Surface electronic structure of Ni-doped Fe$_3$O$_4$(001)

The main data analysis was done with Wavemetrics Igor Pro 7.08 using user-defined macros. General Remarks The calibration factor for our electron analyzer in the laboratory source XPS measurements was determined based on the peak positions of Au 4f7/2 Ag 3d5/2, and Cu 2p3/2 acquired from freshly prepared metallic Au, Ag, and Cu samples. For a pass energy of 50 eV: CKE=(MKE-0.58267)/0.99913 where CKE and MKE represent calibrated and measured kinetic energies, respectively. The XPD and FSM patterns throughout this dataset are presented in a file structure: tab-separated YXZT. To obtain the patterns as they were represented in the manuscript, first plot Y vs. X in marker mode. Assign Z and T as marker size and color, respectively. %%% Figure 1 %%% Figure 1.a and Figure 1.b The high symmetry points: |ΓL|= √3π/a |ΓX|= 2π/a |ΓW|= √5π/a |ΓK|= √3π/2a |ΓU|= √3π/2a Figure 1.c The SBZ boundaries for the bulk and reconstructed cell: |ΓX|bulk= √2π/a |ΓX|rec= π/a Figure 1.d File: "Fig1d.tiff" LEED Image (Energy=20 eV) Figure 1.e File: "Fig1e.txt" File structure(Left-to-right): Tab separated YXZT The Fermi surface of a pristine Fe3O4(001), excitation: He Ia (21.22 eV) Figure 1.f File: "Fig1f.txt" File structure(Left-to-right): Tab separated YXZT The Fermi surface of a pristine Fe3O4(001), excitation: He IIa (40.80 eV) %%% Figure 2 %%% Angular distribution maps of photoelectrons excited from their fixed initial-state energy Ei (EF, 0.22 eV, 0.43 eV, 1.29 eV, 1.49 eV and 1.70 eV) mapped versus parallel momentum. Figure 2.a Files: "Fig2a_EF.txt, Fig2a_0p22eV.txt, Fig2a_0p43eV.txt, Fig2a_1p29eV.txt, Fig2a_1p49eV.txt, Fig2a_1p70eV.txt" File structure(Left-to-right): Tab separated YXZT The measurements were acquired with a He Ia excitation. Figure 2.b Files: "Fig2b_EF.txt, Fig2b_0p22eV.txt, Fig2b_0p43eV.txt, Fig2b_1p29eV.txt, Fig2b_1p49eV.txt, Fig2b_1p70eV.txt" File structure(Left-to-right): Tab separated YXZT The simulations, which were obtained with the RSMS code, were acquired to mimic He Ia excitation. Figure 2.c Files: "Fig2c_EF.txt, Fig2c_0p22eV.txt, Fig2c_0p43eV.txt, Fig2c_1p29eV.txt, Fig2c_1p49eV.txt, Fig2c_1p70eV.txt" File structure(Left-to-right): Tab separated YXZT The measurements were acquired with a He IIa excitation. Figure 2.d Files: "Fig2d_EF.txt, Fig2b_0p22eV.txt, Fig2d_0p43eV.txt, Fig2d_1p29eV.txt, Fig2d_1p49eV.txt, Fig2d_1p70eV.txt" File structure(Left-to-right): Tab separated YXZT The simulations, which were obtained with the RSMS code, were acquired to mimic He IIa excitation. %%% Figure 3 %%% Figure 3.a File: "Fig3a.txt" "File structure: Tab-separated YYYX, where the first three columns (from left to right) represent spectra taken from the pristine, as-grown, and post-annealed samples, respectively. Column X (Ni 2p) denotes the binding energy. Figure 3.b File: "Fig3b.txt" "File structure: Tab-separated YYYX, where the first three columns (from left to right) represent spectra taken from the pristine, as-grown, and post-annealed samples, respectively. Column X (Fe 2p) denotes the binding energy. Figure 3.c-e File: "Fig3c.txt, Fig3d.txt, Fig3e.txt " File structure(Left-to-right): Tab separated YXZT %%% Figure 4 %%% Figure 4.a File: "Fig4a_010.txt, Fig4a_110.txt, Fig4ac_kpar.txt" File structure (Left-to-right): YY….YY (Fig4a_010.txt, Fig4a_110.txt) vs. X (Fig4ac_kpar.txt) Parallel momentum range from k=0 Å-1 to k=1.83 Å-1. Energy range Ebin= 0 eV to Ebin= 2.6 eV. Plot type: MDC, Sample: Pristine Fe3O4(001), Crystal directions: [010] and [110] Note that the data presented in the manuscript were given with a Y-offset. Figure 4.b File: "Fig4b_010.txt, Fig4b_110.txt, Fig4bd_en.txt" File structure (Left-to-right): YY….YY (Fig4b_010.txt, Fig4b_110.txt) vs. X (Fig4bd_en.txt) Parallel momentum range from k=0 Å-1 to k=1.83 Å-1. Energy range Ebin= 0 eV to Ebin= 2.6 eV. Plot type: EDC, Sample: Pristine Fe3O4(001), Crystal directions: [010] and [110] Note that the data presented in the manuscript were given with a Y-offset. Figure 4.c File: "Fig4c_010.txt, Fig4c_110.txt, Fig4ac_kpar.txt " File structure (Left-to-right): YY….YY (Fig4e_010.txt, Fig4e_110.txt) vs. X (Fig4ac_kpar.txt) Parallel momentum range from k=0 Å-1 to k=1.83 Å-1. Energy range Ebin= 0 eV to Ebin= 2.6 eV. Plot type: MDC, Sample: Post-annealed 26-ML Ni/Fe3O4(001), Crystal directions: [010] and [110] Note that the data presented in the manuscript were given with a Y-offset. Figure 4.d File: "Fig4d_010.txt, Fig4d_110.txt , Fig4bd_en.txt" File structure (Left-to-right): YY….YY (Fig4d_010.txt, Fig4d_110.txt) vs. X (Fig4bd_en.txt) Parallel momentum range from k=0 Å-1 to k=1.83 Å-1. Energy range Ebin= 0 eV to Ebin= 2.6 eV. Plot type: EDC, Sample: Post-annealed 26-ML Ni/Fe3O4(001), Crystal directions: [010] and [110] Note that the data presented in the manuscript were given with a Y-offset. %%% Figure 5 %%% Figure 5.a File: "Fig5a.txt" File structure: Tab-separated YYX(Mg Ka) YYX(He Ia), where Y represents spectra taken from the pristine and post-annealed samples from left to right, respectively, and X denotes the binding energies. Figure 5.b File: "Fig5b.txt" File structure : Tab separated YX-YYYX-YX YX(Measurement) Left-to-right (Y: The spectrum from the pristine sample, X: Binding energy) YYYX(TDOS) Left-to-right (Y: Spin up, Y: Spin down, Y: Spin Tot, X: Energy(X-offset: 4.943 eV) for NixFe3-xO4 (x=0)) YX(Gaussian-broadened TDOS) Broadening:0.5 eV Left-to-right (Y: Spin Tot, X: Energy) Figure 5.c File: "Fig5c.txt" File structure: Tab separated YX-YYYX-YX YX(Measurement) Left-to-right (Y: The spectrum from the post-annealed sample, X: Binding energy) YYYX(TDOS) Left-to-right (Y: Spin up, Y: Spin down, Y: Spin Tot, X: Energy(X-offset: 5.343 eV) for NixFe3-xO4 (x=1)) YX(Gaussian-broadened TDOS) Broadening:0.5 eV Left-to-right (Y: Spin Tot, X: Energy) Figure 5.d File: "Fig5d.txt" File structure: Tab separated YX-YYYX-YX YX(Measurement) Left-to-right (Y: XP spectrum from the post-annealed sample, X: Binding Energy) YYYX(TDOS) Left-to-right (Y: Spin up, Y: Spin down, Y: Spin Tot, X: Energy(X-offset: 5.593 eV) for NixFe3-xO4 (x=2)) YX(Gaussian-broadened TDOS) Broadening:0.5 eV Left-to-right (Y: Spin Tot, X: Energy) Figure 5.e File: "Fig5e.txt" File structure: Tab separated Y-YY-YY-X Left-to-right (Y:Fe Total PDOS, Y: Fetet PDOS spin up, Y: Fetet PDOS spin down , Y: Feoct PDOS spin up, Y: Feoct PDOS spin down, X: Energy for for NixFe3-xO4 (x=0)) Gaussian Broadening: 0.2 eV Figure 5.f File: "Fig5f.txt" File structure: Tab separated Y-YY-YY-YY-X Left-to-right (Y: Ni and Fe Total PDOS, Y: Nioct PDOS spin up, Y: Nioct PDOS spin down , Y: Fetet PDOS spin up, Y: Fetet PDOS spin down, Y: Feoct PDOS spin up, Y: Feoct PDOS spin down, X: Energy(X-offset: 1.93 eV) for NixFe3-xO4 (x=1)) Gaussian Broadening: 0.2 eV Figure 5.g File: "Fig5g.txt" File structure: Tab separated Y-YY-YY-X Left-to-right (Y: Ni and Fe Total PDOS, Y: Nioct PDOS spin up, Y: Nioct PDOS spin down, Y: Fetet PDOS spin up, Y: Fetet PDOS spin down, X: Energy(X-offset: 2.12 eV) for NixFe3-xO4 (x=2)) Gaussian Broadening: 0.2 eV %%% Figure 6 %%% Figure 6.a File: "Fig6a.txt" File structure(Left-to-right): Tab separated Y-Y-Y-X (Y: 120 ML, Y:50 ML, Y: 10 ML, X: Energy) (X-offset: 2 eV) Figure 6.b File: "Fig6b.txt" File structure(Left-to-right): Tab separated Y-Y-Y-Y-X (Y: 120 ML, Y:50 ML, Y: 10 ML, Y:Pristine, X: Ni 2p Energy) %%% Figure 7 %%% Figure 7.a File: "Fig7a.txt" File structure(Left-to-right): Tab separated Y-Y-Y-Y-X (Y: 120 ML, Y:50 ML, Y: 10 ML, Y:Pristine, X: Energy) (X-offset: 2.8 eV) Figure 7.b File: "Fig7b.txt" File structure(Left-to-right): Tab separated Y-Y-Y-Y-X (Y: 120 ML, Y:50 ML, Y: 10 ML, Y:Pristine, X: Fe 2p Energy) %%% Figure 8 %%% Figure 8.a File: "Fig8a.txt" File structure(Left-to-right): Tab separated Y-Y-Y-Y-X (Y: 120 ML, Y:50 ML, Y: 10 ML, Y:Pristine, X: Energy) (X-offset: 1.1 eV) Figure 8.b File: "Fig8b.txt" File structure(Left-to-right): Tab separated Y-Y-Y-X (Y: (120 ML-Pristine), Y: (50 ML-Pristine), Y: (10 ML-Pristine), X: Energy) %%% SUPLLEMENTARY INFORMATION %%% %%% Figure SI3 %%% File: "FigSI3_pristine.txt, FigSI3_26ML_AG.txt, FigSI3_26ML_PA.txt" File structure (Left-to-right): XY1-XY2-XY3… XY9-XY10-XY11-XY12 (AG: As-grown, PA: Post-annealed) XY1 – XY9 (Y: Fit Peak, X: Energy) XY10 (Y: Cumulative Fit Peak, X: Energy) XY11 (Y: Residue, X: Energy) XY12 (Y: Shirley BG Subtracted XPS Measurement, X: Energy) %%% Figure SI4 %%% Figure SI4.a File: "FigSI4_oct.txt" File structure(Left-to-right): YYYYYY1-YYYYYY2-YYYYYY3… YYYYYY4-X YYYYYY1 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Layer: S YYYYYY2 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Layer: S-2 YYYYYY3 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Layer: S-6 YYYYYY4 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Layer: S-8 X: Energy Figure SI4.b File: "FigSI4_tet.txt" File structure(Left-to-right): YYYYYY1-YYYYYY2-YYYYYY3… YYYYYY4-X YYYYYY1 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Layer: S-1 YYYYYY2 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Layer: Interstitial Tet YYYYYY3 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Layer: S-3 YYYYYY4 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Layer: S-7 X: Energy Channeltron positions: 0.00 eV, 0.22 eV, 0.43 eV, 1.29 eV, 1.49 eV and 1.70 eV %%% Figure SI5 %%% Figure SI5.a File: "FigSI5a_EF.txt, FigSI5a_0p22eV.txt, FigSI5a_0p43eV.txt, FigSI5a_1p29eV.txt, FigSI5a_1p49eV.txt, FigSI5a_1p70eV.txt " File structure(Left-to-right): Tab separated YXZT Figure SI5.b File: "FigSI5b_EF.txt, FigSI5b_0p22eV.txt, FigSI5b_0p43eV.txt, FigSI5b_1p29eV.txt, FigSI5b_1p49eV.txt, FigSI5b_1p70eV.txt " File structure(Left-to-right): Tab separated YXZT Figure SI5.c File: "FigSI5c_EF.txt, FigSI5c_0p22eV.txt, FigSI5c_0p43eV.txt, FigSI5c_1p29eV.txt, FigSI5c_1p49eV.txt, FigSI5c_1p70eV.txt " File structure(Left-to-right): Tab separated YXZT %%% Figure SI6 %%% Figure SI6.a File: "FigSI6a_EF.txt, FigSI6a_0p22eV.txt, FigSI6a_0p43eV.txt, FigSI6a_1p29eV.txt, FigSI6a_1p49eV.txt, FigSI6a_1p70eV.txt " File structure(Left-to-right): Tab separated YXZT Figure SI6.b File: "FigSI6b_EF.txt, FigSI6b_0p22eV.txt, FigSI6b_0p43eV.txt, FigSI6b_1p29eV.txt, FigSI6b_1p49eV.txt, FigSI6b_1p70eV.txt " File structure(Left-to-right): Tab separated YXZT Figure SI6.c File: "FigSI6c_EF.txt, FigSI6c_0p22eV.txt, FigSI6c_0p43eV.txt, FigSI6c_1p29eV.txt, FigSI6c_1p49eV.txt, FigSI6c_1p70eV.txt " File structure(Left-to-right): Tab separated YXZT %%% Figure SI7 %%% Figure SI7.a File: "FigSI7a.tif" LEED Image (Energy=20 eV), Sample: Pristine Fe3O4(001) Figure SI7.b File: "FigSI7b.tif" LEED Image (Energy=20 eV), Sample: As-grown 26 ML Ni/Fe3O4(001) Figure SI7.c File: "FigSI7c.tif" LEED Image (Energy=20 eV), Sample: Post-annealed 26 ML Ni/Fe3O4(001) %%% Figure SI8 %%% File: "FigSI8_XPS_and_UPS.txt, FigSI8_Fe3O4_DOS.txt, FigSI8_NiFe2O4_DOS.txt, FigSI8_Ni2FeO4_DOS.txt" Experiment: FigSI8_XPS_and_UPS.txt File structure(Left-to-right): Tab separated YYX(Mg Ka) YYX(He Ia), where Y are the spectra taken from the pristine and post-annealed sample left to right, respectively, and X donate the binding energies. DOS (Fe3O4): FigSI8_Fe3O4_DOS.txt File structure: YYYX(TDOS) - YX(Gaussian-broadened TDOS) Broadening:0.5 eV (Y: Spin Tot, Y: Spin up, Y: Spin down, X: Energy) (X-offset: 4.943 eV) (Y: Spin Tot, X: Energy) DOS (NiFe2O4): FigSI8_NiFe2O4_DOS.txt File structure: YYYX(TDOS) - YX(Gaussian-broadened TDOS) Broadening:0.5 eV (Y: Spin Tot, Y: Spin up, Y: Spin down, X: Energy) (X-offset: 5.343 eV) (Y: Spin Tot, X: Energy) DOS (NiFe2O4): FigSI8_Ni2FeO4_DOS.txt File structure: YYYX(TDOS) - YX(Gaussian-broadened TDOS) Broadening:0.5 eV (Y: Spin Tot, Y: Spin up, Y: Spin down, X: Energy) (X-offset: 5.593 eV) (Y: Spin Tot, X: Energy) %%% Figure SI9 %%% Figure SI9.a File: "Fig9a.txt" File structure: YYYYYY1-YYYYYY2-X YYYYYY1 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Coordination: Fe_oct YYYYYY2 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Coordination: Fe_tet X: Energy Figure SI9.b File: "Fig9b.txt" File structure: YYYYYY1-YYYYYY2-YYYYYY3-X YYYYYY1 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Coordination: Fe_oct YYYYYY2 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Coordination: Fe_tet YYYYYY3 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Coordination: Ni_oct X: Energy Figure SI9.c File: "Fig9c.txt" File structure(Left-to-right): YYYYYY1-YYYYYY2-X YYYYYY1 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Coordination: Fe_tet YYYYYY2 (Y: PDOS eg down, PDOS Tot down, PDOS t2g down, PDOS eg up, PDOS Tot up, PDOS t2g up) Coordination: Ni_oct X: Energy %%% Figure SI10 %%% File: "FigSI10_010.txt, FigSI10_110.txt, FigSI10_Energy.txt" File structure(Left-to-right): YY….YY (FigSI10_010.txt, FigSI10_110.txt) vs. X (FigSI10_Energy.txt) Parallel momentum range from k=0 Å-1 to k=1.83 Å-1. Plot type: EDC, Sample: Pristine Fe3O4(001), Crystal directions: [010] and [110] Note that the data presented in the manuscript were given with a Y-offset. %%% Figure SI11 %%% Figure SI11.a File: "Fig SI11a.txt" File structure(Left-to-right): Tab separated Y-Y-Y-X (Y: 120 ML, Y:50 ML, Y: 10 ML, X: Energy) (X-offset: 2 eV) Figure SI11.b File: "Fig SI11b.txt" File structure(Left-to-right): Tab separated Y-Y-Y-Y-X (Y: 120 ML, Y:50 ML, Y: 10 ML, Y:Pristine, X: Ni 2p Energy) Figure SI11.c File: "FigSI11c.txt" File structure(Left-to-right): Tab separated Y-Y-Y-Y-X (Y: 120 ML, Y:50 ML, Y: 10 ML, Y: Pristine, X: Energy) (X-offset: 2.8 eV) Figure SI11.d File: "FigSI11d.txt" File structure(Left-to-right): Tab separated Y-Y-Y-Y-X (Y: 120 ML, Y:50 ML, Y: 10 ML, Y:Pristine, X: Fe 2p Energy) Figure SI11.e File: "FigSI11e.txt" File structure(Left-to-right): Tab separated Y-Y-Y-Y-X (Y: 120 ML, Y:50 ML, Y: 10 ML, Y: Pristine, X: Energy) (X-offset: 1.1 eV) Figure SI11.f File: "FigSI11f.txt" File structure(Left-to-right): Tab separated Y-Y-Y-Y-X (Y: 120 ML, Y:50 ML, Y: 10 ML, Y:Pristine, X: O 1s Energy)