Spin-on spintronics: ultrafast electron spin dynamics in ZnO and Zn1-xCoxO sol-gel films.

We use time-resolved Faraday rotation spectroscopy to probe the electron spin dynamics in ZnO and magnetically doped Zn(1-x)Co(x)O sol-gel thin films. In undoped ZnO, we observe an anomalous temperature dependence of the ensemble spin dephasing time T(2), i.e., longer coherence times at higher temperatures, reaching T(2) ∼ 1.2 ns at room temperature. Time-resolved transmission measurements suggest that this effect arises from hole trapping at grain surfaces. Deliberate addition of Co(2+) to ZnO increases the effective electron Landé g factor, providing the first direct determination of the mean-field electron-Co(2+) exchange energy in Zn(1-x)Co(x)O (N(0)α = +0.25 ± 0.02 eV). In Zn(1-x)Co(x)O, T(2) also increases with increasing temperature, allowing spin precession to be observed even at room temperature.

Electron transfer between colloidal ZnO nanocrystals.

Colloidal ZnO nanocrystals capped with dodecylamine and dissolved in toluene can be charged photochemically to give stable solutions in which electrons are present in the conduction bands of the nanocrystals. These conduction-band electrons are readily monitored by EPR spectroscopy, with g* values that correlate with the nanocrystal sizes. Mixing a solution of charged small nanocrystals (e(-)(CB):ZnO-S) with a solution of uncharged large nanocrystals (ZnO-L) caused changes in the EPR spectrum indicative of quantitative electron transfer from small to large nanocrystals. EPR spectra of the reverse reaction, e(-)(CB):ZnO-L + ZnO-S, showed that electrons do not transfer from large to small nanocrystals. Stopped-flow kinetics studies monitoring the change in the UV band-edge absorption showed that reactions of 50 µM nanocrystals were complete within the 5 ms mixing time of the instrument. Similar results were obtained for the reaction of charged nanocrystals with methyl viologen (MV(2+)). These and related results indicate that the electron-transfer reactions of these colloidal nanocrystals are quantitative and very rapid, despite the presence of ~1.5 nm long dodecylamine capping ligands. These soluble ZnO nanocrystals are thus well-defined redox reagents suitable for studies of electron transfer involving semiconductor nanostructures.

Charge-controlled magnetism in colloidal doped semiconductor nanocrystals.

Electrical control over the magnetic states of doped semiconductor nanostructures could enable new spin-based information processing technologies. To this end, extensive research has recently been devoted to examination of carrier-mediated magnetic ordering effects in substrate-supported quantum dots at cryogenic temperatures, with carriers introduced transiently by photon absorption. The relatively weak interactions found between dopants and charge carriers have suggested that gated magnetism in quantum dots will be limited to cryogenic temperatures. Here, we report the observation of a large, reversible, room-temperature magnetic response to charge state in free-standing colloidal ZnO nanocrystals doped with Mn(2+) ions. Injected electrons activate new ferromagnetic Mn(2+)-Mn(2+) interactions that are strong enough to overcome antiferromagnetic coupling between nearest-neighbour dopants, making the full magnetic moments of all dopants observable. Analysis shows that this large effect occurs in spite of small pairwise electron-Mn(2+) exchange energies, because of competing electron-mediated ferromagnetic interactions involving distant Mn(2+) ions in the same nanocrystal.

Ultrafast spin dynamics in colloidal ZnO quantum dots.

Time-resolved Faraday rotation measurements in the ultraviolet have been performed to reveal the ultrafast spin dynamics of electrons in colloidal ZnO quantum dots. Oscillating Faraday rotation signals are detected at frequencies corresponding to an effective g factor of g = 1.96. Biexponential oscillation decay is observed that is due to (i) rapid depopulation of the fundamental exciton (tau = 250 ps) and (ii) slow electron spin dephasing ( T 2 = 1.2 ns) within a metastable state formed by hole-trapping at the quantum dot surface.

Colloidal ZnO quantum dots in ultraviolet pillar microcavities.

Three dimensional light confinement and distinct pillar microcavity modes in the ultraviolet have been observed in pillar resonators with embedded colloidal ZnO quantum dots fabricated by focused ion beam milling. Results from a waveguide model for the mode patterns and their spectral positions are in excellent agreement with the experimental data.

Room-temperature electron spin dynamics in free-standing ZnO quantum dots.

Conduction band electrons in colloidal ZnO quantum dots have been prepared photochemically and examined by electron paramagnetic resonance spectroscopy. Nanocrystals of 4.6 nm diameter containing single S-shell conduction band electrons have g(*)=1.962 and a room-temperature ensemble spin-dephasing time of T(2)(*)=25 ns, as determined from linewidth analysis. Increasing the electron population leads to increased g(*) and decreased T(2)(*), both associated with formation of P-shell configurations. A clear relationship between T(2)(*) and hyperfine coupling with 67Zn(I=5/2) is observed.

Stable photogenerated carriers in magnetic semiconductor nanocrystals.

We report the preparation and investigation of charged colloidal Co2+:ZnO and Mn2+:ZnO nanocrystals. Although both charged and magnetically doped colloidal semiconductor nanocrystals have been reported previously, colloidal charged and magnetically doped semiconductor nanocrystals as described herein have not. Conduction band electrons were introduced into colloidal ZnO diluted magnetic semiconductor (DMS) nanocrystals photochemically, and the resulting TM2+-e-CB interactions were observed by electron paramagnetic resonance spectroscopy (TM2+ = Co2+ or Mn2+). This new motif of colloidal charged magnetic semiconductor nanocrystals reveals attractive new opportunities for studying spin effects in DMS nanostructures relevant to proposed spintronics technologies.