Quantum dot

Colloidal quantum dots irradiated with a UV light. Different sized quantum dots emit different color light due to quantum confinement.

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.[1][2]

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.[3][4] 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.[5]

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.[6] Additionally, their small size allows for QDs to be suspended in solution which leads to possible uses in inkjet printing and spin-coating.[7] These processing techniques result in less-expensive and less time consuming methods of semiconductor fabrication.

Production

Quantum Dots with gradually stepping emission from violet to deep red are being produced in a kg scale at PlasmaChem GmbH

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.[3] 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".

Cadmium sulfide quantum dots on cells

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, 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.

Ideallized image of colloidal nanoparticle of lead sulfide (selenide) with complete passivation by oleic acid, oleyl amine and hydroxyl ligands (size ~5nm)

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.[8][9][10] 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.[11][12] Doping that seems quite challenging for quantum dots has also been realized in plasma synthesis.[13][14][15] 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[16] or water[17] (i. e., colloidal quantum dots).

Fabrication

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.[19]

Viral assembly

Genetically engineered M13 bacteriophage viruses allow preparation of quantum dot biocomposite structures.[21] It had previously been shown that genetically engineered viruses can recognize specific semiconductor surfaces through the method of selection by combinatorial phage display.[22] 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.[23] 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.[24]

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.[25]

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.[26] On 24 March 2015 Dow announced a partnership deal with LG Electronics to develop the use of cadmium free quantum dots in displays.[27]

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.[28] Since peptides occur naturally in all organisms, such dots would likely be nontoxic and easily biodegraded.

Health and safety

Some quantum dots pose risks to human health and the environment under certain conditions.[29][30][31] Notably, the studies on quantum dot toxicity are focused on cadmium containing particles and has yet to be demonstrated in animal models after physiologically relevant dosing.[31] In vitro studies, based on cell cultures, on quantum dots (QD) toxicity suggests that their toxicity may derive from multiple factors including its physicochemical characteristics (size, shape, composition, surface functional groups, and surface charges) and environment. Assessing their potential toxicity is complex as these factors include properties such as QD size, charge, concentration, chemical composition, capping ligands, and also on their oxidative, mechanical and photolytic stability.[29]

Many studies have focused on the mechanism of QD cytotoxicity using model cell cultures. It has been demonstrated that after exposure to ultraviolet radiation or oxidized by air CdSe QDs release free cadmium ions causing cell death.[32] Group II-VI QDs also have been reported to induce the formation of reactive oxygen species after exposure to light, which in turn can damage cellular components such as proteins, lipids and DNA.[33] Some studies have also demonstrated that addition of a ZnS shell inhibit the process of reactive oxygen species in CdSe QDs. Another aspect of QD toxicity is the process of their size dependent intracellular pathways that concentrate these particles in cellular organelles that are inaccessible by metal ions, which may result in unique patterns of cytotoxicity compared to their constituent metal ions.[34] The reports of QD localization in the cell nucleus[35] present additional modes of toxicity because they may induce DNA mutation, which in turn will propagate through future generation of cells causing diseases.

Although concentration of QDs in certain organelles have been reported in in vivo studies using animal models, interestingly, no alterations in animal behavior, weight, hematological markers or organ damage has been found through either histological or biochemical analysis.[36] These finding have led scientists to believe that intracellular dose is the most important deterring factor for QD toxicity. Therefore, factors determining the QD endocytosis that determine the effective intracellular concentration, such as QD size, shape and surface chemistry determine their toxicity. Excretion of QDs through urine in animal models also have demonstrated via injecting radio-labeled ZnS capped CdSe QDs where the ligand shell was labelled with 99mTc.[37] Though multiple other studies have concluded retention of QDs in cellular levels,[31][38] exocytosis of QDs is still poorly studied in the literature.

While significant research efforts have broadened the understanding of toxicity of QDs, there are large discrepancies in the literature and questions still remains to be answered. Diversity of this class material as compared to normal chemical substances makes the assessment of their toxicity very challenging. As their toxicity may also be dynamic depending on the environmental factors such as pH level, light exposure and cell type, traditional methods of assessing toxicity of chemicals such as LD50 are not applicable for QDs. Therefore, researchers are focusing on introducing novel approaches and adapting existing methods to include this unique class of materials.[31] Furthermore, novel strategies to engineer safer QDs are still under exploration by the scientific community. A recent novelty in the field is the discovery of carbon quantum dots, a new generation of optically-active nanoparticles potentially capable of replacing semiconductor QDs, but with the advantage of much lower toxicity.

Optical properties

Fluorescence spectra of CdTe quantum dots of various sizes. Different sized quantum dots emit different color light due to quantum confinement.

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 [39] 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.[40] 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.

A device that produces visible light, through energy transfer from thin layers of quantum wells to crystals above the layers.[41]

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.[42] 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, or qubits, plus a way of performing operations, quantum calculations and the computers that would perform them might be possible.

Biology

In modern biological analysis, various kinds of organic dyes are used. However, as technology advances, greater flexibility in these dyes is sought.[43] 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 extinction coefficient combined with a comparable quantum yield to fluorescent dyes[44]) as well as their stability (allowing much less photobleaching). It has been estimated that quantum dots are 20 times brighter and 100 times more stable than traditional fluorescent reporters.[43] For single-particle tracking, the irregular blinking of quantum dots is a minor drawback. However, there have been groups which have developed quantum dots which are essentially nonblinking and demonstrated their utility in single molecule tracking experiments.[45][46]

The use of quantum dots for highly sensitive cellular imaging has seen major advances.[47] 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.[48] 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.[49] Antibodies, streptavidin,[50] peptides,[51] DNA,[52] nucleic acid aptamers,[53] or small-molecule ligands [54] can be used to target quantum dots to specific proteins on cells. Researchers were able to observe quantum dots in lymph nodes of mice for more than 4 months.[55]

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.

One application of quantum dots in biology is as donor fluorophores in Förster resonance energy transfer, where the large extinction coefficient and spectral purity of these fluorophores make them superior to molecular fluorophores[56] It is also worth noting that the broad absorbance of QDs allows selective excitation of the QD donor and a minimum excitation of a dye acceptor in FRET-based studies.[57] The applicability of the FRET model, which assumes that the Quantum Dot can be approximated as a point dipole, has recently been demonstrated[58]

The use of quantum dots for tumor targeting under in vivo conditions employ two targeting schemes: active targeting and passive targeting. In the case of active targeting, quantum dots are functionalized with tumor-specific binding sites to selectively bind to tumor cells. Passive targeting uses the 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.

Quantum dot probes exhibit in vivo toxicity. For example, CdSe nanocrystals are highly toxic to cultured cells under UV illumination, because the particles dissolve, 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.[55][59] Hydrogel encapsulation of quantum dots allows for quantum dots to be introduced into a stable aqueous solution, reducing the possibility of cadmium leakage.Then again, only little is known about the excretion process of quantum dots from living organisms.[60]

In another potential application, quantum dots are being investigated as the inorganic fluorophore for intra-operative detection of tumors using fluorescence spectroscopy.

Delivery of undamaged quantum dots to the cell cytoplasm has been a challenge with existing techniques. Vector-based methods have resulted in aggregation and endosomal sequestration of quantum dots while electroporation can damage the semi-conducting particles and aggregate delivered dots in the cytosol. Via cell squeezing, quantum dots can be efficiently delivered without inducing aggregation, trapping material in endosomes, or significant loss of cell viability. Moreover, it has shown that individual quantum dots delivered by this approach are detectable in the cell cytosol, thus illustrating the potential of this technique for single molecule tracking studies.[61]

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,[62] 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%.[63] 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.[63]

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.[64] Incorporation of metal oxides, such as ZnO, TiO2, and Nb2O5 nanomaterials into organic photovoltaics have been commercialized using full roll-to-roll processing.[64] A 13.2% power conversion efficiency is claimed in Si nanowire/PEDOT:PSS hybrid solar cells.[65]

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.[66]

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.[67] 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.[67]

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.[68]

Light emitting devices

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.[69] 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.[70]

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.[71]

Photodetector devices

Quantum dot photodetectors (QDPs) can be fabricated either via solution-processing,[72] or from conventional single-crystalline semiconductors.[73] 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.[74] 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

3D confined electron wave functions in a quantum dot. Here, rectangular and triangular-shaped quantum dots are shown. Energy states in rectangular dots are more s-type and p-type. However, in a triangular dot the wave functions are mixed due to confinement symmetry. (Click for animation)

In a semiconductor crystallite whose size is smaller than twice the size of its exciton Bohr radius, the excitons are squeezed, leading to quantum confinement. The energy levels can then be predicted using the particle in a box model in which the energies of states depend on the length of the box. Comparing the quantum dots size to the Bohr radius of the electron and hole wave functions, 3 regimes can be defined. A 'strong confinement regime' is defined as the quantum dots radius being smaller than both electron and hole Bohr radius, 'weak confinement' is given when the quantum dot is larger than both. For semiconductors in which electron and hole radii are markedly different, an 'intermediate confinement regime' exists, where the quantum dot's radius is larger than the Bohr radius of one charge carrier (typically the hole), but not the other charge carrier.[75]

Splitting of energy levels for small quantum dots due to the quantum confinement effect. The horizontal axis is the radius, or the size, of the quantum dots and ab* is the Exciton Bohr radius.
Band gap energy
The band gap can become smaller in the strong confinement regime as the energy levels split up. The Exciton Bohr radius can be expressed as:
where ab is the Bohr radius=0.053 nm, m is the mass, μ is the reduced mass, and εr is the size-dependent dielectric constant (Relative permittivity). This results in the increase in the total emission energy (the sum of the energy levels in the smaller band gaps in the strong confinement regime is larger than the energy levels in the band gaps of the original levels in the weak confinement regime) and the emission at various wavelengths. If the size distribution of QDs is not enough peaked, the convolution of multiple emission wavelengths is observed as a continuous spectra.
Confinement energy
The exciton entity can be modeled using the particle in the box. The electron and the hole can be seen as hydrogen in the Bohr model with the hydrogen nucleus replaced by the hole of positive charge and negative electron mass. Then the energy levels of the exciton can be represented as the solution to the particle in a box at the ground level (n = 1) with the mass replaced by the reduced mass. Thus by varying the size of the quantum dot, the confinement energy of the exciton can be controlled.
Bound exciton energy
There is Coulomb attraction between the negatively charged electron and the positively charged hole. The negative energy involved in the attraction is proportional to Rydberg's energy and inversely proportional to square of the size-dependent dielectric constant[76] of the semiconductor. When the size of the semiconductor crystal is smaller than the Exciton Bohr radius, the Coulomb interaction must be modified to fit the situation.

Therefore, the sum of these energies can be represented as:

where μ is the reduced mass, a is the radius, me is the free electron mass, mh is the hole mass, and εr is the size-dependent dielectric constant.

Although the above equations were derived using simplifying assumptions, they imply that the electronic transitions of the quantum dots will depend on their size. These quantum confinement effects are apparent only below the critical size. Larger particles do not exhibit this effect. This effect of quantum confinement on the quantum dots has been repeatedly verified experimentally[77] and is a key feature of many emerging electronic structures.[78]

The Coulomb interaction between confined carriers can also be studied by numerical means when results unconstrained by asymptotic approximations are pursued.[79]

Besides confinement in all three dimensions (i.e., a quantum dot), other quantum confined semiconductors include:

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.[80]

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

whose energy terms may be obtained as solutions of the Schrödinger equation. The definition of capacitance,

,

with the potential difference

may be applied to a quantum dot with the addition or removal of individual electrons,

and .

Then

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.[81]

Classical mechanics

Classical models of electrostatic properties of electrons in quantum dots are similar in nature to the Thomson problem of optimally distributing electrons on a unit sphere.

The classical electrostatic treatment of electrons confined to spherical quantum dots is similar to their treatment in the Thomson,[82] or plum pudding model, of the atom.[83]

The classical treatment of both two-dimensional and three-dimensional quantum dots exhibit electron shell-filling behavior. A "periodic table of classical artificial atoms" has been described for two-dimensional quantum dots.[84] As well, several connections have been reported between the three-dimensional Thomson problem and electron shell-filling patterns found in naturally-occurring atoms found throughout the periodic table.[85] This latter work originated in classical electrostatic modeling of electrons in a spherical quantum dot represented by an ideal dielectric sphere.[86]

History

The term “quantum dot” was coined in 1986.[87] They were first discovered in a glass matrix and in colloidal solutions[88] by Alexey Ekimov[89][90][91][92] and Louis Brus.[93][94]

See also

Additional reading

References

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