Engineering polarization surface of hierarchical ZnO microspheres via spray-annealing strategy for wide-frequency electromagnetic wave absorption

doi:10.1016/j.jmst.2022.05.015

Abstract

Abstract:

Regulating orientation growth plays a dominant role in enhancing dielectric properties for the electromagnetic (EM) functional materials, which faces a huge challenge in the synthesis method. By spray-annealing strategy, hierarchical ZnO microspheres assembled by ZnO nanorods and nanoparticles were successfully fabricated. With confined microsphere space and controlling crystal growth, oriented ZnO nanorods possess rich defects, Zn-polar, O-polar faces, and high permittivity. Meanwhile, temperature-dependency of exposed polarization surfaces is discovered in the semiconductor ZnO nanoparticles with evolved aspect ratios. As pure dielectric EM wave absorption material, the hierarchical ZnO microsphere exhibits adjustable complex permittivity and polarization behaviors. When the thickness is 2.4 mm, the hierarchical ZnO-1 absorber shows the widest efficient absorption (RL ≤ -10 dB) region from 9.9 to 18.0 GHz (8.1 GHz, ∼50.6% testing frequency). The minimum reflection loss (RL) of ZnO-1 can reach -31.5 dB at only 2.0 mm. Because of the outstanding dielectric loss ability and wide absorption frequency, large-scale hierarchical ZnO microspheres can be a potential EM absorption candidate.

Key words: ZnO microspheres, Spray drying, Electromagnetic wave absorption, Orientated polarization, Dielectric loss

Lei Wang, Mengqiu Huang, Xuefeng Yu, Wenbin You, Biao Zhao, Chongyun Liang, Xianhu Liu, Xuefeng Zhang, Renchao Che. Engineering polarization surface of hierarchical ZnO microspheres via spray-annealing strategy for wide-frequency electromagnetic wave absorption[J]. J. Mater. Sci. Technol., 2022, 131: 231-239.

Figures/Tables 9

Fig. 1. (a) Schematic diagram of ZnO microspheres, (b) XRD pattern of as-prepared ZnO microspheres, and (c) crystal plane diffraction intensity ratio.

Fig. 2. SEM images of (a, b) Zn-based spray powders; (c, d) ZnO-1, (e, f) ZnO-2, and (g, h) ZnO-3 microspheres.

Fig. 3. TEM images of (a) ZnO-1, (b) ZnO-2, (c) ZnO-3; HRTEM images of (d-i) ZnO-1; (j) interplanar spacing file; (k) HADDF image and (l, m) elements mapping distribution of ZnO-1 microspheres.

Fig. 4. Two-dimensional distribution of the RL values for (a) ZnO-1, (b) ZnO-2, and (c) ZnO-3; 3D histogram distribution of (d) RL values and (e) the EAB values, (f) RL curves of ZnO microspheres at 2.4 mm.

Fig. 5. (a) RL curves and (b) 1/4λ matching feature of ZnO-1 microsphere.

Fig. 6. Electromagnetic parameters of (a) ZnO-1, (b) ZnO-2, and (c) ZnO-3; (d) real part (ε'), (e) imaginary part (ε''),and (f) loss tangent (tanδε) of hierarchical ZnO microspheres.

Fig. 7. HRTEM images of (a) ZnO-1, (d) ZnO-2, and (g) ZnO-3, the corresponding dislocation strain fields distribution map of (b, c) ZnO-1, (e, f) ZnO-2, and (h, i) ZnO-3.

Fig. 8. Microwave absorption mechanism of hollow ZnO microspheres.

Table 1. Reflection loss ability of pure dielectric EM wave absorption composites.

Sample	Adding mass (%)	RL_min (dB)	Thickness (mm)	EAB (GHz)	Refs.
TiO₂ tube	60	-37.0	4.0	1.4	[52]
VO₂ microsheets	20	-45.8	1.9	3.4	[53]
Urchinlike MnO₂	50	-41.0	1.6	2.8	[10]
Dendritic-like ZnO	50	-42.0	2.0	3.5	[54]
Bead-like Co-doped ZnO	-	-12.2	2.5	3.2	[55]
CuS microspheres	30	-31.5	1.8	3.6	[16]
MoS₂ nanosheets	60	-47.8	2.0	5.2	[18]
SnO₂ Foam	30	-37.6	2.0	5.6	[14]
Net-like ZnO	50	-37.0	2.0	5.9	[9]
Hierarchical ZnO microspheres	50	-31.6	2.4	7.6	This work
ZnO whiskers	50	-20.5	1.2	8.8	[56]

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