Ordering phenomena in complex chalcogenides - The showcase of A 2in12Q19 (A = K, Tl, NH4; Q = Se, Te) and pseudobinary in2Q3

Lorenz Kienle, Marc Schlosser, Manolis J. Manos, Christos D. Malliakas, Viola Düppel, Christof Reiner, Hans Jörg Deiseroth, Mercouri G Kanatzidis, Klemens Kelm, Arndt Simon

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

A group of solids with the general composition A2In 12Q19 (A = K, Tl, NH4; O = Se, Te) is characterized by combined Xray single-crystal and high-resolution transmission-electron microscopy (HRTEM). Similar nanosize domains with variable sizes and complex internal structures are common to all three compounds. Although a partial ordering of domains for the bulk of K2In 12Se19 is dominating, the observed ordering patterns in microdomains range from, total random, orientation to a pattern, with a ninefold superstucture (rare precursor phase not stable under HRTEM conditions). In spite of testing various synthesis conditions it was not possible to avoid these unusual structural features for K2In12Se19, which are apparently intrinsic. The formation of significantly larger domains is observed for K2In12Se19-xTex and K2-yTlyIn12Se19 and results in a twofold superstructure that can be observed with X-ray diffraction also on a macroscopic scale. (NH4)2-In12Se19 is a special case where an initial weak ordering is observed that is characterized by ring X-ray reflections forming hexagons around certain, reciprocal lattice positions. This pattern, has apparent similarities to K 2In12Se19 but is not stable in the HRTEM. Instead, it disappears rapidly and is finally replaced by a twofold superstructure similar to K2In12Se19-xTe x and K2-yTIyIn12Se19. The reason was identified, as a combined process of domain broadening and NH3 evaporation. As observed, for K2In12Se 19 at T > 473 K, the superstructure reflections disappear. Surprisingly, the pseudobinary phase In2Q3 (Q: chalcogen) shows strong structural similarities to K2In12Se 19 with respect to the internal structure of the nanodomains, Their three-dimensional arrangement, however, and the resulting superstructure are closer related to K2In12Se19-xTex and K2-yTlyIn12Se19.

Original languageEnglish
Pages (from-to)367-378
Number of pages12
JournalEuropean Journal of Inorganic Chemistry
Issue number3
DOIs
Publication statusPublished - 2010

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Chalcogenides
High resolution transmission electron microscopy
Chalcogens
Evaporation
Single crystals
X ray diffraction
X rays
Testing
Chemical analysis

Keywords

  • Chalcogens
  • Diffuse scattering
  • Disordered structure
  • Electron microscopy
  • Real, structure
  • Solid-state structures
  • X-ray diffraction

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Ordering phenomena in complex chalcogenides - The showcase of A 2in12Q19 (A = K, Tl, NH4; Q = Se, Te) and pseudobinary in2Q3. / Kienle, Lorenz; Schlosser, Marc; Manos, Manolis J.; Malliakas, Christos D.; Düppel, Viola; Reiner, Christof; Deiseroth, Hans Jörg; Kanatzidis, Mercouri G; Kelm, Klemens; Simon, Arndt.

In: European Journal of Inorganic Chemistry, No. 3, 2010, p. 367-378.

Research output: Contribution to journalArticle

Kienle, Lorenz ; Schlosser, Marc ; Manos, Manolis J. ; Malliakas, Christos D. ; Düppel, Viola ; Reiner, Christof ; Deiseroth, Hans Jörg ; Kanatzidis, Mercouri G ; Kelm, Klemens ; Simon, Arndt. / Ordering phenomena in complex chalcogenides - The showcase of A 2in12Q19 (A = K, Tl, NH4; Q = Se, Te) and pseudobinary in2Q3. In: European Journal of Inorganic Chemistry. 2010 ; No. 3. pp. 367-378.
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abstract = "A group of solids with the general composition A2In 12Q19 (A = K, Tl, NH4; O = Se, Te) is characterized by combined Xray single-crystal and high-resolution transmission-electron microscopy (HRTEM). Similar nanosize domains with variable sizes and complex internal structures are common to all three compounds. Although a partial ordering of domains for the bulk of K2In 12Se19 is dominating, the observed ordering patterns in microdomains range from, total random, orientation to a pattern, with a ninefold superstucture (rare precursor phase not stable under HRTEM conditions). In spite of testing various synthesis conditions it was not possible to avoid these unusual structural features for K2In12Se19, which are apparently intrinsic. The formation of significantly larger domains is observed for K2In12Se19-xTex and K2-yTlyIn12Se19 and results in a twofold superstructure that can be observed with X-ray diffraction also on a macroscopic scale. (NH4)2-In12Se19 is a special case where an initial weak ordering is observed that is characterized by ring X-ray reflections forming hexagons around certain, reciprocal lattice positions. This pattern, has apparent similarities to K 2In12Se19 but is not stable in the HRTEM. Instead, it disappears rapidly and is finally replaced by a twofold superstructure similar to K2In12Se19-xTe x and K2-yTIyIn12Se19. The reason was identified, as a combined process of domain broadening and NH3 evaporation. As observed, for K2In12Se 19 at T > 473 K, the superstructure reflections disappear. Surprisingly, the pseudobinary phase In2Q3 (Q: chalcogen) shows strong structural similarities to K2In12Se 19 with respect to the internal structure of the nanodomains, Their three-dimensional arrangement, however, and the resulting superstructure are closer related to K2In12Se19-xTex and K2-yTlyIn12Se19.",
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AU - Kienle, Lorenz

AU - Schlosser, Marc

AU - Manos, Manolis J.

AU - Malliakas, Christos D.

AU - Düppel, Viola

AU - Reiner, Christof

AU - Deiseroth, Hans Jörg

AU - Kanatzidis, Mercouri G

AU - Kelm, Klemens

AU - Simon, Arndt

PY - 2010

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N2 - A group of solids with the general composition A2In 12Q19 (A = K, Tl, NH4; O = Se, Te) is characterized by combined Xray single-crystal and high-resolution transmission-electron microscopy (HRTEM). Similar nanosize domains with variable sizes and complex internal structures are common to all three compounds. Although a partial ordering of domains for the bulk of K2In 12Se19 is dominating, the observed ordering patterns in microdomains range from, total random, orientation to a pattern, with a ninefold superstucture (rare precursor phase not stable under HRTEM conditions). In spite of testing various synthesis conditions it was not possible to avoid these unusual structural features for K2In12Se19, which are apparently intrinsic. The formation of significantly larger domains is observed for K2In12Se19-xTex and K2-yTlyIn12Se19 and results in a twofold superstructure that can be observed with X-ray diffraction also on a macroscopic scale. (NH4)2-In12Se19 is a special case where an initial weak ordering is observed that is characterized by ring X-ray reflections forming hexagons around certain, reciprocal lattice positions. This pattern, has apparent similarities to K 2In12Se19 but is not stable in the HRTEM. Instead, it disappears rapidly and is finally replaced by a twofold superstructure similar to K2In12Se19-xTe x and K2-yTIyIn12Se19. The reason was identified, as a combined process of domain broadening and NH3 evaporation. As observed, for K2In12Se 19 at T > 473 K, the superstructure reflections disappear. Surprisingly, the pseudobinary phase In2Q3 (Q: chalcogen) shows strong structural similarities to K2In12Se 19 with respect to the internal structure of the nanodomains, Their three-dimensional arrangement, however, and the resulting superstructure are closer related to K2In12Se19-xTex and K2-yTlyIn12Se19.

AB - A group of solids with the general composition A2In 12Q19 (A = K, Tl, NH4; O = Se, Te) is characterized by combined Xray single-crystal and high-resolution transmission-electron microscopy (HRTEM). Similar nanosize domains with variable sizes and complex internal structures are common to all three compounds. Although a partial ordering of domains for the bulk of K2In 12Se19 is dominating, the observed ordering patterns in microdomains range from, total random, orientation to a pattern, with a ninefold superstucture (rare precursor phase not stable under HRTEM conditions). In spite of testing various synthesis conditions it was not possible to avoid these unusual structural features for K2In12Se19, which are apparently intrinsic. The formation of significantly larger domains is observed for K2In12Se19-xTex and K2-yTlyIn12Se19 and results in a twofold superstructure that can be observed with X-ray diffraction also on a macroscopic scale. (NH4)2-In12Se19 is a special case where an initial weak ordering is observed that is characterized by ring X-ray reflections forming hexagons around certain, reciprocal lattice positions. This pattern, has apparent similarities to K 2In12Se19 but is not stable in the HRTEM. Instead, it disappears rapidly and is finally replaced by a twofold superstructure similar to K2In12Se19-xTe x and K2-yTIyIn12Se19. The reason was identified, as a combined process of domain broadening and NH3 evaporation. As observed, for K2In12Se 19 at T > 473 K, the superstructure reflections disappear. Surprisingly, the pseudobinary phase In2Q3 (Q: chalcogen) shows strong structural similarities to K2In12Se 19 with respect to the internal structure of the nanodomains, Their three-dimensional arrangement, however, and the resulting superstructure are closer related to K2In12Se19-xTex and K2-yTlyIn12Se19.

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