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Co2+-Doping of Magic-Sized CdSe Clusters: Structural Insights via Ligand Field Transitions.
Yang, Jiwoong; Muckel, Franziska; Choi, Back Kyu; Lorenz, Severin; Kim, In Young; Ackermann, Julia; Chang, Hogeun; Czerney, Tamara; Kale, Vinayak S; Hwang, Seong-Ju; Bacher, Gerd; Hyeon, Taeghwan.
Afiliação
  • Yang J; Center for Nanoparticle Research , Institute for Basic Science (IBS) , Seoul 08826 , Republic of Korea.
  • Muckel F; School of Chemical and Biological Engineering and Institute of Chemical Processes , Seoul National University , Seoul 08826 , Republic of Korea.
  • Choi BK; Werkstoffe der Elektrotechnik und CENIDE , University Duisburg-Essen , Bismarckstraße 81 , 47057 Duisburg , Germany.
  • Lorenz S; Center for Nanoparticle Research , Institute for Basic Science (IBS) , Seoul 08826 , Republic of Korea.
  • Kim IY; School of Chemical and Biological Engineering and Institute of Chemical Processes , Seoul National University , Seoul 08826 , Republic of Korea.
  • Ackermann J; Werkstoffe der Elektrotechnik und CENIDE , University Duisburg-Essen , Bismarckstraße 81 , 47057 Duisburg , Germany.
  • Chang H; Center for Hybrid Interfacial Chemical Structure (CICS), Department of Chemistry and Nanoscience , Ewha Womans University , Seoul 03760 , Republic of Korea.
  • Czerney T; Werkstoffe der Elektrotechnik und CENIDE , University Duisburg-Essen , Bismarckstraße 81 , 47057 Duisburg , Germany.
  • Kale VS; Center for Nanoparticle Research , Institute for Basic Science (IBS) , Seoul 08826 , Republic of Korea.
  • Hwang SJ; School of Chemical and Biological Engineering and Institute of Chemical Processes , Seoul National University , Seoul 08826 , Republic of Korea.
  • Bacher G; Werkstoffe der Elektrotechnik und CENIDE , University Duisburg-Essen , Bismarckstraße 81 , 47057 Duisburg , Germany.
  • Hyeon T; Center for Nanoparticle Research , Institute for Basic Science (IBS) , Seoul 08826 , Republic of Korea.
Nano Lett ; 18(11): 7350-7357, 2018 11 14.
Article em En | MEDLINE | ID: mdl-30265545
ABSTRACT
Magic-sized clusters represent materials with unique properties at the border between molecules and solids and provide important insights into the nanocrystal formation process. However, synthesis, doping, and especially structural characterization become more and more challenging with decreasing cluster size. Herein, we report the successful introduction of Co2+ ions into extremely small-sized CdSe clusters with the intention of using internal ligand field transitions to obtain structural insights. Despite the huge mismatch between the radii of Cd2+ and Co2+ ions (>21%), CdSe clusters can be effectively synthesized with a high Co2+ doping concentration of ∼10%. Optical spectroscopy and mass spectrometry suggest that one or two Co2+ ions are substitutionally embedded into (CdSe)13 clusters, which is known as one of the smallest CdSe clusters. Using magnetic circular dichroism spectroscopy on the intrinsic ligand field transitions between the different 3d orbitals of the transition metal dopants, we demonstrate that the Co2+ dopants are embedded on pseudotetrahedral selenium coordinated sites despite the limited number of atoms in the clusters. A significant shortening of Co-Se bond lengths compared to bulk or nanocrystals is observed, which results in the metastability of Co2+ doping. Our results not only extend the doping chemistry of magic-sized semiconductor nanoclusters, but also suggest an effective method to characterize the local structure of these extremely small-sized clusters.
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Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Nano Lett Ano de publicação: 2018 Tipo de documento: Article

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Nano Lett Ano de publicação: 2018 Tipo de documento: Article