skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b13398· OSTI ID:1422968
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  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)
+ Show Author Affiliations

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.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC52-06NA25396; AC05-76RL01830; AC02-06CH11357
OSTI ID:
1422968
Report Number(s):
LA-UR-17-30767; TRN: US1801678
Journal Information:
Journal of the American Chemical Society, Vol. 140, Issue 9; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

References (37)

Synthesis, structures, and magnetic properties of novel Roddlesden–Popper homologous series Srn+1ConO3n+1 (n=1,2,3,4, and ∞) journal May 2005
Epitaxial growth and magnetic properties of the first five members of the layered Srn+1RunO3n+1 oxide series journal January 2007
Superconductivity in a layered perovskite without copper journal December 1994
Giant magnetoresistance of manganese oxides with a layered perovskite structure journal March 1996
Structural Evolution and Phase Homologies for “Design” and Prediction of Solid-State Compounds journal April 2005
Ae 2 Sb 2 X 4 F 2 (Ae = Sr, Ba):  New Members of the Homologous Series Ae 2 M 1+ n X 3+ n F 2 Designed from Rock Salt and Fluorite 2D Building Blocks journal March 2006
Designing New Inorganic Compounds from 2D Building Blocks journal December 2004
First Step Towards Planning of Syntheses in Solid-State Chemistry: Determination of Promising Structure Candidates by Global Optimization journal July 1996
“Design” in Chemical Synthesis—An Illusion? journal May 2006
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
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
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
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
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
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
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
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
Size-Dependent Structural Distortions in One-Dimensional Nanostructures journal January 2013
Controlling Size-Induced Phase Transformations Using Chemically Designed Nanolaminates journal October 2013
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

Cited By (1)

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

Figures / Tables (11)

Figure 1(p. 4)figure Figure 1
Figure 2(p. 5)figure Figure 2
Table 1(p. 5)table Table 1
Figure 3(p. 6)figure Figure 3
Table 2(p. 6)table Table 2
Table 3(p. 7)table Table 3
Figure 4(p. 8)figure Figure 4
Figure 5(p. 8)figure Figure 5
Figure 6(p. 9)figure Figure 6
Figure 7(p. 9)figure Figure 7
Figure 8(p. 9)figure Figure 8

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
heterostructure
materials chemistry
kinetic product
solid state chemistry