The origin of the narrow particle size distributions obtained in the oleic acid-based synthesis of hexagonal phase β-NaREF(4) nanocrystals (RE = Sm, Eu, Gd, Tb) has been investigated. Compared to the standard synthesis, the growth conditions were simplified by using small purified particles of either α-NaREF(4) (cubic phase) or β-NaREF(4) (hexagonal phase) as single-source precursors, thereby avoiding the complications arising from the simultaneous presence of molecular educts and intermediately formed small particles. The study shows that α-phase as well as β-phase particles grow by Ostwald-ripening but narrow particle size distributions of the β-NaREF(4) product particles are only obtained when α-phase precursor particles are employed. Since the small particles are also formed as intermediate products in the standard synthesis of β-NaSmF(4), β-NaEuF(4), β-NaGdF(4) and β-NaTbF(4) particles, their crystal phase is an important parameter to obtain a narrow size distribution in these systems.
We have studied the Ostwald ripening of colloids containing nanocrystals of two different crystal phases of the same material. Ostwald ripening in such polymorphic systems is shown to result in an intrinsic focusing of the particle size distribution of the thermodynamically preferred phase while the particles of the less stable phase completely dissolve. Experimentally, a colloidal system of this kind was realized by mixing small NaEuF4 nanocrystals of the cubic α-phase with particles of the hexagonal β-phase having the same mean size and size distribution. The temporal evolution of the particle sizes of both phases can be understood and numerically simulated within the framework of LSW theory. The simulations show that small differences in the bulk solubility or the surface energy of the two phases are sufficient to explain the experimentally observed narrowing of the particle size distribution.
Doped nanocrystals of NaYF(4) and NaGdF(4) are currently studied as upconversion luminescence markers and magnetic resonance imaging contrast agents. An EPR investigation on the growth mechanism of NaYF(4):Gd and NaGdF(4) nanocrystals showed that these nanomaterials grow in the standard oleic acid-based reaction medium by a dissolution/recrystallization mechanism and not by the aggregation or oriented attachment of smaller particles.
Lanthanide-doped RbY 2 F 7 nanocrystals with a mean diameter of approximately 10 nm were synthesized at 185 °C in the high boiling organic solvent N-(2-hydroxyethyl)-ethylenediamine (HEEDA) using ammonium fluoride, rare earth chlorides, and a solution of rubidium alkoxide of N-(2-hydroxyethyl)-ethylenediamine in HEEDA as precursors. Transmission electron microscopy images of the particles reveal that they are separated but have a broad size distribution ranging from 6 to 22 nm. Heat-treatment of these nanocrystals (600 °C for 45 min) led to bulk material which shows highly efficient light emission upon continuous wave (CW) excitation at 978 nm. As an alternative to the synthesis procedure carried out in the organic solvent HEEDA, we performed a microwave synthesis under hydrothermal conditions. This procedure led to the same composition of the material, but we obtained a marked increase of the particle size (60 nm). Apart from the optical properties, the structure and the morphology as well as the constitution of the three products were investigated by means of powder X-ray diffraction and X-ray fluorescence spectroscopy.
The standard synthesis of the high-pressure polymorph of
LiFePO4 (Cmcm phase) requires pressures
of 65 000 bar and temperatures of 900 °C. Surprisingly,
the nanocrystalline material can be prepared by a simple liquid-phase
synthesis at ambient pressure and 150 °C. Reversible electrochemical
Li-(de)insertion (Δx = 0.2, charge density
= 30 mAh g−1) was found.
A top-down approach, i.e., creating small particles by mechanical force starting from bulk materials, probably presents the most logical approach to particle size reduction and, therefore, top-down techniques are among the first to achieve small particles. A new solvent-free, amazingly simple approach is reported, suitable to achieve nanoparticles and sub-micro particles.
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