Control of the Speed of a Light-Induced Spin Transition through Mesoscale Core-Shell Architecture.
The rate of the light-induced spin transition in a coordination polymer network solid dramatically increases when included as the core in mesoscale core-shell particles. A series of photomagnetic coordination polymer core-shell heterostructures, based on the light-switchable Rb aCo b[Fe(CN)6] c· mH2O (RbCoFe-PBA) as core with the isostructural K jNi k[Cr(CN)6] l· nH2O (KNiCr-PBA) as shell, are studied using temperature-dependent powder X-ray diffraction and SQUID magnetometry. The core RbCoFe-PBA exhibits a charge transfer-induced spin transition (CTIST), which can be thermally and optically induced. When coupled to the shell, the rate of the optically induced transition from low spin to high spin increases. Isothermal relaxation from the optically induced high spin state of the core back to the low spin state and activation energies associated with the transition between these states were measured. The presence of a shell decreases the activation energy, which is associated with the elastic properties of the core. Numerical simulations using an electro-elastic model for the spin transition in core-shell particles supports the findings, demonstrating how coupling of the core to the shell changes the elastic properties of the system. The ability to tune the rate of optically induced magnetic and structural phase transitions through control of mesoscale architecture presents a new approach to the development of photoswitchable materials with tailored properties.
Design of Bistable Gold@Spin‐Crossover Core–Shell Nanoparticles Showing Large Electrical Responses for the Spin Switching
A simple chemical protocol to prepare core–shell gold@spin‐crossover (Au@SCO) nanoparticles (NPs) based on the 1D spin‐crossover [Fe(Htrz)2(trz)](BF4) coordination polymer is reported. The synthesis relies on a two‐step approach consisting of a partial surface ligand substitution of the citrate‐stabilized Au NPs followed by the controlled growth of a very thin layer of the SCO polymer. As a result, colloidally stable core@shell spherical NPs with a Au core of ca. 12 nm and a thin SCO shell 4 nm thick, are obtained, exhibiting a narrow distribution in sizes. Differential scanning calorimetry proves that a cooperative spin transition in the range 340–360 K is maintained in these Au@SCO NPs, in full agreement with the values reported for pristine 4 nm SCO NPs. Temperature‐dependent charge‐transport measurements of an electrical device based on assemblies of these Au@SCO NPs also support this spin transition. Thus, a large change in conductance upon spin state switching, as compared with other memory devices based on the pristine SCO NPs, is detected. This results in a large improvement in the sensitivity of the device to the spin transition, with values for the ON/OFF ratio which are an order of magnitude better than the best ones obtained in previous SCO devices.
Anomalous Annealing Behavior of Arsenic Implanted Silicon as a Function of Dose and Energy
Anomalous annealing behavior of damage in As implanted Si has been investigated by channeling effect measurements. Room temperature As implants with doses from 1014 to 2 × 1016cm-2 at energies ranging from 50 to 250 keV into Si were annealed over the range of 600°C to 1100°C. Anneal temperatures ≥ 950°C reduce the disorder for ion doses of 0.5 to 1 × 1016 cm-2 at energies between 50 and 250 keV. Anomalously high residual disorder was found for the intermediate doses of 2 × 1014 to 2 × 10/cm2 implanted above 100 keV. For this intermediate dose, annealing of implants performed at liquid nitrogen temperatures did not show significant reduction in this damage. However implants at 200° to 300°C indicate a lower amount of damage compared to the room temperature implants.