Highly Stable Multicrown Heterostructures of Type-II Nanoplatelets for Ultralow Threshold Optical Gain

Solution-processed type-II quantum wells exhibit outstanding optical properties, which make them promising candidates for light-generating applications including lasers and LEDs. However, they may suffer from poor colloidal stability under ambient conditions and show strong tendency to assemble into face-to-face stacks. In this work, to resolve the colloidal stability and uncontrolled stacking issues, we proposed and synthesized CdSe/CdSe1-xTex/CdS core/multicrown hetero-nanoplatelets (NPLs), controlling the amount of Te up to 50% in the crown without changing their thicknesses, which significantly increases their colloidal and photostability under ambient conditions and at the same time preserving their attractive optical properties. Confirming the final lateral growth of CdS sidewalls with X-ray photoelectron spectroscopy, energy-dispersive analysis, and photoelectron excitation spectroscopy, we found that the successful coating of this CdS crown around the periphery of conventional type-II NPLs prevents the unwanted formation of needle-like stacks, which results in reduction of the undesired scattering losses in thin-film samples of these NPLs. Owing to highly efficient exciton funneling from the outmost CdS crown accompanied by the reduced scattering and very low waveguide loss coefficient (similar to 18 cm(-1)), ultralow optical gain thresholds of multicrown type-II NPLs were achieved to be as low as 4.15 mu J/cm(2) and 2.48 mJ/cm(2) under one- and two-photon absorption pumping, respectively. These findings indicate that the strategy of using engineered advanced heterostructures of nanoplatelets provides solutions for improved colloidal stability and enables enhanced photonic performance

Highly Stable, Near-Unity Efficiency Atomically Flat Semiconductor Nanocrystals of CdSe/ZnS Hetero-Nanoplatelets Enabled by ZnS-Shell Hot-Injection Growth

Colloidal semiconductor nanoplatelets (NPLs) offer important benefits in nanocrystal optoelectronics with their unique excitonic properties. For NPLs, colloidal atomic layer deposition (c-ALD) provides the ability to produce their core/shell heterostructures. However, as c-ALD takes place at room temperature, this technique allows for only limited stability and low quantum yield. Here, highly stable, near-unity efficiency CdSe/ZnS NPLs are shown using hot-injection (HI) shell growth performed at 573 K, enabling routinely reproducible quantum yields up to 98%. These CdSe/ZnS HI-shell hetero-NPLs fully recover their initial photoluminescence (PL) intensity in solution after a heating cycle from 300 to 525 K under inert gas atmosphere, and their solid films exhibit 100% recovery of their initial PL intensity after a heating cycle up to 400 K under ambient atmosphere, by far outperforming the control group of c-ALD shell-coated CdSe/ZnS NPLs, which can sustain only 20% of their PL. In optical gain measurements, these core/HI-shell NPLs exhibit ultralow gain thresholds reaching approximate to 7 mu J cm(-2). Despite being annealed at 500 K, these ZnS-HI-shell NPLs possess low gain thresholds as small as 25 mu J cm(-2). These findings indicate that the proposed 573 K HI-shell-grown CdSe/ZnS NPLs hold great promise for extraordinarily high performance in nanocrystal optoelectronics

Giant alloyed hot injection shells enable ultralow optical gain threshold in colloidal quantum wells

As an attractive materials system for high-performance optoelectronics, colloidal nanoplatelets (NPLs) benefit from atomic-level precision in thickness, minimizing emission inhomogeneous broadening. Much progress has been made to enhance their photoluminescence quantum yield (PLQY) and photostability. However, to date, layer-by-layer growth of shells at room temperature has resulted in defects that limit PLQY and thus curtail the performance of NPLs as an optical gain medium. Here, we introduce a hot-injection method growing giant alloyed shells using an approach that reduces core/shell lattice mismatch and suppresses Auger recombination. Near-unity PLQY is achieved with a narrow full-width-at-half-maximum (20 nm), accompanied by emission tunability (from 610 to 650 nm). The biexciton lifetime exceeds 1 ns, an order of magnitude longer than in conventional colloidal quantum dots (CQDs). Reduced Auger recombination enables record-low amplified spontaneous emission threshold of 2.4 μJ cm-2 under one-photon pumping. This is lower by a factor of 2.5 than the best previously reported value in nanocrystals (6 μJ cm-2 for CdSe/CdS NPLs). Here, we also report single-mode lasing operation with a 0.55 mJ cm-2 threshold under two-photoexcitation, which is also the best among nanocrystals (compared to 0.76 mJ cm-2 from CdSe/CdS CQDs in the Fabry-Pérot cavity). These findings indicate that hot-injection growth of thick alloyed shells makes ultrahigh performance NPLs.NRF (Natl Research Foundation, S’pore)ASTAR (Agency for Sci., Tech. and Research, S’pore)Accepted versio

Quantifying the Impact of Al Deposition Method on Underlying Al2O3/Si Interface Quality

Oxide-semiconductor interface quality has often a direct impact on the electrical properties of devices and on their performance. Traditionally, the properties are characterised through metal-oxide-semiconductor (MOS) structures by depositing a metal layer and measuring the capacitance-voltage (C-V) characteristics. However, metal deposition process itself may have an impact on the oxide and the oxide-semiconductor interface. The impact of magnetron sputtering, e-beam evaporation, and thermal evaporation on an Al2O3/Si interface was studied, where atomic layer deposited (ALD) Al2O3 was used, by MOS C-V and Corona Oxide Characterization of Semiconductors (COCOS) measurements. The latter allows characterisation of the interface also in its original state before metallisation. The results show that sputtering induces significant damage at the underlaying Al2O3/Si interface as the measured interface defect density Dit increases from 1011 cm−2eV to 1013 cm−2eV. Interestingly, sputtering also generates a high density of positive charges Qtot at the interface as the charge changes from –2 · 1012 cm−2 to +7 · 1012 cm−2. Thermal evaporation is found to be a softer method, with modest impact on Dit and Qtot. Finally, we show that Alnealing heals the damage but has also a significant impact on the charge of the film recovering the characteristic negative charge of Al2O3 (∼ –4 · 1012 cm−2).Peer reviewe

Ultrathin highly luminescent two-monolayer colloidal CdSe nanoplatelets

Surface effects in atomically flat colloidal CdSe nanoplatelets (NLPs) are significantly and increasingly important with their thickness being reduced to subnanometer level, generating strong surface related deep trap photoluminescence emission alongside the bandedge emission. Herein, colloidal synthesis of highly luminescent two-monolayer (2ML) CdSe NPLs and a systematic investigation of carrier dynamics in these NPLs exhibiting broad photoluminescence emission covering the visible region with quantum yields reaching 90% in solution and 85% in a polymer matrix is shown. The astonishingly efficient Stokes-shifted broadband photoluminescence (PL) emission with a lifetime of ≈100 ns and the extremely short PL lifetime of around 0.16 ns at the bandedge signify the participation of radiative midgap surface centers in the recombination process associated with the underpassivated Se sites. Also, a proof-of-concept hybrid LED employing 2ML CdSe NPLs is developed as color converters, which exhibits luminous efficacy reaching 300 lm Wopt−1. The intrinsic absorption of the 2ML CdSe NPLs (≈2.15 × 106 cm−1) reported in this study is significantly larger than that of CdSe quantum dots (≈2.8 × 105 cm−1) at their first exciton signifying the presence of giant oscillator strength and hence making them favorable candidates for next-generation light-emitting and light-harvesting applications.NRF (Natl Research Foundation, S’pore)ASTAR (Agency for Sci., Tech. and Research, S’pore)MOE (Min. of Education, S’pore)Accepted versio