4.8 Article

Chiral Magneto-Optical Properties of Supra-Assembled Fe3O4 Nanoparticles

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 13, Issue 45, Pages 54301-54307

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.1c16954

Keywords

chirality; magneto-optical property; magnetite; supra-assembly; magnetic circular dichroism

Funding

  1. National Research Foundation of Korea (NRF) - Korea Government (Ministry of Science and ICT) [NRF-2021R1A2C4002523, NRF-2019R1A4A1027627]
  2. Korea Institute of Science and Technology (KIST) Institutional Program [2V08210]
  3. Korea Institute of Energy Technology Evaluation and Planning (KETEP) of the Republic of Korea [20202020800330]
  4. Ministry of Trade, Industry & Energy (MOTIE) of the Republic of Korea [20202020800330]
  5. Korea Evaluation Institute of Industrial Technology (KEIT) [20202020800330] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)

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Research on the chiral magneto-optical properties of inorganic nanomaterials has shown enhanced activity in the visible range when using supra-assembled Fe3O4 magnetite nanoparticles at weak magnetic fields of 1.5 mT. The differences in magnetic circular dichroism responses are attributed to crystallinity, lattice distortion near grain boundaries, and dipolar interactions in the supra-assembled structures.
Research on the chiral magneto-optical properties of inorganic nanomaterials has enabled novel applications in advanced optical and electronic devices. However, the corresponding chiral magneto-optical responses have only been studied under strong magnetic fields of >= 1 T, which limits the wider application of these novel materials. In this paper, we report on the enhanced chiral magneto-optical activity of supra-assembled Fe3O4 magnetite nanoparticles in the visible range at weak magnetic fields of 1.5 mT. The spherical supra-assembled particles with a diameter of similar to 90 nm prepared by solvothermal synthesis had single-crystal-like structures, which resulted from the oriented attachment of nanograins. They exhibited superparamagnetic behavior even with a relatively large supraparticle diameter that exceeded the size limit for superparamagnetism. This can be attributed to the small size of nanograins with a diameter of similar to 12 nm that constitute the suprastructured particles. Magnetic circular dichroism (MCD) measurements at magnetic fields of 1.5 mT showed distinct chiral magneto-optical activity from charge transfer transitions of magnetite in the visible range. For the supraparticles with lower crystallinity, the MCD peaks in the 250-550 nm range assigned as the ligand-to-metal charge transfer (LMCT) and the inter-sublattice charge transfer (ISCT) show increased intensities in comparison to those with higher crystallinity samples. On the contrary, the higher crystallinity sample shows higher MCD intensities near 600-700 nm for the intervalence charge transfer (IVCT) transition. The differences in MCD responses can be attributed to the crystallinity determined by the reaction time, lattice distortion near grain boundaries of the constituent nanocrystals, and dipolar interactions in the supra-assembled structures.

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