Properties In Epitaxial Fe Reversible Oxidation Quantified .

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l the possible difference in optical properties in the thickestregion of the film resulting from such a scenario. We allowed the optical properties of thelayer closest to the substrate (the majority of the film thickness at 40 nm) to vary. Theresult of this analysis can be seen in supplemental Figure S6. The optical properties donot significantly vary for the thick layer close to the substrate by modeling the top 3 nmas magnetite or chromite, especially compared to the changes that occur from oxidationor reduction. While different film layering may exist before and after annealing, thedifference does not in all likelihood have a significant effect on the optical properties basedon this analysis.S7

Supporting Information2.00.30.42.0n1.5With 2.8nm magnetite overlayer, 2nm roughnessWith 2.8nm chromite overlayer, 2nm roughnessWithout overlayer, 2nm roughnessGraded, 2nm m ( m)kk0.50.01234Energy (eV)Figure S6. Optical properties of the film deposited at 250 C modeled without a surfacelayer (thin solid lines), with a 3 nm magnetite surface layer (dotted lines), with a 3 nmchromite surface layer (dashed lines), and as a graded layer (dashed and dotted lines).All models incorporate 2nm of surface roughnessWe also modeled the film as a graded layer in an attempt to induce a larger difference.This result is also shown in supplemental Figure S6. While the graded model doesintroduce the largest difference from the single homogeneous layer model, this model isthe most unrealistic based on XRR data. The result is also not significantly differentS8

Supporting Informationcompared to the changes observed upon oxidizing/reducing anneals around 0.9 eV.Therefore, we are confident that the observed changes in the optical propertiessignificantly result from changes in the electronic structure induced by changing the Fevalence (δ) in the films.S9

Supporting InformationFigure S7.Low-energy-resolution Fe 2p, Cr 2p and O 1s spectra (normalized to constant O 1sintensity). Thick dashed lines represent anneals expected to result in increased oxidation comparedto the previous condition. Thin solid lines represent as-grown or anneals expected to decrease3.02.01.51.00.51.00.6Wavelengthm ( m)0.7Extinction Coefficient (k)oxidation compared to the previous condition.400 C, 8.48Å400 C, 8.60Å500 C, 8.65Å600 C, 8.58Å0.80.60.40.212345Photon Energy (eV)Figure S8. Extinction coefficient (k) versus incident photon energy for various Fe2CrO4 films, asdeposited on MgAl2O4 (001). The measurement listed in the legend for each curve is the OOPlattice parameter for the respective film, in the as-deposited state. The only systematic andsignificant trends are in the low photon energy region which we have previously shown anddiscussed in reference 4.S10

Counts x 105 (arb. units)Supporting Information3.50.253.00.202.50.152.01.51.00.50.0C 1sCa 2p350Na1sAgNa 3dKLLAs-grownAnneal 121200 10008003006004002000Binding Energy (eV)Figure S9. X-ray photoelectron spectra for the film deposited at 250 C in the as deposited stateand after annealing in air at 400 C for 1hr (ox-12). Several dilute contaminants from theannealing apparatus, sample holder, and sample handling are introduced, but no Mg is observedeven after 12 anneals totaling 105 hours. This, along with Figure S8 confirms the insignificanceof Mg contamination on the material properties after heat treatment.S11

Supporting Information S1 Reversible Oxidation Quantified by Optical Properties in Epitaxial Fe2CrO4 δ Films on (001) MgAl2O4 Mark D. Scafetta,1# Tiffany C. Kaspar,1 Mark E. Bowden,2 Steven R. Spurgeon,3 Bethany Matthews,3 Scott A. Chambers1* 1) Physical and Compu

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