with the predictions of the giant oscillator strength effect in 2D we observe a strong increase of the radiative lifetime with temperature. This is attributed to an increase of the homogeneous transition linewidth with temperature. Comparing core only and hetero platelets we observe a significant prolongation of the radiative lifetime in type II platelets by two orders in magnitude while the quantum yield is barely affected. In a careful analysis of the PL decay transients we compare different recombination models, including electron hole pairs and exciton decay, being relevant for the applicability of those structures in photonic applications like solar cells or lasers. We conclude that the observed biexponential PL decay behavior in hetero platelets is predominately due to spatially indirect excitons being present at the hetero junction and not ionized e-h pair recombination

p-State Luminescence in CdSe Nanoplatelets: The Role of Lateral Confinement and an LO Phonon Bottleneck

We report excited state emission from p-states at excitation fluences well below ground state saturation in CdSe nanoplatelets. Size dependent exciton ground state-excited state energies and dynamics are determined by three independent methods, time-resolved photoluminescence (PL), time-integrated PL and Hartree renormalized k$\cdot$p calculations -- all in very good agreement. The ground state-excited state energy spacing strongly increases with the lateral platelet quantization. Our results suggest that the PL decay of CdSe platelets is governed by an LO-phonon bottleneck, related to the reported low exciton phonon coupling in CdSe platelets and only observable due to the very large oscillator strength and energy spacing of both states

A comparative study demonstrates strong size tunability of carrier–phonon coupling in CdSe-based 2D and 0D nanocrystals

In a comparative study we investigate the carrier–phonon coupling in CdSe based core-only and hetero 2D as well as 0D nanoparticles. We demonstrate that the coupling can be strongly tuned by the lateral size of nanoplatelets, while, due to the weak lateral confinement, the transition energies are only altered by tens of meV. Our analysis shows that an increase in the lateral platelet area results in a strong decrease in the phonon coupling to acoustic modes due to deformation potential interaction, yielding an exciton deformation potential of 3.0 eV in line with theory. In contrast, coupling to optical modes tends to increase with the platelet area. This cannot be explained by Fröhlich interaction, which is generally dominant in II–VI materials. We compare CdSe/CdS nanoplatelets with their equivalent, spherical CdSe/CdS nanoparticles. Universally, in both systems the introduction of a CdS shell is shown to result in an increase of the average phonon coupling, mainly related to an increase of the coupling to acoustic modes, while the coupling to optical modes is reduced with increasing CdS layer thickness. The demonstrated size and CdS overgrowth tunability has strong implications for applications like tuning carrier cooling and carrier multiplication – relevant for solar energy harvesting applications. Other implications range from transport in nanosystems e.g. for field effect transistors or dephasing control. Our results open up a new toolbox for the design of photonic materials.TU Berlin, Open-Access-Mittel - 201

Directed emission of CdSe nanoplatelets originating from strongly anisotropic 2D electronic structure

ntrinsically directional light emitters are potentially important for applications in photonics including lasing and energy-efficient display technology. Here, we propose a new route to overcome intrinsic efficiency limitations in light-emitting devices by studying a CdSe nanoplatelets monolayer that exhibits strongly anisotropic, directed photoluminescence. Analysis of the two-dimensional k-space distribution reveals the underlying internal transition dipole distribution. The observed directed emission is related to the anisotropy of the electronic Bloch states governing the exciton transition dipole moment and forming a bright plane. The strongly directed emission perpendicular to the platelet is further enhanced by the optical local density of states and local fields. In contrast to the emission directionality, the off-resonant absorption into the energetically higher 2D-continuum of states is isotropic. These contrasting optical properties make the oriented CdSe nanoplatelets, or superstructures of parallel-oriented platelets, an interesting and potentially useful class of semiconductor-based emitters

Two photon absorption in II-VI semiconductors : the influence of dimensionality and size

We report a comprehensive study on the two-photon absorption cross sections of colloidal CdSe nano-platelets, -rods, and -dots of different sizes by the means of z-scan and two-photon excitation spectroscopy. Platelets combine large particle volumes with ultra strong confinement. In contrast to weakly confined nanocrystals, the TPA cross sections of CdSe nanoplatelets scale superlinearly with volume (V-similar to 2) and show ten times more efficient two-photon absorption than nanorods or dots. This unexpectedly strong shape dependence goes well beyond the effect of local fields. The larger the particles' aspect ratio, the greater is the confinement related electronic contribution to the increased two-photon absorption. Both electronic confinement and local field effects favor the platelets and make them unique two-photon absorbers with outstanding cross sections of up to 10(7) GM, the largest ever reported for (colloidal) semiconductor nanocrystals and ideally suited for two-photon imaging and nonlinear optoelectronics. The obtained results are confirmed by two independent techniques as well as a new self-referencing method

Self-Assembly of CdSe Nanoplatelets into Stacks of Controlled Size Induced by Ligand Exchange

In this paper we present a simple method for the preparation of highly stable colloidal solutions of individual nanoplatelets (NPls) with increased fluorescence quantum yield and a versatile procedure of NPls self-assembly into stacks of controlled size. Dynamic light scattering technique has been demonstrated to be simple and accurate method for in situ studies of the growth kinetics of NPls aggregates. The self-assembly method introduced in this work is based on the exchange of ligands on the surface of CdSe nanoplatelets. Hexadecylphosphonic acid allows control of the average size (length) of NPls stacks in a broad range by varying its concentration and reaction time. The main mechanism governing controlled formation of NPls stacks is based on strong van der Waals interaction between rigid brushes of alkyl chains on the surface of neighboring NPls. The interaction strength and, consequently, the length and colloidal stability of stacks have been shown to be dependent on type and concentration of different ligands