Magneto‐Optical Properties of Electrodeposited Thin Films of the Molecule‐Based Magnet Cr5.5(CN)12·11.5H2O

Coronado, Eugenio; Makarewicz, Magdalena; Prieto-Ruiz, Juan P.; Prima-García, Helena; Romero, Francisco M.

doi:10.1002/adma.201101513

Cited by 31 publications

(37 citation statements)

References 30 publications

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“…The ATR-IR spectra showed for all the different thicknesses a principal band located at 2,186 cm −1 corresponding to the cyanide stretching vibration of the [Cr III (CN) 6 3− anion in concordance with the previous results [10]. The IR frequency associated with this specie is independent of the film thickness [11], indicating that the composition of the film is unaltered as the thickness is decreased.…”

Section: Resultssupporting

confidence: 89%

“…During the initial (nucleation) stages of the electrodeposition process, the reaction takes place at the naked surface of the electrode, and its kinetics is only limited by diffusion of the species, resulting in very small particles that cover homogenously the electrode surface. At longer deposition times, the intensity of the electrochemical current decreases, indicating a slower kinetics that results in the growth of the particles as pyramidal microcrystals as has been studied at thicker films of sample (1) [11]. The roughness of the film surface shows a slight increase with the deposition time, passing from a value of 8 nm for the 40-nm thickness film to a value of 10 nm for the 80-nm thickness film.…”

Section: Resultsmentioning

confidence: 94%

“…Optical absorption spectra of the electrodeposited films of 1 [11] and attenuated total reflectance infrared spectra (ATR-IR) have been studied somewhere else. The ATR-IR spectra showed for all the different thicknesses a principal band located at 2,186 cm −1 corresponding to the cyanide stretching vibration of the [Cr III (CN) 6 3− anion in concordance with the previous results [10].…”

Section: Resultsmentioning

confidence: 99%

“…The images were acquired in tapping mode, with a 5 × 5-μm scan sizes for films with different deposition times. For the thicker films, it is possible to distinguish a polycrystalline structure composed of pyramidal particles of different sizes [11]. This type of morphology has been observed in the epitaxial electrodeposition of Prussian blue on Au(110) surface [12].…”

Section: Resultsmentioning

confidence: 99%

“…The magnetic properties of the films at different thickness have been studied somewhere else [11] exhibiting negligible changes on the magnetic properties when changing the film thickness.…”

Section: Resultsmentioning

confidence: 99%

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Tailoring magnetic properties of electrodeposited thin films of the molecule-based magnet Cr5.5(CN)12 11.5H2O

et al. 2012

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This paper reports on molecular-based magnetic thin films of Prussian blue analogues (PBA) with high critical temperatures composed of mixed-valence chromium cyanides. The thin films of PBA were synthesized by means of electrodeposition technique. Morphology and magnetic study are presented in a function of electrochemical deposition conditions. We present the electrochemical methods as a promising and effective tool for preparing molecular-based magnetic thin films of Prussian blue analogue.

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Tailoring magnetic properties of electrodeposited thin films of the molecule-based magnet Cr5.5(CN)12 11.5H2O

et al. 2012

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Thin Films of Solvatomagnetic CN‐Bridged Coordination Polymers: From Micro to Nanoscale

Pacanowska

Fitta

Kozieł

et al. 2022

Adv Materials Inter

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Cyano-bridged coordination polymers constitute an important group of molecule-based magnets. [12][13][14] The CN-bridges mediate relatively strong magnetic interactions and at the same time they allow reasonable control over the self-assembly process and thus the rational design of versatile topologies by the use of appropriate blocking ligands. Moreover, the CN-bridges are robust but bendable, which may give rise to framework flexibility and structural transformations triggered by desolvation or sorption of small molecules. Since the sign and magnitude of magnetic superexchange for many metal ions depend on the geometry of the CN-bridges, the structurally flexible networks often show sorption-driven changes in magnetic characteristics. Porosity is not common in CN-bridged polymers, since the CN-ligands are relatively short. However, it can be introduced by the use of additional long organic bridging ligands or pre-defined complex building blocks acting as linear linkers. Following the later approach, by using Ni II with equatorial positions blocked by the cyclam ligand (cyclam = 1,4,7,11-tetraazacyclotetradecane), a family of microporous 2D networks of characteristic honeycomblike topology, based on hexa-or octa-cyanometallates have been obtained. [15][16][17] Although these coordination polymers do not contain any coordinated solvent molecules, they show unusually rich solvatomagnetic effect, connected with sorption of guest solvent molecules, like water or methanol, into the microporous channels. The structural transformations upon guest inclusion are restricted to changes in bond geometry and the deformation of the coordination skeleton, which retains its original topology. However, even these relatively small structural changes cause marked differences in magnetic properties between different pseudopolymorphic forms. [18] Two isostructural {[Ni II (cyclam)] 3 [M III (CN) 6 ] 2 •nH 2 O}n (M = Cr or Fe) networks proved to be particularly robust and were characterized as two different hydrates and an anhydrous form, with fully reversible interconversion pathways between them. [19] In view of potential applications of the solvatomagnetic effect we decided to find effective methods of surface deposition for the above mentioned networks and investigate if their properties are retained in thin films.Preparation of molecule-based magnetic materials in the form of thin films is an important step toward exploration of their application potential. [20] Compounds in the form of thin films react more efficiently to external stimuli and are more suitable for the construction of molecular devices. Several Two types of thin films differing in thickness and morphology of microporous CN-bridged hybrid organic-inorganic {[Ni II (cyclam)] 3 [M III (CN) 6 ] 2 •nH 2 O}n (M = Cr or Fe, cyclam = 1,4,7,11-tetraazacyclotetradecane) coordination networks are obtained by using physical and chemical deposition techniques. By adsorption on the PET/ITO substrate of the pre-formed nano-sized crystallites from water suspension, films of 1-2...

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Design of Molecular Spintronics Devices Containing Molybdenum Oxide as Hole Injection Layer

Prieto-Ruiz

Miralles

Großmann

et al. 2017

Adv Elect Materials

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by considering the influence of molybdenum oxide (MoO X ) ultrathin films barriers on a ferromagnetic cobalt electrode. We show that the spin polarization of cobalt electrode is maintained for MoO X thickness of up to 3 nm, the work function modification of the cobalt is 1.1 ± 0.1 eV. These results are subsequently used to fabricate a hybrid device that shows MSV effects and emission of light.Molybdenum oxide [16] (MoO X ) is a well-known material in molecular electronics. [16,17] It has been used as hole injection layer (HIL) in molecular optoelectronic devices, [18][19][20][21][22] due to its deep conduction band, which show energies ranging from −5.5 to −6.7 eV, depending on the deposition conditions and surface contaminations. [14] In fact, it has been recently demonstrated [15] that MoO X creates an interfacial dipole in the M/MoO X interface (M = Au, Al, Co) that increases the metal work function. In the particular case of organic light emission devices (OLEDs) this characteristic facilitates the injection of holes to the highest occupied molecular orbital (HOMO) of the emitting organic layer. [14] To study if molybdenum oxide can be used as a metal-oxide barrier in spintronics we have performed spin resolved ultraviolet photoemission spectroscopy [23] (UPS) in a Co/MoO X bilayer. In a first step MoO X layers with different thicknesses (y = 0, 1, 2, 3, 6, and 9 nm) have been thermally evaporated in high vacuum on an Si-SiO 2 /Co (25 nm) substrate and characterized via X-Ray photoemission spectroscopy (XPS) measurements. Figure S1a (Supporting Information) shows the Co 3p spectra for increasing thicknesses of MoO X . The peaks located at 58.3 and 59.7 eV are associated with pristine cobalt and cobalt oxide, respectively. Analysis of the spectra reveals that after 1 nm of MoO X deposition, the cobalt layer is partially oxidized. The same layers are evaluated in the Mo 3d region in Figure S1b-g (Supporting Information). We observe three different oxidation states of molybdenum located [24] at 229.8 (Mo 4+ ), 231.2 (Mo 5+ ), and 232.6 (Mo 6+ ) eV. The latter is only present in layers with MoO X thicknesses above 1 nm. This molybdenum reduction is related with the cobalt oxidation at the interface. This interfacial cobalt oxide layer avoids oxygen diffusion and reaction.In a second step, we have performed the spin-resolved UPS experiments to investigate both the electronic structure at the Co/MoO X interface as well as the effect of the MoO X barrier on the spin polarization of the magnetic electrode. This characterization was done for the same MoO X thicknesses used in the XPS analysis (1 nm), with the aim of evaluating the impact of this parameter on the properties previously mentioned. The same MoO X material employed for the fabrication of the device and XPS study was evaporated directly on top of the Co without breaking the vacuum. The thickness of the MoO X

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Magneto‐Optical Properties of Electrodeposited Thin Films of the Molecule‐Based Magnet Cr_5.5(CN)₁₂·11.5H₂O

Cited by 31 publications

References 30 publications

Tailoring magnetic properties of electrodeposited thin films of the molecule-based magnet Cr5.5(CN)12 11.5H2O

Tailoring magnetic properties of electrodeposited thin films of the molecule-based magnet Cr5.5(CN)12 11.5H2O

Thin Films of Solvatomagnetic CN‐Bridged Coordination Polymers: From Micro to Nanoscale

Design of Molecular Spintronics Devices Containing Molybdenum Oxide as Hole Injection Layer

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