An official website of the United States government
Abstract X-ray photoelectron spectroscopy (XPS) shows that dramatic changes in the core level binding energies can provide strong indications of transitions between more dielectric and more metallic CoFe2O4and NiCo2O4thin films. These significant variations in the XPS core level binding energies are possible with a combination of annealing and oxygen exposure; however, the behaviors of the CoFe2O4and NiCo2O4thin films are very different. The XPS Co and Fe 2p3/2core levels for the CoFe2O4thin film at room temperature show large photovoltaic surface charging, leading to binding energy shifts, characteristic of a highly dielectric (or insulating) surface at room temperature. The photovoltaic charging, observed in the XPS binding energies of the Co and Fe 2p3/2core levels, decreases with increasing temperature. The XPS core level binding energies of CoFe2O4thin film saturated at lower apparent binding energies above 455 K. This result shows that the prepared CoFe2O4thin film can be dielectric at room temperature but become more metallic at elevated temperatures. The dielectric nature of the CoFe2O4thin film was restored only when the film was annealed in sufficient oxygen, indicating that oxygen vacancies play an important role in the transition of the film from dielectric (or insulating) to metallic. In contrast, the XPS studies of initially metallic NiCo2O4thin film demonstrated that annealing NiCo2O4thin film led to a more dielectric or insulating film. The original more metallic character of the NiCo2O4film was restored when the NiCo2O4was annealed in sufficient oxygen. Effective activation energies are estimated for the carriers from a modified Arrhenius-type model applied to the core level binding energy changes of the CoFe2O4and NiCo2O4thin films, as a function of temperature. The origin of the carriers, however, is not uniquely identified. This work illustrates routes to regulate the surface metal-to-insulator transition of dielectric oxides, especially in the case of insulating NiCo2O4thin film that can undergo reversible metal-to-insulator transition with temperature.
more »
« less
This content will become publicly available on January 1, 2026
Local coordination geometry within cobalt spinel oxides mediates photoinduced polaron formation
Comparison of the optical properties of Co3O4and ZnCo2O4elucidates fundamental differences in mechanisms of photoinduced polaron formation based on the presence or absence of substitutional lattice defects arising from cation inversion.
more »
« less
- PAR ID:
- 10592353
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Chemical Science
- ISSN:
- 2041-6520
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Heat capacities and enthalpies of formation of BaGd2O4were determined by high‐temperature differential scanning calorimetry and high‐temperature oxide melt solution calorimetry, respectively. Thermodynamic stability of BaLn2O4compounds increases with decreasing Ln3+ionic radius. Previously reported data on BaNd2O4and BaSm2O4corroborate this trend. Missing data for compounds in BaO–Ln2O3(Ln = La, Pr, Eu, Er) systems were estimated from established relations, thermodynamic assessment was performed, and binary phase diagrams were calculated.more » « less
-
Abstract Spinel compounds are of great interest in both fundamental and application-oriented perspectives due to the geometric magnetic frustration inherent to their lattice and the resulting complex magnetic states. Here, we applied x-ray diffraction, magnetization, heat capacity and powder inelastic neutron scattering measurements, along with theoretical calculations, to study the exotic properties of chromite-spinel oxides CoCr2O4and MnCr2O4. The temperature dependence of the phonon spectra provides an insight into the correlation between oxygen motion and the magnetic order, as well as the magnetoelectric effect in the ground state of MnCr2O4. Moreover, spin-wave excitations in CoCr2O4and MnCr2O4are compared with Heisenberg model calculations. This approach enables the precise determination of exchange energies and offers a comprehensive understanding of the spin dynamics and relevant exchange interactions in complicated spiral spin ordering.more » « less
-
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
-
Abstract Anionic molecular models for nonhydrolyzed and partially hydrolyzed aluminum and gallium framework sites on silica, M[OSi(OtBu)3]4−and HOM[OSi(OtBu)3]3−(where M=Al or Ga), were synthesized from anionic chlorides Li{M[OSi(OtBu)3]3Cl} in salt metathesis reactions. Sequestration of lithium cations with [12]crown‐4 afforded charge‐separated ion pairs composed of monomeric anions M[OSi(OtBu)3]4−with outer‐sphere [([12]crown‐4)2Li]+cations, and hydroxides {HOM[OSi(OtBu)3]3} with pendant [([12]crown‐4)Li]+cations. These molecular models were characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy, mass spectrometry and NMR spectroscopy. Upon treatment of monomeric [([12]crown‐4)Li]{HOM[OSi(OtBu)3]3} complexes with benzyl alcohol, benzyloxide complexes were formed, modeling a possible pathway for the formation of active sites for Meerwin–Ponndorf–Verley (MPV) transfer hydrogenations with Al/Ga‐doped silica catalysts.more » « less
