Cesium methylammonium lead iodide (Cs
- NSF-PAR ID:
- 10105710
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 10
- Issue:
- 26
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 6539 to 6552
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract x MA1−x PbI3) nanocrystals were obtained with a wide range of A‐site Cs‐MA compositions by post‐synthetic, room temperature cation exchange between CsPbI3nanocrystals and MAPbI3nanocrystals. The alloyed Csx MA1−x PbI3nanocrystals retain their photoactive perovskite phase with incorporated Cs content,x , as high as 0.74 and the expected composition‐tunable photoluminescence (PL). Excess methylammonium oleate from the reaction mixture in the MAPbI3nanocrystal dispersions was necessary to obtain fast Cs‐MA cation exchange. The phase transformation and degradation kinetics of films of Csx MA1−x PbI3nanocrystals were measured and modeled using an Avrami expression. The transformation kinetics were significantly slower than those of the parent CsPbI3and MAPbI3nanocrystals, with Avrami rate constants,k , at least an order of magnitude smaller. These results affirm that A‐site cation alloying is a promising strategy for stabilizing iodide‐based perovskites. -
more » « less
Abstract Cesium methylammonium lead iodide (Cs
x MA1−x PbI3) nanocrystals were obtained with a wide range of A‐site Cs‐MA compositions by post‐synthetic, room temperature cation exchange between CsPbI3nanocrystals and MAPbI3nanocrystals. The alloyed Csx MA1−x PbI3nanocrystals retain their photoactive perovskite phase with incorporated Cs content,x , as high as 0.74 and the expected composition‐tunable photoluminescence (PL). Excess methylammonium oleate from the reaction mixture in the MAPbI3nanocrystal dispersions was necessary to obtain fast Cs‐MA cation exchange. The phase transformation and degradation kinetics of films of Csx MA1−x PbI3nanocrystals were measured and modeled using an Avrami expression. The transformation kinetics were significantly slower than those of the parent CsPbI3and MAPbI3nanocrystals, with Avrami rate constants,k , at least an order of magnitude smaller. These results affirm that A‐site cation alloying is a promising strategy for stabilizing iodide‐based perovskites. -
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.more » « less
-
more » « less
Abstract A new interstellar molecule, FeC (
X 3Δi ), has been identified in the circumstellar envelope of the carbon-rich asymptotic giant branch star IRC+10216. FeC is the second iron-bearing species conclusively observed in the interstellar medium, in addition to FeCN, also found in IRC+10216. TheJ = 4 → 3, 5 → 4, and 6 → 5 rotational transitions of this free radical near 160, 201, and 241 GHz, respectively, were detected in the lowest spin–orbit ladder, Ω = 3, using the Submillimeter Telescope of the Arizona Radio Observatory (ARO) for the 1 mm lines and the ARO 12 m at 2 mm. Because the ground state of FeC is inverted, these transitions are the lowest energy lines. The detected features exhibit slight U shapes with LSR velocities nearV LSR≈ −26 km s−1and linewidths of ΔV 1/2≈ 30 km s−1, line parameters characteristic of IRC+10216. Radiative transfer modeling of FeC suggests that the molecule has a shell distribution with peak radius near 300R *(∼6″) extending out to ∼500R *(∼10″) and a fractional abundance, relative to H2, off ∼ 6 × 10−11. The previous FeCN spectra were also modeled, yielding an abundance off ∼ 8 × 10−11in a larger shell situated near 800R *. These distributions suggest that FeC may be the precursor species for FeCN. Unlike cyanides and carbon-chain molecules, diatomic carbides with a metallic element are rare in IRC+10216, with FeC being the first such detection. -
more » « less
In recent years, Cu2ZnSn(S,Se)4(CZTSSe) materials have enabled important progress in associated thin‐film photovoltaic (PV) technology, while avoiding scarce and/or toxic metals; however, cationic disorder and associated band tailing fundamentally limit device performance. Cu2BaSnS4(CBTS) has recently been proposed as a prospective alternative large bandgap (~2 eV), environmentally friendly PV material, with ~2% power conversion efficiency (PCE) already demonstrated in corresponding devices. In this study, a two‐step process (i.e., precursor sputter deposition followed by successive sulfurization/selenization) yields high‐quality nominally pinhole‐free films with large (>1 µm) grains of selenium‐incorporated (
x = 3) Cu2BaSnS4−x Sex (CBTSSe) for high‐efficiency PV devices. By incorporating Se in the sulfide film, absorber layers with 1.55 eV bandgap, ideal for single‐junction PV, have been achieved within the CBTSSe trigonal structural family. The abrupt transition in quantum efficiency data for wavelengths above the absorption edge, coupled with a strong sharp photoluminescence feature, confirms the relative absence of band tailing in CBTSSe compared to CZTSSe. For the first time, by combining bandgap tuning with an air‐annealing step, a CBTSSe‐based PV device with 5.2% PCE (total area 0.425 cm2) is reported, >2.5× better than the previous champion pure sulfide device. These results suggest substantial promise for the emerging Se‐rich Cu2BaSnS4–x Sex family for high‐efficiency and earth‐abundant PV.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C9SC00989B
