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Quantum dot

Quantum dots (QD) are very small semiconductor particles, only several nanometres in size, so small that their optical and electronic properties differ from those of larger particles. They are a central theme in nanotechnology. Many types of quantum dot will emit light of specific frequencies if electricity or light is applied to them, and these frequencies can be precisely tuned by changing the dots' size, shape and material, giving rise to many applications. In the language of materials science, nanoscale semiconductor materials tightly confine either electrons or electron holes. Quantum dots are also sometimes referred to as artificial atoms, a term that emphasizes that a quantum dot is a single object with bound, discrete electronic states, as is the case with naturally occurring atoms or molecules.{{cite journal |last=Ashoori |first=R. C. |year=1996 |title=Electrons in artificial atoms |journal= Nature |volume=379 |issue=6564 |pages=413–419 |bibcode=1996Natur.379..413A |doi=10.1038/379413a0 }}{{cite journal |last=Kastner |first=M. A. |year=1993 |title=Artificial Atoms |journal= Physics Today |volume=46 |issue=1 |pages=24–31 |bibcode= 1993PhT....46a..24K |doi=10.1063/1.881393 }} Quantum dots exhibit properties that are intermediate between those of bulk semiconductors and those of discrete molecules. Their optoelectronic properties change as a function of both size and shape. Larger QDs (radius of 5–6 nm, for example) emit longer wavelengths resulting in emission colors such as orange or red. Smaller QDs (radius of 2–3 nm, for example) emit shorter wavelengths resulting in colors like blue and green, although the specific colors and sizes vary depending on the exact composition of the QD. Because of their highly tunable properties, QDs are of wide interest. Potential applications include transistors, solar cells, LEDs, diode lasers and second-harmonic generation, quantum computing, and medical imaging. Additionally, their small size allows for QDs to be suspended in solution which leads to possible uses in inkjet printing and spin-coating. These processing techniques result in less expensive and less time-consuming methods of semiconductor fabrication. __TOC__

Production

There are several ways to prepare quantum dots, the principal ones involving colloids.

Colloidal synthesis

Colloidal semiconductor nanocrystals are synthesized from solutions, much like traditional chemical processes. The main difference is the product neither precipitates as a bulk solid nor remains dissolved. Heating the solution at high temperature, the precursors decompose forming monomers which then nucleate and generate nanocrystals. Temperature is a critical factor 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. The concentration of monomers is another critical factor that has to be stringently controlled during nanocrystal growth. 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. Over time, the monomer concentration diminishes, the critical size becomes larger than the average size present, and the distribution "defocuses". There are colloidal methods to produce many different semiconductors. Typical dots are made of binary compounds such as lead sulfide, lead selenide, cadmium selenide, cadmium sulfide, cadmium telluride, indium arsenide, and indium phosphide. Dots may also be made from ternary compounds such as cadmium selenide sulfide. 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 batches of quantum dots may be synthesized via colloidal synthesis. Due to this scalability and the convenience of benchtop conditions, colloidal synthetic methods are promising for commercial applications. It is acknowledged to be the least toxic of all the different forms of synthesis.

Plasma synthesis

Plasma synthesis has evolved to be one of the most popular gas-phase approaches for the production of quantum dots, especially those with covalent bonds. For example, silicon (Si) and germanium (Ge) quantum dots have been synthesized by using nonthermal plasma. The size, shape, surface and composition of quantum dots can all be controlled in nonthermal plasma. Doping that seems quite challenging for quantum dots has also been realized in plasma synthesis. Quantum dots synthesized by plasma are usually in the form of powder, for which surface modification may be carried out. This can lead to excellent dispersion of quantum dots in either organic solvents or water (i. e., colloidal quantum dots).

Fabrication

• Self-assembled quantum dots are typically between 5 and 50 nm in size. Quantum dots defined by lithographically patterned gate electrodes, or by etching on two-dimensional electron gasses in semiconductor heterostructures can have lateral dimensions between 20 and 100 nm.
• Some quantum dots are small regions of one material buried in another with a larger band gap. These can be so-called core–shell structures, e.g., with CdSe in the core and ZnS in the shell, or from special forms of silica called ormosil. Sub-monolayer shells can also be effective ways of passivating the quantum dots, such as PbS cores with sub-monolayer CdS shells.
• Quantum dots sometimes occur spontaneously in quantum well structures due to monolayer fluctuations in the well's thickness.
• Self-assembled quantum dots nucleate spontaneously under certain conditions during molecular beam epitaxy (MBE) and metallorganic vapor phase epitaxy (MOVPE), when a material is grown on a substrate to which it is not lattice matched. The resulting strain produces coherently strained islands on top of a two-dimensional wetting layer. This growth mode is known as Stranski–Krastanov growth. The islands can be subsequently buried to form the quantum dot. This fabrication method has potential for applications in quantum cryptography (i.e. single photon sources) and quantum computation. The main limitations of this method are the cost of fabrication and the lack of control over positioning of individual dots.
• Individual quantum dots can be created from two-dimensional electron or hole gases present in remotely doped quantum wells or semiconductor heterostructures called lateral quantum dots. The sample surface is coated with a thin layer of resist. A lateral pattern is then defined in the resist by electron beam lithography. This pattern can then be transferred to the electron or hole gas by etching, or by depositing metal electrodes (lift-off process) that allow the application of external voltages between the electron gas and the electrodes. Such quantum dots are mainly of interest for experiments and applications involving electron or hole transport, i.e., an electrical current.
• The energy spectrum of a quantum dot can be engineered by controlling the geometrical size, shape, and the strength of the confinement potential. Also, in contrast to atoms, it is relatively easy to connect quantum dots by tunnel barriers to conducting leads, which allows the application of the techniques of tunneling spectroscopy for their investigation.
The quantum dot absorption features correspond to transitions between discrete, three-dimensional particle in a box states of the electron and the hole, both confined to the same nanometer-size box.These discrete transitions are reminiscent of atomic spectra and have resulted in quantum dots also being called artificial atoms.
• Confinement in quantum dots can also arise from electrostatic potentials (generated by external electrodes, doping, strain, or impurities).
• Complementary metal-oxide-semiconductor (CMOS) technology can be employed to fabricate silicon quantum dots. Ultra small (L=20 nm, W=20 nm) CMOS transistors behave as single electron quantum dots when operated at cryogenic temperature over a range of −269 °C (4  K) to about −258 °C (15  K). The transistor displays Coulomb blockade due to progressive charging of electrons one by one. The number of electrons confined in the channel is driven by the gate voltage, starting from an occupation of zero electrons, and it can be set to 1 or many.

Viral assembly

Genetically engineered M13 bacteriophage viruses allow preparation of quantum dot biocomposite structures. It had previously been shown that genetically engineered viruses can recognize specific semiconductor surfaces through the method of selection by combinatorial phage display. 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-assembled, 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.

Electrochemical assembly

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, onto the metal which is then used as a mask for mesa-etching these nanostructures on a chosen substrate.

Bulk-manufacture

Quantum dot manufacturing relies on a process called "high temperature dual injection" which has been scaled by multiple companies for commercial applications that require large quantities (hundreds of kilograms to tonnes) of quantum dots. This reproducible production method can be applied to a wide range of quantum dot sizes and compositions. The bonding in certain cadmium-free quantum dots, such as III-V-based quantum dots, is more covalent than that in II-VI materials, therefore it is more difficult to separate nanoparticle nucleation and growth via a high temperature dual injection synthesis. An alternative method of quantum dot synthesis, the “molecular seeding” process, provides a reproducible route to the production of high quality quantum dots in large volumes. The process utilises identical molecules of a molecular cluster compound as the nucleation sites for nanoparticle growth, thus avoiding the need for a high temperature injection step. Particle growth is maintained by the periodic addition of precursors at moderate temperatures until the desired particle size is reached. The molecular seeding process is not limited to the production of cadmium-free quantum dots; for example, the process can be used to synthesise kilogram batches of high quality II-VI quantum dots in just a few hours. Another approach for the mass production of colloidal quantum dots can be seen in the transfer of the well-known hot-injection methodology for the synthesis to a technical continuous flow system. The batch-to-batch variations arising from the needs during the mentioned methodology can be overcome by utilizing technical components for mixing and growth as well as transport and temperature adjustments. For the production of CdSe based semiconductor nanoparticles this method has been investigated and tuned to production amounts of kg per month. Since the use of technical components allows for easy interchange in regards of maximum through-put and size, it can be further enhanced to tens or even hundreds of kilograms. Continuous Flow Synthesis Method for Fluorescent Quantum Dots. Azonano.com (2013-06-01). Retrieved on 2015-07-19. In 2011 a consortium of U.S. and Dutch companies reported a "milestone" in high volume quantum dot manufacturing by applying the traditional high temperature dual injection method to a flow system. On January 23, 2013 Dow entered into an exclusive licensing agreement with UK-based Nanoco for the use of their low-temperature molecular seeding method for bulk manufacture of cadmium-free quantum dots for electronic displays, and on September 24, 2014 Dow commenced work on the production facility in South Korea capable of producing sufficient quantum dots for "millions of cadmium-free televisions and other devices, such as tablets". Mass production is due to commence in mid-2015. On 24 March 2015 Dow announced a partnership deal with LG Electronics to develop the use of cadmium free quantum dots in displays.

Heavy metal-free quantum dots

In many regions of the world there is now a restriction or ban on the use of heavy metals in many household goods, which means that most cadmium based quantum dots are unusable for consumer-goods applications. For commercial viability, a range of restricted, heavy metal-free quantum dots has been developed showing bright emissions in the visible and near infra-red region of the spectrum and have similar optical properties to those of CdSe quantum dots. Among these systems are InP/ZnS and CuInS/ZnS, for example. Peptides are being researched as potential quantum dot material.{{cite journal | last1 = Hauser | first1 = Charlotte A. E.| last2=Zhang| first2=Shuguang | title = Peptides as biological semiconductors | journal = Nature | volume =468 | issue =7323 | pages = 516–517 | date = 2010 | doi = 10.1038/468516a | pmid = 21107418|bibcode = 2010Natur.468..516H }} Since peptides occur naturally in all organisms, such dots would likely be nontoxic and easily biodegraded.

Optical properties

In semiconductors, light absorption generally leads to an electron being excited from the valence to the conduction band, leaving behind a hole. The electron and the hole can bind to each other to form an exciton. When this exciton recombines (i.e. the electron resumes its ground state), the exciton's energy can be emitted as light. This is called fluorescence. In a simplified model, the energy of the emitted photon can be understood as the sum of the band gap energy between the highest occupied level and the lowest unoccupied energy level, the confinement energies of the hole and the excited electron, and the bound energy of the exciton (the electron-hole pair): As the confinement energy depends on the quantum dot's size, both absorption onset and fluorescence emission can be tuned by changing the size of the quantum dot during its synthesis. The larger the dot, the redder (lower energy) its absorption onset and fluorescence spectrum. Conversely, smaller dots absorb and emit bluer (higher energy) light. Recent articles in Nanotechnology and in other journals have begun to suggest that the shape of the quantum dot may be a factor in the coloration as well, but as yet not enough information is available. Furthermore, it was shown that the lifetime of fluorescence is determined by the size of the quantum dot. 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 causing larger dots to show a longer lifetime. To improve fluorescence quantum yield, quantum dots can be made with "shells" of a larger bandgap semiconductor material around them. The improvement is suggested to be due to the reduced access of electron and hole to non-radiative surface recombination pathways in some cases, but also due to reduced auger recombination in others.

Potential applications

Quantum dots are particularly promising for optical applications due to their high extinction coefficient. They 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. Tuning the size of quantum dots is attractive for many potential applications. For instance, larger quantum dots have a greater spectrum-shift towards red compared to smaller dots, and exhibit less pronounced quantum properties. Conversely, the smaller particles allow one to take advantage of more subtle quantum effects. , through energy transfer from thin layers of quantum wells to crystals above the layers.]] 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. They have potential uses in diode lasers, amplifiers, and biological sensors. Quantum dots may be excited within a locally enhanced electromagnetic field produced by gold nanoparticles, which can then be observed from the surface plasmon resonance in the photoluminescent 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. CdSe nanocrystals are efficient triplet photosensitizers. Laser excitation of small CdSe nanoparticles enables the extraction of the excited state energy from the Quantum Dots into bulk solution, thus opening the door to a wide range of potential applications such as photodynamic therapy, photovoltaic devices, molecular electronics, and catalysis.

Computing

Quantum dot technology is potentially relevant to solid-state quantum computation. By applying small voltages to the leads, current through the quantum dot can be controlled and thereby precise measurements of the spin and other properties therein can be made. With several entangled quantum dots,, plus a way of performing operations, quantum calculations and the computers that would perform them might be possible.

Photovoltaic devices

The tunable absorption spectrum and high extinction coefficients of quantum dots make them attractive for light harvesting technologies such as photovoltaics. Quantum dots may be able to increase the efficiency and reduce the cost of today's typical silicon photovoltaic cells. According to an experimental proof from 2004, quantum dots of lead selenide can produce more than one exciton from one high energy photon via the process of carrier multiplication or multiple exciton generation (MEG). This compares favorably 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. Quantum dot photovoltaics would theoretically be cheaper to manufacture, as they can be made "using simple chemical reactions."

Quantum dot only solar cells

Aromatic self-assembled monolayers (SAMs) (e.g. 4-nitrobenzoic acid) can be used to improve the band alignment at electrodes for better efficiencies. This technique has provided a record power conversion efficiency (PCE) of 10.7%. The SAM is positioned between ZnO-PbS colloidal quantum dot (CQD) film junction to modify band alignment via the dipole moment of the constituent SAM molecule, and the band tuning may be modified via the density, dipole and the orientation of the SAM molecule.

Quantum dot in hybrid solar cells

Colloidal quantum dots are also used in inorganic/organic hybrid solar cells. These solar cells are attractive because of potentially their low-cost fabrication and relatively high efficiency. Incorporation of metal oxides, such as ZnO, TiO2, and Nb2O5 nanomaterials into organic photovoltaics have been commercialized using full roll-to-roll processing. A 13.2% power conversion efficiency is claimed in Si nanowire/PEDOT:PSS hybrid solar cells.

Quantum dot with nanowire in solar cells

Another potential use involves capped single-crystal ZnO nanowires with CdSe quantum dots, immersed in mercaptopropionic acid as hole transport medium in order to obtain a QD-sensitized solar cell. The morphology of the nanowires allowed the electrons to have a direct pathway to the photoanode. This form of solar cell exhibits 50-60% internal quantum efficiencies. Nanowires with quantum dot coatings on silicon nanowires (SiNW) and carbon quantum dots. The use of SiNWs instead of planar silicon enhances the antiflection properties of Si. The SiNW exhibits a light-trapping effect due to light trapping in the SiNW. This use of SiNWs in conjunction with carbon quantum dots resulted in a solar cell that reached 9.10% PCE. Graphene quantum dots have also been blended with organic electronic materials to improve efficiency and lower cost in photovoltaic devices and organic light emitting diodes ( OLEDs) in compared to graphene sheets. These graphene quantum dots were functionalized with organic ligands that experience photoluminescence from UV-Vis absorption.

Light emitting diodes

Several methods are proposed for using quantum dots to improve existing light-emitting diode (LED) design, including "Quantum Dot Light Emitting Diode" (QD-LED) displays and "Quantum Dot White Light Emitting Diode" (QD-WLED) displays. Because Quantum dots naturally produce monochromatic light, they can be more efficient than light sources which must be color filtered. QD-LEDs can be fabricated on a silicon substrate, which allows them to be integrated onto standard silicon-based integrated circuits or microelectromechanical systems.

Quantum dot displays

Quantum dots are valued for displays, because they emit light in very specific gaussian distributions. This can result in a display with visibly more accurate colors. A conventional color liquid crystal display (LCD) is usually backlit by fluorescent lamps (CCFLs) or conventional white LEDs that are color filtered to produce red, green, and blue pixels. An improvement is using conventional blue-emitting LEDs as the light sources and converting part of the emitted light into pure green and red light by the appropriate quantum dots placed in front of the blue LED or using a quantum dot infused diffuser sheet in the backlight optical stack. This type of white light as the backlight of an LCD panel allows for the best color gamut at lower cost than a RGB LED combination using three LEDs. The ability of QDs to precisely convert and tune a spectrum makes them attractive for LCD displays. Previous LCD displays can waste energy converting red-green poor, blue-yellow rich white light into a more balanced lighting. By using QDs, only the necessary colors for ideal images are contained in the screen. The result is a screen that is brighter, clearer, and more energy-efficient. The first commercial application of quantum dots was the Sony XBR X900A series of flat panel televisions released in 2013.Bullis, Kevin. (2013-01-11) Quantum Dots Produce More Colorful Sony TVs | MIT Technology Review. Technologyreview.com. Retrieved on 2015-07-19. In June 2006, QD Vision announced technical success in making a proof-of-concept quantum dot display and show a bright emission in the visible and near infra-red region of the spectrum. A QD-LED integrated at a scanning microscopy tip was used to demonstrate fluorescence near-field scanning optical microscopy ( NSOM) imaging.

Photodetector devices

Quantum dot photodetectors (QDPs) can be fabricated either via solution-processing, or from conventional single-crystalline semiconductors. Conventional single-crystalline semiconductor QDPs are precluded from integration with flexible organic electronics due to the incompatibility of their growth conditions with the process windows required by organic semiconductors. On the other hand, solution-processed QDPs can be readily integrated with an almost infinite variety of substrates, and also postprocessed atop other integrated circuits. Such colloidal QDPs have potential applications in surveillance, machine vision, industrial inspection, spectroscopy, and fluorescent biomedical imaging.

Photocatalysts

Quantum dots also function as photocatalysts for the light driven chemical conversion of water into hydrogen as a pathway to solar fuel. In photocatalysis, electron hole pairs formed in the dot under band gap excitation drive redox reactions in the surrounding liquid. Generally, the photocatalytic activity of the dots is related to the particle size and its degree of quantum confinement. This is because the band gap determines the chemical energy that is stored in the dot in the excited state. An obstacle for the use of quantum dots in photocatalysis is the presence of surfactants on the surface of the dots. These surfactants (or ligands) interfere with the chemical reactivity of the dots by slowing down mass transfer and electron transfer processes. Also, quantum dots made of metal chalcogenides are chemically unstable under oxidizing conditions and undergo photo corrosion reactions.

Theory

Quantum dots are theoretically described as a point like, or a zero dimensional (0D) entity. Most of their properties depend on the dimensions, shape and materials of which QDs are made. Generally QDs present different thermodynamic properties from the bulk materials of which they are made. One of these effects is the Melting-point depression. Optical properties of spherical metallic QDs are well described by the Mie scattering theory.

Quantum confinement in semiconductors

• Quantum wires, which confine electrons or holes in two spatial dimensions and allow free propagation in the third.
• Quantum wells, which confine electrons or holes in one dimension and allow free propagation in two dimensions.

Models

A variety of theoretical frameworks exist to model optical, electronic, and structural properties of quantum dots. These may be broadly divided into quantum mechanical, semiclassical, and classical.

Quantum mechanics

Quantum mechanical models and simulations of quantum dots often involve the interaction of electrons with a pseudopotential or random matrix.

Semiclassical

Semiclassical models of quantum dots frequently incorporate a chemical potential. For example, the thermodynamic chemical potential of an N-particle system is given by \mu(N) = E(N) - E(N-1) whose energy terms may be obtained as solutions of the Schrödinger equation. The definition of capacitance, {1\over C} \equiv {\Delta \,V\over\Delta \,Q}, with the potential difference \Delta \,V = {\Delta \,\mu \,\over e} = {\mu(N+\Delta \,N) -\mu(N) \over e} may be applied to a quantum dot with the addition or removal of individual electrons, \Delta \,N = 1 and \Delta \,Q=e. Then C(N) = {e^2\over\mu(N+1)-\mu(N)} = {e^2 \over I(N)-A(N)} is the "quantum capacitance" of a quantum dot, where we denoted by I(N) the ionization potential and by A(N) the electron affinity of the N-particle system.

History

The term “quantum dot” was coined in 1986. They were first discovered in a glass matrix and in colloidal solutions by Alexey Ekimov and Louis Brus.