A review of Fe3O4 thin films: Synthesis, modification and applications

doi:10.1016/j.jmst.2018.01.011

Abstract

Abstract:

Magnetite (Fe₃O₄) has been used for thousands of years as one of the important magnetic materials. The rapid developments of thin film technology in the past few decades attract the attention of material scientists on the fabrication of magnetite thin films. In this article, we present an overview of recent progress on Fe₃O₄ thin films. The widely used preparation methods are surveyed, and the effect of substrates is discussed. Specifically the modified Fe₃O₄ thin films exhibit excellent electrical and magnetic properties compared with the pure films. It is noteworthy that modified Fe₃O₄ thin films can be put into two categories: (1) doped films, where foreign metal ions substitute iron ions at A or B sites; and (2) hybrid films, where magnetite phases are mixed with other materials. Notably, Fe₃O₄ thin films show great potentials in many applications such as sensors and batteries. It is expected that the investigations of Fe₃O₄ thin films will give us some breakthroughs in materials science and technology.

Key words: Fe₃O₄, Thin film, Preparation method, Modified film, Material science

Xiaoyi Wang, Yulong Liao, Dainan Zhang, Tianlong Wen, Zhiyong Zhong. A review of Fe₃O₄ thin films: Synthesis, modification and applications[J]. J. Mater. Sci. Technol., 2018, 34(8): 1259-1272.

Figures/Tables 18

Fig. 1. Atomic force microscope images of the iron oxide films grown at different substrate temperatures [45].

Fig. 2. Height AFM images of the deposits obtained at a substrate temperature of 750?K and upon irradiation at: (a) 213?nm, (b) 532?nm and (c) 1064?nm. All the images are 80?nm high and the scale bar is 500?nm [50].

Fig. 3. Dependence of the magnetization on temperature (warming curves) with an in-plane applied field of 2?kOe for magnetite films fabricated at a substrate temperature of 750?K and a deposition wavelength: (a) 213?nm, (b) 532?nm, and (c) 1064?nm. Inset to (b) presents the determination of the corresponding Verwey temperature by taking the temperature at which the maximum slope of the magnetization takes place [50].

Fig. 4. RHEED pattern along the 〈110〉 and SEM image for a 1.7?nm layer grown (a) by MBE and (b) by PLD and for a 7.5?nm layer grown (c) by MBE and (d) by PLD. The layer grown by MBE revealed a 2D growth, whereas the layer grown by PLD revealed an island growth. As a reference, the RHEED pattern along the 〈110〉 direction for a clean substrate is shown in the center of the figure [10].

Fig. 5. AFM 2D images (2?μm?×?2?μm) and the corresponding height profiles along the solid lines in the 2D images of the Al2O3 substrate and the Fe3O4 films: (a) Al2O3 substrate; (b)-(f) 2?u.c., 10?u.c., 40?u.c., 100?u.c. and 200?u.c. Fe3O4 film, respectively [60].

Table 1 Summary of the predicted and observed strain relaxation values for the epitaxial magnetite films as a function of film thickness [61].

Sample	Thickness (nm)	Strain relaxation predicted by FKR model (%)	Observed strain relaxation (%)
Fe₃O₄/MgAl₂O₄	40	87	60
	60	91	84
	120	95	95.6

Fig. 6. SEM images of the Fe3O4 particles grown at -1.15?V (Ag/AgCl) for different period of time of (a) 0, (b) 200, (c) 400, (d) 600, (e) 800, and (f) 1000?s [68].

Fig. 7. (a) HRTEM overview image of the Fe3O4/SrTiO3 heterostructure showing uniform film thickness of ～80?nm and a sharp interface between film and substrate. (b) SAD pattern from the interface region. The Fe3O4 and SrTiO3 motifs are outlined (Fe3O4 in red, SrTiO3 in green). (c, d) show SAD simulations of Fe3O4 (red) and SrTiO3 (green) depending on whether the Fe3O4 structure is mirrored around the vertical axis. (c) SAD along the [-110] viewing direction for both SrTiO3 and Fe3O4. (d) SAD along the [-110] viewing direction for SrTiO3 and the [1-10] viewing direction for Fe3O4. The correspondence between (b, d) shows that the Fe3O4 is mirrored from direct cube on cube epitaxy [96].

Fig. 8. (a) Illustration of the self-template process for growing (001)-oriented Fe3O4 films on a SrTiO3(001) substrate. (b) Temperature history of the self-template Fe3O4 film growth process, with gray shading denoting the deposition periods of the 8?nm template layer at 400?°C and the main 142?nm film at 900?°C. The arrows mark the start and end points of each deposition step. The dotted line represents the minimum measurement temperature ofthe infrared optical pyrometer used for process control [38].

Fig. 9. (a) Low magnification cross-sectional TEM image of an 8?nm thick film showing its homogeneity in thickness and structure. (b) Cross-sectional HRTEM image of the same 8?nm thick Fe3O4 (111) film deposited on Al2O3(0001) containing an APB [102].

Fig. 10. Resistivity curves for a selection of Fe3O4(111) films 50, 15, 8, and 5?nm in thickness. The measurements in the main figure were taken using a four-probe setup, whereas the curves for the 8 and 5?nm films shown in the inset were obtained by a two-probe setup in order to measure down to 40?K [102].

Fig. 11. Room temperature hysteresis loops of magnetite thin films deposited on Si(100), MgO(100) and quartz substrates at 400?°C substrate temperature [46].

Fig. 12. Magnetic properties of pure and Co-doped Fe3O4 [139].

Fig. 13. (a), (c) TEM and (b), (d) HRTEM images of pristine Fe3O4 and Fe3O4@SnO2 hybrid nanorods, respectively. Inset in (b) is the FFT [144].

Fig. 14. A schematic illustration of the formation of 3D porous nano-Ni/Fe3O4 composite film [145].

Fig. 15. (a) Current density versus voltage (J-V) characteristics of PSCs measured under 100?mW?cm-2 AM 1.5?G illumination. (b) IPCE spectra of PSCs [154].

Table 2 Effects of different interferents on H2O2 determination by our sensor [160].

Interferent	Current ratio (%)	Interferent	Current ratio (%)	Interferent	Current ratio (%)
Sucrose	5.60	Glycine	4.55	Mg(NO₃)₂	0.85
D-fructose	4.10	Histamine	0.09	CaCl₂	4.64
D-(+)-maltose	1.08	Fumaric acid	2.12	Al₂(SO4)₃	0.88
β-d-lactose	0.02	Caffeine	0.10	BSA^a	3.18
D-(+)-glucose	0.79	Citric acid	3.89	KCl	2.37
Na₂CO₃	0.05	Mannose	2.09	Xanthan gum^a	0.04
NaCl^c	1.57	Dopamine	0.06	Ascorbic acid	0.20
Uric acid	0.40	Casein^b	1.60	β-lactogluboin^a	5.86
KH₂PO₄^c	1.86	Na₂HPO₄^c	2.03

Fig. 16. (a) MRxx plotted versus the magnetic field H applied perpendicular to the film plane at different temperatures for Zn0.1Fe2.9O4 thin films grown in pure Ar atmosphere. (b) MRxx(H) curves measured at 300?K for different ZnxFe3-xO4 grown in pure Ar atmosphere (left) or an Ar/O2 mixture (right) [12].

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A review of Fe₃O₄ thin films: Synthesis, modification and applications

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