Two-Dimensional CdSe-PbSe Heterostructures and PbSe Nanoplatelets: Formation, Atomic Structure, and Optical Properties

Cation exchange enables the preparation of nanocrystals (NCs), which are not reachable by direct synthesis methods. In this work, we applied Pb2+-for-Cd2+ cation exchange on CdSe nanoplatelets (NPLs) to prepare two-dimensional CdSe-PbSe heterostructures and PbSe NPLs. Lowering the reaction temperature slowed down the rate of cation exchange, making it possible to characterize the intermediary NCs ex situ with atomically resolved high-angle annular dark-field scanning transmission electron microscopy and optical spectroscopy. We observe that the Pb2+-for-Cd2+ cation exchange starts from the vertices of the NPLs and grows into the zinc blende CdSe (zb-CdSe) lattice as a rock salt PbSe phase (rs-PbSe), while the anion (selenium) sublattice is being preserved. In agreement with previous works on CdTe-PbTe films, the interfaces between zb-CdSe and rs-PbSe consist of shared {001} and {011} planes. The final PbSe NPLs are highly crystalline and contain protrusions at the edges, which are slightly rotated, indicating an atomic reconfiguration of material. The growth of PbSe domains into CdSe NPLs could also be monitored by the emission peak shift as a function of the exchange time. Temperature-dependent emission measurements confirm a size-dependent change of the band gap energy with temperature and reveal a strong influence of the anisotropic shape. Time-resolved photoluminescence measurements between 4 and 30 K show a dark-bright exciton-state splitting different from PbSe QDs with three-dimensional quantum confinement

Highly luminescent Gd2O2S:Er3+,Yb3+ upconversion microcrystals obtained by a time- and energy-saving microwave-assisted solid-state synthesis

Er3+-doped and Er3+,Yb3+-co-doped Gd2O2S are one of the most efficient upconversion (UC) materials available to date. However, preparing lanthanide oxysulfides can be challenging as it requires several hours of heating at > 1000 degrees C in high power furnaces. Nonetheless, in designing a new synthesis technology for UC materials, one should consider that these systems suffer from defect quenching, responsible for significant optical energy losses. In this work, the microwave-assisted solid-state (MASS) synthesis was explored as an alternative to synthesize this class of materials, using two different starting compounds - lanthanide oxides (Ln2O3) and hydroxycarbonates (Ln(OH)CO3), where Ln3+: Gd, Er, Yb. Different Er3+,Yb3+ concentrations were investigated, and the Er3+(5%),Yb3+(5%) and Er3+ (1%),Yb3+ (10%) were shown to give the most intense UC output comparable to commercially available materials. Using Ln(OH)CO3 instead of the more common Ln2O3 for the MASS synthesis contributed to higher UC efficiencies and a more homogeneous Er3+ and especially Yb3+ distribution through the Gd2O2S lattice as verified by luminescence lifetime measurements. These high-quality materials were prepared in a simple two-step synthesis of 50 min and using a domestic microwave oven, leading to a remarkable decrease of 79% in processing time and 93% in energy consumption, making the MASS method suitable to be explored as an alternative synthesis methodology for high performance UC materials.(c) 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).</p

Sizing Curve, Absorption Coefficient, Surface Chemistry, and Aliphatic Chain Structure of PbTe Nanocrystals

For colloidal semiconductor nanocrystals (NCs), the knowledge of the chemical structure and the size-dependent optical properties is of crucial importance, both from a practical and fundamental perspective. Here, we report the basic properties of PbTe NCs in order to complement the already existing knowledge on PbS and PbSe NCs. The band gap versus NC diameter (sizing) curve was determined by combining transmission electron microscopy with absorption spectroscopy; the energy of the primary optical absorption follows 1/d dependence with the diameter. The lead content of the NCs was determined with inductive coupled plasma optical emission spectrometry and the relative tellurium content with energy-dispersive X-ray spectroscopy. Combining these results yields a relation for the intrinsic absorption coefficient, which is independent of the NC size at 3.1 eV. The PbTe NCs are stabilized by Pb(oleate)2, but different from PbS NCs, oleate is predominantly bound in a chelating bidentate coordination. Besides that, we analyzed the structure of the aliphatic chains on all lead chalcogenide NCs and showed that the aliphatic chains are partly crystalline near the core and more liquid-like at the solvent side

Shedding Light on Host-to-Yb³⁺ Energy Transfer in Cs₂AgBiBr₆:Yb³⁺ (nano)crystals

The optical properties of Cs2AgBiBr6 double perovskite nanocrystals have attracted considerable attention as lead-free alternatives to lead halide perovskites. A promising strategy to create additional flexibility in the emission color is doping lanthanide ions into Cs2AgBiBr6. Incorporating Yb3+ in the lattice has been shown to give rise to near-infrared (NIR) emission, but the energy transfer mechanism remained unclear. Here, we report on the luminescence and sensitization mechanism of Yb3+ in Cs2AgBiBr6 nano- and microcrystals. We observe that the incorporation of Yb3+ in the host lattice does not strongly affect the broadband red emission of the Cs2AgBiBr6 host but does give rise to an additional and characteristic ∼1000 nm NIR line emission from Yb3+. Temperature-dependent and time-resolved photoluminescence studies of undoped and Yb-doped Cs2AgBiBr6 reveal that the energy transfer does not take place through the red emissive state of the Cs2AgBiBr6 host. Instead, there is a competition between relaxation to the red-emitting state and trapping of the photoexcited charge carriers on Yb3+. Trapping on Yb3+ subsequently results in a charge transfer state that relaxes to the 2F5/2 excited state of Yb3+, followed by NIR narrow line f–f emission to the 2F7/2 ground state

Sizing Curve, Absorption Coefficient, Surface Chemistry, and Aliphatic Chain Structure of PbTe Nanocrystals

For colloidal semiconductor nanocrystals (NCs), the knowledge of the chemical structure and the size-dependent optical properties is of crucial importance, both from a practical and fundamental perspective. Here, we report the basic properties of PbTe NCs in order to complement the already existing knowledge on PbS and PbSe NCs. The band gap versus NC diameter (sizing) curve was determined by combining transmission electron microscopy with absorption spectroscopy; the energy of the primary optical absorption follows 1/d dependence with the diameter. The lead content of the NCs was determined with inductive coupled plasma optical emission spectrometry and the relative tellurium content with energy-dispersive X-ray spectroscopy. Combining these results yields a relation for the intrinsic absorption coefficient, which is independent of the NC size at 3.1 eV. The PbTe NCs are stabilized by Pb(oleate)2, but different from PbS NCs, oleate is predominantly bound in a chelating bidentate coordination. Besides that, we analyzed the structure of the aliphatic chains on all lead chalcogenide NCs and showed that the aliphatic chains are partly crystalline near the core and more liquid-like at the solvent side

Alkyl phosphonic acids deliver CsPbBr3 Nanocrystals with high photoluminescence quantum yield and truncated octahedron shape

We devised a colloidal approach for the synthesis of CsPbBr3 nanocrystals (NCs) in which the only ligands employed are alkyl phosphonic acids. Compared to more traditional syntheses of CsPbBr3 NCs, the present scheme delivers NCs with the following distinctive features: (i) The NCs do not have cubic but truncated octahedron shape enclosed by Pb-terminated facets. This is a consequence of the strong binding affinity of the phosphonate groups toward Pb2+ ions. (II) The NCs have near unity photoluminescence quantum yields (PLQYs), with no need of postsynthesis treatments, indicating that alkyl phosphonic acids are effectively preventing the formation of surface traps. (III) Unlike NCs coated with alkylammonium or carboxylate ligands, the PLQY of phosphonate coated NCs remains constant upon dilution, suggesting that the ligands are tightly bound to the surface

Two-dimensional CdSe-PbSe heterostructures and PbSe nanoplatelets : formation, atomic structure, and optical properties

[Image: see text] Cation exchange enables the preparation of nanocrystals (NCs), which are not reachable by direct synthesis methods. In this work, we applied Pb(2+)-for-Cd(2+) cation exchange on CdSe nanoplatelets (NPLs) to prepare two-dimensional CdSe-PbSe heterostructures and PbSe NPLs. Lowering the reaction temperature slowed down the rate of cation exchange, making it possible to characterize the intermediary NCs ex situ with atomically resolved high-angle annular dark-field scanning transmission electron microscopy and optical spectroscopy. We observe that the Pb(2+)-for-Cd(2+) cation exchange starts from the vertices of the NPLs and grows into the zinc blende CdSe (zb-CdSe) lattice as a rock salt PbSe phase (rs-PbSe), while the anion (selenium) sublattice is being preserved. In agreement with previous works on CdTe-PbTe films, the interfaces between zb-CdSe and rs-PbSe consist of shared {001} and {011} planes. The final PbSe NPLs are highly crystalline and contain protrusions at the edges, which are slightly rotated, indicating an atomic reconfiguration of material. The growth of PbSe domains into CdSe NPLs could also be monitored by the emission peak shift as a function of the exchange time. Temperature-dependent emission measurements confirm a size-dependent change of the band gap energy with temperature and reveal a strong influence of the anisotropic shape. Time-resolved photoluminescence measurements between 4 and 30 K show a dark-bright exciton-state splitting different from PbSe QDs with three-dimensional quantum confinement

Alkyl phosphonic acids deliver CsPbBr₃ Nanocrystals with high photoluminescence quantum yield and truncated octahedron shape

We devised a colloidal approach for the synthesis of CsPbBr3 nanocrystals (NCs) in which the only ligands employed are alkyl phosphonic acids. Compared to more traditional syntheses of CsPbBr3 NCs, the present scheme delivers NCs with the following distinctive features: (i) The NCs do not have cubic but truncated octahedron shape enclosed by Pb-terminated facets. This is a consequence of the strong binding affinity of the phosphonate groups toward Pb2+ ions. (II) The NCs have near unity photoluminescence quantum yields (PLQYs), with no need of postsynthesis treatments, indicating that alkyl phosphonic acids are effectively preventing the formation of surface traps. (III) Unlike NCs coated with alkylammonium or carboxylate ligands, the PLQY of phosphonate coated NCs remains constant upon dilution, suggesting that the ligands are tightly bound to the surface

High-Throughput Characterization of Single-Quantum-Dot Emission Spectra and Spectral Diffusion by Multiparticle Spectroscopy

In recent years, quantum dots (QDs) have emerged as bright, color-tunable light sources for various applications such as light-emitting devices, lasing, and bioimaging. One important next step to advance their applicability is to reduce particle-to-particle variations of the emission properties as well as fluctuations of a single QD’s emission spectrum, also known as spectral diffusion (SD). Characterizing SD is typically inefficient as it requires time-consuming measurements at the single-particle level. Here, however, we demonstrate multiparticle spectroscopy (MPS) as a high-throughput method to acquire statistically relevant information about both fluctuations at the single-particle level and variations at the level of a synthesis batch. In MPS, we simultaneously measure emission spectra of many (20-100) QDs with a high time resolution. We obtain statistics on single-particle emission line broadening for a batch of traditional CdSe-based core-shell QDs and a batch of the less toxic InP-based core-shell QDs. The CdSe-based QDs show significantly narrower homogeneous line widths, less SD, and less inhomogeneous broadening than the InP-based QDs. The time scales of SD are longer in the InP-based QDs than in the CdSe-based QDs. Based on the distributions and correlations in single-particle properties, we discuss the possible origins of line-width broadening of the two types of QDs. Our experiments pave the way to large-scale, high-throughput characterization of single-QD emission properties and will ultimately contribute to facilitating rational design of future QD structures.ChemE/Opto-electronic Material