The ternary manganese pnictide phases, MnAs 1− x Sb x , are of interest for magnetic refrigeration and waste heat recovery due to their magnetocaloric properties, maximized at the Curie temperature ( T C ), which varies from 580–240 K, depending on composition. Nanoparticles potentially enable application in microelectronics (cooling) or graded composites that can operate over a wide temperature range, but manganese pnictides are synthetically challenging to realize as discrete nanoparticles and their fundamental magnetic properties have not been extensively studied. Accordingly, colloidal synthesis methods were employed to target discrete MnAs x Sb 1− x nanoparticles ( x = 0.1–0.9) by arrested precipitation reactions of Mn 2 (CO) 10 with (C 6 H 5 ) 3 AsO and (C 6 H 5 ) 3 Sb in coordinating solvents. The MnAs x Sb 1− x particles are spherical in morphology with average diameters 10–13 nm (standard deviations <20% based on transmission electron microscopy analysis). X-Ray fluorescence spectroscopy measurements on ensembles showed that all phases had an excess of Sb relative to the targeted composition, whereas energy dispersive spectroscopic mapping data of single particles revealed that the nanoparticles are inhomogeneous, adopting a core–shell structure, with the amorphous shell rich in Mn and O (and sometimes Sb) while the crystalline core is rich in Mn, As, and Sb. Magnetization measurements of the nanoparticle ensemble demonstrated the presence of both ferromagnetic and paramagnetic phases. By combining the magnetization measurements with precision chemical mapping and simple modeling, we were able to unambiguously attribute ferromagnetism to the MnAs x Sb 1− x crystalline core, whereas paramagnetism was attributed to the amorphous shell. Magnetization measurements at variable temperatures were used to determine the superparamagnetic transition of the nanoparticles, although for some compositions and particle sizes the blocking temperature exceeded room temperature. Preliminary magnetic studies also revealed a conventional dependence between core size and coercivity, in spite of variable compositions of the nanoparticles, an unexpected result.
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Dynamic Emission Tuning of X‐ray Radioluminescent Crystalline Colloidal Arrays: Coupling the Optical Stop Band with Sequential Förster Resonance Energy Transfers
X‐ray radiation exhibits diminished scattering and a greater penetration depth in tissue relative to the visible spectrum and has spawned new medical imaging techniques that exploit X‐ray luminescence of nanoparticles. The majority of the nanoparticles finding applications in this field incorporate metals with high atomic numbers and pose potential toxicity effects. Here, a general strategy for the preparation of a fully organic X‐ray radioluminescent colloidal platform that can be tailored to emit anywhere in the visible spectrum through a judicious choice in donor/acceptor pairing and multiple sequential Förster resonance energy transfers (FRETs) is presented. This is demonstrated with three different types of ≈100 nm particles that are doped with anthracene as the scintillating molecule to “pump” subsequent FRET dye pairs that result in emissions from ≈400 nm out past 700 nm. The particles can be self‐assembled in crystalline colloidal arrays, and the radioluminescence of the particles can be dynamically tuned by coupling the observed rejection wavelength with the dyes' emission.
more » « less- Award ID(s):
- 1632881
- NSF-PAR ID:
- 10462847
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Optical Materials
- Volume:
- 7
- Issue:
- 2
- ISSN:
- 2195-1071
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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