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Bi Alloying into Rare Earth Double Perovskites Enhances Synthesizability and Visible Light Absorption

Newhouse, Paul F. and Zhou, Lan and Umehara, Mitsutaro and Boyd, David A. and Soedarmadji, Edwin and Haber, Joel A. and Gregoire, John M. (2020) Bi Alloying into Rare Earth Double Perovskites Enhances Synthesizability and Visible Light Absorption. ACS Combinatorial Science, 22 (12). pp. 895-901. ISSN 2156-8952. doi:10.1021/acscombsci.0c00177.

[img] PDF (Composition space plots of visual images of the samples and calculated direct allowed band gaps for the additional composition spaces: Bi–Mn–Sm–Ni oxide, Bi–Mn–Sm–Cu oxide, Bi–Mn–Eu–Ni oxide, Bi–Mn–Eu–Co oxide, Bi–Mn–La–Co oxide, Bi–Mn–Yb–Ni oxide...) - Supplemental Material
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A high throughput combinatorial synthesis utilizing inkjet printing of precursor inks was used to rapidly evaluate Bi-alloying into double perovskite oxides for enhanced visible light absorption. The fast visual screening of photo image scans of the library plates identifies 4-metal oxide compositions displaying an increase in light absorption, which subsequent UV–vis spectroscopy indicates is due to bandgap reduction. Structural characterization by X-ray diffraction (XRD) and Raman spectroscopy demonstrates that the visually darker composition range contains Bi-alloyed Sm₂MnNiO₆ (double perovskite structure), of the form (Bi,Sm)₂MnNiO₆. Bi alloying not only increases the visible absorption but also facilitates crystallization of this structure at the relatively low annealing temperature of 615 °C. Investigation of additional seven combinations of a rare earth (RE) and a transition metal (TM) with Bi and Mn indicates that Bi-alloying on the RE site occurs with similar effect in the family of rare earth oxide double perovskites.

Item Type:Article
Related URLs:
URLURL TypeDescription
Newhouse, Paul F.0000-0003-2032-3010
Zhou, Lan0000-0002-7052-266X
Umehara, Mitsutaro0000-0001-8665-0028
Haber, Joel A.0000-0001-7847-5506
Gregoire, John M.0000-0002-2863-5265
Additional Information:© 2020 American Chemical Society. Received: August 28, 2020; Revised: October 12, 2020; Published: October 29, 2020. This study is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy (Award No. DE-SC0004993). The optical analysis to infer phase behavior was supported by the Air Force Office of Scientific Research under award number FA9550-18-1-0136. Author Contributions: The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. P.F.N. Synthesized and collected optical data on the libraries and contributed to manuscript preparation. L.Z. collected and analyzed XRD data. M.U. analyzed Raman data. D.A.B. collected and analyzed Raman data. E.S. designed scripts for extracting individual sample images and arranging in composition space. J.A.H. facilitated aggregation of results and their interpretation in the context of the literature and contributed to manuscript preparation. J.M.G. designed the library printing strategy and supported the design of analysis algorithms and visualization schemes, supervised, and contributed to manuscript preparation. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Air Force Office of Scientific Research (AFOSR)FA9550-18-1-0136
Subject Keywords:high throughput experimentation, alloy, ink jet printing, double perovskite, band gap engineering, bismuth, rare earth, lanthanide, elpasolite
Issue or Number:12
Record Number:CaltechAUTHORS:20201030-154047149
Persistent URL:
Official Citation:Bi Alloying into Rare Earth Double Perovskites Enhances Synthesizability and Visible Light Absorption. Paul F. Newhouse, Lan Zhou, Mitsutaro Umehara, David A. Boyd, Edwin Soedarmadji, Joel A. Haber, and John M. Gregoire. ACS Combinatorial Science 2020 22 (12), 895-901; DOI: 10.1021/acscombsci.0c00177
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:106370
Deposited By: Tony Diaz
Deposited On:30 Oct 2020 23:02
Last Modified:16 Nov 2021 18:53

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