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Register a new userMagnetic anisotropy in thin films of Prussian blue analogues
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The magnetic anisotropy of thin (~ 200 nm) and thick (~ 2 $mu$m) films and of polycrystalline (diameters ~ 60 nm) powders of the Prussian blue analogue Rb$_{0.7}$Ni$_{4.0}$[Cr(CN)$_6$]$_{2.9} cdot n$H$_2$O, a ferromagnetic material with $T_c sim 70$ K, have been investigated by magnetization, ESR at 50 GHz and 116 GHz, and variable-temperature x-ray diffraction (XRD). The origin of the anisotropic magnetic response cannot be attributed to the direct influence of the solid support, but the film growth protocol that preserves an organized two-dimensional film is important. In addition, the anisotropy does not arise from an anisotropic g-tensor nor from magneto-lattice variations above and below $T_c$. By considering effects due to magnetic domains and demagnetization factors, the analysis provides reasonable descriptions of the low and high field data, thereby identifying the origin of the magnetic anisotropy.
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Cubic heterostructured (BA) particles of Prussian blue analogues, composed of a shell of ferromagnetic K_{0.3}Ni[Cr(CN)_6]_{0.8} cdot 1.3H_2O (A), Tc ~ 70 K, surrounding a bulk core of photoactive ferrimagnetic Rb_{0.4}Co[Fe(CN)_6]_{0.8} cdot 1.2H_2O (B), Tc ~20 K, have been studied. Below Tc ~ 70 K, these samples exhibit a persistent photoinduced decrease in low-field magnetization, and these results resemble data from other core-shell particles and analogous ABA heterostructured films. This net decrease suggests that the photoinduced lattice expansion in the B layer generates a strain-induced decrease in the magnetization of the A layer, similar to a pressure-induced decrease observed by others in a pure A-like material and by us in our BA cubes. Upon further examination, the data also reveal a significant portion of the A material whose superexchange, J, is perturbed by the photoinduced strain from the B constituent.
Prussian blue analogues (PBAs) are a broad and important family of microporous inorganic solids, famous for their gas storage, metal-ion immobilisation, proton conduction, and stimuli-dependent magnetic, electronic and optical properties. The family also includes the widely-used double-metal cyanide (DMC) catalysts and the topical hexacyanoferrate/hexacyanomanganate (HCF/HCM) battery materials. Central to the various physical properties of PBAs is the ability to transport mass reversibly, a process made possible by structural vacancies. Normally presumed random, vacancy arrangements are actually crucially important because they control the connectivity of the micropore network, and hence diffusivity and adsorption profiles. The long-standing obstacle to characterising PBA vacancy networks has always been the relative inaccessibility of single-crystal samples. Here we report the growth of single crystals of a range of PBAs. By measuring and interpreting their X-ray diffuse scattering patterns, we identify for the first time a striking diversity of non-random vacancy arrangements that is hidden from conventional crystallographic analysis of powder samples. Moreover, we show that this unexpected phase complexity can be understood in terms of a remarkably simple microscopic model based on local rules of electroneutrality and centrosymmetry. The hidden phase boundaries that emerge demarcate vacancy-network polymorphs with profoundly different micropore characteristics. Our results establish a clear foundation for correlated defect engineering in PBAs as a means of controlling storage capacity, anisotropy, and transport efficiency.
Many Prussian Blue Analogues are known to show a thermally induced phase transition close to room temperature and a reversible, photo-induced phase transition at low temperatures. This work reports on magnetic measurements, X-ray photoemission and Raman spectroscopy on a particular class of these molecular heterobimetallic systems, specifically on Rb0.81Mn[Fe(CN)6]0.95_1.24H2O, Rb0.97Mn[Fe(CN)6]0.98_1.03H2O and Rb0.70Cu0.22Mn0.78[Fe(CN)6]0.86_2.05H2O, to investigate these transition phenomena both in the bulk of the material and at the sample surface. Results indicate a high degree of charge transfer in the bulk, while a substantially reduced conversion is found at the sample surface, even in case of a near perfect (Rb:Mn:Fe=1:1:1) stoichiometry. Thus, the intrinsic incompleteness of the charge transfer transition in these materials is found to be primarily due to surface reconstruction. Substitution of a large fraction of charge transfer active Mn ions by charge transfer inactive Cu ions leads to a proportional conversion reduction with respect to the maximum conversion that is still stoichiometrically possible and shows the charge transfer capability of metal centers to be quite robust upon inclusion of a neighboring impurity. Additionally, a 532 nm photo-induced metastable state, reminiscent of the high temperature Fe(III)Mn(II) ground state, is found at temperatures 50-100 K. The efficiency of photo-excitation to the metastable state is found to be maximized around 90 K. The photo-induced state is observed to relax to the low temperature Fe(II)Mn(III) ground state at a temperature of approximately 123 K.
We report electron transport measurements through nano-scale devices consisting of 1 to 3 Prussian blue analog (PBA) nanocrystals connected between two electrodes. We compare two types of cubic nanocrystals, CsCoFe (15 nm) and CsNiCr (6 nm), deposited on highly oriented pyrolytic graphite and contacted by conducting-AFM. The measured currents show an exponential dependence with the length of the PBA nano-device (up to 45 nm), with low decay factors b{eta}, in the range 0.11 - 0.18 nm-1 and 0.25 - 0.34 nm-1 for the CsCoFe and the CsNiCr nanocrystals, respectively. From the theoretical analysis of the current-voltage curve for the nano-scale device made of a single nanoparticle, we deduce that the electron transport is mediated by the localized d bands at around 0.5 eV from the electrode Fermi energy in the two cases. By comparison with previously reported ab-initio calculations, we tentatively identify the involved orbitals as the filled Fe(II)-t2g d band (HOMO) for CsCoFe and the half-filled Ni(II)-eg d band (SOMO) for CsNiCr. Conductance values measured for multi-nanoparticle nano-scale devices (2 and 3 nanocrystals between the electrodes) are consistent with a multi-step coherent tunneling in the off-resonance regime between adjacent PBAs, a simple model gives a strong coupling (around 0.1 - 0.25 eV) between the adjacent PBA nanocrystals, mediated by electrostatic interactions.
The large curvature effects on micromagnetic energy of a thin ferromagnetic film with nonlocal dipolar energy are considered. We predict that the dipolar interaction and surface curvature can produce perpendicular anisotropy which can be controlled by engineering a special type of periodic surface shape structure. Similar effects can be achieved by a significant surface roughness in the film. We show that in general the anisotropy can point in an arbitrary direction depending on the surface curvature. We provide simple examples of these periodic surface structures to demonstrate how to engineer particular anisotropies in the film.
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