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The insights into effective utilization of perovskite nanocrystals built around a CsPbBr 3 –CdS heterostructure pave the way towards their utilization in photocatalytic reduction and oxidation processes.
Colloidal lead chalcogenide nanocrystals nucleate slowly throughout their synthesis rather than in a burst. There is no correlation between the temporal width of the nucleation phase and the polydispersity.
In our work we develop a base-driven ligand stripping method for metal oxide nanocrystals, replacing oleate ligands with hydroxyls to create an aqueous dispersion. We generalize this method across a range of material compositions, particle sizes, and particle shapes to get stable dispersions.
Piezochromic luminescence materials with optical properties can be adjusted (the colors most sensitive to the human eye range from red to green) to provide powerful means for information acquisition in various applications. Inorganic quantum dots, typically based on heavy metals such as cadmium and lead, have congenital advantages as luminescence materials, including strong inoxidizability and excellent photoelectric properties. However, small band-gap shifts under pressure have hindered the development of inorganic-based piezochromic materials. In this study, we combined in situ high-pressure photoluminescence (PL) and absorption measurements with synchrotron X-ray scattering spectra to elucidate the remarkable modulation of optical properties and morphologies by pressure, particularly that of the piezochromic luminescence, in all-inorganic core–shell InP/ZnSe nanocrystals (NCs). We observed a stepwise PL color change from red to green, and an ultrabroad bandgap tunability of 0.46 eV was observed from 1.99 to 2.45 eV in the pressure range of 14.2 GPa for InP/ZnSe NCs. Moreover, two-dimensional (2D) InP/ZnSe nanosheets were synthesized by the stress-driven attachment of nanoparticles. These results demonstrate the ability of the pressure-stimulus response to trigger remarkable piezochromic luminescence and 2D nanosheet assembly in InP/ZnSe NCs, which paves the way for new applications of all-inorganic InP-based semiconductor NCs.
This study demonstrates dynamically tunable multicolor emissions from a single component, zero-dimensional (0-D) cesium europium chloride (Cs 3 EuCl 6 ) and cesium terbium chloride (Cs 3 TbCl 6 ) nanocrystals (NCs). Highly uniform colloidal Cs 3 EuCl 6 and Cs 3 TbCl 6 NCs are synthesized via the heating-up method. Excitation-wavelength-dependent multicolor emissions from Cs 3 EuCl 6 and Cs 3 TbCl 6 NCs are observed. Under excitation of 330–400 nm, both NCs exhibit blue photoluminescence (PL). Under wavelengths shorter than 330 nm, characteristic red and green emissions are observed from Cs 3 EuCl 6 and Cs 3 TbCl 6 , respectively, owing to the atomic emissions from the f-orbitals in trivalent europium (Eu 3+ ) and terbium (Tb 3+ ) ions. Cs 3 EuCl 6 and Cs 3 TbCl 6 NCs exhibit broadband excitation spectra and enhanced absorption properties. Particularly, Cs 3 EuCl 6 NCs exhibit a very narrow full-width at half-maximum in both blue and red PL and no overlap between the two spectra. Further, the photophysical properties of these NCs are further investigated to understand the multicolor PL origins by time-resolved and temperature-dependent PL measurements. Finally, the potential applications of Cs 3 EuCl 6 and Cs 3 TbCl 6 NCs as anti-counterfeiting inks for high-level security are demonstrated. Given their broadband excitation with enhanced absorption properties and dynamically tunable colors with a wide color gamut, Cs 3 EuCl 6 and Cs 3 TbCl 6 NCs have great potential as novel multicolor NC emitters for many emerging applications.
Correction for ‘Synthesis of lead-free Cs 3 Sb 2 Br 9 perovskite alternative nanocrystals with enhanced photocatalytic CO 2 reduction activity’ by Chang Lu et al. , Nanoscale , 2020, 12 , 2987–2991, https://doi.org/10.1039/C9NR07722G.
Perovskite nanocrystals embedded in metal–organic frameworks (PeMOF) are a new nanoscale heterostructure for stable photonic sources. This perspective discusses the properties of PeMOF structures and their current progress in photonic devices.
Bimetallic nanocrystals (NCs) often show improved catalytic activities compared to their monometallic counterparts, but to optimize the performance it is crucial to understand how they behave under actual reaction conditions, i.e. in gas environments. Here, in this study, we use powder X-ray diffraction (PXRD), total scattering (TS) with pair distribution function (PDF) analysis and in situ high-resolution transmission electron microscopy (HR-TEM) to provide new insights into the atomic-scale behaviour of NC catalysts under a reactive gas environment. By investigating Au, Cu, Pd, PdCu, AuPd and AuCu NCs, we observe that the properties of bimetallic NCs differ significantly from their monometallic counterparts. While metal oxide phases formed for monometallic Pd and Cu under O 2 -exposure, bimetallic PdCu and AuCu NCs showed loss of metallic Cu in the crystalline phases after exposure to O 2 . However, upon introducing the bimetallic NCs to a reducing atmosphere, the Cu was found to reappear and reincorporate into a crystalline phase, forming the initial bimetallic structures. By combining TS, PDF analysis and in situ HR-TEM, we saw that Cu segregates to the NC surfaces or forms small CuO domains under O 2 -exposure. Our results thus indicate that the Cu mobility promotes segregation and formation of CuO along with the formation of a monometallic phase, which ultimately changes the resulting active surface sites of the nanocatalyst. Understanding the dynamical structure–property relations of nanocatalysts is key to enable rational design of efficient and robust catalysts for controlled catalytic reactions.
We report multinary CuZn 2 AS x Se 4− x semiconductor nanocrystals in a wurtzite phase, achieved via hot-injection synthesis.
Parallel-tempering molecular dynamics simulations reveal the temperature- and size-dependent shapes of Cu nanocrystals.
Here, we report the size-controlled synthesis of ultrasmall (3–8 nm), phase-pure, and stoichiometric Cu 3 VS 4 nanocrystals via direct nucleation of the ternary sulvanite phase. An unusual redshift in optical absorption is observed with decreasing size and attributed to the plasmonic-like nature of valence band–intermediate band transitions.
Crystallization of amorphous materials by thermal annealing has been investigated for numerous applications in the fields of nanotechnology, such as thin-film transistors and thermoelectric devices. The phase transition and shape evolution of amorphous germanium (Ge) and Ag@Ge core–shell nanoparticles with average diameters of 10 and 12 nm, respectively, were investigated by high-energy electron beam irradiation and in situ heating within a transmission electron microscope. The transition of a single Ge amorphous nanoparticle to the crystalline diamond cubic structure at the atomic scale was clearly demonstrated. Depending on the heating temperature, a hollow Ge structure can be maintained or transformed into a solid Ge nanocrystal through a diffusive process during the amorphous to crystalline phase transition. Selected area diffraction patterns were obtained to confirm the crystallization process. In addition, the thermal stability of Ag@Ge core–shell nanoparticles with an average core of 7.4 and a 2.1 nm Ge shell was studied by applying the same beam conditions and temperatures. The results show that at a moderate temperature (e.g., 385 °C), the amorphous Ge shell can completely crystallize while maintaining the well-defined core–shell structure, while at a high temperature (e.g., 545 °C), the high thermal energy enables a freely diffusive process of both Ag and Ge atoms on the carbon support film and leads to transformation into a phase segregated Ag–Ge Janus nanoparticle with a clear interface between the Ag and Ge domains. In conclusion, this study provides a protocol as well as insight into the thermal stability and strain relief mechanism of complex nanostructures at the single nanoparticle level with atomic resolution.
Much of the electronic transport, photophysical, or biological functions of molecular materials emerge from intermolecular interactions and associated nanoscale structure and morphology. However, competing phases, defects, and disorder give rise to confinement and many-body localization of the associated wavefunction, disturbing the performance of the material. Here, we employ vibrational excitons as a sensitive local probe of intermolecular coupling in hyperspectral infrared scattering scanning near-field optical microscopy (IR s-SNOM) with complementary small-angle X-ray scattering to map multiscale structure from molecular coupling to long-range order. In the model organic electronic material octaethyl porphyrin ruthenium(II) carbonyl (RuOEP), we observe the evolution of competing ordered and disordered phases, in nucleation, growth, and ripening of porphyrin nanocrystals. From measurement of vibrational exciton delocalization, we identify coexistence of ordered and disordered phases in RuOEP that extend down to the molecular scale. Even when reaching a high degree of macroscopic crystallinity, identify significant local disorder with correlation lengths of only a few nanometers. This minimally invasive approach of vibrational exciton nanospectroscopy and -imaging is generally applicable to provide the molecular-level insight into photoresponse and energy transport in organic photovoltaics, electronics, or proteins.
Among the multi-metallic nanocatalysts, Pt-based alloy nanocrystals (NCs) have demonstrated promising performance in fuel cells and water electrolyzers. In this paper, we demonstrate a facile colloidal synthesis of monodisperse trimetallic Pt–Fe–Ni alloy NCs through a co-reduction of metal precursors. The as-synthesized ternary NCs exhibit superior mass and specific activities toward oxygen reduction reaction (ORR), which are ~2.8 and 5.6 times as high as those of the benchmark Pt/C catalyst, respectively. The ORR activity of the carbon-supported Pt–Fe–Ni nanocatalyst is persistently retained after the durability test. Owing to the incorporation of Fe and Ni atoms into the Pt lattice, the as-prepared trimetallic Pt-alloy electrocatalyst also manifestly enhances the electrochemical activity and durability toward the oxygen evolution reaction with a reduced overpotential when compared with that of the benchmark Pt/C (Δη = 0.20 V, at 10 mA cm –2 ). This synthetic strategy paves the way for improving the reactivity for a broad range of electrocatalytic applications.
Abstract Recently, colloidal perovskite nanocrystals (PNCs) have emerged as an exciting material platform for optoelectronic applications due to their combination of facile synthesis routes, quantum size effects, and exceptional optical properties among other favorable characteristics. Given the focus on their optoelectronic properties, spectroscopic characterization of PNCs is crucial to rational design of their structure and device implementation. In this Perspective, we discuss how multi-dimensional coherent spectroscopy (MDCS) can resolve exciton dynamics and circumvent inhomogeneous broadening to reveal underlying homogeneous spectral lineshapes. We highlight recent applications of MDCS to PNCs in the literature, and suggest compelling problems concerning their microscopic physics to be addressed by MDCS in the future.
Nanostructured materials made through flow-assisted assembly of proteinaceous or polymeric nanosized fibrillar building blocks are promising contenders for a family of high-performance biocompatible materials in a wide variety of applications. Optimization of these processes relies on improving our knowledge of the physical mechanisms from nano- to macroscale and especially understanding the alignment of elongated nanoparticles in flows. Here, we study the full projected orientation distributions of cellulose nanocrystals (CNCs) and nanofibrils (CNFs) in confined flow using scanning microbeam SAXS. For CNCs, we further compare with a simulated system of dilute Brownian ellipsoids, which agrees well at dilute concentrations. However, increasing CNC concentration to a semidilute regime results in locally arranged domains called tactoids, which aid in aligning the CNC at low shear rates, but limit alignment at higher rates. Similarly, shear alignment of CNF at semidilute conditions is also limited owing to probable bundle or flock formation of the highly entangled nanofibrils. Finally, this work provides a quantitative comparison of full projected orientation distributions of elongated nanoparticles in confined flow and provides an important stepping stone towards predicting and controlling processes to create nanostructured materials on an industrial scale.
Nanoscale strain networks are reported in BaTi O 3 (BTO) crystals of 300 nm size using Bragg coherent diffractive imaging. BTO nanocrystals with clear facets were chosen to identify the crystallographic directions, allowing the strain field direction and periodicity to be studied in detail. Stripes of strain were observed, which were both stable and preserved in tetragonal and cubic phases at elevated temperatures, above the tetragonal-to-cubic phase transition. A finite element analysis approach was used to simulate the domain structures inside a BTO crystal and to understand the origins of the strain stripes as piezoelectric blocks. A 180 ∘ domain model gives a better qualitative match to the experimental images. Published by the American Physical Society 2024
Beyond quantum confinement, impurity doping of semiconductor nanocrystals (NCs) offers a degree of control over their optical and electronic properties, which are of interest for potential applications. Manganese (Mn)-doped CsPbCl 3 NCs, for example, show synergistic effects in the visible, with large enhancements in both blue (exciton) and red (dopant) emission over a narrow range of dopant concentration. Although Mn concentration is the primary parameter, NC size offers an additional degree of control over the number of dopants per NC. Size-resolved CsPbCl 3 NCs prepared in the limit of strong Mn doping highlight the emergence of defective NCs with deviations from anticipated confinement trends. In conclusion, the transition correlates with a redshift and increase in the amplitude of dopant emission, and we discuss these observations in the context of atomistic simulations of Ruddlesden-Popper defects in CsPbCl 3 .