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Topic Name: NIST Chemists measure copper levels in zinc oxide nanowires during fabrication

Category: Chemical

Research persons: Susie Eustis

Location: National Institute of Standards and Technology (NIST), United States

Details

Chemists at the National Institute of Standards and Technology (NIST) have been the first to measure significant amounts of copper incorporated into zinc oxide (ZnO) nanowires during fabrication. The issue is important because copper plays a significant—but not well-understood—role in important optical and electrical properties of the nanowires. Previous experiments found only trace amounts of copper.

Although zinc oxide is best known as a strong sunblock, cold remedy, itch reliever and paint pigment, nanotech engineers like it for its photoluminescence (the ability to emit light after absorbing electromagnetic radiation), field emission (the basis for advanced, high-definition flat-panel displays) and piezoelectric properties (stressing or changing shape when electricity is applied and producing electricity when stressed). ZnO nanomaterials may one day be used to improve solar cells, lasers, sensors, ultraviolet light sources, field emission sources and piezoelectric devices.

Copper enters the ZnO nanowires during fabrication. The nanowires—about 50 to 150 nanometers wide and up to 40 micrometers long—are grown on a copper substrate using a chemical vapor deposition process. The copper substrate forms droplets that absorb the zinc and oxygen vapors and deposits the ZnO on the substrate. As the nanowire grows, the zinc pushes the droplets up from the surface, but some copper remains inside the nanowire’s crystal lattice.

In a new paper, NIST chemists report using a variety of measurement techniques to learn that the ZnO wires contain a surprising amount of copper—between 5 and 15 percent. High-resolution imaging studies of ZnO nanowires reveal that the copper manages to fit into zinc oxide’s regular crystalline structure without disrupting it. “It is in there somewhere,” explains chemist Susie Eustis. Because the copper can be easily detected when you know what to look for, she says, researchers plan to use it to better understand the crystal structure of ZnO nanowires with an eye toward manipulating the nanowires to improve performance. “The copper acts like a smart tag that you put on an animal in the wild to trace where it travels,” says Eustis.

The role copper plays in ZnO nanowires is ambiguous. Published studies differ on whether the copper increases or decreases the nanowires’ photoluminescence. Eustis and colleagues found that the copper in the nanowire increases the output of visible light but at the expense of ultraviolet emission.

In addition to determining the role copper plays in ZnO nanowires, the researchers plan to learn how to grow uniform nanowires that may one day be used in commercial products. This research is part of ongoing studies to find the best methods to determine the concentration and distribution of atoms inside nanostructures.

Note for Zinc Oxide
Zinc oxide is a chemical compound with the formula ZnO. It is nearly insoluble in water but soluble in acids and alkalis. It occurs as white hexagonal crystals or a white powder commonly known as zinc white. It remains white when exposed to hydrogen sulfide or ultraviolet light. Crystalline zinc oxide exhibits the piezoelectric effect and is thermochromic (it will change colour from white to yellow when heated, and back again when cooled down). Zinc oxide decomposes into zinc vapor and oxygen at around 1975 °C. High-quality single-crystalline ZnO is almost transparent. Zinc oxide occurs in nature as the mineral zincite.
ZnO is a semiconductor with a direct bandgap energy of 3.37 eV at room temperature. The most common applications are in laser diodes and light emitting diodes since it has an exciton and biexciton energies of 60 meV and 15 meV, respectively. It is expected that this exciton properties of ZnO will be improved further by epitaxy.
Most ZnO has n-type character, even in the absence of intentional doping. Native defects such as oxygen vacancies or zinc interstitials are often assumed to be the origin of this, but the subject remains controversial. An alternative explanation has been proposed, based on theoretical calculations, that unintentional substitutional hydrogen impurities are responsible.
n-type doped films are often used in thin film technology, where zinc oxide serves as a TCO (transparent conducting oxide). n-type doping is possible by introduction of aluminum, indium, or excess zinc. p-type doping is difficult and is currently an active area of research, with arsenic as the leading candidate dopant. Thin-film solar cells, LCD and flat panel displays are typical applications of this material. Appropriately doped ZnO may be transparent and conductive, and can therefore be used as a transparent electrode. Indium tin oxide (ITO) is another transparent conducting oxide often used in microelectronics.
ZnO has also been considered for spintronics applications because of theoretical predictions of room temperature ferromagnetism. Unsubstantiated reports of ferromagnetism have been made, but presence of dilute magnetic semiconductors remains a large unanswered question in physics.
The piezoelectricity in textile fibers coated in ZnO have been shown capable of "self-powering nanosystems" with everyday mechanical stress generated by wind or body movements.
ZnO layers are mainly deposited by sputter deposition and chemical vapor deposition (CVD). The latter method allows the growth of a rough layer, which can diffuse the incoming light by scattering, increasing the efficiency of solar cells.

Note for Nanowire
A nanowire is a wire of diameter of the order of a nanometer (10−9 meters). Alternatively, nanowires can be defined as structures that have a lateral size constrained to tens of nanometers or less and an unconstrained longitudinal size. At these scales, quantum mechanical effects are important — hence such wires are also known as "quantum wires". Many different types of nanowires exist, including metallic (e.g., Ni, Pt, Au), semiconducting (e.g., Si, InP, GaN, etc.), and insulating (e.g., SiO2,TiO2). Molecular nanowires are composed of repeating molecular units either organic (e.g. DNA) or inorganic (e.g. Mo6S9-xIx).
The nanowires could be used, in the near future, to link tiny components into extremely small circuits. Using nanotechnology, such components could be created out of chemical compounds.
Typical nanowires exhibit aspect ratios (length-to-width ratio) of 1000 or more. As such they are often referred to as 1-Dimensional materials. Nanowires have many interesting properties that are not seen in bulk or 3-D materials. This is because electrons in nanowires are quantum confined laterally and thus occupy energy levels that are different from the traditional continuum of energy levels or bands found in bulk materials.
Peculiar features of this quantum confinement exhibited by certain nanowires such as carbon nanotubes mainfest themselves in discrete values of the electrical conductance. Such discrete values arise from a quantum mechanical restraint on the number of electrons that can travel through the wire at the nanometer scale.
There are many applications where nanowires may become important in electronic, opto-electronic and nanoelectromechanical devices, as additives in advanced composites, for metallic interconnects in nanoscale quantum devices, as field-emittors and as leads for biomolecular nanosensors.
Nanowires still belong to the experimental world of laboratories. However, they may complement or replace carbon nanotubes in some applications. Some early experiments have shown how they can be used to build the next generation of computing devices.
To create active electronic elements, the first key step was to chemically dope a semiconductor nanowire. This has already been done to individual nanowires to create p-type and n-type semiconductors.
The next step was to find a way to create a p-n junction, one of the simplest electronic devices. This was achieved in two ways. The first way was to physically cross a p-type wire over an n-type wire. The second method involved chemically doping a single wire with different dopants along the length. This method created a p-n junction with only one wire.
After p-n junctions were built with nanowires, the next logical step was to build logic gates. By connecting several p-n junctions together, researchers have been able to create the basis of all logic circuits: the AND, OR, and NOT gates have all been built from semiconductor nanowire crossings.
It's possible that semiconductor nanowire crossings will be important to the future of digital computing. Though there are other uses for nanowires beyond these, the only ones that actually take advantage of physics in the nanometer regime are electronic.
Nanowires are being studied for use as photon ballistic waveguides as interconnects in quantum dot/quantum effect well photon logic arrays. Photons travel inside the tube, electrons travel on the outside shell.
When two nanowires acting as photon waveguides cross each other the juncture acts as a quantum dot.
Conducting nanowires offer the possibility of connecting molecular-scale entities in a molecular computer. Dispersions of conducing nanowires in different polymers are being investigated for use as transparent electrodes for flexible flat-screen displays.
Due to their high Young's moduli their use in mechanically enhancing composites is being investigated. Because nanowires appear in bundles, they may be used as tribological additives to improve friction characteristics and reliability of electronic transducers and actuators.

Note for Photoluminescence
Photoluminescence (abbreviated as PL) is a process in which a substance absorbs photons (electromagnetic radiation) and then radiates photons back out. Quantum mechanically, this can be described as an excitation to a higher energy state and then a return to a lower energy state accompanied by the emission of a photon. This is one of many forms of luminescence (light emission) and is distinguished by photoexcitation (excitation by photons), hence the prefix photo-. The period between absorption and emission is typically extremely short, in the order of 10 nanoseconds. Under special circumstances, however, this period can be extended into minutes or hours.
Ultimately, available chemical energy states and allowed transitions between states (and therefore wavelengths of light preferentially absorbed and emitted) are determined by the rules of quantum mechanics. A basic understanding of the principles involved can be gained by studying the electron configurations and molecular orbitals of simple atoms and molecules. More complicated molecules and advanced subtleties are treated in the field of computational chemistry.
The simplest photoluminescent processes are resonant radiations, in which a photon of a particular wavelength is absorbed and an equivalent photon is immediately emitted. This process involves no significant internal energy transitions of the chemical substrate between absorption and emission and is extremely fast, of the order of 10 nanoseconds.
More interesting processes occur when the chemical substrate undergoes internal energy transitions before re-emitting the energy from the absorption event. The most familiar such effect is fluorescence, which is also typically a fast process, but in which some of the original energy is dissipated so that the emitted light photons are of lower energy than those absorbed.
Photoluminescence is an important technique for measuring the purity and crystalline quality of semiconductors such as GaAs and InP. Several variations of photoluminescence exist, including photoluminescence excitation (PLE).
An even more specialized form of photoluminescence is phosphorescence, in which the energy from absorbed photons undergoes intersystem crossing into a state of higher spin multiplicity (see term symbol), usually a triplet state. Once the energy is trapped in the triplet state, transition back to the lower singlet energy states is quantum mechanically forbidden, meaning that it happens much more slowly than other transitions. The result is a slow process of radiative transition back to the singlet state, sometimes lasting minutes or hours. This is the basis for "glow in the dark" substances.

In figure 1 and 2, ZnO nanowires to grow out of the circular copper substrate in all directions, as seen in this scanning electron micrograph. Detail image shows copper droplets at the tip of some nanowires.

In figure 3, Zinc Oxide