The effects of Eu3+ doping on the epitaxial growth and photovoltaic properties of BiFeO3 thin films

doi:10.1016/j.jmst.2021.07.025

Abstract

Abstract:

Nowadays, photovoltaic effect has been widely studied in various ferroelectric materials due to its applications as optoelectronic devices. In this work, with BiFeO₃ (BFO) films as the photovoltaic materials, we report the effects of Eu³⁺ doping content on the phase structure, ferroelectric and optical properties of BFO films grown on Ca_0.96Ce_0.04MnO₃/YAlO₃ (001) substrate. We found that a small doping level of 0.05 could induce a phase change of BFO from tetragonal to rhombohedral, due to the shrinking of the lattice upon Eu³⁺ doping and the breaking of surface terrace structure induced by Ca_0.96Ce_0.04MnO₃ layer. This results in a sharp band gap reduction from 3.30 eV to 2.60 eV, and a decrease in the coercivity of ferroelectric polarization switching. Based on these findings, we investigate the photovoltaic effects of ITO/Eu_xBi_1-_xFeO₃/Ca_0.96Ce_0.04MnO₃ vertical capacitors. It is found that the short-circuit current density (J_sc) decreases with increasing Eu³⁺ doping, whereas the open-circuit voltage (V_oc) first increases to a level of 0.1 V and then decreases with further Eu³⁺ doping. This could be explained by the combined effect of Schottky-junction and depolarization field on the photovoltaic process. Our research suggests that a moderate Eu³⁺ doping is helpful for enhancing the photovoltaic effect of BFO thin film devices.

Key words: Ferroelectric, Photovoltaic effect, BiFeO₃, Eu³⁺ doping, Band gap

Dingshuai Feng, Biaohong Huang, Lingli Li, Xiaoqi Li, Youdi Gu, Weijin Hu, Zhidong Zhang. The effects of Eu³⁺ doping on the epitaxial growth and photovoltaic properties of BiFeO₃ thin films[J]. J. Mater. Sci. Technol., 2022, 106: 49-55.

Figures/Tables 6

Fig. 1. Structural characterization of the EuxBi1-xFeO3 (x = 0, 0.05, 0.1, 0.15, 0.2) thin films. (a) High resolution θ-2θ X-ray diffraction patterns of films grown on CCMO (12 nm)/YAO (001). (b) Reciprocal space mapping of the (103) reflection of T phase BiFeO3 film on YAO (001). (c) HRXRD patterns of films grown on YAO (001) substrate and (d) the as-derived c/a ratio for the T-BFO phase. Inset of (d), comparison of T-BFO (001) peaks with and without CCMO bottom electrode.

Fig. 2. Surface characterization of the EuxBi1-xFeO3 (x = 0, 0.1, 0.2) thin films. (a) YAO (001) substrate with terrace steps. (b) CCMO (12 nm) grown on YAO substrate. (c-e) EBFO thin films with (c) x = 0, (d) x = 0.1, and (e) x = 0.2 grown on YAO substrate. (f-h) EBFO thin films with (f) x = 0, (g) x = 0.1, and (h) x = 0.2 grown on CCMO/YAO substrate.

Fig. 3. PFM characterizations of the EuxBi1-xFeO3 (x = 0, 0.1, 0.2) thin films. (a, d, g) The PFM amplitude images, and (b, e, h) the phase images of films after box-in-box writing by opposite voltages of +6 V and -6 V, respectively. (c, f, i) The local piezoresponse amplitude and phase loops of the films, respectively. Scale bars: 1.0 µm.

Fig. 4. Optical absorption of the EuxBi1-xFeO3 (x = 0, 0.05, 0.1, 0.15, 0.2) thin films grown on CCMO/YAO. (a) The optical absorption coefficient α at room temperature. (b) (αhv)2 as a function of photon energy hv, from which the direct band gaps could be derived by linear extrapolation as indicated by the dashed lines. (c) Bandgap as a function of Eu3+ doping content. Error bars are from linear fittings.

Fig. 5. Photovoltaic characteristics of vertical capacitors ITO /EuxBi1-xFeO3 /CCMO (x = 0 - 0.2). (a-d) The current density J vs. voltage V curves, measured in dark (black) and under the illumination of UV light with different polarization states (blue for upward, and red for downward), respectively. (f) Photovoltaic property parameters Jsc (black) and Voc (red) as a function of Eu3+ doping content.

Fig. 6. Light intensity dependent PV effect of T-BFO thin film. (a) I-V curves under light illumination of different intensities up to 2263 mW/cm2. (b) The as-derived Jsc (left) and Voc (right) as a function of light intensity.

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The effects of Eu³⁺ doping on the epitaxial growth and photovoltaic properties of BiFeO₃ thin films

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