Zinc oxide (ZnO) nanostructures are structures with at least one dimension on the nanometre scale, composed predominantly of zinc oxide. They may be combined with other composite substances to change the chemistry, structure or function of the nanostructures in order to be used in various technologies. Many different nanostructures can be synthesised from ZnO using relatively inexpensive and simple procedures. [1] ZnO is a semiconductor material with a wide band gap energy of 3.3eV and has the potential to be widely used on the nanoscale. ZnO nanostructures have found uses in environmental, technological and biomedical purposes including ultrafast optical functions, dye-sensitised solar cells, lithium-ion batteries, biosensors, nanolasers [2] and supercapacitors. [3] Research is ongoing to synthesise more productive and successful nanostructures from ZnO and other composites. [3] ZnO nanostructures is a rapidly growing research field, with over 5000 papers published during 2014-2019. [4]
ZnO creates one of the most diverse range of nanostructures, and there is a great amount of research on different synthesis routes of various ZnO nanostructures. [1] The most common methods to synthesise ZnO structures is using chemical vapor deposition (CVD), which is best used to form nanowires and comb or tree-like structures. [1]
In vapor deposition processes, zinc and oxygen are transported in gaseous form and react with each other, creating ZnO nanostructures. Other vapor molecules or solid and liquid catalysts can also be involved in the reaction, which affect the properties of the resultant nanostructure . To directly create ZnO nanostructures, one can decompose zinc oxide at high temperatures where it splits into zinc and oxygen ions and when cooled it forms various nanostructures, including complex structures such as nanobelts and nanorings. [5] Alternatively, zinc powder can be transported through oxygen vapor which react to form nanostructures . Other vapours such as nitrous oxide or carbon oxides can be used by themselves or in combination. These methods are known as vapor-solid (VS) processes due to their reactants states. VS processes can create a variety of ZnO nanostructures but their morphology and properties are highly dependent on the reactants and reaction conditions such as the temperature and vapor partial pressures. [1]
Vapor deposition processes can also use catalysts to assist the growth of nanostructures. These are known as vapor-liquid-solid (VLS) processes, and use a catalytic liquid alloy phase as an extra step in nanostructure synthesis to accelerate growth. [6] The liquid alloy, which includes zinc, is attached to nucleated seeds made usually of gold or silica. The alloy absorbs the oxygen vapor and saturates, facilitating a chemical reaction between zinc and oxygen. The nanostructure develops as the ZnO solidifies and grows outwards from the gold seed. This reaction can be highly controlled to produce more complex nanostructures by modifying the size and arrangement of gold seeds, and of the alloys and vapor constituents. [1]
A large variety of ZnO nanostructures can also be synthesised by growth in an aqueous solution, which is desirable due to its simplicity and low processing temperature. [7] A ZnO seed layer is used to begin uniform growth and to ensure nanowires are oriented. A solution of catalysts and molecules containing zinc and oxygen are reacted and nanostructures grow from the seed layer. An example of such a reaction involves hydrolysing ZnO(NO3)2 (zinc nitrate) and the decomposition of hexamethyltetramine (HMT) to form ZnO. [1] Altering the growth solution and its concentration, temperature and structure of the seed layer can change the morphology of the synthesised nanostructures. [8] [1] Nanorods, aligned nanowire arrays, flower-like and disc like nanowires and nanobelt arrays, along with other nanostructures, can all be created in aqueous solutions by varying the growth solution. [7]
Another method to synthesise ZnO nanostructures is electrodeposition, which uses electric current to facilitate chemical reactions and deposition on electrodes. Its low temperature and ability to create precise thickness structures makes it a cost-effective and environmentally friendly method. [9] Structured nanocolumnar crystals, porous films, thin films and aligned wires have been synthesised in this way. The quality and size of these structures depends on substrates, current density, deposition time and temperature. [10] [11] [9] The bandgap energy is also dependent on these parameters, since it is dependent not only on the material but also its size due to the nanoscale effect on the band structure. [1]
ZnO has a rich defect and dopant chemistry that can significantly alter properties and behaviour of the material. [1] Doping ZnO nanostructures with other elements and molecules leads to a variety of material characteristics, because the addition or vacancy of atoms changes the energy levels in the band gap. [12] Native defects due to oxygen and zinc vacancies or zinc interstitials create its n-type semiconductor properties, but the behaviour is not fully understood. [13] Carriers created by doping have been found to exhibit a strong dominance over native defects. [1] Nanostructures contain small length scales, and this results in a large surface to volume ratio. Surface defects have hence been the primary focus of research into defects of ZnO nanostructures. Deep level emissions also occur, affecting material characteristics. [4]
ZnO can occupy multiple types of lattices, but is often found in a hexagonal wurtzite structure. In this lattice all of the octahedral sites are empty, hence there is space for intrinsic defects, Zn interstitials, and also external dopants to occupy gaps in the lattice, [1] even when the lattice is at a nanoscale. Zn interstitials occur when extra zinc atoms are located inside the crystal ZnO lattice. They occur naturally but their concentration can be increased by using Zn vapor rich synthesis conditions. Oxygen vacancies are common defects in metal oxides where an oxygen atom is left out of the crystal structure. [14] Both oxygen vacancies and Zn interstitials increase the number of electron charge carriers, thus becoming an n-type semiconductor. Since these defects occur naturally as a by-product of the synthesis process, it is difficult to make p-type ZnO nanostructures. [15]
Defects and dopants are usually introduced during the synthesis of the ZnO nanostructure, either by controlling their formation or accidentally obtained during the growing process through contamination. Since it is difficult to control these processes, defects occur naturally. Dopants can diffuse into the nanostructure during synthesis. Alternatively, the nanostructures can be treated after synthesis such as through plasma injection or exposure to gases. Unwanted dopants and defects can also be manipulated so that they are removed or passivated. Crudely, the region of the nanostructure can be fully removed, such as cutting off the surface layer of a nanowire. Oxygen vacancies can be filled using plasma treatment, where an oxygen containing plasma inserts oxygen back into the lattice. At temperatures where the lattice is mobile, oxygen molecules and gaps can be moved using electric fields to change the nature of the material. [4]
Defects and dopants are used in most ZnO nanostructure applications. Indeed, the defects in ZnO enable a variety of semiconductor properties with different band gaps. By combining ZnO with dopants, a variety of electrical and material characteristics can be achieved. For example, optical properties of ZnO can change through defects and dopants. [16] Ferromagnetic properties can be introduced into ZnO nanostructures through doping with transition metal elements. This creates magnetic semiconductors, which is a focus of spintronics. [12]
ZnO nanostructures can be used for many different applications. Here are a few examples.
Dye sensitised solar cells (DSSCs) are a type of thin film solar cell that uses a liquid dye to absorb sunlight. Currently TiO2 (titanium dioxide) is mostly in use for DSSCs as the photoanode material. However ZnO is found to be a good candidate for photoanode material in DSSCs. [1] [3] This is because the nanostructure synthesis is easy to control, [1] it has higher electron transport properties, [3] and it is possible to use organic material as hole transporter, unlike when TiO2 is the photoanode material. [1] Researchers have found that the structure of ZnO nanostructure affects the solar cell performance. [17] There are also disadvantages for using ZnO nanostructures, like a so called voltage leakage that needs more investigation. [3]
Rechargeable lithium-ion batteries (LIBs) are currently the most common power source since they produce high power and have a high energy density. The use of metal oxides as anodes has largely improved the limitations of the batteries, and ZnO is particularly seen as an up-and-coming potential anode. This is due to its low toxicity and costs, and its high theoretical capacity (978 mAhg−1).
ZnO experiences volume expansion during processes resulting in a loss of electrical disconnection, decreasing capacity. A solution may be to dope with different materials and to develop on the nanoscale with nanostructures, such as porous surfaces, that allow for volume changes during the chemical process. Alternatively, lithium storage components can be mixed in with the ZnO nanostructures to create a more stable capacity. Research has been successful in synthesising such composite ZnO nanostructures with carbon, graphite, and other metal oxides. [3]
Another commonly used energy storage appliance are supercapacitors (SCs). The SCs are mostly used in electric vehicles and as backup power systems. They are known for being environmentally friendly and may replace the currently used energy storage devices. This is due to its more advanced stability, power density and overall greater performance. Because of its remarkable energy density of 650Aħg−1 and electrical conductivity of 230Scm−1 ZnO is recognized as a great potential electrode material. Nonetheless it has poor electrical conductivity as its small surface area makes for a restricted capacity. Just as for the batteries, multiple combinations of carbon structures, graphene, metal oxides with ZnO nanostructures have improved capacitance of these materials. A composite with ZnO base has not only a better power density and energy density, but is also more cost-effective and eco-friendly. [3]
It has already been discovered that ZnO nanostructures are able to bind biological substances. Recent research shows that because of this trait and because of its surface selectivity, ZnO is a good candidate for a biosensor. It can naturally form anisotropic nanostructures that are used to deliver drugs. ZnO based biosensors can also help in diagnosing the early stages of cancer. [3] There is ongoing research to see if ZnO nanostructures can be used for bioimaging. It has so far only been tested on mice and shows positive results. [3] In addition, ZnO nanomaterials are already used in cosmetic products, like face creams and sun cream [18]
It is, however, not yet clear what the effect of ZnO nanostructures is on human cells and the environment. Since used ZnO biosensors will eventually dissolve and release Zn ions, they may be absorbed by the cells and the local effect of this is not yet known. Nanomaterials in cosmetics will eventually be washed off and released in the environment. Due to these unknown risks, there needs to be a lot more research before ZnO can be safely applied in the biomedical field. [18]
A nanowire is a nanostructure in the form of a wire with the diameter of the order of a nanometre. More generally, nanowires can be defined as structures that have a thickness or diameter constrained to tens of nanometers or less and an unconstrained length. At these scales, quantum mechanical effects are important—which coined the term "quantum wires".
A phosphor is a substance that exhibits the phenomenon of luminescence; it emits light when exposed to some type of radiant energy. The term is used both for fluorescent or phosphorescent substances which glow on exposure to ultraviolet or visible light, and cathodoluminescent substances which glow when struck by an electron beam in a cathode-ray tube.
Indium tin oxide (ITO) is a ternary composition of indium, tin and oxygen in varying proportions. Depending on the oxygen content, it can be described as either a ceramic or an alloy. Indium tin oxide is typically encountered as an oxygen-saturated composition with a formulation of 74% In, 8% Sn, and 18% O by weight. Oxygen-saturated compositions are so typical that unsaturated compositions are termed oxygen-deficient ITO. It is transparent and colorless in thin layers, while in bulk form it is yellowish to gray. In the infrared region of the spectrum it acts as a metal-like mirror.
Thermoelectric materials show the thermoelectric effect in a strong or convenient form.
Zinc oxide is an inorganic compound with the formula ZnO. It is a white powder which is insoluble in water. ZnO is used as an additive in numerous materials and products including cosmetics, food supplements, rubbers, plastics, ceramics, glass, cement, lubricants, paints, sunscreens, ointments, adhesives, sealants, pigments, foods, batteries, ferrites, fire retardants, semi conductors, and first-aid tapes. Although it occurs naturally as the mineral zincite, most zinc oxide is produced synthetically.
A nanoring is a cyclic nanostructure with a thickness small enough to be on the nanoscale. Note that this definition allows the diameter of the ring to be larger than the nanoscale. Nanorings are a relatively recent development within the realm of nanoscience; the first peer-reviewed journal article mentioning these nanostructures came from researchers at the Institute of Physics and Center for Condensed Matter Physics in Beijing who synthesized nanorings made of gallium nitride in 2001. Zinc oxide, a compound very commonly used in nanostructures, was first synthesized into nanorings by researchers at Georgia Institute of Technology in 2004, and several other common nanostructure compounds have been synthesized into nanorings since. More recently, carbon-based nanorings have been synthesized from cyclo-para-phenylenes as well as porphyrins.
Magnetic semiconductors are semiconductor materials that exhibit both ferromagnetism and useful semiconductor properties. If implemented in devices, these materials could provide a new type of control of conduction. Whereas traditional electronics are based on control of charge carriers, practical magnetic semiconductors would also allow control of quantum spin state. This would theoretically provide near-total spin polarization, which is an important property for spintronics applications, e.g. spin transistors.
In nanotechnology, nanorods are one morphology of nanoscale objects. Each of their dimensions range from 1–100 nm. They may be synthesized from metals or semiconducting materials. Standard aspect ratios are 3-5. Nanorods are produced by direct chemical synthesis. A combination of ligands act as shape control agents and bond to different facets of the nanorod with different strengths. This allows different faces of the nanorod to grow at different rates, producing an elongated object.
Lutetium aluminum garnet (commonly abbreviated LuAG, molecular formula Lu3Al5O12) is an inorganic compound with a unique crystal structure primarily known for its use in high-efficiency laser devices. LuAG is also useful in the synthesis of transparent ceramics.
Dimethylzinc, also known as zinc methyl, DMZ, or DMZn, is a toxic organozinc compound with the chemical formula Zn(CH3)2. It belongs to the large series of similar compounds such as diethylzinc.
The vapor–liquid–solid method (VLS) is a mechanism for the growth of one-dimensional structures, such as nanowires, from chemical vapor deposition. The growth of a crystal through direct adsorption of a gas phase on to a solid surface is generally very slow. The VLS mechanism circumvents this by introducing a catalytic liquid alloy phase which can rapidly adsorb a vapor to supersaturation levels, and from which crystal growth can subsequently occur from nucleated seeds at the liquid–solid interface. The physical characteristics of nanowires grown in this manner depend, in a controllable way, upon the size and physical properties of the liquid alloy.
Transparent conducting films (TCFs) are thin films of optically transparent and electrically conductive material. They are an important component in a number of electronic devices including liquid-crystal displays, OLEDs, touchscreens and photovoltaics. While indium tin oxide (ITO) is the most widely used, alternatives include wider-spectrum transparent conductive oxides (TCOs), conductive polymers, metal grids and random metallic networks, carbon nanotubes (CNT), graphene, nanowire meshes and ultra thin metal films.
The Center of Excellence (CoE) in Nanotechnology is located at the Asian Institute of Technology campus. It is one of the eight centers of excellence in Thailand.
A nanogenerator is a compact device that converts mechanical or thermal energy into electricity, serving to harvest energy for small, wireless autonomous devices. It uses ambient energy sources like solar, wind, thermal differentials, and kinetic energy. Nanogenerators can use ambient background energy in the environment, such as temperature gradients from machinery operation, electromagnetic energy, or even vibrations from motions.
Most of the synthesized Zinc oxide (ZnO) nanostructures in different geometric configurations such as nanowires, nanorods, nanobelts and nanosheets are usually in the wurtzite crystal structure. However, it was found from density functional theory calculations that for ultra-thin films of ZnO, the graphite-like structure was energetically more favourable as compared to the wurtzite structure. The stability of this phase transformation of wurtzite lattice to graphite-like structure of the ZnO film is only limited to the thickness of about several Zn-O layers and was subsequently verified by experiment. Similar phase transition was also observed in ZnO nanowire when it was subjected to uniaxial tensile loading. However, with the use of the first-principles all electron full-potential method, it was observed that the wurtzite to graphite-like phase transformation for ultra-thin ZnO films will not occur in the presence of a significant amount of oxygen vacancies (Vo) at the Zn-terminated (0001) surface of the thin film. The absence of the structural phase transformation was explained in terms of the Coulomb attraction at the surfaces. The graphitic ZnO thin films are structurally similar to the multilayer of graphite and are expected to have interesting mechanical and electronic properties for potential nanoscale applications. In addition, density functional theory calculations and experimental observations also indicate that the concentration of the Vo is the highest near the surfaces as compared to the inner parts of the nanostructures. This is due to the lower Vo defect formation energies in the interior of the nanostructures as compared to their surfaces.
Band-gap engineering is the process of controlling or altering the band gap of a material. This is typically done to semiconductors by controlling the composition of alloys, constructing layered materials with alternating compositions, or by inducing strain either epitaxially or topologically. A band gap is the range in a solid where no electron state can exist. The band gap of insulators is much larger than in semiconductors. Conductors or metals have a much smaller or nonexistent band gap than semiconductors since the valence and conduction bands overlap. Controlling the band gap allows for the creation of desirable electrical properties.
Gallium nitride nanotubes (GaNNTs) are nanotubes of gallium nitride. They can be grown by chemical vapour deposition.
Silicon nanowires, also referred to as SiNWs, are a type of semiconductor nanowire most often formed from a silicon precursor by etching of a solid or through catalyzed growth from a vapor or liquid phase. Such nanowires have promising applications in lithium-ion batteries, thermoelectrics and sensors. Initial synthesis of SiNWs is often accompanied by thermal oxidation steps to yield structures of accurately tailored size and morphology.
Praseodymium(III,IV) oxide is the inorganic compound with the formula Pr6O11 that is insoluble in water. It has a cubic fluorite structure. It is the most stable form of praseodymium oxide at ambient temperature and pressure.
Zinc oxide nanoparticles are nanoparticles of zinc oxide (ZnO) that have diameters less than 100 nanometers. They have a large surface area relative to their size and high catalytic activity. The exact physical and chemical properties of zinc oxide nanoparticles depend on the different ways they are synthesized. Some possible ways to produce ZnO nano-particles are laser ablation, hydrothermal methods, electrochemical depositions, sol–gel method, chemical vapor deposition, thermal decomposition, combustion methods, ultrasound, microwave-assisted combustion method, two-step mechanochemical–thermal synthesis, anodization, co-precipitation, electrophoretic deposition, and precipitation processes using solution concentration, pH, and washing medium. ZnO is a wide-bandgap semiconductor with an energy gap of 3.37 eV at room temperature.