Ag2Se to KAg3Se2: Suppressing Order–Disorder Transitions via Reduced Dimensionality
Abstract
Here we report an order–disorder phase transition in the 2D semiconductor KAg3Se2, which is a dimensionally reduced derivative of 3D Ag2Se. At ~695 K, the room temperature β-phase (CsAg3S2 structure type, monoclinic space group C2/m) transforms to the high temperature α-phase (new structure type, hexagonal space group R$$ \overline{3}\ $$m, a = 4.5638(5) Å, c = 25.4109(6) Å), as revealed by in situ temperature-dependent X-ray diffraction. Significant Ag+ ion disorder accompanies the phase transition, which resembles the low temperature (~400 K) superionic transition in the 3D parent compound. Ultralow thermal conductivity of ~0.4 W m–1 K–1 was measured in the “ordered” β-phase, suggesting anharmonic Ag motion efficiently impedes phonon transport even without extensive disordering. The optical and electronic properties of β-KAg3Se2 are modified as expected in the context of the dimensional reduction framework. UV–vis spectroscopy shows an optical band gap of ~1 eV that is indirect in nature as confirmed by electronic structure calculations. Electronic transport measurements on β-KAg3Se2 yielded n-type behavior with a high electron mobility of ~400 cm2 V–1 s–1 at 300 K due to a highly disperse conduction band. Finally, our results thus imply that dimensional reduction may be used as a design strategy to frustrate order–disorder phenomena while retaining desirable electronic and thermal properties.
- Authors:
-
[1];
[5]
- Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
- Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
- Center for High Pressure Science and Technology Advanced Research, Shanghai (China); Carnegie Inst. of Washington, Argonne, IL (United States). HPSynC. Geophysical Lab.
- Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science
- Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Center for High Pressure Science and Technology Advanced Research, Shanghai (China)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1482168
- Grant/Contract Number:
- AC02-06CH11357; 5J-30161-0010A; ECCS-1542205
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 29; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Rettie, Alexander J. E., Malliakas, Christos D., Botana, Antia S., Hodges, James M., Han, Fei, Huang, Ruiyun, Chung, Duck Young, and Kanatzidis, Mercouri G. Ag2Se to KAg3Se2: Suppressing Order–Disorder Transitions via Reduced Dimensionality. United States: N. p., 2018.
Web. doi:10.1021/jacs.8b04888.
Rettie, Alexander J. E., Malliakas, Christos D., Botana, Antia S., Hodges, James M., Han, Fei, Huang, Ruiyun, Chung, Duck Young, & Kanatzidis, Mercouri G. Ag2Se to KAg3Se2: Suppressing Order–Disorder Transitions via Reduced Dimensionality. United States. https://doi.org/10.1021/jacs.8b04888
Rettie, Alexander J. E., Malliakas, Christos D., Botana, Antia S., Hodges, James M., Han, Fei, Huang, Ruiyun, Chung, Duck Young, and Kanatzidis, Mercouri G. Wed .
"Ag2Se to KAg3Se2: Suppressing Order–Disorder Transitions via Reduced Dimensionality". United States. https://doi.org/10.1021/jacs.8b04888. https://www.osti.gov/servlets/purl/1482168.
@article{osti_1482168,
title = {Ag2Se to KAg3Se2: Suppressing Order–Disorder Transitions via Reduced Dimensionality},
author = {Rettie, Alexander J. E. and Malliakas, Christos D. and Botana, Antia S. and Hodges, James M. and Han, Fei and Huang, Ruiyun and Chung, Duck Young and Kanatzidis, Mercouri G.},
abstractNote = {Here we report an order–disorder phase transition in the 2D semiconductor KAg3Se2, which is a dimensionally reduced derivative of 3D Ag2Se. At ~695 K, the room temperature β-phase (CsAg3S2 structure type, monoclinic space group C2/m) transforms to the high temperature α-phase (new structure type, hexagonal space group R$ \overline{3}\ $m, a = 4.5638(5) Å, c = 25.4109(6) Å), as revealed by in situ temperature-dependent X-ray diffraction. Significant Ag+ ion disorder accompanies the phase transition, which resembles the low temperature (~400 K) superionic transition in the 3D parent compound. Ultralow thermal conductivity of ~0.4 W m–1 K–1 was measured in the “ordered” β-phase, suggesting anharmonic Ag motion efficiently impedes phonon transport even without extensive disordering. The optical and electronic properties of β-KAg3Se2 are modified as expected in the context of the dimensional reduction framework. UV–vis spectroscopy shows an optical band gap of ~1 eV that is indirect in nature as confirmed by electronic structure calculations. Electronic transport measurements on β-KAg3Se2 yielded n-type behavior with a high electron mobility of ~400 cm2 V–1 s–1 at 300 K due to a highly disperse conduction band. Finally, our results thus imply that dimensional reduction may be used as a design strategy to frustrate order–disorder phenomena while retaining desirable electronic and thermal properties.},
doi = {10.1021/jacs.8b04888},
journal = {Journal of the American Chemical Society},
number = 29,
volume = 140,
place = {United States},
year = {2018},
month = {6}
}
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Works referenced in this record:
Unraveling the Role of Order-to-Disorder Transition in Shear Thickening Suspensions
journal, January 2018
- Lee, Jonghun; Jiang, Zhang; Wang, Jin
- Physical Review Letters, Vol. 120, Issue 2
Vacancy Ordering as the Cause for the Electrical Resistivity Anomalies and Superlattice Modulations inACu7−xS4(A=Tl, K, Rb)
journal, November 1997
- Lee, K. -S.; Seo, D. -K.; Whangbo, M. -H.
- Journal of Solid State Chemistry, Vol. 134, Issue 1
Superionics: crystal structures and conduction processes
journal, June 2004
- Hull, Stephen
- Reports on Progress in Physics, Vol. 67, Issue 7
Copper ion liquid-like thermoelectrics
journal, March 2012
- Liu, Huili; Shi, Xun; Xu, Fangfang
- Nature Materials, Vol. 11, Issue 5, p. 422-425
Liquid-like thermal conduction in intercalated layered crystalline solids
journal, January 2018
- Li, B.; Wang, H.; Kawakita, Y.
- Nature Materials, Vol. 17, Issue 3
Potential for superionic conductors in thermoelectric applications
journal, April 2017
- Bailey, Trevor P.; Uher, Ctirad
- Current Opinion in Green and Sustainable Chemistry, Vol. 4
Are Binary Copper Sulfides/Selenides Really New and Promising Thermoelectric Materials?
journal, February 2014
- Dennler, Gilles; Chmielowski, Radoslaw; Jacob, Stéphane
- Advanced Energy Materials, Vol. 4, Issue 9
Chemical Stability of (Ag,Cu)2Se: a Historical Overview
journal, March 2013
- Brown, David R.; Day, Tristan; Caillat, Thierry
- Journal of Electronic Materials, Vol. 42, Issue 7
Superionic conductors: Transitions, structures, dynamics
journal, April 1979
- Boyce, J. B.; Huberman, B. A.
- Physics Reports, Vol. 51, Issue 4
Room-temperature stabilization of nanoscale superionic Ag 2 Se
journal, September 2014
- Hu, T.; Wittenberg, J. S.; Lindenberg, A. M.
- Nanotechnology, Vol. 25, Issue 41
Size Dependence of a Temperature-Induced Solid–Solid Phase Transition in Copper(I) Sulfide
journal, September 2011
- Rivest, Jessy B.; Fong, Lam-Kiu; Jain, Prashant K.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 19
Liquid-like cationic sub-lattice in copper selenide clusters
journal, February 2017
- White, Sarah L.; Banerjee, Progna; Jain, Prashant K.
- Nature Communications, Vol. 8, Issue 1
Experimental Study of the Polymorphism of AgI
journal, November 1959
- Majumdar, A. J.; Roy, Rustum
- The Journal of Physical Chemistry, Vol. 63, Issue 11
The Copper–Selenium System at Temperatures to 850 K and Pressures To 50 Kbar
journal, March 1975
- Murray, Ritchie MacLaren; Heyding, Robert Donald
- Canadian Journal of Chemistry, Vol. 53, Issue 6
Pressure Dependence of the Alpha-Beta Transition Temperature in Silver Selenide
journal, February 1965
- Banus, M. D.
- Science, Vol. 147, Issue 3659
Copper Vacancies and Heavy Holes in the Two-Dimensional Semiconductor KCu 3– x Se 2
journal, July 2017
- Rettie, Alexander J. E.; Sturza, Mihai; Malliakas, Christos D.
- Chemistry of Materials, Vol. 29, Issue 14
Thermoelectric and Crystallographic Properties of Ag[sub 2]Se
journal, January 1960
- Conn, J. B.; Taylor, R. C.
- Journal of The Electrochemical Society, Vol. 107, Issue 12
Thermoelectric properties of Ag2Te and Ag2Se
journal, January 1961
- Taylor, P. F.; Wood, C.
- Advanced Energy Conversion, Vol. 1
Preparation and thermoelectric properties of β-Ag2Se
journal, April 1963
- Simon, R.; Bourke, R. C.; Lougher, E. H.
- Advanced Energy Conversion, Vol. 3, Issue 2
Crystal structure of potassium diselenotriargentate, KAg3Se2
journal, December 1997
- Bensch, W.; Dürichen, P.
- Zeitschrift für Kristallographie - New Crystal Structures, Vol. 212, Issue 1
Dimensional reduction in II-VI materials: A2Cd3Q4 (A = K, Q = S, Se, Te; A = Rb, Q = S, Se), novel ternary low-dimensional cadmium chalcogenides produced by incorporation of A2Q in CdQ
journal, June 1996
- Axtell, Enos A.; Liao, Ju-Hsiou; Pikramenou, Zoe
- Chemistry - A European Journal, Vol. 2, Issue 6
Dimensional Reduction: A Design Tool for New Radiation Detection Materials
journal, August 2011
- Androulakis, John; Peter, Sebastian C.; Li, Hao
- Advanced Materials, Vol. 23, Issue 36
Dimensional Reduction: A Practical Formalism for Manipulating Solid Structures
journal, April 2001
- Tulsky, Eric G.; Long, Jeffrey R.
- Chemistry of Materials, Vol. 13, Issue 4
Crystal structure of potassium telluro triargentate(I), KAg 3 Te 2
journal, June 1996
- ,
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 211, Issue 6
Neue tern�re Sulfide des Sibers
journal, November 1973
- Eyck, J.; Burschka, C.; Bronger, W.
- Die Naturwissenschaften, Vol. 60, Issue 11
Ternäre selenide des silbers
journal, July 1978
- Bronger, W.; Eyck, J.; Schils, H.
- Journal of the Less Common Metals, Vol. 60, Issue 1
CsAg5Te3: a new metal-rich telluride with a unique tunnel structure
journal, February 1995
- Li, Jing; Guo, Hong-You; Zhang, Xiang
- Journal of Alloys and Compounds, Vol. 218, Issue 1
In situ studies of a platform for metastable inorganic crystal growth and materials discovery
journal, July 2014
- Shoemaker, D. P.; Hu, Y. -J.; Chung, D. Y.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 30
Molten salt synthesis and properties of three new solid-state ternary bismuth chalcogenides, .beta.-CsBiS2, .gamma.-CsBiS2, and K2Bi8Se13
journal, March 1993
- McCarthy, Timothy J.; Ngeyi, Stanley Pierre; Liao, Ju Hsiou
- Chemistry of Materials, Vol. 5, Issue 3
An alternative way of linearizing the augmented plane-wave method
journal, March 2000
- Sjöstedt, E.; Nordström, L.; Singh, D. J.
- Solid State Communications, Vol. 114, Issue 1
Accurate Band Gaps of Semiconductors and Insulators with a Semilocal Exchange-Correlation Potential
journal, June 2009
- Tran, Fabien; Blaha, Peter
- Physical Review Letters, Vol. 102, Issue 22
Merits and limits of the modified Becke-Johnson exchange potential
journal, May 2011
- Koller, David; Tran, Fabien; Blaha, Peter
- Physical Review B, Vol. 83, Issue 19
Electronic structure of CrN: A comparison between different exchange correlation potentials
journal, June 2012
- Botana, A. S.; Tran, F.; Pardo, V.
- Physical Review B, Vol. 85, Issue 23
Accelerating materials development for photoelectrochemical hydrogen production: Standards for methods, definitions, and reporting protocols
journal, January 2010
- Chen, Zhebo; Jaramillo, Thomas F.; Deutsch, Todd G.
- Journal of Materials Research, Vol. 25, Issue 1
Electrical Properties of β‐Ag 2 Te and β‐Ag 2 Se from 4.2° to 300°K
journal, February 1967
- Dalven, Richard; Gill, Robert
- Journal of Applied Physics, Vol. 38, Issue 2
Evaluating the potential for high thermoelectric efficiency of silver selenide
journal, January 2013
- Day, Tristan; Drymiotis, Fivos; Zhang, Tiansong
- Journal of Materials Chemistry C, Vol. 1, Issue 45
Thermoelectric transport of Se-rich Ag 2 Se in normal phases and phase transitions
journal, March 2014
- Mi, Wenlong; Qiu, Pengfei; Zhang, Tiansong
- Applied Physics Letters, Vol. 104, Issue 13
Ionic Conduction in β-Ag 2 Te and β-Ag 2 Se
journal, August 1959
- Miyatani, Shin-ya
- Journal of the Physical Society of Japan, Vol. 14, Issue 8
α-Ag 2 Se as a Degenerate Semiconductor
journal, July 1967
- Miyatani, Shin-ya; Toyota, Yukio; Yanagihara, Takashi
- Journal of the Physical Society of Japan, Vol. 23, Issue 1
�ber die Struktur von CsAg3S2 und RbAg3S2
journal, April 1977
- Burschka, C.; Bronger, W.
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 430, Issue 1
Reinvestigation of the low-temperature form of Ag 2 Se (naumannite) based on single-crystal data
journal, August 2011
- Yu, Jaemin; Yun, Hoseop
- Acta Crystallographica Section E Structure Reports Online, Vol. 67, Issue 9
In situ high-temperature X-ray diffraction characterization of silver sulfide, Ag 2 S
journal, June 2011
- Blanton, Thomas; Misture, Scott; Dontula, Narasimharao
- Powder Diffraction, Vol. 26, Issue 2
Recommended Values for the Thermal Expansivity of Silicon from 0 to 1000 K
journal, April 1983
- Swenson, C. A.
- Journal of Physical and Chemical Reference Data, Vol. 12, Issue 2
Specific Heat of Superionic Conductor Ag 2 S, Ag 2 Se and Ag 2 Te in α-Phase
journal, May 1987
- Honma, Koji; Iida, Keiichi
- Journal of the Physical Society of Japan, Vol. 56, Issue 5
Thermal expansion of lead
journal, November 1932
- Hidnert, P.; Sweeney, W. T.
- Bureau of Standards Journal of Research, Vol. 9, Issue 5
Silver-109 NMR Spectroscopy of Inorganic Solids
journal, September 2004
- Penner, Glenn H.; Li, Wenli
- Inorganic Chemistry, Vol. 43, Issue 18
Ag + dynamics in the superionic and liquid phases of Ag 2 Se and Ag 2 Te by coherent quasi-elastic neutron scattering
journal, March 2001
- Hamilton, M. A.; Barnes, A. C.; Howells, W. S.
- Journal of Physics: Condensed Matter, Vol. 13, Issue 11
The solid electrolyte transition and melting in salts
journal, February 1976
- O'keeffe, M.; Hyde, B. G.
- Philosophical Magazine, Vol. 33, Issue 2
Heat capacity, thermodynamic properties, and transitions of silver iodide
journal, June 1989
- Shaviv, Roey; Westrum, Edgar F.; Grønvold, Fredrik
- The Journal of Chemical Thermodynamics, Vol. 21, Issue 6
Heat capacity and thermodynamic properties of silver(I) selenide, oP-Ag2Se from 300 to 406 K and of cI-Ag2Se from 406 to 900 K: transitional behavior and formation properties
journal, March 2003
- Grønvold, Fredrik; Stølen, Svein; Semenov, Yuri
- Thermochimica Acta, Vol. 399, Issue 1-2
Anharmonic thermal motion of Ag in AgCrSe2: A high-temperature single-crystal X-ray diffraction study
journal, October 1989
- Van Der Lee, A.; Wiegers, G. A.
- Journal of Solid State Chemistry, Vol. 82, Issue 2
Crystal structures and magnetic structures of some metal(I) chromium(III) sulfides and selenides
journal, April 1973
- Engelsman, F. M. R.; Wiegers, G. A.; Jellinek, F.
- Journal of Solid State Chemistry, Vol. 6, Issue 4
High thermoelectric performance of superionic argyrodite compound Ag 8 SnSe 6
journal, January 2016
- Li, Lin; Liu, Yuan; Dai, Jiyan
- Journal of Materials Chemistry C, Vol. 4, Issue 24
High Electron Mobility and Disorder Induced by Silver Ion Migration Lead to Good Thermoelectric Performance in the Argyrodite Ag 8 SiSe 6
journal, May 2017
- Heep, Barbara K.; Weldert, Kai S.; Krysiak, Yasar
- Chemistry of Materials, Vol. 29, Issue 11
Concerted Rattling in CsAg 5 Te 3 Leading to Ultralow Thermal Conductivity and High Thermoelectric Performance
journal, August 2016
- Lin, Hua; Tan, Gangjian; Shen, Jin-Ni
- Angewandte Chemie International Edition, Vol. 55, Issue 38
Hopping Time Scales and the Phonon-Liquid Electron-Crystal Picture in Thermoelectric Copper Selenide
journal, April 2017
- Voneshen, D. J.; Walker, H. C.; Refson, K.
- Physical Review Letters, Vol. 118, Issue 14
Crystal structure across the β to α phase transition in thermoelectric Cu 2− x Se
journal, June 2017
- Eikeland, Espen; Blichfeld, Anders B.; Borup, Kasper A.
- IUCrJ, Vol. 4, Issue 4
Polycrystalline thin‐film Cu 2− x Se/CdS solar cell
journal, June 1985
- Chen, Wen S.; Stewart, J. M.; Mickelsen, R. A.
- Applied Physics Letters, Vol. 46, Issue 11
Influence of Compensating Defect Formation on the Doping Efficiency and Thermoelectric Properties of Cu 2-y Se 1– x Br x
journal, October 2015
- Day, Tristan W.; Weldert, Kai S.; Zeier, Wolfgang G.
- Chemistry of Materials, Vol. 27, Issue 20
Synthesis of Two New Metallic Alkali Metal Silver Selenides, K2Ag12Se7.11and RbAg5Se3, from Supercritical Ethylenediamine
journal, May 1999
- Emirdag, Mehtap; Schimek, George L.; Pennington, William T.
- Journal of Solid State Chemistry, Vol. 144, Issue 2
Beiträge zu den Stabilitätskriterien des pbFCl-typs: Darstellung und Struktur von KAgSe
journal, August 1981
- Savelsberg, Gerhard; Schäfer, Herbert
- Journal of the Less Common Metals, Vol. 80, Issue 2
K2Ag4Se3, Darstellung und kristallstruktur
journal, February 1982
- Bronger, W.; Schils, H.
- Journal of the Less Common Metals, Vol. 83, Issue 2
Works referencing / citing this record:
Solar light-driven reduction of crystal violet by a composite of g-C 3 N 4 , β-Ag 2 Se, γ-Fe 2 O 3 and graphite
journal, February 2020
- Dante, Roberto C.; Martín-Ramos, Pablo; Chamorro-Posada, Pedro
- Fullerenes, Nanotubes and Carbon Nanostructures, Vol. 28, Issue 7