Enhancement of photovoltage by electronic structure evolution in multiferroic Mn-doped BiFeO₃ thin films

The bulk photovoltaic effect (BPVE) is a mechanism of recent focus for novel solar cells that exceed the power conversion efficiency of p-n junction solar cells because of the quantum mechanical effect to generate photocurrent known as shift current. Ferroelectrics are receiving attention again because of their high voltage generation by the BPVE and converse piezoelectric effect to realize high performance optical actuators. We have investigated the BPVE in ferroelectric BiFeO₃ (BFO) single crystal thin films, whereby the photovoltage was enhanced by Mn doping, and 852 V generation was demonstrated at 80 K. The enhancement mechanism was also investigated using soft and hard X-ray photoelectron spectroscopy (SXPES, HAXPES), and soft X-ray absorption spectroscopy with synchrotron radiation. This report reveals a way to new voltage source applications employing the BPVE for high impedance devices with ferroelectrics. Important aspects for designing ferroelectric materials by impurity doping are also discussed.