Morphological Changes in ZnO Nano- and Microstructures Synthesized by Pyrolytic Technology

Abstract:

Pyrolytic technology was developed to grow Zn-based nano- and microstructures. It was based on the application of a mixture of ammonium chloride, Zn and ZnO powders as source materials. Two temperature profiles were used for the synthesis. In the first and second growth processes, the maximum substrate temperatures of 250 and 410°C were reached, respectively. The granular layer of micrometer range ZnO crystals was produced in the first process. By depleting the source with NH₄Cl, the Zn polyhedra, and layered spheres were produced within 50–65 min in the second process. By increasing the NH₄Cl content in the source to 0.9 g, the Zn/ZnO core–shell spheres were synthesized. The further increase of process duration led to the out-diffusion of Zn from the core, its oxidation, and the formation of a thick, dense ZnO spherical shell. Even further annealing in residual gases caused the increase of the Zn vapor pressure inside the shell. As a result, at a certain Zn vapor pressure, the shell bursts, causing the formation of a hollow ZnO microsphere.

• Periodical: Materials Science Forum (Volume 1166)
• Pages: 71-81
• DOI: https://doi.org/10.4028/p-9lKM4Z
• Online since: November 2025
• Authors: David Jishiashvili*, Zeinab Shiolashvili, Ekaterine Sanaia, Nino Makhatadze, Alexander Jishiashvili
• Keywords: Ammonium Chloride, Hollow Sphere, Metallic Zinc, Morphology, Nanocrystal, Pyrolysis, Zinc Oxide

References

[1] E. Maruccia, S. Galliano, E. Schiavo, N. Garino, A.Y.S. Zarate, A.B. Munoz–Garcia, M. Pavone, C. Gerbaldi, C. Barolo, V. Cauda, F. Bella, Exploring zinc oxide morphologies for aqueous solar cells by a photoelectrochemical, computational, and multivariate approach, Energy Adv. 3 (2024) 1062-1072.

DOI: 10.1039/d4ya00010b

[2] A.F. Gouveia, S.C.S. Lemos, E.R. Leite, E. Longo, J. Andres, Back to the basics: Probing the role of surfaces in the experimentally observed morphological evolution of ZnO, Nanomaterials 13 (2023) 978 (1-15).

DOI: 10.3390/nano13060978

[3] H.F. Wilson, Ch. Tang, A.S. Barnard, Morphology of zinc oxide nanoparticles and nanowires: Role of surface and edge energies, J. Phys. Chem. C 120 (2016) 9498-9505.

DOI: 10.1021/acs.jpcc.6b01479

[4] A. Fallatah, M. Kuku, L. Alqahtani, A. Bubshait, N.S. Almutairi, S. Padalkar, A.M. Alotaibi, Role of morphology on zinc oxide nanostructures for efficient photoelectrochemical activity and hydrogen production, Materials 17 (2024) 5135 (1-15).

DOI: 10.3390/ma17205135

[5] S.K. Jha, A. Mishra, A comprehensive review on nanoflowers: Synthesis, characterization and applications, Int. J. Multidiscip. Res. 6 (2024) 1-20.

[6] A.A. Ansari, R. Lv, S. Gai, A.K. Parchur, P.R. Solanki, Archana, Z.A. Ansari, M. Dhayal, P. Yang, M.K. Nazeeruddin, M.M. Tavakoli, ZnO nanostructures – Future frontiers in photocatalysis, solar cells, sensing, supercapacitor, fingerprint technologies, toxicity, and clinical diagnostics, Coord. Chem. Rev. 515 (2024) 215942 (1-55).

DOI: 10.1016/j.ccr.2024.215942

[7] A. Galdamez–Martinez, G. Santana, F. Guell, P.R. Martinez–Alanis, A. Dutt, Photoluminescence of ZnO nanowires: A review, Nanomaterials 10 (2020) 857 (1-23).

DOI: 10.3390/nano10050857

[8] A. Barzinjy, S. Hamad, H. Azeez, Structure, synthesis and applications of ZnO nanoparticles: A review, Jordan J. Appl. Sci. 13 (2020) 123-135.

[9] J. Piqueras, P. Hidalgo, Growth of metal oxide nanostructures by thermal oxidation of metals under influence of external electric fields and electric current flow, Physica Status Solidi A (2021) 2100323 (1-8).

DOI: 10.1002/pssa.202100323

[10] M.A. Borysiewicz, ZnO as a functional material, a review, Crystals 9 (2019) 505-529.

[11] V. Cauda, R. Gazia, S. Porro, S. Stassi, G. Canavese, I. Roppolo, A. Chiolerio, Nanostructured ZnO materials: Synthesis, properties and applications, in: B. Bhushan, D. Luo, S. Schricker, W. Sigmund, S. Zauscher (Eds.), Handbook of Nanomaterials Properties, Springer, Berlin–Heidelberg, 2014, pp.137-177.

DOI: 10.1007/978-3-642-31107-9_32

[12] N.D. Dien, Preparation of various morphologies of ZnO nanostructure through wet chemical methods, Adv. Mater. Sci. 4 (2019) 1-5.

DOI: 10.15761/ams.1000147

[13] Y. Ding, Z.L. Wang, T. Sun, J. Qiu, Zinc-blende ZnO and its role in nucleating wurtzite tetrapods and twinned nanowires, Appl. Phys. Lett. 90 (2007) 153510 (1-3).

DOI: 10.1063/1.2722671

[14] X. Chang, S. Vijay, Y. Zhao, N. J. Oliveira, K. Chan, B. Xu, Understanding the complementarities of surface-enhanced infrared and Raman spectroscopies in CO adsorption and electrochemical reduction, Nat. Commun. 13 (2022) 2656 (1-12).

DOI: 10.1038/s41467-022-30262-2

[15] Y. Jiao, Y. Pan, M. Yang, Zh. Li, J. Yu, R. Fu, B. Man, C. Zhang, X. Zhao, Micro–nano hierarchical urchin-like ZnO/Ag hollow sphere for SERS detection and photodegradation of antibiotics, Nanophotonics 13 (2024) 307-318.

DOI: 10.1515/nanoph-2023-0659

[16] X. Zhou, W. Feng, C. Wang, H. Xiaolong, X. Li, P. Sun, K. Shimanoe, N. Yamazoe, G. Lu, Porous ZnO/ZnCo2O4 hollow spheres: Synthesis, characterization, and applications in gas sensing, J. Mater. Chem. A 2 (2014) 17683 (1-8).

DOI: 10.1039/c4ta04386c

[17] S.K. Guang, X. J. Xie, J. Zheng, Y.N. Wang, Y.F. Guo, C. Cheng, Y. Wu, X.Y. Zheng, C.C. Wang, Synthesis of hierarchical ZnO/C hollow spheres constructed by octahedron for water treatment, J. Mater. Sci. 55 (2020) 11938-11948.

DOI: 10.1007/s10853-020-04879-x

[18] L.A. Zadorozhnaya, A.P. Tarasov, V.M. Kanevsky, The growth mechanism, luminescence, and lasing of polyhedral ZnO microcrystals with whispering-gallery modes, Photonics 10 (2023) 1328 (1-12).

DOI: 10.3390/photonics10121328

[19] T.H.B. Ngo, Y.C. Chang, Whispering gallery modes in hybrid Au–ZnO microsphere resonators: Experimental and theoretical investigations, Opt. Mater. Express 7 (2017) 2962-2967.

DOI: 10.1364/ome.7.002962

[20] Y. Liu, C. Xu, Z. Zhu, D. You, R. Wang, F. Qin, X. Wang, Q. Cui, Z. Shi, Controllable fabrication of ZnO microspheres for whispering gallery mode microcavity, Cryst. Growth Des. 18 (2018) 5279-5286.

DOI: 10.1021/acs.cgd.8b00716

[21] V.A. Borisov, A.N. D'yachenko, R.I. Kraidenko, Reaction of zinc oxide with ammonium chloride, Russian J. Inorg. Chem. 57 (2012) 499-501.

DOI: 10.1134/s0036023612040043

[22] S.-H. Na, Ch-H. Park, First-principles study of the surface of wurtzite ZnO and ZnS – Implications for nanostructure formation, J. Korean Phys. Soc. 54 (2009) 867-872.

DOI: 10.3938/jkps.54.867

[23] H.F. Wilson, Ch. Tang, A.S. Barnard, Morphology of zinc oxide nanoparticles and nanowires: Role of surface and edge energies, Phys. Chem. C. 120 (2016) 9498-9505.

DOI: 10.1021/acs.jpcc.6b01479

[24] V. Jabbari, T. Foroozan, R. Shahbazian–Yassar, Dendritic Zn deposition in zinc-metal batteries and mitigation strategies, Adv. Energy Sustainability Res. 2 (2021) 2000082 (1-15).

DOI: 10.1002/aesr.202000082

[25] P.X. Gao, Ch.Sh. Lao, Y. Ding, Z.L. Wang, Metal/semiconductor core/shell nanodisks and nanotubes, Adv. Funct. Mater. 16 (2006) 53-62.

DOI: 10.1002/adfm.200500301

[26] Ch.F. Guo, Y. Wang, P. Jiang, S. Cao, J. Miao, Zh. Zhang, Q. Liu, Zinc oxide nanostructures: Epitaxially growing from hexagonal zinc nanostructures, Nanotechnology 19 (2008) 445710 (1-8).

DOI: 10.1088/0957-4484/19/44/445710

[27] L. Ren, Zh. Hub, Ch. Peng, L. Zhang, N. Wang, F. Wang, Y. Xi, S. Zhang, E. Hu, J. Luo, Suppressing metal corrosion through identification of optimal crystallographic plane for Zn batteries, Proc. Natl. Acad. Sci. USA 121 (2024) e2309981121 (1-9).

DOI: 10.1073/pnas.2309981121

[28] T. Shen, T. Wei, Sh. Zhang, H. Liu, Ch. Li, Zh. Li, M. Yang, Ch. Liu, Y. P. Single, Crystalline Zn(002) facet enables ultrastable anode–electrolyte interface, Small Str. 6 (2025) 2400325 (1-7).

DOI: 10.1002/sstr.202400325

[29] L. Kabalan, I. Kowalec, C. Richard, A. Catlow, A.J. Logsdail, A computational study of the properties of low- and high-index Pd, Cu and Zn surfaces, Phys. Chem. Chem. Phys. 23 (2021) 14649 (1-13).

DOI: 10.1039/d1cp01602d

[30] H.A. Wriedt, The O–Zn (oxygen–zinc) system, J. Phase Equilibrium 8 (1987) 166-167.

[31] C.B. Alcock, Vapor pressure of the metallic elements, in: CRC Handbook of Chemistry and Physics, 83rd ed., CRC Press, Boca Raton, 2002–2003, p.4.134-4.136.

[32] C.L. Yaws, The Yaws Handbook of Vapor Pressure. Antoine Coefficients, 2nd ed., Gulf Professional Publ., Oxford–Waltham, 2015.

[33] L. Castaneda, Synthesis and characterization of ZnO micro- and nano-cages, Acta Materialia 57 (2009) 1385-1391.

DOI: 10.1016/j.actamat.2008.11.022

[34] P. X. Gao, Zh.L. Wang, Mesoporous polyhedral cages and shells formed by textured self-assembly of ZnO nanocrystals, J. American Chem. Soc. 125 (2003) 11299-11305.

DOI: 10.1021/ja035569p

[35] H.J. Fan, R. Scholz, F.M. Kolb, M. Zacharias, U. Gosele, Growth mechanism and characterization of zinc oxide microcages, Solid State Commun. 130 (2004) 517-521.

DOI: 10.1016/j.ssc.2004.03.014

[36] J .Q. Hu, Q. Li, X.M. Men, C.S. Lee, S.T. Lee, Thermal reduction route to the fabrication coaxial Zn/ZnO nanocables and nanotubes, Chem. Mater. 15 (2003) 305-308.

DOI: 10.1021/cm020649y

[37] X.Y. Kong, Y. Ding, Z.L. Wang, Metal–semiconductor Zn–ZnO core–shell nanobelts and nanotubes, J. Phys. Chem. B 108 (2004) 570-574.

DOI: 10.1021/jp036993f

[38] Ch.-Y. Hsu, K.-H. Chang, J.-A. Gong, J. Tiren, Y.-Y. Liab, A. Sakoda, Kirkendall void formation and selective directional growth of urchin-like ZnO/Zn microspheres through thermal oxidation in air, RSC Adv. 5 (2015) 103884-103894.

DOI: 10.1039/c5ra19168h

[39] A.-A. El Mel, R. Nakamura, C. Bittencourt, The Kirkendall effect and nanoscience: Hollow nanospheres and nanotubes, Beilstein J. Nanotechnol. 6 (2015) 1348-1361.

DOI: 10.3762/bjnano.6.139

[40] R.D. Vais, H. Heli, The Kirkendall effect: Its efficacy in the formation of hollow nanostructures, J. Biol. Today's World. 5 (2016) 137-149.

DOI: 10.15412/j.jbtw.01050802

[41] D. Weibel, Z.R. Jovanovic, E. Galvez, A. Steinfeld, Mechanism of Zn particle oxidation by H2O and CO2 in the presence of ZnO, Chem. Mater. 26 (2014) 6486-6495.

DOI: 10.1021/cm503064f