2.5.
Hydrothermal Method
Spray pyrolysis is a versatile and cost-effective technique widely employed to
synthesize high-quality ZnO nanostructures. This method involves several key steps:
preparing a precursor solution, generating an aerosol mist, and transporting the mist to
a heated substrate using a carrier gas. The final product forms as a thin film or
nanostructure on the substrate surface, while volatile by-products are removed. The
deposition temperature is a critical parameter-ideally, it must be high enough to allow
only the desired ZnO to remain while other components evaporate.
In one study, Htay et al. (2012) utilized zinc acetate dihydrate dissolved in deionized
water to prepare ZnO nanowires. Ammonium acetate was added to adjust the pH,
optimizing the reaction environment. The deposition occurred on glass substrates at
temperatures ranging from 250°C to 400°C, which facilitated the growth of uniform
nanowires with controlled stoichiometry and morphology [1].
In another approach, Karber et al. (2010) synthesized ZnO nanorods using ZnCl₂ as
the precursor. Substrates included soda-lime glass and indium tin oxide (ITO) coated
glass. The deposition was carried out at 550°C, resulting in nanostructures with
superior optical characteristics [2]. Despite these advantages, spray pyrolysis is still
associated with relatively low material yield, which limits its scalability.
2.6. Molecular beam epitaxy
Molecular Beam Epitaxy (MBE) is a precise technique for growing high-purity ZnO
nanostructures through the controlled interaction of atomic or molecular beams with a
heated substrate under ultra-high vacuum. Tien et al. (2006) utilized metallic zinc and
an O₃/O₂ plasma as precursors to grow ZnO nanorods selectively on silver (Ag)
islands pre-deposited on SiO₂ and SiNₓ substrates. The Ag islands ranged from 8–30
nm and 10–65 nm, respectively. Growth occurred at 600°C under a base pressure of 5
× 10⁻⁸ mbar, with oxygen pressures between 5 × 10⁻⁶ and 5 × 10 ⁻⁴ mbar [3].
Similarly, Heo et al. (2002) synthesized ZnO nanowires with diameters of 30–150 nm
and lengths up to 14 µm on Ag-coated Al₂O₃ substrates [4]. Additionally, Feng et al.
(2007) reported the fabrication of ZnO nanotubes using plasma-assisted MBE on
silicon substrates [5]. Although MBE yields high structural and compositional quality,
its slow deposition rate limits scalability for industrial applications.
2.7. Electrochemical deposition
ZnO nanostructures can be synthesized through electrochemical deposition, where
nanorods or nanotubes are formed by simple electrolysis of a solution containing the
desired material and its complexes. The deposition process occurs on substrates such
as ITO or ZnO-coated ITO, using a three-electrode system, with a working electrode
(often glass/SnO2:F), a reference electrode (saturated calomel electrode), and a Pt
wire counter electrode[6],[7]. The electrolyte typically consists of 5 mM KCl and 0.1
M ZnCl2. A ZnO buffer layer is first coated onto the working electrode, followed by
the deposition of nanostructures. The concentration of ZnCl2 controls the diameter of
the rods. This process operates at low temperatures, with deposition times generally
ranging from a few minutes to several hours, depending on the desired thickness and
size of the nanostructures[8].
2.8. Thermal evaporation
In the thermal evaporation process, ZnO nanostructures are synthesized by heating
ZnO powder to high temperatures, causing the material to evaporate and deposit onto
a substrate. Ni-coated Si is commonly used as the substrate, with N2 and O2 gases
pumped into the system at flow rates of 5–15 and 10–30 sccm, respectively[9]. The
deposition time typically ranges from 30 to 120 minutes, with temperatures of 500–
550°C, resulting in nanorods with lengths of 4–5 mm and diameters between 300–350
nm[10]. Doping of ZnO can be achieved by placing dopant powders such as Ga, Sn,
or In along with ZnO powder. For example, Ga-doped ZnO is synthesized by placing
Ga powder with ZnO in the source material. The synthesis of nanotubes involves Zn
powder as the source material, with a reaction temperature of 475°C, using Ar gas for
transport and O2/O3 for oxidation[11]. Thermal evaporation avoids catalyst
contamination, but the high temperatures required limit substrate choices.
2.9. Hydrothermal method
The hydrothermal method is widely used for synthesizing ZnO nanostructures due to
its simplicity, low temperature operation, and catalyst-free nature, which ensures high
purity. In this method, zinc nitrate hexahydrate is commonly used as a precursor, often
combined with agents such as hexamethylene tetramine (HMTA), polyethylene glycol
(PEG), or ammonium compounds. For instance, nanowires have been synthesized
using 1 M (N H 4 )2 C O3and 0.04% PEG in distilled water with gradual addition of zinc
nitrate, followed by spin-coating onto a substrate and heating at 200°C for 10 hours
[12]. Nanorods can be formed using zinc nitrate hexahydrate and HMTA, with
polyethylene added to enhance the aspect ratio. These structures are typically annealed
at 200°C to 600°C, which promotes (001) orientation and improves crystallinity [13].
Nanotubes with diameters of 500 nm and lengths of 3 µm have been produced using
ZnCl₂ and ammonia at 95°C [14]. While the hydrothermal method yields controlled
morphology, it often results in lower aspect ratios and crystallinity, which may reduce
UV emission and optical quality. Improvements can be made by introducing a ZnO
seed layer and post-deposition annealing [15]. This method is chosen based on the
required nanostructure and application.
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