BiFeO3 thin films via aqueous solution deposition: a study of phase formation and stabilization
Source abstract
Abstract
This paper reports a thorough microstructural investigation of bismuth ferrite (BFO) thin films subjected to various processing conditions and discusses their influence on the stability of the BiFeO3 perovskite phase. The formation of secondary phases in BFO thin films is studied as a function of annealing temperature and time, film thickness, Bi excess, and Ti substitution. While films annealed at 600 °C consist of the desired BiFeO3 phase, higher temperatures induce the decomposition leading to a significant amount of secondary phases, particularly the iron-rich Bi2Fe4O9 phase. A longer annealing time at 700 °C further enhances the decomposition of BiFeO3. Qualitative microstructural analysis of the films is performed by electron backscattered diffraction which provides phase analysis of individual grains. The morphology of the single-crystalline Bi2Fe4O9 grains that are embedded in the BiFeO3 matrix drastically changes as a function of the film thickness. Nucleation of these Bi2Fe4O9 grains probably occurs at the film/substrate interface, after which grain growth continues toward the surface of the film through the depletion of the BFO phase. Addition of Bi excess or the substitution of Fe with Ti in the precursor solutions significantly reduces the formation of an iron-rich secondary phase. Influence of the secondary phases as well as Ti substitution on magnetic properties of BFO films was investigated.
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Research context
OpenAlex topics: Multiferroics and related materials · Ferroelectric and Piezoelectric Materials
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References (70)
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1. Catalan G, Scott JF (2009) Physics and applications of bismuth ferrite. Adv Mater 21(24):2463–2485. doi: 10.1002/adma.20080284910.1002/adma.200802849 ↗
2. Arnold DC, Knight KS, Morrison FD, Lightfoot P (2009) Ferroelectric-paraelectric transition in BiFeO3: crystal structure of the orthorhombic beta phase. Phys Rev Lett 102(2):027602. doi: 10.1103/PhysRevLett.102.02760210.1103/PhysRevLett.102.027602 ↗
3. Selbach SM, Tybell T, Einarsrud MA, Grande T (2008) The ferroic phase transitions of BiFeO3. Adv Mater 20(19):3692–3696. doi: 10.1002/adma.20080021810.1002/adma.200800218 ↗
4. Palewicz A, Przenioslo R, Sosnowska I, Hewat AW (2007) Atomic displacements in BiFeO3 as a function of temperature: neutron diffraction study. Acta Crystallogr Sect B-Struct Sci 63:537–544. doi: 10.1107/s010876810702395610.1107/S0108768107023956 ↗
5. Achenbac GD, James WJ, Gerson R (1967) Preparation of single-phase polycrystalline BiFeO3. J Am Ceram Soc 50(8):437. doi: 10.1111/j.1151-2916.1967.tb15153.x10.1111/j.1151-2916.1967.tb15153.x ↗
6. Selbach SM, Einarsrud MA, Grande T (2009) On the thermodynamic stability of BiFeO3. Chem Mater 21(1):169–173. doi: 10.1021/cm802607p10.1021/cm802607p ↗
7. Valant M, Axelsson AK, Alford N (2007) Peculiarities of a solid-state synthesis of multiferroic polycrystalline BiFeO3. Chem Mater 19(22):5431–5436. doi: 10.1021/cm071730+10.1021/cm071730+ ↗
8. Morozov MI, Lomanova NA, Gusarov VV (2003) Specific features of BiFeO3 formation in a mixture of bismuth(III) and iron(III) oxides. Russ J Gen Chem 73(11):1676–1680. doi: 10.1023/b:rugc.0000018640.30953.7010.1023/B:RUGC.0000018640.30953.70 ↗
9. Bea H, Bibes M, Fusil S, Bouzehouane K, Jacquet E, Rode K, Bencok P, Barthelemy A (2006) Investigation on the origin of the magnetic moment of BiFeO3 thin films by advanced X-ray characterizations. Phys Rev B 74(2):020101–020104. doi: 10.1103/PhysRevB.74.02010110.1103/PhysRevB.74.020101 ↗
10. Filip’ev VS, Smolyaninov NP, Fesenko EG, Belyaev IN (1960) Synthesis of BiFeO3 and determination of the unit cell. Kristallografiya 5(6):958
11. Selbach SM, Tybell T, Einarsrud MA, Grande T (2010) Phase transitions, electrical conductivity and chemical stability of BiFeO3 at high temperatures. J Solid State Chem 183(5):1205–1208. doi: 10.1016/j.jssc.2010.03.01410.1016/j.jssc.2010.03.014 ↗
12. Palai R, Katiyar RS, Schmid H, Tissot P, Clark SJ, Robertson J, Redfern SAT, Catalan G, Scott JF (2008) Beta phase and gamma-beta metal-insulator transition in multiferroic BiFeO3. Phys Rev B 77(1):014110–014120. doi: 10.1103/PhysRevB.77.01411010.1103/PhysRevB.77.014110 ↗
13. Maitre A, Francois M, Gachon JC (2004) Experimental study of the Bi2O3-Fe2O3 pseudo-binary system. J Phase Equilib Diffus 25(1):59–67. doi: 10.1361/1054971041768710.1007/s11669-004-0171-0 ↗
14. Rojac T, Bencan A, Malic B, Tutuncu G, Jones JL, Daniels JE, Damjanovic D (2014) BiFeO3 ceramics: processing, electrical, and electromechanical properties. J Am Ceram Soc 97(7):1993–2011. doi: 10.1111/jace.1298210.1111/jace.12982 ↗
15. Bucci JD, Robertso BK, James WJ (1972) Precision determination of lattice parameters and coefficients of thermal expansion of BiFeO3. J Appl Crystallogr 5(JUN1):187–191. doi: 10.1107/s002188987200917310.1107/S0021889872009173 ↗
16. Rojac T, Kosec M, Budic B, Setter N, Damjanovic D (2010) Strong ferroelectric domain-wall pinning in BiFeO3 ceramics. J Appl Phys 108(7):174107–174114. doi: 10.1063/1.349024910.1063/1.3490249 ↗
17. Wang J, Neaton JB, Zheng H, Nagarajan V, Ogale SB, Liu B, Viehland D, Vaithyanathan V, Schlom DG, Waghmare UV, Spaldin NA, Rabe KM, Wuttig M, Ramesh R (2003) Epitaxial BiFeO3 multiferroic thin film heterostructures. Science 299(5613):1719–1722. doi: 10.1126/science.108061510.1126/science.1080615 ↗
18. Bea H, Bibes M, Barthelemy A, Bouzehouane K, Jacquet E, Khodan A, Contour JP, Fusil S, Wyczisk F, Forget A, Lebeugle D, Colson D, Viret M (2005) Influence of parasitic phases on the properties of BiFeO3 epitaxial thin films. Appl Phys Lett 87(7):072508–072510. doi: 10.1063/1.200980810.1063/1.2009808 ↗
19. Ihlefeld JF, Kumar A, Gopalan V, Schlom DG, Chen YB, Pan XQ, Heeg T, Schubert J, Ke X, Schiffer P, Orenstein J, Martin LW, Chu YH, Ramesh R (2007) Adsorption-controlled molecular-beam epitaxial growth of BiFeO3. Appl Phys Lett 91(7):071922–071924. doi: 10.1063/1.276777110.1063/1.2767771 ↗
20. Das RR, Kim DM, Baek SH, Eom CB, Zavaliche F, Yang SY, Ramesh R, Chen YB, Pan XQ, Ke X, Rzchowski MS, Streiffer SK (2006) Synthesis and ferroelectric properties of epitaxial BiFeO3 thin films grown by sputtering. Appl Phys Lett 88(24):242904–242906. doi: 10.1063/1.221334710.1063/1.2213347 ↗
21. Zheng R, Gao X, Wang J, Ramakrishna S (2008) Multiferroic BiFeO3 thin films buffered by a SrRuO3 layer. J Am Ceram Soc 91(2):463–466. doi: 10.1111/j.1551-2916.2007.02128.x10.1111/j.1551-2916.2007.02128.x ↗
22. Lee CC, Wu LJ, Wu JM (2007) Studies on forming gas annealing treated BiFeO3 thin films and capacitors. Appl Phys Lett 91(20):202902–202904. doi: 10.1063/1.280619110.1063/1.2806191 ↗
23. Yang SY, Zavaliche F, Mohaddes-Ardabili L, Vaithyanathan V, Schlom DG, Lee YJ, Chu YH, Cruz MP, Zhan Q, Zhao T, Ramesh R (2005) Metalorganic chemical vapor deposition of lead-free ferroelectric BiFeO3 films for memory applications. Appl Phys Lett 87(10):102903–102905. doi: 10.1063/1.204183010.1063/1.2041830 ↗
24. Wang Y, Jiang QH, He HC, Nan CW (2006) Multiferroic BiFeO3 thin films prepared via a simple sol-gel method. Appl Phys Lett 88(14):142503–142505. doi: 10.1063/1.219194710.1063/1.2191947 ↗
25. Qi XD, Dho JH, Blamire M, Jia QX, Lee JS, Foltyn S, MacManus-Driscoll JL (2004) Epitaxial growth of BiFeO3 thin films by LPE and sol-gel methods. J Magn Magn Mater 283(2–3):415–421. doi: 10.1016/j.jmmm.2004.06.014
26. Singh SK, Kim YK, Funakubo H, Ishiwara H (2006) Epitaxial BiFeO3 thin films fabricated by chemical solution deposition. Appl Phys Lett 88(16):162904–162906. doi: 10.1063/1.219647710.1063/1.2196477 ↗
27. Casper MD, Losego MD, Maria JP (2013) Optimizing phase and microstructure of chemical solution-deposited bismuth ferrite (BiFeO3) thin films to reduce DC leakage. J Mater Sci 48(4):1578–1584. doi: 10.1007/s10853-012-6914-010.1007/s10853-012-6914-0 ↗
28. Tyholdt F, Jorgensen S, Fjellvag H, Gunnaes AE (2005) Synthesis of oriented BiFeO3 thin films by chemical solution deposition: phase, texture, and microstructural development. J Mater Res 20(8):2127–2139. doi: 10.1577/jmr.2005.026310.1557/JMR.2005.0263 ↗
29. Yakovlev S, Zekonyte J, Solterbeck CH, Es-Souni M (2005) Interfacial effects on the electrical properties of multiferroic BiFeO3/Pt/Si thin film heterostructures. Thin Solid Films 493(1–2):24–29. doi: 10.1016/j.tsf.2005.06.02010.1016/j.tsf.2005.06.020 ↗
30. Liu KH, Cai W, Fu CL, Lei K, Xiang L, Gong XB (2014) Preparation and electric properties of BiFeO3 film by electrophoretic deposition. J Alloys Compd 605:21–28. doi: 10.1016/j.jallcom.2014.03.16110.1016/j.jallcom.2014.03.161 ↗
31. Toupet H, Le Marrec F, Holc J, Kosec M, Vilarhino P, Karkut MG (2009) Growth and thermal stability of epitaxial BiFeO3 thin films. J Magn Magn Mater 321(11):1702–1705. doi: 10.1016/j.jmmm.2009.02.02410.1016/j.jmmm.2009.02.024 ↗
32. Fujino S, Murakami M, Lim SH, Wuttig M, Salamanca-Riba LG, Takeuchi I (2007) Ferroelectric properties of multiphase Bi-Fe-O thin films. Solid State Ion 178(21–22):1257–1261. doi: 10.1016/j.ssi.2007.07.00410.1016/j.ssi.2007.07.004 ↗
33. Calzada ML, Gonzalez A, Garcia-Lopez J, Jimenez R (2003) Crystallization, heterostructure, microstructure, and properties of ferroelectric strontium bismuth tantalate films derived from tantalum glycolate solutions. Chem Mater 15(25):4775–4783. doi: 10.1021/cm031065e10.1021/cm031065e ↗
34. Schwartz RW (1997) Chemical solution deposition of perovskite thin films. Chem Mater 9(11):2325–2340. doi: 10.1021/cm970286f10.1021/cm970286f ↗
35. Hardy A, Gielis S, Van den Rul H, D’Haen J, Van Bael MK, Mullens J (2009) Effects of precursor chemistry and thermal treatment conditions on obtaining phase pure bismuth ferrite from aqueous gel precursors. J Eur Ceram Soc 29(14):3007–3013. doi: 10.1016/j.jeurceramsoc.2009.05.01810.1016/j.jeurceramsoc.2009.05.018 ↗
36. Hardy A, D’Haen J, Van Bael MK, Mullens J (2007) An aqueous solution-gel citratoperoxo-Ti(IV) precursor: synthesis, gelation, thermo-oxidative decomposition and oxide crystallization. J Sol-Gel Sci Technol 44(1):65–74. doi: 10.1007/s10971-007-1601-310.1007/s10971-007-1601-3 ↗
37. Van Bael MK, Nelis D, Hardy A, Mondelaers D, Van Werde K, D’Haen J, Vanhoyland G, Van den Rul H, Mullens J, Van Poucke LC, Frederix F, Wouters DJ (2002) Aqueous chemical solution deposition of ferroelectric thin films. Integr Ferroelectr 45:113–122. doi: 10.1080/1058458019004401010.1080/10584580215353 ↗
38. Schwartz RW, Schneller T, Waser R (2004) Chemical solution deposition of electronic oxide films. CR Chim 7(5):433–461. doi: 10.1016/j.crci.2004.01.00710.1016/j.crci.2004.01.007 ↗
39. Calzada ML, Jimenez R, Gonzalez A, Garcia-Lopez J, Leinen D, Rodriguez-Castellon E (2005) Interfacial phases and electrical characteristics of ferroelectric strontium bismuth tantalate films on Pt/TiO2 and Ti/Pt/Ti heterostructure electrodes. Chem Mater 17(6):1441–1449. doi: 10.1021/cm048996q10.1021/cm048996q ↗
40. Stojakovic D (2012) Electron backscatter diffraction in materials characterization. Process Appl Ceram 6(1):1–1310.2298/PAC1201001S ↗
41. Tyholdt F, Fjellvag H, Gunnaes AE, Olsen A (2007) Synthesis of epitaxial BiFeO3 films by chemical solution deposition on Pt(100). J Appl Phys 102(7):074108–074114. doi: 10.1063/1.278499910.1063/1.2784999 ↗
42. Okamoto H (1991) The Bi-Pt (Bismuth-Platinum) system. J Phase Equilib 12(2):207–210. doi: 10.1007/BF0264571810.1007/BF02645718 ↗
43. Bretos I, Jimenez R, Rodriguez-Castellon E, Garcia-Lopez J, Calzada ML (2008) Heterostructure and compositional depth profile of low-temperature processed lead titanate-based ferroelectric thin films prepared by photochemical solution deposition. Chem Mater 20(4):1443–1450. doi: 10.1021/cm702581210.1021/cm7025812 ↗
44. Dippel AC, Schneller T, Waser R, Park D, Mayer J (2010) Formation sequence of lead platinum interfacial phases in chemical solution deposition derived Pb(Zr1−x Ti x )O3 thin films. Chem Mater 22(23):6209–6211. doi: 10.1021/cm101195t10.1021/cm101195t ↗
45. Zhang X, Bourgeois L, Yao J, Wang H, Webley PA (2007) Tuning the morphology of bismuth ferrite nano- and microcrystals: from sheets to fibers. Small 3(9):1523–1528. doi: 10.1002/smll.20070018210.1002/smll.200700182 ↗
46. Han JT, Huang YH, Wu XJ, Wu CL, Wei W, Peng B, Huang W, Goodenough JB (2006) Tunable synthesis of bismuth ferrites with various morphologies. Adv Mater 18(16):2145–2148. doi: 10.1002/adma.20060007210.1002/adma.200600072 ↗
47. Ruan QJ, Zhang WD (2009) Tunable morphology of Bi2Fe4O9 crystals for photocatalytic oxidation. J Phys Chem C 113(10):4168–4173. doi: 10.1021/jp810098f10.1021/jp810098f ↗
48. Tsai CJ, Yang CY, Liao YC, Chueh YL (2012) Hydrothermally grown bismuth ferrites: controllable phases and morphologies in a mixed KOH/NaOH mineralizer. J Mater Chem 22(34):17432–17436. doi: 10.1039/c2jm33859a10.1039/c2jm33859a ↗
49. Hu ZT, Chen B, Lim TT (2014) Single-crystalline Bi2Fe4O9 synthesized by low-temperature co-precipitation: performance as photo- and Fenton catalysts. RSC Adv 4(53):27820–27829. doi: 10.1039/c4ra02555e10.1039/c4ra02555e ↗
50. Zhang XY, Lv J, Bourgeois L, Cui JW, Wu YC, Wang HT, Webley PA (2011) Formation and photocatalytic properties of bismuth ferrite submicrocrystals with tunable morphologies. New J Chem 35(4):937–941. doi: 10.1039/c1nj00008j10.1039/c1nj00008j ↗
51. Lahmar A, Zhao K, Habouti S, Dietze M, Solterbeck CH, Es-Souni M (2011) Off-stoichiometry effects on BiFeO3 thin films. Solid State Ion 202(1):1–5. doi: 10.1016/j.ssi.2011.03.01710.1016/j.ssi.2011.03.017 ↗
52. Singh SK, Funakuba H, Uchida H, Ishiwara H (2005) Structural and electrical properties of BiFeO3 thin films. Integr Ferroelectr 76:139–146. doi: 10.1080/1058458050041385510.1080/10584580500413855 ↗
53. Kalantari K, Sterianou I, Karimi S, Ferrarelli MC, Miao S, Sinclair DC, Reaney IM (2011) Ti-doping to reduce conductivity in Bi0.85Nd0.15FeO3 ceramics. Adv Funct Mater 21(19):3737–3743. doi: 10.1002/adfm.20110019110.1002/adfm.201100191 ↗
54. Yasui S, Uchida H, Nakaki H, Nishida K, Funakubo H, Koda S (2007) Analysis for crystal structure of Bi(Fe, Sc)O3 thin films and their electrical properties. Appl Phys Lett 91(2):022906–022908. doi: 10.1063/1.275635610.1063/1.2756356 ↗
55. Chung CF, Lin JP, Wu JM (2006) Influence of Mn and Nb dopants on electric properties of chemical-solution-deposited BiFeO3 films. Appl Phys Lett 88(24):242909–242911. doi: 10.1063/1.221413810.1063/1.2214138 ↗
56. Do D, Kim JW, Kim SS (2011) Effects of Dy and Mn codoping on ferroelectric properties of BiFeO3 thin films. J Am Ceram Soc 94(9):2792–2795. doi: 10.1111/j.1551-2916.2011.04720.x10.1111/j.1551-2916.2011.04720.x ↗
57. Yan F, Lai MO, Lu L, Zhu TJ (2010) Enhanced multiferroic properties and valence effect of Ru-doped BiFeO3 thin films. J Phys Chem C 114(15):6994–6998. doi: 10.1021/jp100912710.1021/jp1009127 ↗
58. Khomchenko VA, Kiselev DA, Kopcewicz M, Maglione M, Shvartsman VV, Borisov P, Kleemann W, Lopes AML, Pogorelov YG, Araujo JP, Rubinger RM, Sobolev NA, Vieira JM, Kholkin AL (2009) Doping strategies for increased performance in BiFeO3. J Magn Magn Mater 321(11):1692–1698. doi: 10.1016/j.jmmm.2009.02.00810.1016/j.jmmm.2009.02.008 ↗
59. Wu JG, Wang J (2010) Ferroelectric and impedance behavior of La- and Ti-codoped BiFeO3 thin films. J Am Ceram Soc 93(9):2795–2803. doi: 10.1111/j.1551-2916.2010.03816.x10.1111/j.1551-2916.2010.03816.x ↗
60. Bernardo MS, Jardiel T, Peiteado M, Caballero AC, Villegas M (2011) Sintering and microstructural characterization of W6+, Nb5+ and Ti4+ iron-substituted BiFeO3. J Alloys Compd 509(26):7290–7296. doi: 10.1016/j.jallcom.2011.04.08710.1016/j.jallcom.2011.04.087 ↗
61. Bernardo MS, Jardiel T, Peiteado M, Mompean FJ, Garcia-Hernandez M, Garcia MA, Villegas M, Caballero AC (2013) Intrinsic compositional inhomogeneities in bulk Ti-doped BiFeO3: microstructure development and multiferroic properties. Chem Mater 25(9):1533–1541. doi: 10.1021/cm303743h10.1021/cm303743h ↗
62. Wang Y, Nan CW (2006) Enhanced ferroelectricity in Ti-doped multiferroic BiFeO3 thin films. Appl Phys Lett 89(5):052903–052905. doi: 10.1063/1.222224210.1063/1.2222242 ↗
63. Zheng CD, Yu J, Zhang DM, Yang B, Wu YY, Wang LH, Wang YB, Zhou WL (2007) Processing and ferroelectric properties of Ti-doped BiFeO3 ceramics. Integr Ferroelectr 94:31–36. doi: 10.1080/1058458070175587210.1080/10584580701755872 ↗
64. Hu GD, Fan SH, Yang CH, Wu WB (2008) Low leakage current and enhanced ferroelectric properties of Ti and Zn codoped BiFeO3 thin film. Appl Phys Lett 92(19):192905–192907. doi: 10.1063/1.291813010.1063/1.2918130 ↗
65. Chan HM, Harmer MP, Smyth DM (1986) Compensating defects in highly donor-doped BaTiO3. J Am Ceram Soc 69(6):507–510. doi: 10.1111/j.1151-2916.1986.tb07453.x10.1111/j.1151-2916.1986.tb07453.x ↗
66. Bernardo MS, Jardiel T, Peiteado M, Caballero AC, Villegas M (2011) Reaction pathways in the solid state synthesis of multiferroic BiFeO3. J Eur Ceram Soc 31(16):3047–3053. doi: 10.1016/j.jeurceramsoc.2011.03.01810.1016/j.jeurceramsoc.2011.03.018 ↗
67. Bea H, Bibes M, Petit S, Kreisel J, Barthelemy A (2007) Structural distortion and magnetism of BiFeO3 epitaxial thin films: a Raman spectroscopy and neutron diffraction study. Philos Mag Lett 87(3–4):165–174. doi: 10.1080/0950083070123580210.1080/09500830701235802 ↗
68. Ederer C, Spaldin NA (2005) Weak ferromagnetism and magnetoelectric coupling in bismuth ferrite. Phys Rev B 71(6):060401–060404. doi: 10.1103/PhysRevB.71.06040110.1103/PhysRevB.71.060401 ↗
69. Tian ZM, Yuan SL, Wang XL, Zheng XF, Yin SY, Wang CH, Liu L (2009) Size effect on magnetic and ferroelectric properties in Bi2Fe4O9 multiferroic ceramics. J Appl Phys 106(10):103912–103915. doi: 10.1063/1.325939210.1063/1.3259392 ↗
70. Murari NM, Thomas R, Melgarejo RE, Pavunny SP, Katiyar RS (2009) Structural, electrical, and magnetic properties of chemical solution deposited BiFe1−x Ti x O3 and BiFe0.9Ti0.05Co0.05O3 thin films. J Appl Phys 106(1):014103–014107. doi: 10.1063/1.315855610.1063/1.3158556 ↗