Nanostructural Maze, Phase Diversity, and Coherent Growth in PbS-NaSbS2 Semiconductors

Stavros Kozakos; Nikolaos Vouroutzis; Christos B. Lioutas; Tyler J. Slade; Nikolaos Frangis; Mercouri G. Kanatzidis

doi:10.1021/acs.chemmater.4c00715

Nanostructural Maze, Phase Diversity, and Coherent Growth in PbS-NaSbS₂ Semiconductors

Stavros Kozakos, Nikolaos Vouroutzis, Christos B. Lioutas, Tyler J. Slade, Nikolaos Frangis^*, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

We present findings from an electron diffraction and high-resolution transmission electron microscopy (HRTEM) study of composites mPbS + NaSbS₂ (m = 10, 18). The study reveals that these materials exhibit a nanostructured nature. The dominant observed structure corresponds to the NaCl type, characterized by numerous inhomogeneities. Interestingly, nanocrystals with a cubic structure, but possessing distinct lattice parameters (i.e., different compositions) compared to their surroundings, were observed. Additionally, some nanocrystals exhibited an orthorhombic structure distortion and some nanocrystals with a modulated structure resulting from long-range ordering effects were observed. All types of nanocrystals were observed to grow endotaxially within the matrix. Evidence was also found, suggesting a remarkable phenomenon where, in some areas, S atoms migrate from octahedral to tetrahedral sites, thereby validating previous predictions. These findings significantly contribute to our understanding of these semiconductors and motivate future studies of the thermoelectric properties in PbS-NaSbS₂ materials.

Original language	English (US)
Pages (from-to)	6074-6085
Number of pages	12
Journal	Chemistry of Materials
Volume	36
Issue number	12
DOIs	https://doi.org/10.1021/acs.chemmater.4c00715
State	Published - Jun 25 2024

Funding

This work was supported by (1) the General Secretariat for Research and Technology (GSRT) of Greece and the Hellenic Foundation for Research and Innovation (HFRI) (Scholarship Code: 95077) and (2) the U.S Department of Energy, Office of Science, and Office of Basic Energy Sciences under award number DE-SC001452 (Northwestern University). Work at Ames National Laboratory (T.J.S.) was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Ames National Laboratory is operated for the U.S. Department of Energy by Iowa State University under Contract No. DEAC02-07CH11358.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

Access to Document

10.1021/acs.chemmater.4c00715

Cite this

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title = "Nanostructural Maze, Phase Diversity, and Coherent Growth in PbS-NaSbS2 Semiconductors",

abstract = "We present findings from an electron diffraction and high-resolution transmission electron microscopy (HRTEM) study of composites mPbS + NaSbS2 (m = 10, 18). The study reveals that these materials exhibit a nanostructured nature. The dominant observed structure corresponds to the NaCl type, characterized by numerous inhomogeneities. Interestingly, nanocrystals with a cubic structure, but possessing distinct lattice parameters (i.e., different compositions) compared to their surroundings, were observed. Additionally, some nanocrystals exhibited an orthorhombic structure distortion and some nanocrystals with a modulated structure resulting from long-range ordering effects were observed. All types of nanocrystals were observed to grow endotaxially within the matrix. Evidence was also found, suggesting a remarkable phenomenon where, in some areas, S atoms migrate from octahedral to tetrahedral sites, thereby validating previous predictions. These findings significantly contribute to our understanding of these semiconductors and motivate future studies of the thermoelectric properties in PbS-NaSbS2 materials.",

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AU - Kozakos, Stavros

AU - Vouroutzis, Nikolaos

AU - Lioutas, Christos B.

AU - Slade, Tyler J.

AU - Frangis, Nikolaos

AU - Kanatzidis, Mercouri G.

PY - 2024/6/25

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N2 - We present findings from an electron diffraction and high-resolution transmission electron microscopy (HRTEM) study of composites mPbS + NaSbS2 (m = 10, 18). The study reveals that these materials exhibit a nanostructured nature. The dominant observed structure corresponds to the NaCl type, characterized by numerous inhomogeneities. Interestingly, nanocrystals with a cubic structure, but possessing distinct lattice parameters (i.e., different compositions) compared to their surroundings, were observed. Additionally, some nanocrystals exhibited an orthorhombic structure distortion and some nanocrystals with a modulated structure resulting from long-range ordering effects were observed. All types of nanocrystals were observed to grow endotaxially within the matrix. Evidence was also found, suggesting a remarkable phenomenon where, in some areas, S atoms migrate from octahedral to tetrahedral sites, thereby validating previous predictions. These findings significantly contribute to our understanding of these semiconductors and motivate future studies of the thermoelectric properties in PbS-NaSbS2 materials.

AB - We present findings from an electron diffraction and high-resolution transmission electron microscopy (HRTEM) study of composites mPbS + NaSbS2 (m = 10, 18). The study reveals that these materials exhibit a nanostructured nature. The dominant observed structure corresponds to the NaCl type, characterized by numerous inhomogeneities. Interestingly, nanocrystals with a cubic structure, but possessing distinct lattice parameters (i.e., different compositions) compared to their surroundings, were observed. Additionally, some nanocrystals exhibited an orthorhombic structure distortion and some nanocrystals with a modulated structure resulting from long-range ordering effects were observed. All types of nanocrystals were observed to grow endotaxially within the matrix. Evidence was also found, suggesting a remarkable phenomenon where, in some areas, S atoms migrate from octahedral to tetrahedral sites, thereby validating previous predictions. These findings significantly contribute to our understanding of these semiconductors and motivate future studies of the thermoelectric properties in PbS-NaSbS2 materials.

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