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Manganous ion dictated morphology change and ferromagnetism in CdS nanocrystals

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Abstract

We report a simple chemical route for converting the dimorphic CdS nanocrystals into pure hexagonal structure by loading ~5 % Mn2+ into CdS in presence of a surfactant rather than under harsh conditions reported earlier. Differential scanning calorimetric measurement was used to quantify the percentages of cubic and hexagonal components at lower manganese ion loading, which correlated well with the Short and Steward procedure using X-ray diffraction analysis. Annealing of all lower (<5 %) manganese ion-loaded samples transforms the cubic component into its hexagonal form. Systematic variation of manganese ion concentration in the range of 0–5 % helps tune in a new combination of photoluminescence bands, composed of a band edge, surface and manganese d–d emissions. The manganese ions located inside the CdS matrix studied by electron paramagnetic resonance (EPR) reveal progressively changing presence of (i) distorted tetrahedral nature of isolated Mn2+ and (ii) cluster formation through dipolar and/or exchange coupling arising from Mn2+–Mn2+ interaction. There is a neat correlation between PL and EPR properties on the one hand and between EPR and magnetism on the other. Most important part of this investigation lies in manganese coupled ferromagnetism (FM) as compared to our earlier reported anti-FM-coupled superparamagnetism, the difference originating from the use of different ligands. Pre-annealed (as synthesized) and post-annealed CdS/Mn2+ nanocrystals exhibit FM of manganese origin, the latter exhibiting increased FM due to annealing promoted migration of manganese ions to form more clusters, as confirmed by magnetization experiments. Electron microscopy reveals the formation of nanorods and nanoparticles.

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Acknowledgments

PTM acknowledges the DST, Government of India for a research scheme (SR/S1/RFIC-02/2006) and for the Ramanna Fellowship and Indian National Science Academy for the senior scientistship. He also thanks the IGNOU, Delhi for having offered the Sir C.V. Raman Chair Professorship. Balaji thanks the CSIR for his Senior Research Fellowship. We thank Professor J. Subramanian of CLRI and Dr. J. M. Rifkind and Dr. Maria Selagado of NIA/NIH, Baltimore for help in low temperature EPR measurement. SA wishes to acknowledge DST and UGC, New Delhi for the financial support.

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Authors and Affiliations

  1. Department of Chemistry, Indian Institute of Technology, Madras, Chennai, 600036, India

    Balaji Sambandam, R. Jude Vimal Michael & Periakaruppan T. Manoharan

  2. Department of Chemistry, Anna University, Chennai, 600025, India

    Balaji Sambandam & Nalliyan Rajendran

  3. School of Physics, Centre for High Pressure Research, Bharathidasan University, Tiruchirappalli, 620024, India

    Sonachalam Arumugam

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  1. Balaji Sambandam
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  4. Sonachalam Arumugam
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  5. Periakaruppan T. Manoharan
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Correspondence to Periakaruppan T. Manoharan.

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11051_2012_1067_MOESM1_ESM.doc

Supplementary data file contains: Powder XRD deconvolution for 0.1, 0.5, 1, and 5 % Mn/CdS nanocrystals in the 2θ range of 30°–40°, XRD deconvolution of 5 % Mn/CdS in the 2θ range of 20°–35°, DSC and XRD comparison table, EPR at 300 K for pre-annealed samples, EPR- after bleaching. (DOC 1036 kb)

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Sambandam, B., Michael, R.J.V., Rajendran, N. et al. Manganous ion dictated morphology change and ferromagnetism in CdS nanocrystals. J Nanopart Res 14, 1067 (2012). https://doi.org/10.1007/s11051-012-1067-2

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