Skip to main content
Cu2ZnSnS4 Nanorods Doped with Tetrahedral, High Spin Transition Metal Ions: Mn2+, Co2+, and Ni2+
Chemistry of Materials
  • Michelle J. Thompson, Iowa State University
  • Kyle J. Blakeney, Iowa State University
  • Sarah D. Cady, Iowa State University
  • Malinda D. Reichert, Iowa State University
  • Joselyn Del Pilar-Albaladejo, Iowa State University
  • Seth T. White, Iowa State University
  • Javier Vela, Iowa State University
Document Type
Publication Version
Published Version
Publication Date

Because of its useful optoelectronic properties and the relative abundance of its elements, the quaternary semiconductor Cu2ZnSnS4 (CZTS) has garnered considerable interest in recent years. In this work, we dope divalent, high spin transition metal ions (M2+ = Mn2+, Co2+, Ni2+) into the tetrahedral Zn2+ sites of wurtzite CZTS nanorods. The resulting Cu2MxZn1–xSnS4 (CMTS) nanocrystals retain the hexagonal crystalline structure, elongated morphology, and broad visible light absorption profile of the undoped CZTS nanorods. Electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), and infrared (IR) spectroscopy help corroborate the composition and local ion environment of the doped nanocrystals. EPR shows that, similarly to MnxCd1–xSe, washing Cu2MnxZn1–xSnS4 nanocrystals with trioctylphosphine oxide (TOPO) is an efficient way to remove excess Mn2+ ions from the particle surface. XPS and IR of as-isolated and thiol-washed samples show that, in contrast to binary chalcogenides, Cu2MnxZn1–xSnS4nanocrystals aggregate not through dichalcogenide bonds, but through excess metal ions cross-linking the sulfur-rich surfaces of neighboring particles. Our results may help in expanding the synthetic applicability of CZTS and CMTS materials beyond photovoltaics and into the fields of spintronics and magnetic data storage.


Reprinted with permission from Chemistry of Materials 28 (2016): 1668, doi:10.1021/acs.chemmater.5b04411. Copyright 2016 American Chemical Society.

Copyright Owner
American Chemical Society
File Format
Citation Information
Michelle J. Thompson, Kyle J. Blakeney, Sarah D. Cady, Malinda D. Reichert, et al.. "Cu2ZnSnS4 Nanorods Doped with Tetrahedral, High Spin Transition Metal Ions: Mn2+, Co2+, and Ni2+" Chemistry of Materials Vol. 28 (2016) p. 1668 - 1677
Available at: