Anisotropic Fe3O4/Mn3O4 Hybrid Nanocrystals with Unique Magnetic Properties.

This work explores novel nanomagnets by site- and facet-selective epitaxy of Mn3O4 nanodomains onto colloidal Fe3O4 nanoprisms in solution. At 190 °C, the Mn3O4 nanodomains epitaxially grow at three vertexes of the Fe3O4 nanoprisms in solution and form horns-on-prism hybrid nanocrystals. At 240 °C and in the same reaction solution, the epitaxy occurs on the top facet of the Fe3O4 nanoprisms, which results in prism-on-prism hybrid nanocrystals. As the temperature increases from 190 to 240 °C, the ratio between the prism-on-prism and horns-on-prism nanocrystals increases. A possible formation mechanism of Fe3O4/Mn3O4 hybrid nanocrystals is proposed. Novel magnetic behaviors, such as compensation point, large positive (or negative) exchange bias, and unusual hysteresis loop character (constricted at low field and expanded at high field), have been observed for both types of anisotropic hybrid nanomagnets. These unique magnetic properties are consistent with controlled switch of relative magnetization orientations between Fe3O4 and Mn3O4 nanodomains from parallel to antiparallel exchange-coupled configurations.

Entropic Ligands for Nanocrystals: From Unexpected Solution Properties to Outstanding Processability.

Solution processability of nanocrystals coated with a stable monolayer of organic ligands (nanocrystal-ligands complexes) is the starting point for their applications, which is commonly measured by their solubility in media. A model described in the other report (10.1021/acs.nanolett.6b00737) reveals that instead of offering steric barrier between inorganic cores, it is the rotation/bending entropy of the C-C σ bonds within typical organic ligands that exponentially enhances solubility of the complexes in solution. Dramatic ligand chain-length effects on the solubility of CdSe-n-alkanoates complexes shall further reveal the power of the model. Subsequently, "entropic ligands" are introduced to maximize the intramolecular entropic effects, which increases solubility of various nanocrystals by 10(2)-10(6). Entropic ligands can further offer means to greatly improve performance of nanocrystals-based electronic and optoelectronic devices.

Efficient Perovskite Nanograin Light-Emitting Diodes in Green-to-Blue Gamut with Co-Additive Engineering.

Perovskite nanograins exceeding the Bohr exciton diameter show great potential for high-performance light-emitting diodes (LEDs) owing to their bandgap homogeneity, spatial charge confinement, and nonlocal interaction. However, it is challenging to directly synthesize proper nanograins along with reduced crystal defects on functional substrate, and the corresponding high-efficiency perovskite LEDs (PeLEDs) have rarely been reported. In this study, crystallization modulation for perovskites with an effective co-additive system, including lithium bromide, p-fluorophenethylammonium bromide, and 18-crown-6, is performed. Furthermore, it is demonstrated that the proposed co-additive system can synergistically retard perovskite crystallization and reduce crystal defects. Consequently, high-quality perovskite nanograin solids (≈22.8 nm) are obtained with a high photoluminescence quantum yield (≈88%). These superior optical properties contribute to developing efficient green PeLEDs with a champion external quantum efficiency (EQE) of 28.4% and an average EQE of 27.1%. The co-additive system can be universally applied to mixed-halide perovskite nanograin LED, presenting a maximum EQE of 24.4%, 21.6%, 17.5%, and 11.1% for the blue device at 496, 488, 478, and 472 nm, respectively, along with a narrow spectral linewidth (17-14 nm) and stable color. These results supplement the research on high-efficiency perovskite nanograin LEDs for multicolor displays and lighting.

Inverse Growth of Large-Grain-Size and Stable Inorganic Perovskite Micronanowire Photodetectors.

Control of forward and inverse reactions between perovskites and precursor materials is key to attaining high-quality perovskite materials. Many techniques focus on synthesizing nanostructured CsPbX3 materials (e.g., nanowires) via a forward reaction (CsX + PbX2 → CsPbX3). However, low solubility of inorganic perovskites and complex phase transition make it difficult to realize the precise control of composition and length of nanowires using the conventional forward approach. Herein, we report the self-assembly inverse growth of CsPbBr3 micronanowires (MWs) (CsPb2Br5 → CsPbBr3 + PbBr2↑) by controlling phase transition from CsPb2Br5 to CsPbBr3. The two-dimensional (2D) structure of CsPb2Br5 serves as nucleation sites to induce initial CsPbBr3 MW growth. Also, phase transition allows crystal rearrangement and slows down crystal growth, which facilitates the MW growth of CsPbBr3 crystals along the 2D planes of CsPb2Br5. A CsPbBr3 MW photodetector constructed based on the inverse growth shows a high responsivity of 6.44 A W-1 and detectivity of ∼1012 Jones. Large grain size, high crystallinity, and large thickness can effectively alleviate decomposition/degradation of perovskites, which leads to storage stability for over 60 days in humid environment (relative humidity = 45%) and operational stability for over 3000 min under illumination (wavelength = 400 nm, light intensity = 20.06 mW cm-2).

Pt/Fe3O4 Core/Shell Triangular Nanoprisms by Heteroepitaxy: Facet Selectivity at the Pt-Fe3O4 Interface and the Fe3O4 Outer Surface.

Pt/Fe3O4 core/shell triangular nanoprisms were synthesized using seed-mediated heteroepitaxy. Their well-defined shape, facets, and ordered-assembly allowed detailed analysis of mechanism of the heteroepitaxy. At the Pt-Fe3O4 interface, existence of both lattice and chemical mismatch resulted in facet-selective epitaxy along ⟨111⟩ directions of two lattices. X-ray absorption fine structure measurements demonstrated that the Pt seed nanocrystals were composed of an iron-rich Pt-Fe metallic thin layer sandwiched between the Pt core and a Fe-O outer-surface. The Fe-O outer-surface of the seed nanocrystals presumably offered epitaxial sites for the following deposition of the Fe3O4 shell. Each tip and side of a triangular nanoprism respectively possessed a groove and a ridge, and a (111) plane parallel to the basal planes linked all grooves and ridges. This interesting (111) plane approximately bisected the triangle nanoprisms and located near the Pt-seed. The outer surface of the hybrid nanocrystals was also found to be facet-selective, that is, solely {111} facets of Fe3O4 lattice. These polar {111} facets allowed the surface to be only occupied with high-density iron ions, and thus offered best surface coordination for the electron donating ligands in the solution.