Band structure of FeBO3: Implications for tailoring the band gap of nanoparticles

Shang, Shun‐Li; Wang, Yi; Liu, Zhe; Yang, Chia En; Yin, Shizhuo

doi:10.1063/1.2824869

Cited by 13 publications

(9 citation statements)

References 19 publications

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“…The band gap of FeBO 3 computed here at 3.26 eV also differs significantly from the much smaller value of 1.59 eV obtained by Seo et al The discrepancy likely comes from the lack of account for the variation in effective U value with the degree of Fe oxidation state in the previous calculations, given that a physically reasonable increase in U upon oxidation of Fe sites should lead to a widening of the band gap. Similar DFT+ U calculations for the R 3̅ c polymorph of FeBO 3 suggest that a value U = 6 eV (some 1.7 eV in excess of the value used by Seo et al for C 2/ c FeBO 3 ) is necessary to accurately reproduce the experimental band gap …”

Section: Resultsmentioning

confidence: 57%

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Structural Modulation in the High Capacity Battery Cathode Material LiFeBO₃

Janssen

Middlemiss

et al. 2012

J. Am. Chem. Soc.

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The crystal structure of the promising Li-ion battery cathode material LiFeBO(3) has been redetermined based on the results of single crystal X-ray diffraction data. A commensurate modulation that doubles the periodicity of the lattice in the a-axis direction is observed. When the structure of LiFeBO(3) is refined in the 4-dimensional superspace group C2/c(α0γ)00, with α = 1/2 and γ = 0 and with lattice parameters of a = 5.1681 Å, b = 8.8687 Å, c = 10.1656 Å, and β = 91.514°, all of the disorder present in the prior C2/c structural model is eliminated and a long-range ordering of 1D chains of corner-shared LiO(4) is revealed to occur as a result of cooperative displacements of Li and O atoms in the c-axis direction. Solid-state hybrid density functional theory calculations find that the modulation stabilizes the LiFeBO(3) structure by 1.2 kJ/mol (12 meV/f.u.), and that the modulation disappears after delithiation to form a structurally related FeBO(3) phase. The band gaps of LiFeBO(3) and FeBO(3) are calculated to be 3.5 and 3.3 eV, respectively. Bond valence sum maps have been used to identify and characterize the important Li conduction pathways, and suggest that the activation energies for Li diffusion will be higher in the modulated structure of LiFeBO(3) than in its unmodulated analogue.

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Section: Resultsmentioning

confidence: 57%

“…Similar DFT+U calculations for the R3̅ c polymorph of FeBO 3 suggest that a value U = 6 eV (some 1.7 eV in excess of the value used by Seo et al for C2/c FeBO 3 16 ) is necessary to accurately reproduce the experimental band gap. 37 3.7. Li-Ion Diffusion Pathways.…”

Section: Resultsmentioning

confidence: 99%

Structural Modulation in the High Capacity Battery Cathode Material LiFeBO₃

Janssen

Middlemiss

et al. 2012

J. Am. Chem. Soc.

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“…The literature values for J are spread from 0.35 eV to 1 eV. 10,12,47 Based on optical studies, Ovchinnikov and Zabluda 10 obtained U = 2.97 eV using J =0.7 eV and 10Dq = 1.57 eV. In our case, we are measuring 10Dq = 1.4 eV (see Fig.…”

Section: B Mott-hubbard Excitationmentioning

confidence: 66%

“…9 The first-principles local-density approximation (LDA) energy band calculations predicted an antiferromagnetic (AFM) metal instead of an AFM insulator. 11 Shang et al 12 have performed first-principles band-structure calculations using the density functional theory within the generalized gradient approximation (GGA) and the GGA+U approach. The electronic structure was predicted to be high-spin, antiferromagnetic and insulating, in agreement with experiments.…”

Section: Introductionmentioning

confidence: 99%

Charge transfer and Mott-Hubbard excitations in FeBO3: An FeK-edge resonant inelastic x-ray scattering study

2011

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Momentum-resolved resonant inelastic x-ray scattering (RIXS) spectroscopy has been carried out at the Fe K edge, successfully for the first time. The RIXS spectra of a FeBO3 single crystal reveal a wealth of information on 1 − 10 eV electronic excitations. The IXS signal resonates both when the incident photon energy approaches the pre-edge (1s-3d) and the main-edge (1s-4p) of the Fe K edge absorption spectrum. The RIXS spectra measured at the pre-edge and the mainedge show quantitatively different dependences on the incident photon energy, momentum transfer, polarization, and temperature. Electronic excitations observed in the pre-edge and main-edge RIXS spectra are interpreted as Mott-Hubbard (MH) and charge-transfer (CT) excitations, respectively. The charge-transfer gap ∆ G = 3.81 ± 0.04 eV and the Mott-Hubbard gap U G = 3.96 ± 0.04 eV, are determined, model independently from the experimental data. The CT and MH excitations are assigned using molecular orbitals (MO) in the cluster model and multiplet calculation in the many-electron multiband model, respectively.

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“…Unfortunately, the first-principles method has difficulty predicting properties such as the band gap and ionic charges for rareearth and ionic compounds due to their strongly localized and correlated electronic structure. 7,8 However, first-principles calculations are adequate for the purposes of CALPHAD modeling as they have been successful in predicting phase stability and thermochemical data that agree well with experiment. [9][10][11] It will be shown that this combined first-principles and CALPHAD approach can be successfully applied to the Al 2 O 3 -Nd 2 O 3 system.…”

Section: Introductionmentioning

confidence: 99%

First‐Principles Calculations and Thermodynamic Modeling of the Al₂O₃–Nd₂O₃ System

Saal¹,

Shin²,

Stevenson³

et al. 2008

Journal of the American Ceramic Society

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Using first‐principles calculations, the enthalpies of formation of NdAlO3 and Nd4Al2O9 from neodymia and alumina are predicted to be −41.1 and −104.5 kJ/mol‐form, respectively, and Nd4Al2O9 is predicted to be a stable compound at all temperatures up to its peritectic decomposition temperature. In the case of NdAlO3, where reported experimental enthalpies of formation differ, our predicted value is used to determine which experimental value is more accurate. The enthalpies of formation calculated by the first‐principles method are combined with experimental phase equilibria to evaluate the Gibbs energies of phases in the Al2O3–Nd2O3 system. The resulting Gibbs energy functions are compared with previous modelings of the system and are shown to be an improvement as more thermochemical data have been included. The combined first‐principles/thermodynamic modeling approach employed in the current work shows promise in enabling the evaluation of important ceramic systems in which experimental thermochemical data are scarce.

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Band structure of FeBO3: Implications for tailoring the band gap of nanoparticles

Cited by 13 publications

References 19 publications

Structural Modulation in the High Capacity Battery Cathode Material LiFeBO₃

Structural Modulation in the High Capacity Battery Cathode Material LiFeBO₃

Charge transfer and Mott-Hubbard excitations in FeBO3: An FeK-edge resonant inelastic x-ray scattering study

First‐Principles Calculations and Thermodynamic Modeling of the Al₂O₃–Nd₂O₃ System

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Band structure of FeBO3: Implications for tailoring the band gap of nanoparticles

Cited by 13 publications

References 19 publications

Structural Modulation in the High Capacity Battery Cathode Material LiFeBO3

Structural Modulation in the High Capacity Battery Cathode Material LiFeBO3

Charge transfer and Mott-Hubbard excitations in FeBO3: An FeK-edge resonant inelastic x-ray scattering study

First‐Principles Calculations and Thermodynamic Modeling of the Al2O3–Nd2O3 System

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Product

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Structural Modulation in the High Capacity Battery Cathode Material LiFeBO₃

Structural Modulation in the High Capacity Battery Cathode Material LiFeBO₃

First‐Principles Calculations and Thermodynamic Modeling of the Al₂O₃–Nd₂O₃ System