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Quantum dots |
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Part of a series of articles on |
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Fullerenes |
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Nanoparticles |
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A quantum dot is a nano-particulate semiconductor, whose excitons are confined in all three spatial dimensions. As a result, they have properties that are between those of bulk semiconductors and those of discrete molecules.123
Researchers have studied quantum dots in transistors, solar cells, LEDs4, and diode lasers. They have also investigated quantum dots as agents for medical imaging and hope to use them as qubits. Some quantum dots are commercially available.56
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In an unconfined (bulk) semiconductor, an electron-hole pair is typically bound within a characteristic length called the Bohr exciton radius. If the electron and hole are constrained further, then the semiconductor's properties change. This effect is a form of quantum confinement, and it is a key feature in many emerging electronic structures.78
Other quantum confined semiconductors include:
There are several ways to confine excitons in semiconductors, resulting in different methods to produce quantum dots. In general, quantum wires, wells and dots are grown by advanced epitaxial techniques in nanocrystals produced by chemical methods or by ion implantation, or in nanodevices made by state-of-the-art lithographic techniques.9
Colloidal semiconductor nanocrystals are synthesized from precursor compounds dissolved in solutions, much like traditional chemical processes. The synthesis of colloidal quantum dots is based on a three component system composed of: precursors, organic surfactants, and solvents. When heating a reaction medium to a sufficiently high temperature, the precursors chemically transform into monomers. Once the monomers reach a high enough supersaturation level, the nanocrystal growth starts with a nucleation process. The temperature during the growth process is one of the critical factors in determining optimal conditions for the nanocrystal growth. It must be high enough to allow for rearrangement and annealing of atoms during the synthesis process while being low enough to promote crystal growth. Another critical factor that has to be stringently controlled during nanocrystal growth is the monomer concentration. The growth process of nanocrystals can occur in two different regimes, “focusing” and “defocusing”. At high monomer concentrations, the critical size (the size where nanocrystals neither grow nor shrink) is relatively small, resulting in growth of nearly all particles. In this regime, smaller particles grow faster than large ones (since larger crystals need more atoms to grow than small crystals) resulting in “focusing” of the size distribution to yield nearly monodisperse particles. The size focusing is optimal when the monomer concentration is kept such that the average nanocrystal size present is always slightly larger than the critical size. When the monomer concentration is depleted during growth, the critical size becomes larger than the average size present, and the distribution “defocuses” as a result of Ostwald ripening.
There are colloidal methods to produce many different semiconductors, including cadmium selenide, cadmium sulfide, indium arsenide, and indium phosphide. These quantum dots can contain as few as 100 to 100,000 atoms within the quantum dot volume, with a diameter of 10 to 50 atoms. This corresponds to about 2 to 10 nanometers, and at 10 nm in diameter, nearly 3 million quantum dots could be lined up end to end and fit within the width of a human thumb.
Large quantities of quantum dots may be synthesized via colloidal synthesis. Colloidal synthesis is by far the cheapestcitation needed and has the advantage of being able to occur at benchtop conditions. It is acknowledgedcitation needed to be the least toxic of all the different forms of synthesis.
Lee et al. (2002) reported using genetically engineered M13 bacteriophage viruses to create quantum dot biocomposite structures.10 As a background to this work, it had previously been shown that genetically engineered viruses can recognize specific semiconductor surfaces through the method of selection by combinatorial phage display.11 Additionally, it is known that liquid crystalline structures of wild-type viruses (Fd, M13, and TMV) are adjustable by controlling the solution concentrations, solution ionic strength, and the external magnetic field applied to the solutions. Consequently, the specific recognition properties of the virus can be used to organize inorganic nanocrystals, forming ordered arrays over the length scale defined by liquid crystal formation. Using this information, Lee et al. (2000) were able to create self-assemble highly oriented, self-supporting films from a phage and ZnS precursor solution. This system allowed them to vary both the length of bacteriophage and the type of inorganic material through genetic modification and selection.
Highly ordered arrays of quantum dots may also be self assembled by electrochemical techniques. A template is created by causing an ionic reaction at an electrolyte-metal interface which results in the spontaneous assembly of nanostructures, including quantum dots, on the metal which is then used as a mask for mesa-etching these nanostructures on a chosen substrate.
An immediate optical feature of colloidal quantum dots is their coloration. While the material which makes up a quantum dot defines its intrinsic energy signature, the quantum confined size of the nanocrystal is more significant at energies near the band gap. Thus quantum dots of the same material, but with different sizes, can emit light of different colors.
The larger the dot, the redder (lower energy) its fluorescence spectrum. Conversely, smaller dots emit bluer (higher energy) light. The coloration is directly related to the energy levels of the quantum dot. Quantitatively speaking, the bandgap energy that determines the energy (and hence color) of the fluoresced light is inversely proportional to the square of the size of the quantum dot. Larger quantum dots have more energy levels which are more closely spaced. This allows the quantum dot to absorb photons containing less energy, i.e. those closer to the red end of the spectrum. Recent articles in nanotechnology and other journals have begun to suggest that the shape of the quantum dot may well also be a factor in the coloration, but as yet not enough information has become available. Furthermore it was shown recently12 that the lifetime of fluorescence is determined by the size. Larger dots have more closely spaced energy levels in which the electron-hole pair can be trapped. Therefore, electron-hole pairs in larger dots live longer and thus these large dots show a larger lifetime.
As with any crystalline semiconductor, a quantum dot's electronic wave functions extend over the crystal lattice. Similar to a molecule, a quantum dot has both a quantized energy spectrum and a quantized density of electronic states near the band edge.
Quantum dots are particularly significant for optical applications due to their theoretically high quantum yield. In electronic applications they have been proven to operate like a single-electron transistor and show the Coulomb blockade effect. Quantum dots have also been suggested as implementations of qubits for quantum information processing.
The ability to tune the size of quantum dots is advantageous for many applications. For instance, larger quantum dots have spectra shifted towards the red compared to smaller dots, and exhibit less pronounced quantum properties. Conversely the smaller particles allow one to take advantage of quantum properties.
Being zero dimensional, quantum dots have a sharper density of states than higher-dimensional structures. As a result, they have superior transport and optical properties, and are being researched for use in diode lasers, amplifiers, and biological sensors. Quantum dots may be excited within the locally enhanced electromagnetic field produced by the gold nanoparticles, which can be observed from the surface Plasmon resonance in the photoluminescence excitation spectrum of (CdSe)ZnS nanocrystals. High-quality quantum dots are well suited for optical encoding and multiplexing applications due to their broad excitation profiles and narrow/symmetric emission spectra. The new generations of quantum dots have far-reaching potential for the study of intracellular processes at the single-molecule level, high-resolution cellular imaging, long-term in vivo observation of cell trafficking, tumor targeting, and diagnostics.
Quantum dot technology is one of the most promising candidates for use in solid-state quantum computation. By applying small voltages to the leads, one can control the flow of electrons through the quantum dot and thereby make precise measurements of the spin and other properties therein. With several entangled quantum dots, or qubits, plus a way of performing operations, quantum calculations might be possible.
In modern biological analysis, various kinds of organic dyes are used. However, with each passing year, more flexibility is being required of these dyes, and the traditional dyes are often unable to meet the expectations. To this end, quantum dots have quickly filled in the role, being found to be superior to traditional organic dyes on several counts, one of the most immediately obvious being brightness (owing to the high quantum yield) as well as their stability (much less photodestruction). For single-particle tracking, the irregular blinking of quantum dots is a minor drawback.
The use of quantum dots for highly sensitive cellular imaging has seen major advances over the past decade. The improved photostability of quantum dots for example, allows the acquisition of many consecutive focal-plane images that can be reconstructed into a high-resolution three-dimensional image. Another application that takes advantage of the extraordinary photostability of quantum dot probes is the real-time tracking of molecules and cells over extended periods of time 13. Researchers were able to observe quantum dots in lymph nodes of mice for more than 4 months 14.
Semiconductor quantum dots have also been employed for in vitro imaging of pre-labeled cells. The ability to image single-cell migration in real time is expected to be important to several research areas such as embryogenesis, cancer metastasis, stem-cell therapeutics, and lymphocyte immunology.
Scientists have proven that quantum dots are dramatically better than existing methods for delivering a gene-silencing tool, known as siRNA, into cells.15
First attempts have been made in using quantum dots for tumor targeting under in vivo conditions. There exist two basic targeting schemes: active targeting and passive targeting. In the case of active targeting, quantum dots are functionalized with tumor specific binding sites to specifically bind to tumor cells. Passive targeting utilizes enhanced permeation and retention of tumor cells for the delivery of quantum dot probes. Fast growing tumor cells typically have more permeable membranes than healthy cells, allowing the leakage of small nanoparticles into the cell body. Moreover, tumor cells lack an effective lymphatic drainage system, which leads to subsequent nanoparticle accumulation.
One of the remaining issues with quantum dot probes is their in vivo toxicity. CdSe nanocrystals for example are highly toxic to cultured cells under UV illumination. The energy of UV irradiation is close to the covalent chemical bond energy of CdSe nanocrystals. As a result, semiconductor particles can be dissolved, in a process known as photolysis, to release toxic cadmium ions into the culture medium. In the absence of UV irradiation, however, quantum dots with a stable polymer coating have been found to be essentially nontoxic. Then again, only little is known about the excretion process of polymer-protected quantum dots from living organisms. These and other questions must be carefully examined before quantum dot applications in tumor or vascular imaging can be approved for human clinical use.
Another cutting edge application of quantum dots is also being researched as potential artificial fluorophore for intra-operative detection of tumors using fluorescence spectroscopy.
Quantum dots may have the potential to increase the efficiency and reduce the cost of today's typical silicon photovoltaic cells. According to experimental proof from 2006, quantum dots of lead selenide can produce as many as seven excitons from one high energy photon of sunlight (7.8 times the bandgap energy).16 This compares favourably to today's photovoltaic cells which can only manage one exciton per high-energy photon, with high kinetic energy carriers losing their energy as heat. This would not result in a 7-fold increase in final output however, but could boost the maximum theoretical efficiency from 31% to 42%. Quantum dot photovoltaics would theoretically be cheaper to manufacture, as they can be made "using simple chemical reactions."16
There are several inquiries into using quantum dots as light-emitting diodes to make displays and other light sources: "QD-LED" displays, and "QD-WLED" (White LED). In June, 2006, QD Vision announced technical success in making a proof-of-concept quantum dot display. Quantum dots are valued for displays, because they emit light in very specific gaussian distributions. This can result in a display that can more accurately render the colors that the human eye can perceive. Quantum dots also require very little power since they are not color filtered. Additionally, since the discovery of "white-light emitting" QD, general solid-state lighting applications are closer than ever. 17 A liquid crystal display (LCD), for example, is powered by a single fluorescent lamp that is color filtered to produce red, green, and blue pixels. Displays that intrinsically produce monochromatic light can be more efficient, since more of the light produced reaches the eye.18
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This article or section includes a list of references or external links, but its sources remain unclear because it has insufficient inline citations. You can improve this article by introducing more precise citations where appropriate. (February 2008) |
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