Synthesis of colloidal Mn2+:ZnO quantum dots and high-TC ferromagnetic nanocrystalline thin films.
We report the synthesis of colloidal Mn(2+)-doped ZnO (Mn(2+):ZnO) quantum dots and the preparation of room-temperature ferromagnetic nanocrystalline thin films. Mn(2+):ZnO nanocrystals were prepared by a hydrolysis and condensation reaction in DMSO under atmospheric conditions. Synthesis was monitored by electronic absorption and electron paramagnetic resonance (EPR) spectroscopies. Zn(OAc)(2) was found to strongly inhibit oxidation of Mn(2+) by O(2), allowing the synthesis of Mn(2+):ZnO to be performed aerobically. Mn(2+) ions were removed from the surfaces of as-prepared nanocrystals using dodecylamine to yield high-quality internally doped Mn(2+):ZnO colloids of nearly spherical shape and uniform diameter (6.1 +/- 0.7 nm). Simulations of the highly resolved X- and Q-band nanocrystal EPR spectra, combined with quantitative analysis of magnetic susceptibilities, confirmed that the manganese is substitutionally incorporated into the ZnO nanocrystals as Mn(2+) with very homogeneous speciation, differing from bulk Mn(2+):ZnO only in the magnitude of D-strain. Robust ferromagnetism was observed in spin-coated thin films of the nanocrystals, with 300 K saturation moments as large as 1.35 micro(B)/Mn(2+) and T(C) > 350 K. A distinct ferromagnetic resonance signal was observed in the EPR spectra of the ferromagnetic films. The occurrence of ferromagnetism in Mn(2+):ZnO and its dependence on synthetic variables are discussed in the context of these and previous theoretical and experimental results.
Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, USA.
Nick S
NS
Norberg
Kevin R
KR
Kittilstved
James E
JE
Amonette
Ravi K
RK
Kukkadapu
Dana A
DA
Schwartz
Daniel R
DR
Gamelin
D003102:Colloids / Q000737:chemistry; D003460:Crystallization; D004578:Electron Spin Resonance Spectroscopy; D008280:Magnetics; D008345:Manganese / Q000737:chemistry*; D036103:Nanotechnology; D045663:Quantum Dots; D014961:X-Ray Diffraction; D015034:Zinc Oxide / Q000737:chemistry*
D003102:Colloids; D008345:Manganese; D015034:Zinc Oxide