Encapsulation of Cadmium-Free InP-based Quantum Dots in Cross-Linked Core-Shell Microparticles via Coaxial Electrospraying.

Quantum dots (QDs) are inorganic semiconductor nanocrystals capable of emitting light. The current major challenge lies in the use of heavy metals, which are known to be highly toxic to humans and pose significant environmental risks. Researchers have turned to indium (In) as a promising option for more environmentally benign QDs, specifically indium phosphide (InP). A significant obstacle remains in sustaining the long-term photostability of InP-based QDs when exposed to the environment. To tackle this, electrospraying is used in this work to protect indium phosphide/zinc selenide/zinc sulfide (InP/ZnSe/ZnS) QDs by embedding them within polymer core-shell microparticles of poly[(lauryl methacrylate)-co-(ethylene glycol dimethacrylate)]/poly(methyl methacrylate) (poly(LMA-co-EGDMA)/PMMA). During the flight of droplets, the liquid monomer core of LMA and EGDMA with QDs is encapsulated by the solid shell of PMMA formed due to solvent evaporation, resulting in a liquid-core/solid-shell particle structure. After that, the captured core of monomers is polymerized into a cross-linked polymer with the embedded QDs via a thermal initiation. They demonstrate how a successful core-shell particle formation is achieved to produce structures for initially liquid monomer systems via coaxial electrospraying that are used for cross-linked polymers, which are of major interest for the encapsulation of InP-based QDs for generally improved photostability over pristine QDs.

Bridging the Green Gap: Monochromatic InP-Based Quantum-Dot-on-Chip LEDs with over 50% Color Conversion Efficiency.

Solid-state light-emitting diodes (LEDs) emit nearly monochromatic light, yet seamless tuning of emission color throughout the visible region remains elusive. Color-converting powder phosphors are therefore used for making LEDs with a bespoke emission spectrum, yet broad emission lines and low absorption coefficients compromise the formation of small-footprint monochromatic LEDs. Color conversion by quantum dots (QDs) can address these issues, but high-performance monochromatic LEDs made using QDs free of restricted, hazardous elements remain to be demonstrated. Here, we show green, amber, and red LEDs formed using InP-based QDs as on-chip color convertor for blue LEDs. Implementing QDs with near-unity photoluminescence efficiency yields a color conversion efficiency over 50% with little intensity roll-off and nearly complete blue light rejection. Moreover, as the conversion efficiency is mostly limited by package losses, we conclude that on-chip color conversion using InP-based QDs can provide spectrum-on-demand LEDs, including monochromatic LEDs that bridge the green gap.

The Dynamic Interaction of Surfactants with Colloidal Molybdenum Disulfide Nanosheets Calls for Thermodynamic Stabilization by Solvents.

Top-down liquid-phase exfoliation (LPE) and bottom-up hot-injection synthesis are scalable methods to produce colloids of two-dimensional (2D) van der Waals (vdW) solids. Generally thought off as two entirely different fields, we show that similar stabilization mechanisms apply to colloids of molybdenum disulfide (MoS2) produced by both methods. By screening the colloidal stability of MoS2 produced in a hot-injection synthesis in a wide range of solvents, we observe that colloidal stability can be understood based on solution thermodynamics, wherein matching the solubility parameter of solvent and nanomaterial maximizes colloidal stability. Identical to MoS2 produced through LPE, optimal solvents to disperse MoS2 produced from the bottom-up have similar solubility parameters of ≈22 MPa1/2 and include aromatic solvents with polar functionalities, such as o-dichlorobenzene, and polar aprotic solvents, such as N,N-dimethylformamide. We further complemented our findings by nuclear magnetic resonance (NMR) spectrscopy, highlighting that organic surfactants, such as oleylamine and oleic acid, have a minimal affinity toward the nanocrystal surface and engage in a highly dynamic adsorption/desorption equilibrium. We thus conclude that hot injection yields MoS2 colloids with comparable surfaces as those produced by LPE. These similarities might offer the prospect of using established procedures developed for LPE nanomaterials to postprocess colloidally synthesized dispersions of 2D colloids as processable inks.

A roadmap to decipher ultrafast photophysics in two-dimensional nanomaterials.

Atomically thin two-dimensional (2D) semiconductors are extensively investigated for optoelectronic applications that require strong light-matter interactions. In view of such applications, it is essential to understand how (photo)excitation alters the non-linear optical response of these materials under high carrier density conditions. Broadband transient absorption (TA) spectroscopy is by now a widely used tool to study the semiconductor physics in such highly excited systems. However, the complex interplay between different many-body interactions in 2D materials produces highly congested spectral information and an ensuing non-trivial non-linear photo-response, thereby masking the desired intrinsic photophysics. Herein, we outline a concise roadmap for analyzing such congested datasets based on examples of TA analysis of various 2D materials. In particular, we emphasize the synergy between an initial qualitative understanding of the transient photo-response based on line shapes and their derivatives and a consequent quantitative spectral deconvolution backed by such insights.

Mechanistic study of ZnSe nanocrystal formation from zinc halides.

We studied the formation of zinc selenide (ZnSe) from zinc chloride (ZnCl2) and trioctylphosphine selenide (TOP=Se) in oleylamine, a chemistry originally proposed to grow ZnSe shells around InP core quantum dots. By monitoring the formation of ZnSe in reactions with and without InP seeds by quantitative absorbance and nuclear magnetic resonance (NMR) spectroscopy, we observe that the ZnSe formation rate is independent of the presence of InP cores. Similar to the seeded growth of CdSe and CdS, this observation supports a ZnSe growth mechanism through the inclusion of reactive ZnSe monomers that form homogeneously in the solution. Furthermore, by combining NMR and mass spectrometry, we identified the dominant reaction products of the ZnSe formation reaction as oleylammonium chloride and amino-substitutions of TOP, i.e., iminophosphoranes (TOP=NR), aminophosphonium chloride salts [TOP(NHR)Cl], and bis(amino)phosphoranes [TOP(NHR)2]. Based on the acquired results, we outline a reaction scheme that involves the complexation of TOP=Se by ZnCl2, followed by the nucleophilic addition of oleylamine onto the Lewis acid activated P-Se bond, thereby eliminating ZnSe monomers and forming amino-substitutions of TOP. Our work highlights the central role of oleylamine, acting as both the nucleophile and Brønsted base, in the transformation of metal halides and alkylphosphine chalcogenides into metal chalcogenides.

Liquid-Phase Exfoliation of Rhenium Disulfide by Solubility Parameter Matching.

In this work, we provide a detailed account of the liquid-phase exfoliation (LPE) of rhenium disulfide (ReS2), a promising new-generation two-dimensional material. By screening LPE in a wide range of solvents, we show that the most optimal solvents are characterized by similar Hildebrand or dispersive Hansen solubility parameters of 25 and 18 MPa1/2, respectively. Such values are attained by solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, and 1-butanol. In line with solution thermodynamics, we interpret the conditions for high-yield exfoliation as a matching of the solvent and ReS2 solubility parameters. Using N-methyl-2-pyrrolidone as an exemplary exfoliation solvent, we undertook a detailed analysis of the exfoliated ReS2. In-depth morphological, structural, and elemental characterization outlined that the LPE procedure presented here produces few-layer, anisotropically stacked, and chemically pure ReS2 platelets with long-term stability against oxidation. These results underscore the suitability of LPE to batch-produce few-layer and pristine ReS2 in solvents that have a solubility parameter close to 25 MPa1/2.

Ultrafast carrier dynamics in colloidal WS2 nanosheets obtained through a hot injection synthesis.

In recent years, hot injection synthesis has emerged as a promising route for the production of nanostructured transition metal dichalcogenides, in large due to its better control over the crystallinity and monodispersity compared to other solution based methods. Understanding the photophysics of excitons in the thus obtained colloidal nanosheets is of great importance to explore their potential for applications in optoelectronics. Here, we study the carrier dynamics in these few-layer colloidal WS2 nanosheets by use of broadband transient absorption spectroscopy. The dynamics of both the bleach, linewidth broadening and energy shift across the entire visible and near-infrared spectrum, allows us to identify subpicosecond electron trapping as the main carrier loss channel. A more quantitative analysis shows that the intrinsic properties of colloidally synthesized nanosheets are on par with other synthesis methods, paving the way for this method to produce high quality nanosheets.

Near-Unity Photoluminescence Quantum Yield of Core-Only InP Quantum Dots via a Simple Postsynthetic InF3 Treatment.

Indium phosphide (InP) quantum dots (QDs) are considered the most promising alternative for Cd and Pb-based QDs for lighting and display applications. However, while core-only QDs of CdSe and CdTe have been prepared with near-unity photoluminescence quantum yield (PLQY), this is not yet achieved for InP QDs. Treatments with HF have been used to boost the PLQY of InP core-only QDs up to 85%. However, HF etches the QDs, causing loss of material and broadening of the optical features. Here, we present a simple postsynthesis HF-free treatment that is based on passivating the surface of the InP QDs with InF3. For optimized conditions, this results in a PLQY as high as 93% and nearly monoexponential photoluminescence decay. Etching of the particle surface is entirely avoided if the treatment is performed under stringent acid-free conditions. We show that this treatment is applicable to InP QDs with various sizes and InP QDs obtained via different synthesis routes. The optical properties of the resulting core-only InP QDs are on par with InP/ZnSe/ZnS core-shell QDs, with significantly higher absorption coefficients in the blue, and with potential for faster charge transport. These are important advantages when considering InP QDs for use in micro-LEDs or photodetectors.

Quantum Dot Patterning and Encapsulation by Maskless Lithography for Display Technologies.

For their unique optical properties, quantum dots (QDs) have been extensively used as light emitters in a number of photonic and optoelectronic applications. They even met commercialization success through their implementation in high-end displays with unmatched brightness and color rendering. For such applications, however, QDs must be shielded from oxygen and water vapor, which are known to degrade their optical properties over time. Even with highly qualitative QDs, this can only be achieved through their encapsulation between barrier layers. With the emergence of mini- and microLED for higher contrast and miniaturized displays, new strategies must be found for the concomitant patterning and encapsulation of QDs, with sub-millimeter resolution. To this end, we developed a new approach for the direct patterning of QDs through maskless lithography. By combining QDs in photopolymerizable resins with digital light processing (DLP) projectors, we developed a versatile and massively parallel fabrication process for the additive manufacturing of functional structures that we refer to as QD pockets. These 3D heterostructures are designed to provide isotropic encapsulation of the QDs, and hence prevent edge ingress from the lateral sides of QD films, which remains a shortcoming of the current technologies.

Charge Carrier Dynamics in Colloidally Synthesized Monolayer MoX2 Nanosheets.

Transition metal dichalcogenides (TMDs) are nanostructured semiconductors with prospects in optoelectronics and photocatalysis. Several bottom-up procedures to synthesize such materials have been developed yielding colloidal transition metal dichalcogenides (c-TMDs). Where such methods initially yielded multilayered sheets with indirect band gaps, recently, also the formation of monolayered c-TMDs became possible. Despite these advances, no clear picture on the charge carrier dynamics in monolayer c-TMDs exists to date. Here, we show through broadband and multiresonant pump-probe spectroscopy, that the carrier dynamics in monolayer c-TMDs are dominated by a fast electron trapping mechanism, universal to both MoS2 and MoSe2, contrasting hole-dominated trapping in their multilayered counterparts. Through a detailed hyperspectral fitting procedure, sizable exciton red shifts are found and assigned to static shifts originating from both interactions with the trapped electron population and lattice heating. Our results pave the way to optimizing monolayer c-TMDs via passivation of predominantly the electron-trap sites.

Full-Spectrum InP-Based Quantum Dots with Near-Unity Photoluminescence Quantum Efficiency.

Photoluminescent color conversion by quantum dots (QDs) makes possible the formation of spectrum-on-demand light sources by combining blue LEDs with the light generated by a specific blend of QDs. Such applications, however, require a near-unity photoluminescence quantum efficiency since self-absorption magnifies disproportionally the impact of photon losses on the overall conversion efficiency. Here, we present a synthesis protocol for forming InP-based QDs with +90% quantum efficiency across the full visible spectrum from blue/cyan to red. The central features of our approach are as follows: (1) the formation of InP core QDs through one-batch-one-size reactions based on aminophosphine as the phosphorus precursor, (2) the introduction of a core/shell/shell InP/Zn(Se,S)/ZnS structure, and (3) the use of specific interfacial treatments, most notably the saturation of the ZnSe surface with zinc acetate prior to ZnS shell growth. Moreover, we adapted the composition of the Zn(Se,S) inner shell to attain the intended emission color while minimizing line broadening induced by the InP/ZnS lattice mismatch. The protocol is established by analysis of the QD composition and structure using multiple techniques, including solid-state nuclear magnetic resonance spectroscopy and Raman spectroscopy, and verified for reproducibility by having different researchers execute the same protocol. The realization of full-spectrum, +90% quantum efficiency will strongly facilitate research into light-matter interaction in general and luminescent color conversion in particular through InP-based QDs.

Generating Triplets in Organic Semiconductor Tetracene upon Photoexcitation of Transition Metal Dichalcogenide ReS2.

We studied the dynamics of transfer of photoexcited electronic states in a bilayer of the two-dimensional transition metal dichalcogenide ReS2 and tetracene, with the aim to produce triplets in the latter. This material combination was used as the band gap of ReS2 (1.5 eV) is slightly larger than the triplet energy of tetracene (1.25 eV). Using time-resolved optical absorption spectroscopy, transfer of photoexcited states from ReS2 to triplet states in tetracene was found to occur within 5 ps with an efficiency near 38%. This result opens up new possibilities for heterostructure design of two-dimensional materials with suitable organics to produce long-lived triplets. Triplets are of interest as sensitizers in a wide variety of applications including optoelectronics, photovoltaics, photocatalysis, and photon upconversion.