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Title: Design and synthesis of multigrain nanocrystals via geometric misfit strain

Journal Article · · Nature (London)
 [1];  [2];  [2];  [3];  [4];  [5];  [6];  [7];  [8];  [9];  [2];  [2];  [2];  [4];  [10];  [2];  [11];  [2]
  1. Inst. for Basic Science (IBS), Seoul (Korea, Republic of). Center for Nanoparticle Research; Seoul National Univ. (Korea, Republic of); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Kavli Energy NanoScience Institute, Berkeley, CA (United States)
  2. Inst. for Basic Science (IBS), Seoul (Korea, Republic of). Center for Nanoparticle Research; Seoul National Univ. (Korea, Republic of)
  3. Inst. for Basic Science (IBS), Seoul (Korea, Republic of). Center for Nanoparticle Research; Seoul National Univ. (Korea, Republic of). Research Institute of Advanced Materials (RIAM)
  4. Univ. of California, Berkeley, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  6. Inst. for Basic Science (IBS), Seoul (Korea, Republic of). Center for Nanoparticle Research; Seoul National Univ. (Korea, Republic of); Hanyang Univ., Seoul (Korea, Republic of)
  7. Pohang Accelerator Lab. (PAL) (Korea, Republic of); Pohang Univ. of Science and Technology (POSTECH) (Korea, Republic of)
  8. Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)
  9. Stanford Univ., CA (United States)
  10. Inst. for Basic Science (IBS), Seoul (Korea, Republic of). Center for Nanoparticle Research; Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)
  11. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Kavli Energy NanoScience Institute, Berkeley, CA (United States)

The impact of topological defects associated with grain boundaries (GB defects) on the electrical, optical, magnetic, mechanical and chemical properties of nanocrystalline materials is well known. Yet, elucidating this influence experimentally is difficult because grains typically exhibit a large range of sizes, shapes and random relative orientations. Here we demonstrate that precise control of the heteroepitaxy of colloidal polyhedral nanocrystals enables ordered grain growth and can thereby produce material samples with uniform GB defects. We highlight our approach with a multigrain nanocrystal comprising a Co3O4 nanocube core that carries a Mn3O4 shell on each facet. The individual shells are symmetry-related interconnected grains, and the large geometric misfit between adjacent tetragonal Mn3O4 grains results in tilt boundaries at the sharp edges of the Co3O4 nanocube core that join via disclinations. We identify four design principles that govern the production of these highly ordered multigrain nanostructures. First, the shape of the substrate nanocrystal must guide the crystallographic orientation of the overgrowth phase. Second, the size of the substrate must be smaller than the characteristic distance between the dislocations. Third, the incompatible symmetry between the overgrowth phase and the substrate increases the geometric misfit strain between the grains. Fourth, for GB formation under near-equilibrium conditions, the surface energy of the shell needs to be balanced by the increasing elastic energy through ligand passivation. With these principles, we can produce a range of multigrain nanocrystals containing distinct GB defects.

Research Organization:
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1619158
Journal Information:
Nature (London), Vol. 577, Issue 7790; ISSN 0028-0836
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (28)

Multiferroic Heterostructures Integrating Ferroelectric and Magnetic Materials journal November 2015
Domain Wall Architecture in Tetragonal Ferroelectric Thin Films journal December 2016
Atomimetic Mechanical Structures with Nonlinear Topological Domain Evolution Kinetics journal March 2017
Functional Materials Under Stress: In Situ TEM Observations of Structural Evolution journal November 2019
Intrinsic ferroelectric switching from first principles journal June 2016
Atomic mechanism of polarization-controlled surface reconstruction in ferroelectric thin films journal April 2016
Microwave a.c. conductivity of domain walls in ferroelectric thin films journal May 2016
Semiconductor/relaxor 0–3 type composites without thermal depolarization in Bi0.5Na0.5TiO3-based lead-free piezoceramics journal March 2015
Ferroelectric polarization reversal via successive ferroelastic transitions journal October 2014
Highly mobile ferroelastic domain walls in compositionally graded ferroelectric thin films journal February 2016
Manipulating topological transformations of polar structures through real-time observation of the dynamic polarization evolution journal October 2019
Physics and applications of charged domain walls journal November 2018
Atomic-scale mapping of dipole frustration at 90° charged domain walls in ferroelectric PbTiO3 films journal February 2014
Anomalous piezoelectric response of ferroelectric mesocrystalline BaTiO 3 /Bi 0.5 Na 0.5 TiO 3 nanocomposites designed by strain engineering journal January 2018
Mechanical switching in ferroelectrics by shear stress and its implications on charged domain wall generation and vortex memory devices journal January 2018
Formation of polarization needle-like domain and its unusual switching in compositionally graded ferroelectric thin films: an improved phase field model journal January 2019
A new ferroelastic hybrid material with a large spontaneous strain: (Me 3 NOH) 2 [ZnCl 4 ] journal January 2019
Seeing atomic-scale structural origins and foreseeing new pathways to improved thermoelectric materials journal January 2019
First-principles study of charged steps on 180° domain walls in ferroelectric PbTiO 3 journal August 2017
Superdomain dynamics in ferroelectric-ferroelastic films: Switching, jamming, and relaxation journal December 2017
Stress-induced reversible and irreversible ferroelectric domain switching journal April 2018
Atomically resolved domain boundary structure in lead zirconate-based antiferroelectrics journal September 2019
Local deformation gradients in epitaxial Pb(Zr 0.2 Ti 0.8 )O 3 layers investigated by transmission electron microscopy journal April 2018
Real-time studies of ferroelectric domain switching: a review journal November 2019
Facilitation of Ferroelectric Switching via Mechanical Manipulation of Hierarchical Nanoscale Domain Structures journal January 2017
Atomic-Scale Measurement of Flexoelectric Polarization at SrTiO 3 Dislocations journal June 2018
Periodicity-Doubling Cascades: Direct Observation in Ferroelastic Materials. text January 2019
Operando Imaging of All-Electric Spin Texture Manipulation in Ferroelectric and Multiferroic Rashba Semiconductors text January 2018

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