Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals

Huang, Xin1; Suit, Elizabeth1; Zhu, Jinlong2; Ge, Binghui3; Gerdes, Frauke4; Klinke, Christian5,6; Wang, Zhongwu1

2023-02-01

10.1021/jacs.2c11120

Journal of the American Chemical Society   Impact Factor & Quartile

0002-7863

1520-5126

Diffusion-mediated assembly of octahedral PbS nanocrystals (NCs) in a confined antisolvent environment displays a primary burst nucleation and Ostwald ripening growth of rhombic bcc supercrystals, followed by a secondary seed-based nucleation and oriented attachment growth of triangle fcc supercrystals. As the diffusion proceeds from ethanol across a sharp interface into NC-suspended toluene, a burst nucleation of supercrystal seeds occurs, and such supercrystals are quickly developed into rhombic grains that have a bcc structure. At a critical size of 10 mu m, an Ostwald ripening event appears to guide the supercrystal growth. Upon grain growth above 30 mu m, the fcc supercrystals start a nucleation at two symmetrical tips of individual rhombic crystals. Such fcc supercrystals are developed with a triangle shape, and two triangles are combined with one bcc rhombus in-between to form a butterfly-like bowtie stacking structure. The fcc triangle wings grow larger at a reduction of bcc rhombus cores. As the bcc cores gradually fade, such butterfly-like bowtie crystals aggregate and undergo an oriented attachment process, leading to the formation of freestanding 3D triangle crystals that have a single fcc lattice. Analysis of experimental observations and defined diffusion parameters reveals that fast solvent diffusion and high-NC concentration promote the growth of rhombic bcc supercrystals, while slow solvent diffusion and low-NC concentration accelerate the development of triangle fcc supercrystals. Upon succeeding in designable growth of 3D fcc supercrystals, this study provides designing principles for controlled fabrication of supercrystals with desired superlattices for additional engineering and applications.

SCI

English

NI Journal Papers ; NI论文

Non-SUSTech

NSF["DMR-1332208","DMR-1829070"] ; NSF MRSEC program[DMR-1719875]

Chemistry

Chemistry, Multidisciplinary

WOS:000933923500001

AMER CHEMICAL SOC

Web of Science

1.Cornell Univ, Cornell High Energy Synchrotron Source, Ithaca, NY 14853 USA
2.South Univ Sci & Technol, Dept Phys, Shenzhen 518055, Guangdong, Peoples R China
3.Anhui Univ, Inst Phys Sci & Informat Technol, Key Lab Struct Funct Regulat Hybrid Mat, Minist Educ, Hefei 230601, Anhui, Peoples R China
4.Univ Hamburg, Inst Phys Chem, D-20146 Hamburg, Germany
5.Univ Rostock, Inst Phys, D-18059 Rostock, Germany
6.Swansea Univ, Dept Chem, Singleton Pk, Swansea, Wales

Huang, Xin,Suit, Elizabeth,Zhu, Jinlong,et al. Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals[J]. Journal of the American Chemical Society,2023.

Huang, Xin.,Suit, Elizabeth.,Zhu, Jinlong.,Ge, Binghui.,Gerdes, Frauke.,...&Wang, Zhongwu.(2023).Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals.Journal of the American Chemical Society.

Huang, Xin,et al."Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals".Journal of the American Chemical Society (2023).