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Ferroelectrics materials, as a candidate of materials, have recently received attention, for they possess applications in photovoltaic devices and can couple the light absorption with other functional properties. In these materials, the strong inversion symmetry is broken, which is because the spontaneous electric polarization promotes the desirable separation of photo-excited carriers and allows voltages higher than the band-gap, thus permitting efficiency beyond the maximum possible value in a conventional p-n junction solar cell. Much effort has been made to study the ferroelectric photovoltaic effect in several families of ferroelectric perovskite oxides, such as Pb(Zr,Ti)O3, LiNbO3, BaTiO3, KNbO3, Na0.5Bi0.5TiO3-BaTiO3, AgNbO3 and BiFeO3. However, their photo-electric conversion efficiency is now still very low though this field is being studied. The observed output photocurrent is very low due to the negative influence of a wide band-gap and small absorption coefficient, which is caused by the wide band-gaps for most of ferroelectric materials such as Pb(Zr,Ti)O3 (~3.5 eV), and BaTiO3 (~3.3 eV), especially. Although the BiFeO3 system with low band-gap (2.7 eV), which can absorb most visible light for electron transition, is considered as a potential photovoltaic material, it is difficult to synthesize pure perovskite structure. The BiFeO3-BaTiO3 (BF-BT) ferroelectric material with excellent piezoelectric and ferroelectric properties has been widely concerned by researchers in recent years. However, it is still unclear whether this system has the same advantages as BiFeO3 materials with excellent photovoltaic properties. In this work, the Bi(Fe0.96Mg0.02–xTi0.02+x)O3-0.3BaTiO3 ferroelectric ceramics are prepared by the conventional synthesis method to uncover the piezoelectric and ferroelectric properties, as well as the photovoltaic performance with different ratios of Mg2+/Ti4. Because of the electronic production caused by replacing Mg2+ ions with Ti4+ ions, the conductivity of sample increases, and thus its piezoelectric and ferroelectric properties deteriorate. The piezoelectric coefficient d33 decreases from 195 pC/N at x = 0 to 27 pC/N at x = 0.02. Conversely, the range of absorption spectrum increases when the Mg2+ ions are replaced by Ti4+ ions. The band gap of sample decreases from 1.954 eV at x = 0 to 1.800 eV at x = 0.02. The photocurrent of sample increases from 3.71 nA/cm2 at x = 0 to 32.45 nA/cm2 at x = 0.02 because of the combined action of reducing the band gap and internal bias field.
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Keywords:
- bismuth ferrite /
- ferroelectric materials /
- photovoltaic /
- perovskite structure
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图 1 BFM0.02–xT0.02+x-BT (0 ≤ x ≤ 0.02)基陶瓷的XRD图谱 (a) 20°—70°; (b) 38°—40°, 43.5°—46.5°
Figure 1. X-ray diffraction patterns of BFM0.02–xT0.02+x-BT ceramics with different x content (0 ≤ x ≤ 0.02) in a selected 2θ range of 20°—70° (a), 38°—40° and 43.5°—46.5° (b).
图 2 BFM0.02–xT0.02+x-BT陶瓷样品的SEM形貌图
Figure 2. SEM images of the fracture surface for BFM0.02–xT0.02+x-BT ceramics with different x content (0 ≤ x ≤ 0.02).
图 3 BFM0.02–xT0.02+x-BT陶瓷样品的(a)电滞回线, (b)剩余极化Pr和矫顽场EC随含量x的变化, (c)漏电流I-E曲线, 以及(d)压电性能d33和kp随含量x的变化
Figure 3. Ferroelectric hysteresis loops (a), the variation of polarization (Pr) and electric field (EC) (b), leakage current density (I)-electric field (E) (c), as well as the piezoelectric coefficient d33, planar mode eletromechanical coupling coefficient kp (d) as a function of x for BFM0.02–xT0.02+x-BT (0 ≤ x ≤ 0.02).
图 4 BFM0.02–xT0.02+x-BT铁电陶瓷的光吸收谱图
Figure 4. UV-vis-NIR absorption spectra of the BFM0.02–xT0.02+x-BT ceramics with different x content (0 ≤ x ≤ 0.02).
图 5 BFM0.02–xT0.02+x-BT铁电陶瓷的(αhν)1/2-(hν)曲线 (a) x = 0; (b) x = 0.005; (c) x = 0.01; (d) x = 0.02
Figure 5. Plots of (αhν)1/2 versus hν for the BFM0.02–xT0.02+x-BT ceramics with different x content: (a) x = 0; (b) x = 0.005; (c) x = 0.01; (d) x = 0.02.
图 6 BFMT-BT铁电陶瓷的光电流密度-时间(J-t)曲线图, 其中(I)区为未极化; (II)区为1 kV下极化; (III)区为2 kV下极化; (IV)区为3 kV下极化
Figure 6. J-t characteristics of BFMT-BT ceramics, which are polarized at different voltage: (I) V = 0 kV; (II) V = 1 kV; (III) V = 2 kV; (IV) V = 3 kV.
图 7 BFM0.02–xT0.02+x-BT铁电陶瓷的光电流密度-电压(J-V)曲线图 (a) x = 0; (b) x = 0.005; (c) x = 0.01; (d) x = 0.02
Figure 7. J-V characteristics of BFM0.02–xT0.02+x-BT ceramics with different x content: (a) x = 0; (b) x = 0.005; (c) x = 0.01; (d) x = 0.02
图 8 BFM0.02–xT0.02+x-BT铁电陶瓷光伏效应原理图 (a)未极化、无光条件; (b)未极化、有光条件; (c)极化、无光条件; (d)极化、光照条件
Figure 8. Schematic diagram of photovoltaic effect for BFM0.02–xT0.02+x-BT ceramics, non-polarization and dark condition (a), non-polarization and light condition (b), polarization and dark condition (c), as well as polarization and light condition (d), respectively.
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[1] Lines M E, Glass A M 1971 Principles and Applications of Ferroelectrics and Related Materials (Oxford: Oxford University Press) pp110−677
[2] Jaffe B, Cook W R, Jaffe H 1971 Piezoelectric Ceramics (New York: Academic Press) pp136−337
[3] Choi T, Lee S, Choi Y J, Kiryukhin V, Cheong S W 2009 Science 324 63
Google Scholar
[4] Katiyar R K, Sharma Y, Barrionuevo D, Kooriyattil S, Pavunny S P, Young J S, Morell G, Weiner B R, Katiyar R S, Scott J F 2015 Appl. Phys. Lett. 106 082903
Google Scholar
[5] Agarwal R, Sharma Y, Katiyar R S 2015 Appl. Phys. Lett. 107 162904
Google Scholar
[6] Zang Y Y, Xie D, Wu X, Chen Y, Lin Y X, Li M H, He T, Li X, Li Z, Zhu H W, Ren T L, Plant D 2011 Appl. Phys. Lett. 99 132904
Google Scholar
[7] Wu J, Fan Z, Xiao D, Zhu J, Wang J 2016 Prog. Mater. Sci. 84 335
Google Scholar
[8] Chen B, Li M, Liu Y W, Zuo Z H, Zhuge F, Zhan Q F, Li R W 2011 Nanotechnology 22 195201
Google Scholar
[9] Yan T L, Chen B, Liu G, Niu R P, Shang J, Gao S, Xue W H, Jin J, Yang J R, Li R W 2017 Chin. Phys. B 26 067702
Google Scholar
[10] Lee M H, Kim D J, Park J S, Kim S W, Song T K, Kim M H, Kim W J, Do D, Jeong I K 2015 Adv. Mater. 27 6976
Google Scholar
[11] Zhu L F, Zhang B P, Li S, Zhao G L 2017 J. Alloy. Compd. 727 382
Google Scholar
[12] Zheng T, Ding Y, Wu J 2016 RSC Adv. 6 90831
Google Scholar
[13] Zhu L F, Zhang B P, Zhang Z C, Li S, Wang L J, Zheng L J 2018 J. Mater. Sci.-Mater. El. 29 2307
Google Scholar
[14] Lin Y, Zhang L, Zheng W, Yu J 2015 J. Mater. Sci.-Mater. El. 26 7351
Google Scholar
[15] Zhu L F, Zhang B P, Duan J Q, Xun B W, Wang N, Tang Y C, Zhao G L 2018 J. Eur. Ceram. Soc. 38 3463
Google Scholar
[16] Wei J, Fu D, Cheng J, Cheng J 2017 J. Mater. Sci. 52 10726
Google Scholar
[17] Zhu LF, Liu Q, Zhang B P, Cen Z Y, Wang K, Li J, Bai Y, Wang X H, Li J F 2018 RSC Adv. 8 35794
Google Scholar
[18] Liu N, Liang R, Zhou Z, Dong X 2018 J. Mater. Chem. C 6 10211
Google Scholar
[19] Wang D, Fan Z, Li W, Zhou D, Feteira A, Wang G, Murakami S, Sun S, Zhao Q, Tan X, Reaney I M 2018 ACS Appl. Energy Mater. 1 4403
Google Scholar
[20] Li Q, Wei J X, Cheng J R, Chen J G 2017 J. Mater. Sci. 52 229
Google Scholar
[21] Yang H B, Zhou C R, Liu X Y, Zhou Q, Chen G H, Li W Z, Wang H 2013 J. Eur. Ceram. Soc. 33 1177
Google Scholar
[22] Pavana S V, Mocherla, Karthik C, Ubic R, Ramachandra R M S, Sudakar C 2013 Appl. Phys. Lett. 103 022910
Google Scholar
[23] Liu H, Chen J, Ren Y, Zhang L X, Pan Z, Fan L L, Xing X R 2015 Adv. Electron. Mater. 1 1400051
Google Scholar
[24] Xiao H, Dong W, Guo Y, Wang Y, Zhong H, Li Q, Yang M M 2019 Adv. Mater. 31 1805802
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