In Situ Constructing the Kinetic Roadmap of Octahedral Nanocrystal Assembly Toward Controlled Superlattice Fabrication

Huang，Xin1; Zhu，Jinlong2; Ge，Binghui3; Gerdes，Frauke4; Klinke，Christian5,6; Wang，Zhongwu1

2021

10.1021/jacs.0c12087

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

Crystallization and growth of anisotropic nanocrystals (NCs) into distinct superlattices were studied in real time, yielding kinetic details and designer parameters for scale-up fabrication of functional materials. Using octahedral PbS NC blocks, we discovered that NC assembly involves a primary lamellar ordering of NC-detached Pb(OA)2 molecules on the front-spreading solvent surfaces. Upon a spontaneous increase of NC concentration during solvent processing, PbS NCs preferentially self-assembled into an orientation-disordered face-centered cubic (fcc) superlattice, which subsequently transformed into a body-centered cubic (bcc) superlattice with single NC-orientational ordering across individual domains. Unlike the deformation-based transformation route claimed previously, this solid-solid phase transformation involved a hidden intermediate formation of a lamellar-confined liquid interface at cost of the disassembly (melting) of small fcc grains. Such highly condensed and liquidized NCs recrystallized into the stable bcc phase with an energy reduction of 1.16 kBT. This energy-favorable and high NC-fraction-driven bcc phase grew as a 2D film at a propagation rate of 0.74 μm/min, smaller than the 1.23 μm/min observed in the early nucleated fcc phase under a dilute NC environment. Taking such insights and defined parameters, we designed experiments to manipulate the NC assembly pathway and achieved scalable fabrication of a large/single bcc supercrystal with coherent ordering of NC translation and atomic plane orientation. This study not only provides a design avenue for controllable fabrication of a large supercrystal with desired superlattices for application but also sheds new light on the nature of crystal nucleation/growth and phase transformation by extending the lengths from the nanoscale into the atomic scale, molecular scale, and microscale levels.

SCI ; EI

英语

NI期刊

其他

NSF["DMR-1332208","DMR-1829070"] ; Center for Alkaline-Based Energy Solutions (CABES) - U.S. Department of Energy[DE-SC0019445] ; NSF MRSEC program[DMR-1719875]

Chemistry

Chemistry, Multidisciplinary

WOS:000634761500023

AMER CHEMICAL SOC

20211410168796

Chromium compounds ; Fabrication ; Functional materials ; IV-VI semiconductors ; Molecules ; Nanocrystals ; Phase interfaces ; Phase transitions

Nanotechnology:761 ; Physical Chemistry:801.4 ; Atomic and Molecular Physics:931.3 ; Materials Science:951

2-s2.0-85103439291

Scopus

1.Cornell High Energy Synchrotron Source,Cornell University,Ithaca,14853,United States
2.Department of Physics,South University of Science and Technology,Shenzhen, Guangdong,518055,China
3.Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education,Institutes of Physical Science and Information Technology,Anhui University,Hefei, Anhui,230601,China
4.Institute of Physical Chemistry,University of Hamburg,Hamburg,20146,Germany
5.Institute of Physics,University of Rostock,Rostock,18059,Germany
6.Department of Chemistry,Swansea University,Singleton Park,Swansea,SA2 8PP,United Kingdom

Huang，Xin,Zhu，Jinlong,Ge，Binghui,et al. In Situ Constructing the Kinetic Roadmap of Octahedral Nanocrystal Assembly Toward Controlled Superlattice Fabrication[J]. Journal of the American Chemical Society,2021,143(11):4234-4243.

Huang，Xin,Zhu，Jinlong,Ge，Binghui,Gerdes，Frauke,Klinke，Christian,&Wang，Zhongwu.(2021).In Situ Constructing the Kinetic Roadmap of Octahedral Nanocrystal Assembly Toward Controlled Superlattice Fabrication.Journal of the American Chemical Society,143(11),4234-4243.

Huang，Xin,et al."In Situ Constructing the Kinetic Roadmap of Octahedral Nanocrystal Assembly Toward Controlled Superlattice Fabrication".Journal of the American Chemical Society 143.11(2021):4234-4243.