Zinc Oxide – ZnO

Chemical properties

Pure ZnO is a white powder, but in nature it occurs as the rare mineral zincite, which usually contains manganese and other impurities that confer a yellow to red color.

Crystalline zinc oxide is thermochromic, changing from white to yellow when heated in air and reverting to white on cooling. This color change is caused by a small loss of oxygen to the environment at high temperatures to form the non-stoichiometric Zn_1+xO, where at 800 °C, x = 0.00007.^[14]

Zinc oxide is an amphoteric oxide. It is nearly insoluble in water, but it will dissolve in most acids, such as hydrochloric acid:

ZnO + 2 HCl → ZnCl₂ + H₂O

Solid zinc oxide will also dissolve in alkalis to give soluble zincates:

ZnO + 2 NaOH + H₂O → Na₂[Zn(OH)₄]

ZnO reacts slowly with fatty acids in oils to produce the corresponding carboxylates, such as oleate or stearate. ZnO forms cement-like products when mixed with a strong aqueous solution of zinc chloride and these are best described as zinc hydroxy chlorides. This cement was used in dentistry.

ZnO also forms cement-like material when treated with phosphoric acid; related materials are used in dentistry. A major component of zinc phosphate cement produced by this reaction is hopeite, Zn₃(PO₄)₂·4H₂O.

ZnO decomposes into zinc vapor and oxygen at around 1975 °C with a standard oxygen pressure. In a carbothermic reaction, heating with carbon converts the oxide into zinc vapor at a much lower temperature (around 950 °C).

ZnO + C → Zn_(Vapor) + CO

Zinc oxide can react violently with aluminium and magnesium powders, with chlorinated rubber and linseed oil on heating causing fire and explosion hazard.

It reacts with hydrogen sulfide to give zinc sulfide. This reaction is used commercially.

ZnO + H₂S → ZnS + H₂O

Physical properties

Structure

Zinc oxide crystallizes in two main forms, hexagonal wurtzite and cubic zincblende. The wurtzite structure is most stable at ambient conditions and thus most common. The zincblende form can be stabilized by growing ZnO on substrates with cubic lattice structure. In both cases, the zinc and oxide centers are tetrahedral, the most characteristic geometry for Zn(II). ZnO converts to the rocksalt motif at relatively high pressures about 10 GPa. The many remarkable medical properties of creams containing ZnO can be explained by its elastic softness, which is characteristic of tetrahedral coordinated binary compounds close to the transition to octahedral structures.

Hexagonal and zincblende polymorphs have no inversion symmetry (reflection of a crystal relative to any given point does not transform it into itself). This and other lattice symmetry properties result in piezoelectricity of the hexagonal and zincblende ZnO, and pyroelectricity of hexagonal ZnO.

The hexagonal structure has a point group 6 mm (Hermann-Mauguin notation) or C_6v (Schoenflies notation), and the space group is P6₃mc or C_6v⁴. The lattice constants are a = 3.25 Å and c = 5.2 Å; their ratio c/a ~ 1.60 is close to the ideal value for hexagonal cell c/a = 1.633. As in most group II-VI materials, the bonding in ZnO is largely ionic (Zn²⁺–O²⁻) with the corresponding radii of 0.074 nm for Zn²⁺ and 0.140 nm for O²⁻. This property accounts for the preferential formation of wurtzite rather than zinc blende structure, as well as the strong piezoelectricity of ZnO. Because of the polar Zn-O bonds, zinc and oxygen planes are electrically charged. To maintain electrical neutrality, those planes reconstruct at atomic level in most relative materials, but not in ZnO – its surfaces are atomically flat, stable and exhibit no reconstruction. This anomaly of ZnO is not fully explained. However, studies using wurtzoid structures explained the origin of surface flatness and the absence of reconstruction at ZnO wurtzite surfaces in addition to the origin of charges on ZnO planes.

Mechanical properties

ZnO is a relatively soft material with approximate hardness of 4.5 on the Mohs scale. Its elastic constants are smaller than those of relevant III-V semiconductors, such as GaN. The high heat capacity and heat conductivity, low thermal expansion and high melting temperature of ZnO are beneficial for ceramics. The E2 optical phonon in ZnO exhibits an unusually long lifetime of 133 ps at 10 K.

Among the tetrahedrally bonded semiconductors, it has been stated that ZnO has the highest piezoelectric tensor, or at least one comparable to that of GaN and AlN. This property makes it a technologically important material for many piezoelectrical applications, which require a large electromechanical coupling.

Electrical properties[edit]

ZnO has a relatively large direct band gap of ~3.3 eV at room temperature. Advantages associated with a large band gap include higher breakdown voltages, ability to sustain large electric fields, lower electronic noise, and high-temperature and high-power operation. The bandgap of ZnO can further be tuned to ~3–4 eV by its alloying with magnesium oxide or cadmium oxide.

Most ZnO has n-type character, even in the absence of intentional doping. Nonstoichiometry is typically the origin of n-type character, but the subject remains controversial. An alternative explanation has been proposed, based on theoretical calculations, that unintentional substitutional hydrogen impurities are responsible. Controllable n-type doping is easily achieved by substituting Zn with group-III elements such as Al, Ga, In or by substituting oxygen with group-VII elements chlorine or iodine.

Reliable p-type doping of ZnO remains difficult. This problem originates from low solubility of p-type dopants and their compensation by abundant n-type impurities. This problem is observed with GaN and ZnSe. Measurement of p-type in “intrinsically” n-type material is complicated by the inhomogeneity of samples.

Current limitations to p-doping limit electronic and optoelectronic applications of ZnO, which usually require junctions of n-type and p-type material. Known p-type dopants include group-I elements Li, Na, K; group-V elements N, P and As; as well as copper and silver. However, many of these form deep acceptors and do not produce significant p-type conduction at room temperature.^[12]

Electron mobility of ZnO strongly varies with temperature and has a maximum of ~2000 cm²/(V·s) at 80 K.Data on hole mobility are scarce with values in the range 5–30 cm²/(V·s).

ZnO discs, acting as a varistor, are the active material in most surge arresters.

Production

For industrial use, ZnO is produced at levels of 10⁵ tons per year by three main processes:

Indirect process

In the indirect or French process, metallic zinc is melted in a graphite crucible and vaporized at temperatures above 907 °C (typically around 1000 °C). Zinc vapor reacts with the oxygen in the air to give ZnO, accompanied by a drop in its temperature and bright luminescence. Zinc oxide particles are transported into a cooling duct and collected in a bag house. This indirect method was popularized by LeClaire (France) in 1844 and therefore is commonly known as the French process. Its product normally consists of agglomerated zinc oxide particles with an average size of 0.1 to a few micrometers. By weight, most of the world’s zinc oxide is manufactured via French process.

Direct process

The direct or American process starts with diverse contaminated zinc composites, such as zinc ores or smelter by-products. The zinc precursors are reduced (carbothermal reduction) by heating with a source of carbon such as anthracite to produce zinc vapor, which is then oxidized as in the indirect process. Because of the lower purity of the source material, the final product is also of lower quality in the direct process as compared to the indirect one.

Wet chemical process

A small amount of industrial production involves wet chemical processes, which start with aqueous solutions of zinc salts, from which zinc carbonate or zinc hydroxide is precipitated. The solid precipitate is then calcined at temperatures around 800 °C.

Laboratory synthesis

Numerous specialised methods exist for producing ZnO for scientific studies and niche applications. These methods can be classified by the resulting ZnO form (bulk, thin film, nanowire), temperature (“low”, that is close to room temperature or “high”, that is T ~ 1000 °C), process type (vapor deposition or growth from solution) and other parameters.

Large single crystals (many cubic centimeters) can be grown by the gas transport (vapor-phase deposition), hydrothermal synthesis, or melt growth. However, because of high vapor pressure of ZnO, growth from the melt is problematic. Growth by gas transport is difficult to control, leaving the hydrothermal method as a preference. Thin films can be produced by chemical vapor deposition, metalorganic vapour phase epitaxy, electrodeposition, pulsed laser deposition, sputtering, sol-gel synthesis, atomic layer deposition, spray pyrolysis, etc.

Ordinary white powdered zinc oxide can be produced in the laboratory by electrolyzing a solution of sodium bicarbonate with a zinc anode. Zinc hydroxide and hydrogen gas are produced. The zinc hydroxide upon heating decomposes to zinc oxide.

Zn + 2 H₂O → Zn(OH)₂ + H₂

Zn(OH)₂ → ZnO + H₂O

ZnO nanostructures[edit]

Nanostructures of ZnO can be synthesized into a variety of morphologies including nanowires, nanorods, tetrapods, nanobelts, nanoflowers, nanoparticles etc. Nanostructures can be obtained with most above-mentioned techniques, at certain conditions, and also with the vapor-liquid-solid method. The synthesis is typically carried out at temperatures of about 90 °C, in an equimolar aqueous solution of zinc nitrate and hexamine, the latter providing the basic environment. Certain additives, such as polyethylene glycol or polyethylenimine, can improve the aspect ratio of the ZnO nanowires. Doping of the ZnO nanowires has been achieved by adding other metal nitrates to the growth solution. The morphology of the resulting nanostructures can be tuned by changing the parameters relating to the precursor composition (such as the zinc concentration and pH) or to the thermal treatment (such as the temperature and heating rate).

Aligned ZnO nanowires on pre-seeded silicon, glass, and gallium nitride substrates have been grown using aqueous zinc salts such as zinc nitrate and zinc acetate in basic environments. Pre-seeding substrates with ZnO creates sites for homogeneous nucleation of ZnO crystal during the synthesis. Common pre-seeding methods include in-situ thermal decomposition of zinc acetate crystallites, spincoating of ZnO nanoparticles and the use of physical vapor deposition methods to deposit ZnO thin films. Pre-seeding can be performed in conjunction with top down patterning methods such as electron beam lithography and nanosphere lithography to designate nucleation sites prior to growth. Aligned ZnO nanowires can be used in dye-sensitized solar cells and field emission devices.