The development of nanocrystals has been intensively pursued, not only for their fundamental scientific interest, but also for many technological applications. The synthesis of monodisperse nanocrystals (size variation <5%) is of key importance, because the properties of these nanocrystals depend strongly on their dimensions. For example, the colour sharpness of semiconductor nanocrystal-based optical devices is strongly dependent on the uniformity of the nanocrystals, and monodisperse magnetic nanocrystals are critical for the next-generation multi-terabit magnetic storage media. For these monodisperse nanocrystals to be used, an economical mass-production method needs to be developed. Unfortunately, however, in most syntheses reported so far, only sub-gram quantities of monodisperse nanocrystals were produced. Uniform-sized nanocrystals of CdSe (refs 10,11) and Au (refs 12,13) have been produced using colloidal chemical synthetic procedures. In addition, monodisperse magnetic nanocrystals such as Fe (refs 14,15), Co (refs 16-18), gamma-Fe(2)O(3) (refs 19,20), and Fe(3)O(4) (refs 21,22) have been synthesized by using various synthetic methods. Here, we report on the ultra-large-scale synthesis of monodisperse nanocrystals using inexpensive and non-toxic metal salts as reactants. We were able to synthesize as much as 40 g of monodisperse nanocrystals in a single reaction, without a size-sorting process. Moreover, the particle size could be controlled simply by varying the experimental conditions. The current synthetic procedure is very general and nanocrystals of many transition metal oxides were successfully synthesized using a very similar procedure.
Uniform and extremely small-sized iron oxide nanoparticles (ESIONs) of < 4 nm were synthesized via the thermal decomposition of iron-oleate complex in the presence of oleyl alcohol. Oleyl alcohol lowered the reaction temperature by reducing iron-oleate complex, resulting in the production of small-sized nanoparticles. XRD pattern of 3 nm-sized nanoparticles revealed maghemite crystal structure. These nanoparticles exhibited very low magnetization derived from the spin-canting effect. The hydrophobic nanoparticles can be easily transformed to water-dispersible and biocompatible nanoparticles by capping with the poly(ethylene glycol)-derivatized phosphine oxide (PO-PEG) ligands. Toxic response was not observed with Fe concentration up to 100 μg/mL in MTT cell proliferation assay of POPEG-capped 3 nm-sized iron oxide nanoparticles. The 3 nm-sized nanoparticles exhibited a high r(1) relaxivity of 4.78 mM(-1) s(-1) and low r(2)/r(1) ratio of 6.12, demonstrating that ESIONs can be efficient T(1) contrast agents. The high r(1) relaxivities of ESIONs can be attributed to the large number of surface Fe(3+) ions with 5 unpaired valence electrons. In the in vivo T(1)-weighted magnetic resonance imaging (MRI), ESIONs showed longer circulation time than the clinically used gadolinium complex-based contrast agent, enabling high-resolution imaging. High-resolution blood pool MR imaging using ESIONs enabled clear observation of various blood vessels with sizes down to 0.2 mm. These results demonstrate the potential of ESIONs as T(1) MRI contrast agents in clinical settings.
Magnetism in two-dimensional materials is not only of fundamental scientific interest but also a promising candidate for numerous applications. However, studies so far, especially the experimental ones, have been mostly limited to the magnetism arising from defects, vacancies, edges or chemical dopants which are all extrinsic effects. Here, we report on the observation of intrinsic antiferromagnetic ordering in the two-dimensional limit. By monitoring the Raman peaks that arise from zone folding due to antiferromagnetic ordering at the transition temperature, we demonstrate that FePS3 exhibits an Ising-type antiferromagnetic ordering down to the monolayer limit, in good agreement with the Onsager solution for two-dimensional order-disorder transition.The transition temperature remains almost independent of the thickness from bulk to the 2 monolayer limit with TN ~118 K, indicating that the weak interlayer interaction has little effect on the antiferromagnetic ordering. KEYWORDSIsing model, Antiferromagentism, Magnetic ordering in 2 Dimension, FePS3, Iron phosphorus trisulfide, Raman spectroscopy 3 Magnetism has played an important role in advancing our understanding of the quantum nature of materials. Especially, low-dimensional magnetism has been a fertile playground, in which novel physical concepts have been learned and thereby moved the frontiers of the modern understanding of materials science. Most of the three-dimensional magnetic systems, other than some exceptional cases of quantum spin and/or strong frustration, host a magnetic order. On the other hand, fluctuations are so strong and easily destroy stabilization of order parameters in onedimensional systems as pointed out in the seminal work by Bethe. 1 Two-dimensional (2D) systems, on the other hand, have attracted much attention because the presence or absence of long-range order depends on the type of spin-spin interactions, which themselves compete with intrinsic fluctuations of either quantum and/or thermal nature.The XXZ Hamiltonian reads 2 ( )where XY J and I J are spin-exchange energies on the basal plane and along the c-axis, respectively; using an order-converting dual transformation that unlike the 1D system there is a phase transition at a finite temperature in the 2D Ising system. 4 Therefore, ferromagnetic or antiferromagnetic ordering in the 2D limit is possible only in the Ising model. There has been some indirect test of this prediction including the most notable one by Kim and Chan using CH4 molecules adsorbed 4 on graphite. 5 However, despite its fundamental importance, there has been no experimental work using a real 2D magnetic material.2D van der Waals (vdW) materials could be an ideal system for the study of 2D magnetism. 6 Unfortunately, however, finding suitable vdW materials and producing atomically thin magnetic materials have been a challenge. Although there have been a few reports of producing atomically thin samples of magnetic materials, 7-10 observation of magnetic ordering in the atomically thin limit has been l...
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