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Title: Kinetically Controlled Formation and Decomposition of Metastable [(BiSe)1+δ]m[TiSe2]m Compounds

Abstract

We report that preparing homologous series of compounds allows chemists to rapidly discover new compounds with predictable structure and properties. Synthesizing compounds within such a series involves navigating a free energy landscape defined by the interactions within and between constituent atoms. Historically, synthesis approaches are typically limited to forming only the most thermodynamically stable compound under the reaction conditions. Presented here is the synthesis, via self-assembly of designed precursors, of isocompositional incommensurate layered compounds [(BiSe)1+δ]m[TiSe2]m with m = 1, 2, and 3. The structure of the BiSe bilayer in the m = 1 compound is not that of the binary compound, and this is the first example of compounds where a BiSe layer thicker than a bilayer in heterostructures has been prepared. Specular and in-plane X-ray diffraction combined with high-resolution electron microscopy data was used to follow the formation of the compounds during low-temperature annealing and the subsequent decomposition of the m = 2 and 3 compounds into [(BiSe)1+δ]1[TiSe2]1 at elevated temperatures. These results show that the structure of the precursor can be used to control reaction kinetics, enabling the synthesis of kinetically stable compounds that are not accessible via traditional techniques. Lastly, the data collected as a function ofmore » temperature and time enabled us to schematically construct the topology of the free energy landscape about the local free energy minima for each of the products.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
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  1. Univ. of Oregon, Eugene, OR (United States)
  2. Univ. of Oregon, Eugene, OR (United States) ; Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1422968
Report Number(s):
LA-UR-17-30767
Journal ID: ISSN 0002-7863; TRN: US1801678
Grant/Contract Number:  
AC52-06NA25396; AC05-76RL01830; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 9; 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; 36 MATERIALS SCIENCE; heterostructure; materials chemistry; kinetic product; solid state chemistry

Citation Formats

Lygo, Alexander C., Hamann, Danielle M., Moore, Daniel B., Merrill, Devin R., Ditto, Jeffrey, Esters, Marco, Orlowicz, Jacob, Wood, Suzannah R., and Johnson, David C. Kinetically Controlled Formation and Decomposition of Metastable [(BiSe)1+δ]m[TiSe2]m Compounds. United States: N. p., 2018. Web. doi:10.1021/jacs.7b13398.
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Lygo, Alexander C., Hamann, Danielle M., Moore, Daniel B., Merrill, Devin R., Ditto, Jeffrey, Esters, Marco, Orlowicz, Jacob, Wood, Suzannah R., & Johnson, David C. Kinetically Controlled Formation and Decomposition of Metastable [(BiSe)1+δ]m[TiSe2]m Compounds. United States. https://doi.org/10.1021/jacs.7b13398
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Lygo, Alexander C., Hamann, Danielle M., Moore, Daniel B., Merrill, Devin R., Ditto, Jeffrey, Esters, Marco, Orlowicz, Jacob, Wood, Suzannah R., and Johnson, David C. Mon . "Kinetically Controlled Formation and Decomposition of Metastable [(BiSe)1+δ]m[TiSe2]m Compounds". United States. https://doi.org/10.1021/jacs.7b13398. https://www.osti.gov/servlets/purl/1422968.
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@article{osti_1422968,
title = {Kinetically Controlled Formation and Decomposition of Metastable [(BiSe)1+δ]m[TiSe2]m Compounds},
author = {Lygo, Alexander C. and Hamann, Danielle M. and Moore, Daniel B. and Merrill, Devin R. and Ditto, Jeffrey and Esters, Marco and Orlowicz, Jacob and Wood, Suzannah R. and Johnson, David C.},
abstractNote = {We report that preparing homologous series of compounds allows chemists to rapidly discover new compounds with predictable structure and properties. Synthesizing compounds within such a series involves navigating a free energy landscape defined by the interactions within and between constituent atoms. Historically, synthesis approaches are typically limited to forming only the most thermodynamically stable compound under the reaction conditions. Presented here is the synthesis, via self-assembly of designed precursors, of isocompositional incommensurate layered compounds [(BiSe)1+δ]m[TiSe2]m with m = 1, 2, and 3. The structure of the BiSe bilayer in the m = 1 compound is not that of the binary compound, and this is the first example of compounds where a BiSe layer thicker than a bilayer in heterostructures has been prepared. Specular and in-plane X-ray diffraction combined with high-resolution electron microscopy data was used to follow the formation of the compounds during low-temperature annealing and the subsequent decomposition of the m = 2 and 3 compounds into [(BiSe)1+δ]1[TiSe2]1 at elevated temperatures. These results show that the structure of the precursor can be used to control reaction kinetics, enabling the synthesis of kinetically stable compounds that are not accessible via traditional techniques. Lastly, the data collected as a function of temperature and time enabled us to schematically construct the topology of the free energy landscape about the local free energy minima for each of the products.},
doi = {10.1021/jacs.7b13398},
journal = {Journal of the American Chemical Society},
number = 9,
volume = 140,
place = {United States},
year = {2018},
month = {2}
}
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https://doi.org/10.1021/jacs.7b13398
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Cited by: 13 works
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Figures / Tables:

Figure 1 Figure 1: (a) Specular and (b) in-plane X-ray diffraction patterns for a (Ti-Se)1-(Bi-Se)1 precursor after annealing at each temperature for 30 minutes.
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Works referenced in this record:

Synthesis, structures, and magnetic properties of novel Roddlesden–Popper homologous series Srn+1ConO3n+1 (n=1,2,3,4, and ∞)
journal, May 2005

  • Wang, X. L.; Sakurai, H.; Takayama-Muromachi, E.
  • Journal of Applied Physics, Vol. 97, Issue 10
  • DOI: 10.1063/1.1855534

Epitaxial growth and magnetic properties of the first five members of the layered Srn+1RunO3n+1 oxide series
journal, January 2007

  • Tian, W.; Haeni, J. H.; Schlom, D. G.
  • Applied Physics Letters, Vol. 90, Issue 2
  • DOI: 10.1063/1.2430941

Superconductivity in a layered perovskite without copper
journal, December 1994

  • Maeno, Y.; Hashimoto, H.; Yoshida, K.
  • Nature, Vol. 372, Issue 6506
  • DOI: 10.1038/372532a0

Giant magnetoresistance of manganese oxides with a layered perovskite structure
journal, March 1996

  • Moritomo, Y.; Asamitsu, A.; Kuwahara, H.
  • Nature, Vol. 380, Issue 6570
  • DOI: 10.1038/380141a0

Structural Evolution and Phase Homologies for “Design” and Prediction of Solid-State Compounds
journal, April 2005

  • Kanatzidis, Mercouri G.
  • Accounts of Chemical Research, Vol. 38, Issue 4
  • DOI: 10.1021/ar040176w

Designing New Inorganic Compounds from 2D Building Blocks
journal, December 2004

  • Cario, Laurent; Kabbour, Houria; Meerschaut, Alain
  • Chemistry of Materials, Vol. 17, Issue 2
  • DOI: 10.1021/cm048180p

First Step Towards Planning of Syntheses in Solid-State Chemistry: Determination of Promising Structure Candidates by Global Optimization
journal, July 1996

  • Schön, J. Christian; Jansen, Martin
  • Angewandte Chemie International Edition in English, Vol. 35, Issue 12
  • DOI: 10.1002/anie.199612861

“Design” in Chemical Synthesis—An Illusion?
journal, May 2006

  • Jansen, Martin; Schön, J. Christian
  • Angewandte Chemie International Edition, Vol. 45, Issue 21
  • DOI: 10.1002/anie.200504510

Electronic structure of the misfit-layer compounds PbTiS 3 and SnNbS 3
journal, July 1991

An X-ray photoemission spectroscopy study of interlayer charge transfer in some misfit layer compounds
journal, June 1993

Strong multiple resonances in the photoemission spectra of transition-metal-layer and misfit-layer compounds
journal, May 1993

Electronic structure of the misfit layer compound : band-structure calculations and photoelectron spectra
journal, July 1996

  • Fang, C. M.; Smaalen, S. van; Wiegers, G. A.
  • Journal of Physics: Condensed Matter, Vol. 8, Issue 29
  • DOI: 10.1088/0953-8984/8/29/012

Charge transfer in misfit layered compounds
journal, June 2003

Stabilization of the Misfit Layer Compound ( PbS ) 1.13 TaS 2 by Metal Cross Substitution
journal, February 2008

Cyano-Bridged Re 6 Q 8 (Q = S, Se) Cluster-Metal Framework Solids:  A New Class of Porous Materials
journal, December 1998

  • Beauvais, Laurance G.; Shores, Matthew P.; Long, Jeffrey R.
  • Chemistry of Materials, Vol. 10, Issue 12
  • DOI: 10.1021/cm980564q

Synthesis of Crystalline Superlattices by Controlled Crystallization of Modulated Reactants
journal, November 1995

Heterostructures containing dichalcogenides-new materials with predictable nanoarchitectures and novel emergent properties
journal, August 2017

  • Hamann, Danielle M.; Hadland, Erik C.; Johnson, David C.
  • Semiconductor Science and Technology, Vol. 32, Issue 9
  • DOI: 10.1088/1361-6641/aa7785

The new misfit compound (BiSe)1.15(TiSe2)2 and the role of dimensionality in the Cux(BiSe)1+δ(TiSe2)n series
journal, January 2014

  • Trump, Benjamin A.; Livi, Kenneth J. T.; McQueen, Tyrel M.
  • Journal of Solid State Chemistry, Vol. 209
  • DOI: 10.1016/j.jssc.2013.10.014

Preparation and characterization of Bi-containing ternary chalcogenides with layered composite crystal structure
journal, November 1991

Preparation and Characterization of BiMX 3 (M = Ti, V, Nb, Ta; X = S, Se), New Composite-Layered Chalcogenides
journal, September 1989

  • Gotoh, Yoshito; Onoda, Mitsuko; Uchida, Katsuhiro
  • Chemistry Letters, Vol. 18, Issue 9
  • DOI: 10.1246/cl.1989.1559

Synthesis and characterization of turbostratically disordered (BiSe) 1.15 TiSe 2
journal, May 2014

Synthesis of [(SnSe) 1.15 ] m (TaSe 2 ) n Ferecrystals: Structurally Tunable Metallic Compounds
journal, November 2012

  • Atkins, Ryan; Wilson, Jason; Zschack, Paul
  • Chemistry of Materials, Vol. 24, Issue 23
  • DOI: 10.1021/cm302948x

Determination of the composition of Ultra-thin Ni-Si films on Si: constrained modeling of electron probe microanalysis and x-ray reflectivity data
journal, November 2008

  • Phung, Tran M.; Jensen, Jacob M.; Johnson, David C.
  • X-Ray Spectrometry, Vol. 37, Issue 6
  • DOI: 10.1002/xrs.1102

WinCSD : software package for crystallographic calculations (Version 4)
journal, March 2014

Ab-initio structure determination of LiSbWO6 by X-ray powder diffraction
journal, March 1988

WinPLOTR: A Windows Tool for Powder Diffraction Pattern Analysis
journal, October 2001

Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993

Ultra-thin TEM Sample Preparation with Advanced Backside FIB Milling Method
journal, July 2010

Sample preparation for atomic-resolution STEM at low voltages by FIB
journal, March 2012

Structural refinement of superlattices from x-ray diffraction
journal, April 1992

  • Fullerton, Eric E.; Schuller, Ivan K.; Vanderstraeten, H.
  • Physical Review B, Vol. 45, Issue 16
  • DOI: 10.1103/PhysRevB.45.9292

Size-Dependent Structural Distortions in One-Dimensional Nanostructures
journal, January 2013

  • Anderson, Michael D.; Heideman, Colby L.; Lin, Qiyin
  • Angewandte Chemie International Edition, Vol. 52, Issue 7
  • DOI: 10.1002/anie.201207825

Controlling Size-Induced Phase Transformations Using Chemically Designed Nanolaminates
journal, October 2013

  • Beekman, Matt; Disch, Sabrina; Rouvimov, Sergei
  • Angewandte Chemie International Edition, Vol. 52, Issue 50
  • DOI: 10.1002/anie.201305377

Tuning Electrical Properties through Control of TiSe 2 Thickness in (BiSe) 1+δ (TiSe 2 ) n Compounds
journal, August 2015

Some Defect Structures in Crystalline Solids
journal, August 1974

Antiphase Boundaries in the Turbostratically Disordered Misfit Compound (BiSe) 1+δ NbSe 2
journal, October 2015

Structural Changes in 2D BiSe Bilayers as n Increases in (BiSe) 1+δ (NbSe 2 ) n ( n = 1–4) Heterostructures
journal, September 2016

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    Works referencing / citing this record:

    Non-linear enhancement of thermoelectric performance of a TiSe 2 monolayer due to tensile strain, from first-principles calculations
    journal, January 2019

    • Nayeb Sadeghi, Safoura; Zebarjadi, Mona; Esfarjani, Keivan
    • Journal of Materials Chemistry C, Vol. 7, Issue 24
    • DOI: 10.1039/c9tc00183b
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