Z[nm] Role of domain walls in the abnormal photovoltaic effect in BiFeO3 Akash Bhatnagar, Ayan Roy Chaudhuri, Young Heon Kim, Dietrich Hesse, and Marin Alexe a) 6.46 nm b) c) 8nm. nm 8 d) e) 7 6 5 4 3.5.5.5 3 3.5 X[µm] Supplementary Figure S. AFM and PFM. Atomic and piezo force microscopy (AFM/PFM) images (4 x 4 m) showing a periodic domain pattern in a sample with 9 domains. a) Topography and line scan profile along X and Y directions. Out-of-plane (OOP) PFM signal: b) amplitude, and c) phase. In-plane (IP) PFM signal: d) amplitude, and e) phase.
out of plane [Å] out of plane [Å] Z[nm] a) b) c) 44.5 nm 68nm. nm.5 d) e).5.5.5.5.5 X[µm] Supplementary Figure S. AFM and PFM. Atomic and piezo force microscopy (AFM/PFM) images (3.5 x 3.5 m) showing a periodic domain pattern in a sample with 7 domains. a) Topography and line scan profile along X and Y directions. Out-of-plane (OOP) PFM signal: b) amplitude, and c) phase. In-plane (IP) PFM signal: d) amplitude, and e) phase. 4. a) b) 4. 3.98 4. 3.99 3.98 3.97 3.96 3.94 3.9 * 3.9 3.95 4. 4.5 in-plane [Å] 3.96 3.95 3.94 3.93 3.75 3.8 3.85 3.9 3.95 4. 4.5 4. 4.5 * in-plane [Å] Supplementary Figure S3. Reciprocal space maps. XRD-Reciprocal space maps around the (3) pc peak of BiFeO 3 films grown on TbScO 3 (). Films with a thickness of nm and with a) 7 and b) 9 domains were measured. The substrate peaks have been marked with a star.
a) b) Supplementary Figure S4. Measurement geometries. Schematic showing, on an exaggerated scale, the patterned electrodes on top of a film with majority 9 domains. The arrows indicate the direction of polarization in out of plane (up-down) and in-plane (left-right) directions, viz. a) when the electrodes are running parallel to the domain walls (PLDW), and (b) when the electrodes are perpendicular to the domain wall (PPDW). a) b) Supplementary Figure S5. Polarization orientation in a 7 domain film. a) Schematic of the measurement geometry for a sample with alternating 7 domains parallel to the electrodes (PLDW) along with the lab coordinate system. b) Pseudo cubic schematic of two kinds of domains in a sample with 7 domains. P R and P L show the direction of polarization for the two kinds of domain. 3
Response [a.u.] Energy [e.v.] 4 3.6 3..8.4..8.6.4. 3 375 45 55 6 675 75 Wavelength [nm] Supplementary Figure S6. Spectral distribution of the photocurrent. Normalized spectral distribution of the photocurrent response of a BFO film. The response we measured per light intensity on our samples is shown in Figure S6. We used a white light source along with a monochromator and measured the photocurrent as a function of different wavelengths. The photoconductive (PC) response we obtained from our samples is largely in agreement with the results obtained from first principle calculations 6. The peak in the spectral distribution of the PC response is approximately.85 ev which is.8 ev higher than previously reported values 3. Interestingly, it can be noted from Figure S6 that there is a significant increase in measured response at an energy approx..4 ev which indicates the presence of shallow trap levels or sub-band levels just below the conduction band 5. The trap levels in the band gap and the asymmetry of the structure are necessary conditions for the bulk photovoltaic effect, as it has been specifically stated in early theoretical work of Ruppel et al 9. 4
Open circuit voltage [V].5 9. Predicted values Measured values 7.5 6. 4.5 3..5. 5 5 3 35 4 Temperature [K] Supplementary Figure S7. Measured and predicted values of V oc for a sample with 7 domains measured in PPDW geometry. Relationship between conductivity behavior and Voc values: In order to predict the open circuit voltage (VOC) values we have used the expression V J OC ph L (S) σ σ d ph From our measurements we found that both dark ( d ) and photo conductivity ( ph ) are thermally activated with two, high and low temperature, regimes and follow the relations which can be expressed as: d d exp( Ead d ( Ead (S) ph ph exp( Eaph ph( Eaph (S3) where T is the temperature. E ad and E ad are the activation energies for dark conductivity in the high and low temperature regimes. Similarly E aph and E aph are the activation energies for photo conductivity. Based on equations and 3 we were able to simulate the conductivity responses in our samples. Henceforth we used a constant value of J PH and equation to predict the V oc values. This is shown in Figure S7. 5
Supplementary References 3 Ihlefeld, J. F. et al. Optical band gap of BiFeO 3 grown by molecular-beam epitaxy. Applied Physics Letters 9, 498 (8). 6