Two Polymorphs of BaZn2P2: Crystal Structures, Phase Transition, and Transport Properties
Abstract
Here, the novel α-BaZn2P2 structural polymorph has been synthesized and structurally characterized for the first time. Its structure, elu-cidated from single crystal X-ray diffraction, indicates that the compound crystallizes in the orthorhombic α-BaCu2S2 structure type, with unit cell parameters a = 9.7567(14) Å, b = 4.1266(6) Å, and c = 10.6000(15) Å. With β-BaZn2P2 being previously iden-tified as belonging to the ThCr2Si2 family, and with the precedent of structural phase transitions between the α-BaCu2S2 type and the ThCr2Si2 type, the potential for the pattern to be extended to the two different structural forms of BaZn2P2 was explored. Thermal analysis suggest that a first order phase transition occurs at ~1123 K, whereby the low-temperature orthorhombic α-phase transforms to a high-temperature tetragonal β-BaZn2P2; the structure of which was also studied and confirmed by single-crystal X-ray diffraction. Preliminary transport properties and band structure calculations indicate that α-BaZn2P2 is a p-type, narrow-gap semiconductor with a direct bandgap (Eg) of 0.5 eV. The Seebeck coefficient, S(T), for the material increases steadily from the room temperature value of 119 µV/K to 184 µV/K at 600 K. The electrical resistivity of α-BaZn2P2 is relatively high, on the order of 40 mΩ·cm, and the ρ(T) dependence shows gradualmore »
- Publication Date:
- Research Org.:
- Univ. of Delaware, Newark, DE (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1876203
- Grant/Contract Number:
- SC0008885
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 60; Journal Issue: 18; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Balvanz, Adam, Baranets, Sviatoslav, Ogunbunmi, Michael O., and Bobev, Svilen. Two Polymorphs of BaZn2P2: Crystal Structures, Phase Transition, and Transport Properties. United States: N. p., 2021.
Web. doi:10.1021/acs.inorgchem.1c02209.
Balvanz, Adam, Baranets, Sviatoslav, Ogunbunmi, Michael O., & Bobev, Svilen. Two Polymorphs of BaZn2P2: Crystal Structures, Phase Transition, and Transport Properties. United States. https://doi.org/10.1021/acs.inorgchem.1c02209
Balvanz, Adam, Baranets, Sviatoslav, Ogunbunmi, Michael O., and Bobev, Svilen. Wed .
"Two Polymorphs of BaZn2P2: Crystal Structures, Phase Transition, and Transport Properties". United States. https://doi.org/10.1021/acs.inorgchem.1c02209. https://www.osti.gov/servlets/purl/1876203.
@article{osti_1876203,
title = {Two Polymorphs of BaZn2P2: Crystal Structures, Phase Transition, and Transport Properties},
author = {Balvanz, Adam and Baranets, Sviatoslav and Ogunbunmi, Michael O. and Bobev, Svilen},
abstractNote = {Here, the novel α-BaZn2P2 structural polymorph has been synthesized and structurally characterized for the first time. Its structure, elu-cidated from single crystal X-ray diffraction, indicates that the compound crystallizes in the orthorhombic α-BaCu2S2 structure type, with unit cell parameters a = 9.7567(14) Å, b = 4.1266(6) Å, and c = 10.6000(15) Å. With β-BaZn2P2 being previously iden-tified as belonging to the ThCr2Si2 family, and with the precedent of structural phase transitions between the α-BaCu2S2 type and the ThCr2Si2 type, the potential for the pattern to be extended to the two different structural forms of BaZn2P2 was explored. Thermal analysis suggest that a first order phase transition occurs at ~1123 K, whereby the low-temperature orthorhombic α-phase transforms to a high-temperature tetragonal β-BaZn2P2; the structure of which was also studied and confirmed by single-crystal X-ray diffraction. Preliminary transport properties and band structure calculations indicate that α-BaZn2P2 is a p-type, narrow-gap semiconductor with a direct bandgap (Eg) of 0.5 eV. The Seebeck coefficient, S(T), for the material increases steadily from the room temperature value of 119 µV/K to 184 µV/K at 600 K. The electrical resistivity of α-BaZn2P2 is relatively high, on the order of 40 mΩ·cm, and the ρ(T) dependence shows gradual decrease upon heating. Such behavior is comparable to those of the typical semimetals or degenerate semiconductors. Although the observed values of the as-synthesized samples are not optimal, the carrier concentration can apparently be tuned to fall between the values of metals and semiconductors, thus providing an open window for optimizing this phase towards achieving an enhanced thermoelectric figure of merit zT. The calculated indirect band gap for the β-BaZn2P2 phase is Eg = 0.03 eV which is about an order of magnitude lower than that of α-BaZn2P2. It is expected that the cage-like structural motif and layered structure possessed by α-BaZn2P2 and β-BaZn2P2 phases, respectively, would promote the realiza-tion of a low thermal conductivity in both compounds.},
doi = {10.1021/acs.inorgchem.1c02209},
journal = {Inorganic Chemistry},
number = 18,
volume = 60,
place = {United States},
year = {Wed Sep 08 00:00:00 EDT 2021},
month = {Wed Sep 08 00:00:00 EDT 2021}
}
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