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Title: Two-Dimensional CsAg5Te3–xSx Semiconductors: Multi-anion Chalcogenides with Dynamic Disorder and Ultralow Thermal Conductivity

Journal Article · · Chemistry of Materials

Metal chalcogenides underpin a wide variety of energyrelated applications and are ideal systems for probing lattice dynamics and fundamental transport phenomena. Here we describe the synthesis and transport properties of CsAg5TeS2 and its solid solution CsAg5Te3-xSx (x = 1-2), new semiconductors with tunable band gaps ranging from 0.17 to 0.30 eV. CsAg5TeS2 has a fully ordered two-dimensional structure that includes a group of Ag atoms in a heteroleptic tetrahedral coordination geometry (AgTe2S2). Single-crystal X-ray diffraction indicates that the compounds crystallize in the tetragonal space group P4/mmm, while pair distribution function (PDF) analysis reveals off-centering at the heteroleptic Ag sites, signifying the lower-symmetry I4/mcm space group. The underlying disorder as a phonon-blocking mechanism that helps facilitate an ultralow lattice thermal conductivity below 0.40 Wm-1 • K-1 at , ~ 300 K , highlighting the importance of local disorder in thermal transport. In conclusion, density functional theory provides additional insight into the electronic and thermal properties of the materials, which are good candidates for p-type thermoelectrics.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1487454
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 20 Vol. 30; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (55)

Rapid-acquisition pair distribution function (RA-PDF) analysis journal November 2003
Introduction to Thermoelectricity book January 2010
Thermoelectric Properties of the New Polytelluride Ba 3 Cu 14 - δ Te 12 journal August 2006
Phonon scattering at grain boundaries in heavily doped fine-grained silicon–germanium alloys journal April 1981
Theory of displacive phase transitions in minerals journal April 1997
An iterative approach to the phonon Boltzmann equation in the theory of thermal conductivity journal July 1995
VESTA : a three-dimensional visualization system for electronic and structural analysis journal May 2008
Concerted Rattling in CsAg 5 Te 3 Leading to Ultralow Thermal Conductivity and High Thermoelectric Performance journal August 2016
Convergence of multi-valley bands as the electronic origin of high thermoelectric performance in CoSb3 skutterudites journal October 2015
Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals journal April 2014
Generalized gradient approximation for the exchange-correlation hole of a many-electron system journal December 1996
Square planar silver(I) complexes: A rare but increasingly observed stereochemistry for silver(I) journal July 2008
Two-dimensional detector software: From real detector to idealised image or two-theta scan journal January 1996
Structural properties and thermal conductivity of crystalline Ge clathrates journal February 2000
Many-Particle Physics book January 1990
High thermoelectric performance in (Bi 0.25 Sb 0.75 ) 2 Te 3 due to band convergence and improved by carrier concentration control journal October 2017
Structural Characterization and Thermal Conductivity of Type-I Tin Clathrates journal July 2000
Enhanced Figure-of-Merit in Se-Doped p-Type AgSbTe 2 Thermoelectric Compound journal October 2010
Lattice Anharmonicity and Thermal Conductivity from Compressive Sensing of First-Principles Calculations journal October 2014
High Thermoelectric Performance in Electron-Doped AgBi 3 S 5 with Ultralow Thermal Conductivity journal May 2017
Accelerating materials development for photoelectrochemical hydrogen production: Standards for methods, definitions, and reporting protocols journal January 2010
Projector augmented-wave method journal December 1994
Thermoelectric Enhancement of Different Kinds of Metal Chalcogenides journal June 2016
Crystal structure, electronic and transport properties of AgSbSe2 and AgSbTe2 journal November 2008
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Dynamic Stereochemical Activity of the Sn 2+ Lone Pair in Perovskite CsSnBr 3 journal September 2016
Discovery-Synthesis, Design, and Prediction of Chalcogenide Phases journal March 2017
Intrinsic lattice thermal conductivity of semiconductors from first principles journal December 2007
Beyond crystallography: the study of disorder, nanocrystallinity and crystallographically challenged materials with pair distribution functions journal January 2004
Inhomogeneous Electron Gas journal November 1964
ShengBTE: A solver of the Boltzmann transport equation for phonons journal June 2014
Thermal conductivity of bulk and nanowire Mg 2 Si x Sn 1 − x alloys from first principles journal November 2012
Intrinsically Minimal Thermal Conductivity in Cubic I−V−VI2 Semiconductors journal July 2008
PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions journal March 2013
First-Principles Determination of the Soft Mode in Cubic ZrO 2 journal May 1997
Local off-centering symmetry breaking in the high-temperature regime of SnTe journal January 2014
Synthesis in Molten Alkali Metal Polyselenophosphate Fluxes: A New Family of Transition Metal Selenophosphate Compounds, A2MP2Se6 (A = K, Rb, Cs; M = Mn, Fe) and A2M'2P2Se6 (A = K, Cs; M' = Cu, Ag) journal March 1995
Thermoelectric Cooling and Power Generation journal July 1999
Crystal structure refinement with SHELXL journal January 2015
Multiple Converged Conduction Bands in K 2 Bi 8 Se 13 : A Promising Thermoelectric Material with Extremely Low Thermal Conductivity journal December 2016
Phonon engineering through crystal chemistry journal January 2011
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Ab initiomolecular dynamics for liquid metals journal January 1993
Hybrid functionals based on a screened Coulomb potential journal May 2003
Generalized Gradient Approximation Made Simple journal October 1996
SnSe: a remarkable new thermoelectric material journal January 2016
Spontaneous Octahedral Tilting in the Cubic Inorganic Cesium Halide Perovskites CsSnX 3 and CsPbX 3 (X = F, Cl, Br, I) journal September 2017
Electrons and Phonons book January 2001
Quaternary rubidium copper tin sulfides (Rb2Cu2SnS4, A2Cu2Sn2S6 (A = Na, K, Rb, Cs), A2Cu2Sn2Se6 (A = K, Rb), potassium gold tin sulfides, K2Au2SnS4, and K2Au2Sn2S6. Syntheses, structures, and properties of new solid-state chalcogenides based on tetrahedral [SnS4]4- units journal October 1993
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals journal July 2007
Thinking Like a Chemist: Intuition in Thermoelectric Materials journal April 2016
Impact of Rattlers on Thermal Conductivity of a Thermoelectric Clathrate: A First-Principles Study journal March 2015
Liquid-like thermal conduction in intercalated layered crystalline solids journal January 2018
Redetermination of the structure of hessite, Ag2Te-III journal August 1993
Lead telluride alloy thermoelectrics journal November 2011

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