Fluorine intercalation in the n = 1 and n = 2 layered manganites Sr 2MnO3.5+x and Sr3Mn2O6

Eirin Sullivan, Lisa J. Gillie, Joke Hadermann, Colin Greaves

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Fluorine insertion into the oxygen defect superstructure manganite Sr 2MnO3.5+x has been shown by transmission electron microscopy (TEM) to result in two levels of fluorination. In the higher fluorine content sections, the fluorine anions displace oxygen anions from their apical positions into the equatorial vacancies, thus destroying the superstructure and reverting to a K2NiF4-type structure (a = 3.8210(1) a and c = 12.686(1) a). Conversely, lower fluorine content sections retain the Sr 2MnO3.5+x defect superstructure, crystallising in the P21/c space group. Fluorine intercalation into the reduced double-layer manganite Sr3Mn2O6 occurs in a step-wise fashion according to the general formula Sr3Mn 2O6Fy with y = 1, 2, and 3. It is proposed that the y = 1 phase (a = 3.815(1) a, c = 20.29(2) a) is produced by the filling of all the equatorial oxygen vacancies by fluorine atoms whilst the y = 2 phase (a = 3.8222(2) a, c = 21.2435(3) a) has a random distribution of fluorine anions throughout both interstitial rocksalt and equatorial sites. Neutron powder diffraction data suggest that the fully fluorinated y = 3 phase (a = 3.8157(6) a, c = 23.666(4) a) corresponds to the complete occupation of all the equatorial oxygen vacancies and the interstitial sites by intercalated fluorine.

LanguageEnglish
Pages1598-1605
Number of pages8
JournalMaterials Research Bulletin
Volume48
Issue number4
DOIs
Publication statusPublished - Apr 2013

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Manganites
Fluorine
Intercalation
intercalation
fluorine
Anions
Negative ions
oxygen
Oxygen vacancies
anions
interstitials
Oxygen
Fluorination
Defects
Neutron powder diffraction
fluorination
defects
statistical distributions
occupation
Vacancies

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Sullivan, Eirin ; Gillie, Lisa J. ; Hadermann, Joke ; Greaves, Colin. / Fluorine intercalation in the n = 1 and n = 2 layered manganites Sr 2MnO3.5+x and Sr3Mn2O6. In: Materials Research Bulletin. 2013 ; Vol. 48, No. 4. pp. 1598-1605.
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Fluorine intercalation in the n = 1 and n = 2 layered manganites Sr 2MnO3.5+x and Sr3Mn2O6. / Sullivan, Eirin; Gillie, Lisa J.; Hadermann, Joke; Greaves, Colin.

In: Materials Research Bulletin, Vol. 48, No. 4, 04.2013, p. 1598-1605.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Fluorine intercalation in the n = 1 and n = 2 layered manganites Sr 2MnO3.5+x and Sr3Mn2O6

AU - Sullivan, Eirin

AU - Gillie, Lisa J.

AU - Hadermann, Joke

AU - Greaves, Colin

PY - 2013/4

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N2 - Fluorine insertion into the oxygen defect superstructure manganite Sr 2MnO3.5+x has been shown by transmission electron microscopy (TEM) to result in two levels of fluorination. In the higher fluorine content sections, the fluorine anions displace oxygen anions from their apical positions into the equatorial vacancies, thus destroying the superstructure and reverting to a K2NiF4-type structure (a = 3.8210(1) a and c = 12.686(1) a). Conversely, lower fluorine content sections retain the Sr 2MnO3.5+x defect superstructure, crystallising in the P21/c space group. Fluorine intercalation into the reduced double-layer manganite Sr3Mn2O6 occurs in a step-wise fashion according to the general formula Sr3Mn 2O6Fy with y = 1, 2, and 3. It is proposed that the y = 1 phase (a = 3.815(1) a, c = 20.29(2) a) is produced by the filling of all the equatorial oxygen vacancies by fluorine atoms whilst the y = 2 phase (a = 3.8222(2) a, c = 21.2435(3) a) has a random distribution of fluorine anions throughout both interstitial rocksalt and equatorial sites. Neutron powder diffraction data suggest that the fully fluorinated y = 3 phase (a = 3.8157(6) a, c = 23.666(4) a) corresponds to the complete occupation of all the equatorial oxygen vacancies and the interstitial sites by intercalated fluorine.

AB - Fluorine insertion into the oxygen defect superstructure manganite Sr 2MnO3.5+x has been shown by transmission electron microscopy (TEM) to result in two levels of fluorination. In the higher fluorine content sections, the fluorine anions displace oxygen anions from their apical positions into the equatorial vacancies, thus destroying the superstructure and reverting to a K2NiF4-type structure (a = 3.8210(1) a and c = 12.686(1) a). Conversely, lower fluorine content sections retain the Sr 2MnO3.5+x defect superstructure, crystallising in the P21/c space group. Fluorine intercalation into the reduced double-layer manganite Sr3Mn2O6 occurs in a step-wise fashion according to the general formula Sr3Mn 2O6Fy with y = 1, 2, and 3. It is proposed that the y = 1 phase (a = 3.815(1) a, c = 20.29(2) a) is produced by the filling of all the equatorial oxygen vacancies by fluorine atoms whilst the y = 2 phase (a = 3.8222(2) a, c = 21.2435(3) a) has a random distribution of fluorine anions throughout both interstitial rocksalt and equatorial sites. Neutron powder diffraction data suggest that the fully fluorinated y = 3 phase (a = 3.8157(6) a, c = 23.666(4) a) corresponds to the complete occupation of all the equatorial oxygen vacancies and the interstitial sites by intercalated fluorine.

KW - A. Fluorides

KW - A. Oxides

KW - C. Neutron scattering

KW - C. X-ray diffraction

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