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Here, we examine the conductance changes associated with the change in spin state in a variety of different structures, using the example of the spin crossover complex [Fe(H2B(pz)2)2(bipy)] (pz = (pyrazol-1-yl)-borate and bipy = 2,2′-bipyridine) and [Fe(Htrz)2(trz)](BF4)] (Htrz = 1H-1,2,4-triazole) thin films. This conductance change is highly variable depending on the mechanism driving the change in spin state, the substrate, and the device geometry. Simply stated, the choice of spin crossover complex used to build a device is not the only factor in determining the change in conductance with the change in spin state.more » « less
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Abstract In an effort to reconcile the various interpretations for the cation components of the 2p3/2observed in x-ray photoelectron spectroscopy (XPS) of several spinel oxide materials, the XPS spectra of both spinel alloy nanoparticles and crystalline thin films are compared. We observed that different components of the 2p3/2core level XPS spectra, of these inverse spinel thin films, are distinctly surface and bulk weighted, indicating surface-to-bulk core level shifts in the binding energies. Surface-to-bulk core level shifts in binding energies of Ni and Fe 2p3/2core levels of NiFe2O4thin film are observed in angle-resolved XPS. The ratio between surface-weighted components and bulk-weighted components of the Ni and Fe core levels shows appreciable dependency on photoemission angle, with respect to surface normal. XPS showed that the ferrite nanoparticles NixCo1−xFe2O4(x= 0.2, 0.5, 0.8, 1) resemble the surface of the NiFe2O4thin film. Surface-to-bulk core level shifts are also observed in CoFe2O4and NiCo2O4thin films but not as significantly as in NiFe2O4thin film. Estimates of surface stoichiometry of some spinel oxide nanoparticles and thin films suggested that the apportionment between cationic species present could be farther from expectations for thin films as compared to what is seen with nanoparticles.more » « less
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Spin crossover complexes are a route toward designing molecular devices with a facile readout due to the change in conductance that accompanies the change in spin state. Because substrate effects are important for any molecular device, there are increased efforts to characterize the influence of the substrate on the spin state transition. Several classes of spin crossover molecules deposited on different types of surface, including metallic and non-metallic substrates, are comprehensively reviewed here. While some non-metallic substrates like graphite seem to be promising from experimental measurements, theoretical and experimental studies indicate that 2D semiconductor surfaces will have minimum interaction with spin crossover molecules. Most metallic substrates, such as Au and Cu, tend to suppress changes in spin state and affect the spin state switching process due to the interaction at the molecule–substrate interface that lock spin crossover molecules in a particular spin state or mixed spin state. Of course, the influence of the substrate on a spin crossover thin film depends on the molecular film thickness and perhaps the method used to deposit the molecular film.more » « less
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NiCo2O4 (NCO) films grown on MgAl2O4 (001) substrates have been studied using magnetometry and x-ray magnetic circular dichroism based on x-ray absorption spectroscopy and spin-polarized inverse photoemission spectroscopy with various thicknesses down to 1.6 nm. The magnetic behavior can be understood in terms of a layer of optimal NCO and an interfacial layer (1.2 ± 0.1 nm), with a small canting of magnetization at the surface. The thickness dependence of the optimal layer can be described by the finite-scaling theory with a critical exponent consistent with the high perpendicular magnetic anisotropy. The interfacial layer couples antiferromagnetically to the optimal layer, generating exchange-spring styled magnetic hysteresis in the thinnest films. The non-optimal and measurement-speed-dependent magnetic properties of the interfacial layer suggest substantial interfacial diffusion.more » « less
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The coordination chemistry of uranyl ions with surface immobilized peptides was studied using X-ray photoemission spectroscopy (XPS). All the peptides in the study were modified using a six-carbon alkanethiol as a linker on a gold substrate with methylene blue as the redox label. The X-ray photoemission spectra reveal that each modified peptide interacts differently with the uranyl ion. For all the modified peptides, the XPS spectra were taken in both the absence and presence of the uranium, and their comparison reveals that the interaction depends on the chemical group present in the peptides. The XPS results show that, among all the modified peptides in the current study, the (arginine)9 (R9) modified peptide showed the largest response to uranium. In the order of response to uranium, the second largest response was shown by the modified (arginine)6 (R6) peptide followed by the modified (lysine)6 (K6) peptide. Other modified peptides, (alanine)6 (A6), (glutamic acid)6 (E6) and (serine)6 (S6), did not show any response to uranium.more » « less
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Abstract Adding Fe3O4nanoparticles to composites of [Fe(Htrz)2(trz)](BF4) spin-crossover polymer and polyaniline (PANI) drives a phase separation of both and restores the molecular structure and cooperative effects of the spin-crossover polymer without compromising the increased conductivity gained through the addition of PANI. We observe an increased on-off ratio for the DC conductivity owing to an enlarged off state resistivity and a 20 times larger AC conductivity of the on state compared with DC values. The Fe3O4nanoparticles, primarily confined to the [Fe(Htrz)2(trz)](BF4) phase, are ferromagnetically coupled to the local moment of the spin-crossover molecule suggesting the existence of an exchange interaction between both components.more » « less
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Abstract Transition metal trichalcogenides (TMTs) are two-dimensional (2D) systems with quasi-one-dimensional (quasi-1D) chains. These 2D materials are less susceptible to undesirable edge defects, which enhances their promise for low-dimensional optical and electronic device applications. However, so far, the performance of 2D devices based on TMTs has been hampered by contact-related issues. Therefore, in this review, a diligent effort has been made to both elucidate and summarize the interfacial interactions between gold and various TMTs, namely, In4Se3, TiS3, ZrS3, HfS3, and HfSe3. X-ray photoemission spectroscopy data, supported by the results of electrical transport measurements, provide insights into the nature of interactions at the Au/In4Se3, Au/TiS3, Au/ZrS3, Au/HfS3, and Au/HfSe3interfaces. This may help identify and pave a path toward resolving the contemporary contact-related problems that have plagued the performance of TMT-based nanodevices. Graphical abstract I–Vcharacteristics of (a) TiS3, (b) ZrS3, and (c) HfS3more » « less
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A chiral 3D coordination compound, [Gd 2 (L) 2 (ox) 2 (H 2 O) 2 ], arranged around a dinuclear Gd unit has been characterized by X-ray photoemission and X-ray absorption measurements in the context of density functional theory studies. Core level photoemission of the Gd 5p multiplet splittings indicates that spin orbit coupling dominates over j–J coupling evident in the 5p core level spectra of Gd metal. Indications of spin–orbit coupling are consistent with the absence of inversion symmetry due to the ligand field. Density functional theory predicts antiferromagnet alignment of the Gd 2 dimers and a band gap of the compound consistent with optical absorption.more » « less