Bismuth ferrite

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Bismuth ferrite
Identifiers
3D model (JSmol)
  • InChI=1S/Bi.Fe.3O/q2*+3;3*-2
    Key: UKOQHRZDRNXQCP-UHFFFAOYSA-N
  • [Bi+3].[Fe+3].[O-2].[O-2].[O-2]
Properties
BiFeO3
Molar mass 312.822 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Bismuth ferrite (BiFeO3, also commonly referred to as BFO in materials science) is an inorganic chemical compound with perovskite structure and one of the most promising multiferroic materials. [1] The room-temperature phase of BiFeO3 is classed as rhombohedral belonging to the space group R3c. [2] [3] [4] It is synthesized in bulk and thin film form and both its antiferromagnetic (G type ordering) Néel temperature (approximately 653 K) and ferroelectric Curie temperature are well above room temperature (approximately 1100K). [5] [6] Ferroelectric polarization occurs along the pseudocubic direction () with a magnitude of 90–95 μC/cm2. [7] [8]

Contents

Sample Preparation

Bismuth ferrite is not a naturally occurring mineral and several synthesis routes to obtain the compound have been developed.

Solid state synthesis

In the solid state reaction method [9] bismuth oxide (Bi2O3) and iron oxide (Fe2O3) in a 1:1 mole ratio are mixed with a mortar or by ball milling and then fired at elevated temperatures. Preparation of pure stoichiometric BiFeO3 is challenging due to the volatility of bismuth during firing which leads to the formation of stable secondary Bi25FeO39 (selenite) and Bi2Fe4O9 (mullite) phase. Typically a firing temperature of 800 to 880 Celsius is used for 5 to 60 minutes with rapid subsequent cooling. Excess Bi2O3 has also been used a measure to compensate for bismuth volatility and to avoid formation of the Bi2Fe4O9 phase.

Single crystal growth

Bismuth ferrite melts incongruently, but it can be grown from a bismuth oxide rich flux (e.g. a 4:1:1 mixture of Bi2O3, Fe2O3 and B2O3 at approximately 750-800 Celsius). [2] High quality single crystals have been important for studying the ferroelectric, antiferromagnetic and magnetoelectric properties of bismuth ferrite.

Chemical routes

Wet chemical synthesis routes based on sol-gel chemistry, modified Pechini routes, [10] hydrothermal [11] synthesis and precipitation have been used to prepare phase pure BiFeO3. The advantage of the chemical routes is the compositional homogeneity of the precursors and the reduced loss of bismuth due to the much lower temperatures needed. In sol-gel routes, an amorphous precursor is calcined at 300-600 Celsius to remove organic residuals and to promote crystallization of the bismuth ferrite perovskite phase, while the disadvantage is that the resulting powder must be sintered at high temperature to make a dense polycrystal.

Solution combustion reaction is a low-cost method used to synthesize porous BiFeO3. In this method, a reducing agent (such glycine, citric acid, urea, etc.) and an oxidizing agent (nitrate ions, nitric acid, etc.) are used to generate the reduction-oxidation (RedOx) reaction. The appearance of the flame, and consequently the temperature of the mixture, depends on the oxidizing/reducing agents ratio used. [12] Annealing up to 600 °C is sometimes needed to decompose the bismuth oxo-nitrates generated as intermediates. Since the content of Fe cations in this semiconductor material, Mӧssbauer spectroscopy is a proper technique to detect the presence of a paramagnetic component in the phase.

Thin films

The electric and magnetic properties of high quality epitaxial thin films of bismuth ferrite reported in 2003 [1] revived the scientific interest for bismuth ferrite. Epitaxial thin films have the great advantage that their properties can be tuned by processing [13] or chemical doping, [14] and that they can be integrated in electronic circuitry. Epitaxial strain induced by single crystalline substrates with different lattice parameters than bismuth ferrite can be used to modify the crystal structure to monoclinic or tetragonal symmetry and change the ferroelectric, piezoelectric or magnetic properties. [15] Pulsed laser deposition (PLD) is a very common route to epitaxial BiFeO3 films, and SrTiO3 substrates with SrRuO3 electrodes are typically used. Sputtering, molecular-beam epitaxy (MBE), [16] metal organic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), and chemical solution deposition are other methods to prepare epitaxial bismuth ferrite thin films. Apart from its magnetic and electric properties bismuth ferrite also possesses photovoltaic properties which is known as ferroelectric photovoltaic (FPV) effect.

Applications

Being a room temperature multiferroic material and due to its ferroelectric photovoltaic (FPV) effect, bismuth ferrite has several applications in the field of magnetism, spintronics, photovoltaics, etc.

Photovoltaics

In the FPV effect, a photocurrent is generated in a ferroelectric material under illumination and its direction is dependent upon the ferroelectric polarization of that material. The FPV effect has a promising potential as an alternative to conventional photovoltaic devices. But the main hindrance is that a very small photocurrent is generated in ferroelectric materials like LiNbO3, [17] which is due to its large bandgap and low conductivity. In this direction bismuth ferrite has shown a great potential since a large photocurrent effect and above bandgap voltage [18] is observed in this material under illumination. Most of the works using bismuth ferrite as a photovoltaic material has been reported on its thin film form but in a few reports researchers have formed a bilayer structure with other materials like polymers, graphene and other semiconductors. In a report p-i-n heterojunction has been formed with bismuth ferrite nanoparticles along with two oxide based carrier transporting layers. [19] In spite of such efforts the power conversion efficiency obtained from bismuth ferrite is still very low.

Related Research Articles

Ferroelectricity is a characteristic of certain materials that have a spontaneous electric polarization that can be reversed by the application of an external electric field. All ferroelectrics are also piezoelectric and pyroelectric, with the additional property that their natural electrical polarization is reversible. The term is used in analogy to ferromagnetism, in which a material exhibits a permanent magnetic moment. Ferromagnetism was already known when ferroelectricity was discovered in 1920 in Rochelle salt by Joseph Valasek. Thus, the prefix ferro, meaning iron, was used to describe the property despite the fact that most ferroelectric materials do not contain iron. Materials that are both ferroelectric and ferromagnetic are known as multiferroics.

<span class="mw-page-title-main">Perovskite (structure)</span> Type of crystal structure

A perovskite is any material with a crystal structure following the formula ABX3, which was first discovered as the mineral called perovskite, which consists of calcium titanium oxide (CaTiO3). The mineral was first discovered in the Ural mountains of Russia by Gustav Rose in 1839 and named after Russian mineralogist L. A. Perovski (1792–1856). 'A' and 'B' are two positively charged ions (i.e. cations), often of very different sizes, and X is a negatively charged ion (an anion, frequently oxide) that bonds to both cations. The 'A' atoms are generally larger than the 'B' atoms. The ideal cubic structure has the B cation in 6-fold coordination, surrounded by an octahedron of anions, and the A cation in 12-fold cuboctahedral coordination. Additional perovskite forms may exist where either/both the A and B sites have a configuration of A1x-1A2x and/or B1y-1B2y and the X may deviate from the ideal coordination configuration as ions within the A and B sites undergo changes in their oxidation states.

In chemistry, titanate usually refers to inorganic compounds composed of titanium oxides, or oxides containing the titanium element. Together with niobate, titanate salts form the Perovskite group.

<span class="mw-page-title-main">Strontium titanate</span> Chemical compound

Strontium titanate is an oxide of strontium and titanium with the chemical formula SrTiO3. At room temperature, it is a centrosymmetric paraelectric material with a perovskite structure. At low temperatures it approaches a ferroelectric phase transition with a very large dielectric constant ~104 but remains paraelectric down to the lowest temperatures measured as a result of quantum fluctuations, making it a quantum paraelectric. It was long thought to be a wholly artificial material, until 1982 when its natural counterpart—discovered in Siberia and named tausonite—was recognised by the IMA. Tausonite remains an extremely rare mineral in nature, occurring as very tiny crystals. Its most important application has been in its synthesized form wherein it is occasionally encountered as a diamond simulant, in precision optics, in varistors, and in advanced ceramics.

<span class="mw-page-title-main">Bismuth(III) oxide</span> Chemical compound

Bismuth(III) oxide is perhaps the most industrially important compound of bismuth. It is also a common starting point for bismuth chemistry. It is found naturally as the mineral bismite (monoclinic) and sphaerobismoite, but it is usually obtained as a by-product of the smelting of copper and lead ores. Dibismuth trioxide is commonly used to produce the "Dragon's eggs" effect in fireworks, as a replacement of red lead.

Multiferroics are defined as materials that exhibit more than one of the primary ferroic properties in the same phase:

<span class="mw-page-title-main">Barium ferrite</span> Chemical compound

Barium ferrite, abbreviated BaFe, BaM, is the chemical compound with the formula BaFe
12O
19. This and related ferrite materials are components in magnetic stripe cards and loudspeaker magnets.

<span class="mw-page-title-main">Barium titanate</span> Chemical compound

Barium titanate (BTO) is an inorganic compound with chemical formula BaTiO3. Barium titanate appears white as a powder and is transparent when prepared as large crystals. It is a ferroelectric, pyroelectric, and piezoelectric ceramic material that exhibits the photorefractive effect. It is used in capacitors, electromechanical transducers and nonlinear optics.

<span class="mw-page-title-main">Lithium niobate</span> Chemical compound

Lithium niobate is a synthetic salt consisting of niobium, lithium, and oxygen. Its single crystals are an important material for optical waveguides, mobile phones, piezoelectric sensors, optical modulators and various other linear and non-linear optical applications. Lithium niobate is sometimes referred to by the brand name linobate.

<span class="mw-page-title-main">Sodium bismuthate</span> Chemical compound

Sodium bismuthate is an inorganic compound, and a strong oxidiser with chemical formula NaBiO3. It is somewhat hygroscopic, but not soluble in cold water, which can be convenient since the reagent can be easily removed after the reaction. It is one of the few water insoluble sodium salts. Commercial samples may be a mixture of bismuth(V) oxide, sodium carbonate and sodium peroxide.

In its most general form, the magnetoelectric effect (ME) denotes any coupling between the magnetic and the electric properties of a material. The first example of such an effect was described by Wilhelm Röntgen in 1888, who found that a dielectric material moving through an electric field would become magnetized. A material where such a coupling is intrinsically present is called a magnetoelectric.

Aurivillius phases are a form of perovskite represented by the general formulae is (Bi2O2)(An−1BnO3n+1) (where A is a large 12 co-ordinate cation, and B is a small 6 co-ordinate cation).

A complex oxide is a chemical compound that contains oxygen and at least two other elements. Complex oxide materials are notable for their wide range of magnetic and electronic properties, such as ferromagnetism, ferroelectricity, and high-temperature superconductivity. These properties often come from their strongly correlated electrons in d or f orbitals.

<span class="mw-page-title-main">Nicola Spaldin</span>

Nicola Ann Spaldin FRS is professor of materials science at ETH Zurich, known for her pioneering research on multiferroics.

<span class="mw-page-title-main">Sillénite</span> Oxide mineral of bismuth and silicon

Sillénite or sillenite is a mineral with the chemical formula Bi12SiO20. It is named after the Swedish chemist Lars Gunnar Sillén, who mostly studied bismuth-oxygen compounds. It is found in Australia, Europe, China, Japan, Mexico and Mozambique, typically in association with bismutite.

<span class="mw-page-title-main">Bismuth titanate</span> Chemical compound

Bismuth titanate or bismuth titanium oxide is a solid inorganic compound of bismuth, titanium and oxygen with the chemical formula of Bi12TiO20, Bi 4Ti3O12 or Bi2Ti2O7.

Sodium bismuth titanate or bismuth sodium titanium oxide (NBT or BNT) is a solid inorganic compound of sodium, bismuth, titanium and oxygen with the chemical formula of Na0.5Bi0.5TiO3 or Bi0.5Na0.5TiO3. This compound adopts the perovskite structure.

Magnetochromism is the term applied when a chemical compound changes colour under the influence of a magnetic field. In particular the magneto-optical effects exhibited by complex mixed metal compounds are called magnetochromic when they occur in the visible region of the spectrum. Examples include K2V3O8, lithium molybdenum purple bronze Li0.9Mo6O17, and related mixed oxides. Reported magnetochromic compounds are multiferroic manganese tungsten oxide and multiferroic bismuth ferrite.

<span class="mw-page-title-main">Julia Mundy</span> American physicist

Julia Mundy is an American experimental condensed matter physicist. She was awarded the 2019 George E. Valley Jr. Prize by the American Physical Society (APS) for "the pico-engineering and synthesis of the first room-temperature magnetoelectric multi-ferroic material." This prize recognizes an "individual in the early stages of his or her career for an outstanding scientific contribution to physics that is deemed to have significant potential for a dramatic impact on the field." She is an assistant professor of physics at Harvard University in Cambridge, Massachusetts.

References

  1. 1 2 Wang, J.; Neaton, B.; Zheng, H.; Nagarajan, V.; Ogale, S. B.; Liu, B.; Viehland, D.; Vaithyanathan, V.; Schlom, D. G.; Waghmare, U. V.; Spaldin, N. A.; Rabe, K. M.; Wuttig, M.; Ramesh, R. (14 March 2003). "Epitaxial BiFeO3 Multiferroic Thin Film Heterostructures". Science . 299 (5613): 1719–1722. Bibcode:2003Sci...299.1719W. doi:10.1126/science.1080615. hdl: 10220/7391 . PMID   12637741. S2CID   4789558.
  2. 1 2 Kubel, Frank; Schmid, Hans (1990). "Structure of a Ferroelectric and Ferroelastic Monodomain Crystal of the Perovskite BiFeO3". Acta Crystallographica . B46 (6): 698–702. doi: 10.1107/S0108768190006887 .
  3. ↑ Catalan, Gustau; Scott, James F. (26 June 2009). "Physics and Applications of Bismuth Ferrite" (PDF). Advanced Materials . 21 (24): 2463–2485. doi:10.1002/adma.200802849. S2CID   49689448. Archived from the original (PDF) on 3 January 2011. Retrieved 2 February 2012.
  4. ↑ D. Varshney, A. Kumar, K. Verma, Effect of A site and B site doping on structural, thermal, and dielectric properties of BiFeO3 ceramics, https://doi.org/10.1016/j.jallcom.2011.05.106
  5. ↑ Kiselev, S. V.; Ozerov, R. P.; Zhdanov, G. S. (February 1963). "Detection of magnetic order in ferroelectric BiFeO3 by neutron diffraction". Soviet Physics Doklady. 7 (8): 742–744. Bibcode:1963SPhD....7..742K.
  6. ↑ Spaldin, Nicola A.; Cheong, Sang-Wook; Ramesh, Ramamoorthy (1 January 2010). "Multiferroics: Past, present, and future". Physics Today . 63 (10): 38. Bibcode:2010PhT....63j..38S. doi:10.1063/1.3502547. hdl: 20.500.11850/190313 . Retrieved 15 February 2012.
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  8. ↑ Seidel, J.; Martin, L. W.; He, Q.; Zhan, Q.; Chu, Y.-H.; Rother, A.; Hawkridge, M. E.; Maksymovych, P.; Yu, P.; Gajek, M.; Balke, N.; Kalinin, S. V.; Gemming, S.; Wang, F.; Catalan, G.; Scott, J. F.; Spaldin, N. A.; Orenstein, J.; Ramesh, R. (2009). "Conduction at domain walls in oxide multiferroics". Nature Materials . 8 (3): 229–234. Bibcode:2009NatMa...8..229S. doi:10.1038/NMAT2373. PMID   19169247.
  9. ↑ Sharma, Poorva; Varshney, Dinesh; Satapathy, S.; Gupta, P.K. (15 January 2014). "Effect of Pr substitution on structural and electrical properties of BiFeO3 ceramics". Materials Chemistry and Physics . 143 (2): 629–636. doi:10.1016/j.matchemphys.2013.09.045.
  10. ↑ Ghosh, Sushmita; Dasgupta, Subrata; Sen, Amarnath; Sekhar Maiti, Himadri (1 May 2005) [14 April 2005]. "Low-Temperature Synthesis of Nanosized Bismuth Ferrite by Soft Chemical Route". Journal of the American Ceramic Society . 88 (5): 1349–1352. doi:10.1111/j.1551-2916.2005.00306.x.
  11. ↑ Han, J.-T.; Huang, Y.-H.; Wu, X.-J.; Wu, C.-L.; Wei, W.; Peng, B.; Huang, W.; Goodenough, J. B. (18 August 2006) [18 July 2006]. "Tunable Synthesis of Bismuth Ferrites with Various Morphologies". Advanced Materials . 18 (16): 2145–2148. doi:10.1002/adma.200600072. S2CID   97665976.
  12. ↑ Ortiz-Quiñonez, José-Luis; Pal, Umapada; Villanueva, Martin Salazar (10 May 2018). "Effects of Oxidizing/Reducing Agent Ratio on Phase Purity, Crystallinity, and Magnetic Behavior of Solution-Combustion-Grown BiFeO Submicroparticles". Inorganic Chemistry. 57 (10): 6152–6160. doi:10.1021/acs.inorgchem.8b00755. PMID   29746118.
  13. ↑ Mei, Antonio B.; Saremi, Sahar; Miao, Ludi; Barone, Matthew; Tang, Yongjian; Zeledon, Cyrus; Schubert, Jürgen; Ralph, Daniel C.; Martin, Lane W.; Schlom, Darrell G. (2019-11-01). "Ferroelectric properties of ion-irradiated bismuth ferrite layers grown via molecular-beam epitaxy". APL Materials. 7 (11): 111101. Bibcode:2019APLM....7k1101M. doi: 10.1063/1.5125809 .
  14. ↑ Müller, Marvin; Huang, Yen-Lin; Velez, Saul; Ramesh, Ramamoorthy; Fiebig, Manfred; Trassin, Morgan (2021-10-04). "Training the Polarization in Integrated La0.15Bi0.85FeO3-Based Devices". Advanced Materials. 33 (52): 2104688. doi: 10.1002/adma.202104688 . hdl: 10486/704259 . PMID   34606122. S2CID   238258729.
  15. ↑ Zeches, R. J.; Rossell, M. D.; Zhang, J. X.; Hatt, A. J.; He, Q.; Yang, C.-H.; Kumar, A.; Wang, C. H.; Melville, A.; Adamo, C.; Sheng, G.; Chu, Y.-H.; Ihlefeld, J. F.; Erni, R.; Ederer, C.; Gopalan, V.; Chen, L. Q.; Schlom, D. G.; Spaldin, N. A.; Martin, L. W.; Ramesh, R. (12 November 2009). "A Strain-Driven Morphotropic Phase Boundary in BiFeO3". Science . 326 (5955): 977–980. Bibcode:2009Sci...326..977Z. doi:10.1126/science.1177046. PMID   19965507. S2CID   21497135.
  16. ↑ Mei, Antonio B.; Tang, Yongjian; Schubert, Jürgen; Jena, Debdeep; Xing, Huili (Grace); Ralph, Daniel C.; Schlom, Darrell G. (2019-07-01). "Self-assembly and properties of domain walls in BiFeO3 layers grown via molecular-beam epitaxy". APL Materials. 7 (7): 071101. Bibcode:2019APLM....7g1101M. doi: 10.1063/1.5103244 .
  17. ↑
  18. ↑ Yang, S.Y.; Seidel, J.; Byrnes, S.J.; Shafer, P.; Yang, C.H.; Rossell, M.D.; Yu, P.; Chu, Y.H.; Scott, J.F.; Ager, J.W.; Martin, L.W.; Ramesh, R. (2010). "Above-Bandgap Voltages from Ferroelectric Photovoltaic Devices". Nature Nanotechnology. 5 (2): 143–147. Bibcode:2010NatNa...5..143Y. doi:10.1038/nnano.2009.451. PMID   20062051. S2CID   16970573.
  19. ↑ Chatterjee, S.; Bera, A.; Pal, A.J. (2014). "p–i–n Heterojunctions with BiFeO3 Perovskite Nanoparticles and p- and n-Type Oxides: Photovoltaic Properties". ACS Applied Materials & Interfaces. 6 (22): 20479–20486. doi:10.1021/am506066m. PMID   25350523.

https://doi.org/10.1016/j.jallcom.2011.05.106

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