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Title: Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]
  1. Materials Department and Materials Research Laboratory, University of California, Santa Barbara, California 93106, United States
  2. Department of Chemistry and Biochemistry, Bates College, Lewiston, Maine 04240, United States
  3. Department of Chemistry and Argonne-Northwestern Solar Energy Research Center, Northwestern University, Evanston, Illinois 60208, United States
  4. Materials Department and Materials Research Laboratory, University of California, Santa Barbara, California 93106, United States; Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1419872
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 57; Journal Issue: 2
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Schueller, Emily C., Laurita, Geneva, Fabini, Douglas H., Stoumpos, Constantinos C., Kanatzidis, Mercouri G., and Seshadri, Ram. Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.7b02576.
Schueller, Emily C., Laurita, Geneva, Fabini, Douglas H., Stoumpos, Constantinos C., Kanatzidis, Mercouri G., & Seshadri, Ram. Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide. United States. doi:10.1021/acs.inorgchem.7b02576.
Schueller, Emily C., Laurita, Geneva, Fabini, Douglas H., Stoumpos, Constantinos C., Kanatzidis, Mercouri G., and Seshadri, Ram. 2017. "Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide". United States. doi:10.1021/acs.inorgchem.7b02576.
@article{osti_1419872,
title = {Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide},
author = {Schueller, Emily C. and Laurita, Geneva and Fabini, Douglas H. and Stoumpos, Constantinos C. and Kanatzidis, Mercouri G. and Seshadri, Ram},
abstractNote = {},
doi = {10.1021/acs.inorgchem.7b02576},
journal = {Inorganic Chemistry},
number = 2,
volume = 57,
place = {United States},
year = 2017,
month =
}
  • New La-deficient double perovskites with P2{sub 1}/n symmetry, La{sub ∼1.90}(Co{sup 2+}{sub 1−x}Mg{sup 2+}{sub x})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} with x=0, 0.13 and 0.33, and La{sub 2}(Co{sup 2+}{sub 1/2}Mg{sup 2+}{sub 1/2}) (Co{sup 3+}{sub 1/2}Nb{sup 5+}{sub 1/2})O{sub 6} were prepared by solid state reaction at 1450 °C. Their crystal structures were refined using time-of-flight neutron powder diffraction data. Our results show that certain cations such as Nb{sup 5+}, with very strong B–O bonds in the perovskite structure, can induce A-site vacancies in double perovskites. Upon heating in N{sub 2} gas atmosphere at 1200 °C ∼1% O atom vacancies are formed togethermore » with a partial reduction of the Co{sup 3+} content. The average thermal expansion coefficient between 25 and 900 °C of La{sub 1.90}(Co{sup 2+}{sub 2/3}Mg{sup 2+}{sub 1/3})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} was determined to be 17.4 ppm K{sup −1}. Four-point electronic conductivity measurements showed that the compounds are semiconductors, with conductivities varying between 3.7·10{sup −2} and 7.7·10{sup −2} S cm{sup −1} at 600 °C and activation energies between 0.77 and 0.81 eV. Partial replacement of La{sup 3+} with Sr{sup 2+} does not lead to any increase of conductivity, while replacement of Mg{sup 2+} with Cu{sup 2+} in La{sub 1.9}CoCu{sub 1/3}Nb{sub 2/3}O{sub 6} and La{sub 1.8}CoCu{sub 1/2}Nb{sub 1/2}O{sub 6} leads to ∼100 times larger conductivities at 600 °C, 0.35 and 1.0 S cm{sup −1}, respectively, and lower activation energies, 0.57 and 0.73 eV, respectively. - Highlights: • Double perovskites, P2{sub 1}/n, La{sub 2−z}(Co{sup 2+}{sub 1−x}Mg{sup 2+}{sub x})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} have been synthesized. • Crystal structures have been refined using neutron powder diffraction data. • Strong Nb–O bond and size ordering of Mg{sup 2+}/Co{sup 2+} and Nb{sup 5+}/Co{sup ~3+} leads to La-deficiency. • The compounds are semi conductors (~10{sup −2} S cm{sup −1}) at 600 °C. • Replacement of Mg{sup 2+} with Cu{sup 2+} leads to higher conductivity (~1.0 S cm{sup −1}) at 600 °C.« less
  • Mixed tin (Sn)-lead (Pb) perovskites with high Sn content exhibit low bandgaps suitable for fabricating the bottom cell of perovskite-based tandem solar cells. In this work, we report on the fabrication of efficient mixed Sn-Pb perovskite solar cells using precursors combining formamidinium tin iodide (FASnI 3) and methylammonium lead iodide (MAPbI 3). The best-performing cell fabricated using a (FASnI 3) 0.6(MAPbI 3) 0.4 absorber with an absorption edge of ~1.2 eV achieved a power conversion efficiency (PCE) of 15.08 (15.00)% with an open-circuit voltage of 0.795 (0.799) V, a short-circuit current density of 26.86(26.82) mA/cm 2, and a fill factormore » of 70.6(70.0)% when measured under forward (reverse) voltage scan. In conclusion, the average PCE of 50 cells we have fabricated is 14.39 ± 0.33%, indicating good reproducibility.« less
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