Quantum dot

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

Quantum dots (QDs) are semiconductor particles a few nanometres in size, having optical and electronic properties that differ from larger particles due to quantum mechanics. They are a central topic in nanotechnology. When the quantum dots are illuminated by UV light, an electron in the quantum dot can be excited to a state of higher energy. In the case of a semiconducting quantum dot, this process corresponds to the transition of an electron from the valence band to the conductance band. The excited electron can drop back into the valence band releasing its energy by the emission of light. This light emission (photoluminescence) is illustrated in the figure on the right. The color of that light depends on the energy difference between the conductance band and the valence band, or transition between discretized energy states when band structure is no longer a good definition in QDs.

In the language of materials science, nanoscale semiconductor materials tightly confine either electrons or electron holes. Quantum dots are sometimes referred to as artificial atoms, emphasizing their singularity, having bound, discrete electronic states, like naturally occurring atoms or molecules. It was shown that the electronic wave functions in quantum dots resemble the ones in real atoms. By coupling two or more such quantum dots an artificial molecule can be made, exhibiting hybridization even at room temperature.

Quantum dots have properties intermediate between bulk semiconductors and discrete atoms or molecules. Their optoelectronic properties change as a function of both size and shape. Larger QDs of 5–6 nm diameter emit longer wavelengths, with colors such as orange or red. Smaller QDs (2–3 nm) emit shorter wavelengths, yielding colors like blue and green. However, the specific colors vary depending on the exact composition of the QD.

Potential applications of quantum dots include single-electron transistors, solar cells, LEDs, lasers, single-photon sources, second-harmonic generation, quantum computing, cell biology research, microscopy, and medical imaging. Their small size allows for some QDs to be suspended in solution, which may lead to use in inkjet printing and spin-coating. They have been used in Langmuir-Blodgett thin-films. 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

There are several ways to fabricate quantum dots. Possible methods include colloidal synthesis, self-assembly, and electrical gating.

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 the size distribution focusing, yielding an improbable distribution of nearly monodispersed 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, cadmium telluride, indium arsenide, and indium phosphide. Dots may also be made from ternary compounds such as cadmium selenide sulfide. Further, recent advances have been made which allow for synthesis of colloidal perovskite quantum dots. 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.

Idealized 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.

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 gases 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.

Atomic resolution scanning transmission electron microscopy image of an indium gallium arsenide (InGaAs) quantum dot buried in gallium arsenide (GaAs).

• Self-assembled quantum dots nucleate spontaneously under certain conditions during molecular beam epitaxy (MBE) and metalorganic vapour-phase epitaxy (MOVPE), when a material is grown on a substrate to which it is not lattice matched. The resulting strain leads to the formation of 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. A widely used type of quantum dots grown with this method are indium gallium arsenide (InGaAs) quantum dots in gallium arsenide (GaAs). Such quantum dots have the 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 (holes) one by one. The number of electrons (holes) confined in the channel is driven by the gate voltage, starting from an occupation of zero electrons (holes), 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 throughput and size, it can be further enhanced to tens or even hundreds of kilograms.

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 23 January 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 24 September 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-infrared region of the spectrum and have similar optical properties to those of CdSe quantum dots. Among these materials are InP/ZnS, CuInS/ZnS, Si, Ge and C.

Peptides are being researched as potential quantum dot material.

Health and safety

Main articles: Health and safety hazards of nanomaterials and Nanotoxicology

Some quantum dots pose risks to human health and the environment under certain conditions. Notably, the studies on quantum dot toxicity have focused on particles containing cadmium and have yet to be demonstrated in animal models after physiologically relevant dosing. In vitro studies, based on cell cultures, on quantum dots (QD) toxicity suggest that their toxicity may derive from multiple factors including their physicochemical characteristics (size, shape, composition, surface functional groups, and surface charges) and their 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.

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 oxidation by air, CdSe QDs release free cadmium ions causing cell death. 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. Some studies have also demonstrated that addition of a ZnS shell inhibits the process of reactive oxygen species in CdSe QDs. Another aspect of QD toxicity is that there are, in vivo, 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. The reports of QD localization in the cell nucleus 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, no alterations in animal behavior, weight, hematological markers or organ damage has been found through either histological or biochemical analysis. These findings have led scientists to believe that intracellular dose is the most important determining 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. Though multiple other studies have concluded retention of QDs in cellular levels, 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 remain to be answered. Diversity of this class of 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. 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 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.

Applications

Quantum dots are particularly promising for optical applications due to their high extinction coefficient. and ultrafast optical nonlinearities with potential applications for developing all-optical systems. 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, and as active elements for thermoelectrics.

Tuning the size of quantum dots is attractive for many potential applications. For instance, larger quantum dots have a greater spectrum-shift toward 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.

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.

Subcutaneous record-keeping

In December 2019, Robert S. Langer and his team developed and patented a technique whereby transdermal patches could be used to label people with invisible ink in order to store medical and other information subcutaneously. This was presented as a boon to "developing nations" where lack of infrastructure means an absence of medical records. The technology, which is assigned to the Massachusetts Institute of Technology, uses a "quantum dot dye that is delivered, in this case along with a vaccine, by a microneedle patch." The research "was funded by the Bill and Melinda Gates Foundation and the Koch Institute for Integrative Cancer Research."

Biology

In modern biological analysis, various kinds of organic dyes are used. However, as technology advances, greater flexibility in these dyes is sought. 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) 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. 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.

The use of quantum dots for highly sensitive cellular imaging has seen major advances. 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. Antibodies, streptavidin, peptides, DNA, nucleic acid aptamers, or small-molecule ligands 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.

Quantum dots can have antibacterial properties similar to nanoparticles and can kill bacteria in a dose-dependent manner. One mechanism by which quantum dots can kill bacteria is through impairing the functions of antioxidative system in the cells and down regulating the antioxidative genes. In addition, quantum dots can directly damage the cell wall. Quantum dots have been shown to be effective against both gram- positive and gram-negative bacteria.

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 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. The applicability of the FRET model, which assumes that the Quantum Dot can be approximated as a point dipole, has recently been demonstrated.

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. 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.

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.

Photovoltaic devices

Main article: Quantum dot solar cell

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 report 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 the potential for 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

See also: Light-emitting diode § Quantum-dot LEDs, and Quantum dot display

Several methods are proposed for using quantum dots to improve existing light-emitting diode (LED) design, including quantum dot light-emitting diode (QD-LED or QLED) 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

See also: Quantum dot display

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. Quantum dot displays use blue-emitting LEDs rather than white LEDs as the light sources. The converting part of the emitted light is converted into pure green and red light by the corresponding color quantum dots placed in front of the blue LED or using a quantum dot infused diffuser sheet in the backlight optical stack. Blank pixels are also used to allow the blue LED light to still generate blue hues. This type of white light as the backlight of an LCD panel allows for the best color gamut at lower cost than an RGB LED combination using three LEDs.

Another method by which quantum dot displays can be achieved is the electroluminescent (EL) or electro-emissive method. This involves embedding quantum dots in each individual pixel. These are then activated and controlled via an electric current application. Since this is often light emitting itself, the achievable colors may be limited in this method. Electro-emissive QD-LED TVs exist in laboratories only.

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.

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 infrared 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 visible- and infrared-light cameras, machine vision, industrial inspection, spectroscopy, and fluorescent biomedical imaging.

Photocatalysts

Main article: Photocatalysis

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

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)

Main article: Potential well

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 dot's 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.

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 a_b* 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:

${\displaystyle a_{\rm {B}}^{*}=\varepsilon _{\rm {r}}\left({\frac {m}{\mu }}\right)a_{\rm {B}}}$

where a_B=0.053 nm is the Bohr radius, m is the mass, μ is the reduced mass, and ε_r 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 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:

${\displaystyle {\begin{aligned}E_{\textrm {confinement}}&={\frac {\hbar ^{2}\pi ^{2}}{2a^{2}}}\left({\frac {1}{m_{\rm {e}}}}+{\frac {1}{m_{h}}}\right)={\frac {\hbar ^{2}\pi ^{2}}{2\mu a^{2}}}\\E_{\textrm {exciton}}&=-{\frac {1}{\epsilon _{\rm {r}}^{2}}}{\frac {\mu }{m_{\rm {e}}}}R_{y}=-R_{y}^{*}\\E&=E_{\textrm {bandgap}}+E_{\textrm {confinement}}+E_{\textrm {exciton}}\\&=E_{\textrm {bandgap}}+{\frac {\hbar ^{2}\pi ^{2}}{2\mu a^{2}}}-R_{y}^{*}\end{aligned}}}$

where μ is the reduced mass, a is the radius of the quantum dot, m_e is the free electron mass, m_h is the hole mass, and ε_r 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 and is a key feature of many emerging electronic structures.

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

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

• 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

${\displaystyle \mu (N)=E(N)-E(N-1)}$

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

${\displaystyle {1 \over C}\equiv {\Delta \,V \over \Delta \,Q}}$,

with the potential difference

${\displaystyle \Delta \,V={\Delta \,\mu \, \over e}={\mu (N+\Delta \,N)-\mu (N) \over e}}$

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

${\displaystyle \Delta \,N=1}$ and ${\displaystyle \Delta \,Q=e}$.

Then

${\displaystyle C(N)={e^{2} \over \mu (N+1)-\mu (N)}={e^{2} \over I(N)-A(N)}}$

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.

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, or plum pudding model, of the atom.

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. 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. This latter work originated in classical electrostatic modeling of electrons in a spherical quantum dot represented by an ideal dielectric sphere.

History

The term quantum dot was coined in 1986. They were first synthesized in a glass matrix by Alexey Ekimov in 1981 and in colloidal suspension by Louis Brus in 1983. They were first theorized by Alexander Efros in 1982.

History of nanotechnology

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/History_of_nanotechnology 

The history of nanotechnology traces the development of the concepts and experimental work falling under the broad category of nanotechnology. Although nanotechnology is a relatively recent development in scientific research, the development of its central concepts happened over a longer period of time. The emergence of nanotechnology in the 1980s was caused by the convergence of experimental advances such as the invention of the scanning tunneling microscope in 1981 and the discovery of fullerenes in 1985, with the elucidation and popularization of a conceptual framework for the goals of nanotechnology beginning with the 1986 publication of the book Engines of Creation. The field was subject to growing public awareness and controversy in the early 2000s, with prominent debates about both its potential implications as well as the feasibility of the applications envisioned by advocates of molecular nanotechnology, and with governments moving to promote and fund research into nanotechnology. The early 2000s also saw the beginnings of commercial applications of nanotechnology, although these were limited to bulk applications of nanomaterials rather than the transformative applications envisioned by the field.

Early uses of nanomaterials

The earliest evidence of nanotechnology and its application is traced back to 600 BC at Keeladi, India. Subsequently carbon nanotubes, cementite nanowires found in the microstructure of wootz steel manufactured in ancient India from the time period of 900 AD and exported globally.

Although nanoparticles are associated with modern science, they were used by artisans as far back as the ninth century in Mesopotamia for creating a glittering effect on the surface of pots.

In modern times, pottery from the Middle Ages and Renaissance often retains a distinct gold- or copper-colored metallic glitter. This luster is caused by a metallic film that was applied to the transparent surface of a glazing, which contains silver and copper nanoparticles dispersed homogeneously in the glassy matrix of the ceramic glaze. These nanoparticles are created by the artisans by adding copper and silver salts and oxides together with vinegar, ochre, and clay on the surface of previously-glazed pottery. The technique originated in the Muslim world. As Muslims were not allowed to use gold in artistic representations, they sought a way to create a similar effect without using real gold. The solution they found was using luster.

Conceptual origins

Richard Feynman

Main article: There's Plenty of Room at the Bottom

Richard Feynman gave a 1959 talk which many years later inspired the conceptual foundations of nanotechnology.

The American physicist Richard Feynman lectured, "There's Plenty of Room at the Bottom," at an American Physical Society meeting at Caltech on December 29, 1959, which is often held to have provided inspiration for the field of nanotechnology. Feynman had described a process by which the ability to manipulate individual atoms and molecules might be developed, using one set of precise tools to build and operate another proportionally smaller set, so on down to the needed scale. In the course of this, he noted, scaling issues would arise from the changing magnitude of various physical phenomena: gravity would become less important, surface tension and Van der Waals attraction would become more important.

After Feynman's death, a scholar studying the historical development of nanotechnology has concluded that his actual role in catalyzing nanotechnology research was limited, based on recollections from many of the people active in the nascent field in the 1980s and 1990s. Chris Toumey, a cultural anthropologist at the University of South Carolina, found that the published versions of Feynman’s talk had a negligible influence in the twenty years after it was first published, as measured by citations in the scientific literature, and not much more influence in the decade after the Scanning Tunneling Microscope was invented in 1981. Subsequently, interest in “Plenty of Room” in the scientific literature greatly increased in the early 1990s. This is probably because the term “nanotechnology” gained serious attention just before that time, following its use by K. Eric Drexler in his 1986 book, Engines of Creation: The Coming Era of Nanotechnology, which took the Feynman concept of a billion tiny factories and added the idea that they could make more copies of themselves via computer control instead of control by a human operator; and in a cover article headlined "Nanotechnology", published later that year in a mass-circulation science-oriented magazine, Omni. Toumey’s analysis also includes comments from distinguished scientists in nanotechnology who say that “Plenty of Room” did not influence their early work, and in fact most of them had not read it until a later date.

These and other developments hint that the retroactive rediscovery of Feynman’s “Plenty of Room” gave nanotechnology a packaged history that provided an early date of December 1959, plus a connection to the charisma and genius of Richard Feynman. Feynman's stature as a Nobel laureate and as an iconic figure in 20th century science surely helped advocates of nanotechnology and provided a valuable intellectual link to the past.

Norio Taniguchi

Main article: Norio Taniguchi

The Japanese scientist called Norio Taniguchi of Tokyo University of Science was first to use the term "nano-technology" in a 1974 conference, to describe semiconductor processes such as thin film deposition and ion beam milling exhibiting characteristic control on the order of a nanometer. His definition was, "'Nano-technology' mainly consists of the processing of, separation, consolidation, and deformation of materials by one atom or one molecule." However, the term was not used again until 1981 when Eric Drexler, who was unaware of Taniguchi's prior use of the term, published his first paper on nanotechnology in 1981.

K. Eric Drexler

K. Eric Drexler developed and popularized the concept of nanotechnology and founded the field of molecular nanotechnology.

Main article: Eric Drexler

In the 1980s the idea of nanotechnology as a deterministic, rather than stochastic, handling of individual atoms and molecules was conceptually explored in depth by K. Eric Drexler, who promoted the technological significance of nano-scale phenomena and devices through speeches and two influential books.

In 1980, Drexler encountered Feynman's provocative 1959 talk "There's Plenty of Room at the Bottom" while preparing his initial scientific paper on the subject, “Molecular Engineering: An approach to the development of general capabilities for molecular manipulation,” published in the Proceedings of the National Academy of Sciences in 1981. The term "nanotechnology" (which paralleled Taniguchi's "nano-technology") was independently applied by Drexler in his 1986 book Engines of Creation: The Coming Era of Nanotechnology, which proposed the idea of a nanoscale "assembler" which would be able to build a copy of itself and of other items of arbitrary complexity. He also first published the term "grey goo" to describe what might happen if a hypothetical self-replicating machine, capable of independent operation, were constructed and released. Drexler's vision of nanotechnology is often called "Molecular Nanotechnology" (MNT) or "molecular manufacturing."

His 1991 Ph.D. work at the MIT Media Lab was the first doctoral degree on the topic of molecular nanotechnology and (after some editing) his thesis, "Molecular Machinery and Manufacturing with Applications to Computation," was published as Nanosystems: Molecular Machinery, Manufacturing, and Computation, which received the Association of American Publishers award for Best Computer Science Book of 1992. Drexler founded the Foresight Institute in 1986 with the mission of "Preparing for nanotechnology.” Drexler is no longer a member of the Foresight Institute.

Experimental research and advances

In nanoelectronics, nanoscale thickness was demonstrated in the gate oxide and thin films used in transistors as early as the 1960s, but it was not until the late 1990s that MOSFETs (metal–oxide–semiconductor field-effect transistors) with nanoscale gate length were demonstrated. Nanotechnology and nanoscience got a boost in the early 1980s with two major developments: the birth of cluster science and the invention of the scanning tunneling microscope (STM). These developments led to the discovery of fullerenes in 1985 and the structural assignment of carbon nanotubes in 1991. The development of FinFET in the 1990s aldo laid the foundations for modern nanoelectronic semiconductor device fabrication.

Invention of scanning probe microscopy

Gerd Binnig (left) and Heinrich Rohrer (right) won the 1986 Nobel Prize in Physics for their 1981 invention of the scanning tunneling microscope.

The scanning tunneling microscope, an instrument for imaging surfaces at the atomic level, was developed in 1981 by Gerd Binnig and Heinrich Rohrer at IBM Zurich Research Laboratory, for which they were awarded the Nobel Prize in Physics in 1986. Binnig, Calvin Quate and Christoph Gerber invented the first atomic force microscope in 1986. The first commercially available atomic force microscope was introduced in 1989.

IBM researcher Don Eigler was the first to manipulate atoms using a scanning tunneling microscope in 1989. He used 35 Xenon atoms to spell out the IBM logo. He shared the 2010 Kavli Prize in Nanoscience for this work.

Advances in interface and colloid science

Interface and colloid science had existed for nearly a century before they became associated with nanotechnology. The first observations and size measurements of nanoparticles had been made during the first decade of the 20th century by Richard Adolf Zsigmondy, winner of the 1925 Nobel Prize in Chemistry, who made a detailed study of gold sols and other nanomaterials with sizes down to 10 nm using an ultramicroscope which was capable of visualizing particles much smaller than the light wavelength. Zsigmondy was also the first to use the term "nanometer" explicitly for characterizing particle size. In the 1920s, Irving Langmuir, winner of the 1932 Nobel Prize in Chemistry, and Katharine B. Blodgett introduced the concept of a monolayer, a layer of material one molecule thick. In the early 1950s, Derjaguin and Abrikosova conducted the first measurement of surface forces.

In 1974 the process of atomic layer deposition for depositing uniform thin films one atomic layer at a time was developed and patented by Tuomo Suntola and co-workers in Finland.

In another development, the synthesis and properties of semiconductor nanocrystals were studied. This led to a fast increasing number of semiconductor nanoparticles of quantum dots.

Discovery of fullerenes

Harry Kroto (left) won the 1996 Nobel Prize in Chemistry along with Richard Smalley (pictured below) and Robert Curl for their 1985 discovery of buckminsterfullerene, while Sumio Iijima (right) won the inaugural 2008 Kavli Prize in Nanoscience for his 1991 discovery of carbon nanotubes.

Fullerenes were discovered in 1985 by Harry Kroto, Richard Smalley, and Robert Curl, who together won the 1996 Nobel Prize in Chemistry. Smalley's research in physical chemistry investigated formation of inorganic and semiconductor clusters using pulsed molecular beams and time of flight mass spectrometry. As a consequence of this expertise, Curl introduced him to Kroto in order to investigate a question about the constituents of astronomical dust. These are carbon rich grains expelled by old stars such as R Corona Borealis. The result of this collaboration was the discovery of C₆₀ and the fullerenes as the third allotropic form of carbon. Subsequent discoveries included the endohedral fullerenes, and the larger family of fullerenes the following year.

The discovery of carbon nanotubes is largely attributed to Sumio Iijima of NEC in 1991, although carbon nanotubes have been produced and observed under a variety of conditions prior to 1991. Iijima's discovery of multi-walled carbon nanotubes in the insoluble material of arc-burned graphite rods in 1991 and Mintmire, Dunlap, and White's independent prediction that if single-walled carbon nanotubes could be made, then they would exhibit remarkable conducting properties helped create the initial buzz that is now associated with carbon nanotubes. Nanotube research accelerated greatly following the independent discoveries by Bethune at IBM and Iijima at NEC of single-walled carbon nanotubes and methods to specifically produce them by adding transition-metal catalysts to the carbon in an arc discharge.

In the early 1990s Huffman and Kraetschmer, of the University of Arizona, discovered how to synthesize and purify large quantities of fullerenes. This opened the door to their characterization and functionalization by hundreds of investigators in government and industrial laboratories. Shortly after, rubidium doped C₆₀ was found to be a mid temperature (Tc = 32 K) superconductor. At a meeting of the Materials Research Society in 1992, Dr. T. Ebbesen (NEC) described to a spellbound audience his discovery and characterization of carbon nanotubes. This event sent those in attendance and others downwind of his presentation into their laboratories to reproduce and push those discoveries forward. Using the same or similar tools as those used by Huffman and Kratschmer, hundreds of researchers further developed the field of nanotube-based nanotechnology.

Nanoscale transistors

Main article: Nanoelectronics

See also: List of semiconductor scale examples, Semiconductor device fabrication, and Transistor count

A nanolayer-base metal–semiconductor junction (M–S junction) transistor was initially proposed and demonstrated by A. Rose in 1960, L. Geppert, Mohamed Atalla and Dawon Kahng in 1962. Decades later, advances in multi-gate technology enabled the scaling of metal–oxide–semiconductor field-effect transistor (MOSFET) devices down to nano-scale levels smaller than 20 nm gate length, starting with the FinFET (fin field-effect transistor), a three-dimensional, non-planar, double-gate MOSFET. At UC Berkeley, a team of researchers including Digh Hisamoto, Chenming Hu, Tsu-Jae King Liu, Jeffrey Bokor and others fabricated FinFET devices down to a 17 nm process in 1998, then 15 nm in 2001, and then 10 nm in 2002.

In 2006, a team of Korean researchers from the Korea Advanced Institute of Science and Technology (KAIST) and the National Nano Fab Center developed a 3 nm MOSFET, the world's smallest nanoelectronic device. It was based on gate-all-around (GAA) FinFET technology.

Government and corporate support

National Nanotechnology Initiative

Mihail Roco of the National Science Foundation formally proposed the National Nanotechnology Initiative to the White House, and was a key architect in its initial development.

Main article: National Nanotechnology Initiative

The National Nanotechnology Initiative is a United States federal nanotechnology research and development program. “The NNI serves as the central point of communication, cooperation, and collaboration for all Federal agencies engaged in nanotechnology research, bringing together the expertise needed to advance this broad and complex field." Its goals are to advance a world-class nanotechnology research and development (R&D) program, foster the transfer of new technologies into products for commercial and public benefit, develop and sustain educational resources, a skilled workforce, and the supporting infrastructure and tools to advance nanotechnology, and support responsible development of nanotechnology. The initiative was spearheaded by Mihail Roco, who formally proposed the National Nanotechnology Initiative to the Office of Science and Technology Policy during the Clinton administration in 1999, and was a key architect in its development. He is currently the Senior Advisor for Nanotechnology at the National Science Foundation, as well as the founding chair of the National Science and Technology Council subcommittee on Nanoscale Science, Engineering and Technology.

President Bill Clinton advocated nanotechnology development. In a 21 January 2000 speech at the California Institute of Technology, Clinton said, "Some of our research goals may take twenty or more years to achieve, but that is precisely why there is an important role for the federal government." Feynman's stature and concept of atomically precise fabrication played a role in securing funding for nanotechnology research, as mentioned in President Clinton's speech:

My budget supports a major new National Nanotechnology Initiative, worth $500 million. Caltech is no stranger to the idea of nanotechnology the ability to manipulate matter at the atomic and molecular level. Over 40 years ago, Caltech's own Richard Feynman asked, "What would happen if we could arrange the atoms one by one the way we want them?"

President George W. Bush further increased funding for nanotechnology. On December 3, 2003 Bush signed into law the 21st Century Nanotechnology Research and Development Act, which authorizes expenditures for five of the participating agencies totaling US$3.63 billion over four years. The NNI budget supplement for Fiscal Year 2009 provides $1.5 billion to the NNI, reflecting steady growth in the nanotechnology investment.

Other international government and corporate support

Over sixty countries created nanotechnology research and development (R&D) government programs between 2001 and 2004. Government funding was exceeded by corporate spending on nanotechnology R&D, with most of the funding coming from corporations based in the United States, Japan and Germany. The top five organizations that filed the most intellectual patents on nanotechnology R&D between 1970 and 2011 were Samsung Electronics (2,578 first patents), Nippon Steel (1,490 first patents), IBM (1,360 first patents), Toshiba (1,298 first patents) and Canon (1,162 first patents). The top five organizations that published the most scientific papers on nanotechnology research between 1970 and 2012 were the Chinese Academy of Sciences, Russian Academy of Sciences, Centre national de la recherche scientifique, University of Tokyo and Osaka University.

Growing public awareness and controversy

"Why the future doesn't need us"

Main article: Why the future doesn't need us

"Why the future doesn't need us" is an article written by Bill Joy, then Chief Scientist at Sun Microsystems, in the April 2000 issue of Wired magazine. In the article, he argues that "Our most powerful 21st-century technologies — robotics, genetic engineering, and nanotech — are threatening to make humans an endangered species." Joy argues that developing technologies provide a much greater danger to humanity than any technology before it has ever presented. In particular, he focuses on genetics, nanotechnology and robotics. He argues that 20th-century technologies of destruction, such as the nuclear bomb, were limited to large governments, due to the complexity and cost of such devices, as well as the difficulty in acquiring the required materials. He also voices concern about increasing computer power. His worry is that computers will eventually become more intelligent than we are, leading to such dystopian scenarios as robot rebellion. He notably quotes the Unabomber on this topic. After the publication of the article, Bill Joy suggested assessing technologies to gauge their implicit dangers, as well as having scientists refuse to work on technologies that have the potential to cause harm.

In the AAAS Science and Technology Policy Yearbook 2001 article titled A Response to Bill Joy and the Doom-and-Gloom Technofuturists, Bill Joy was criticized for having technological tunnel vision on his prediction, by failing to consider social factors. In Ray Kurzweil's The Singularity Is Near, he questioned the regulation of potentially dangerous technology, asking "Should we tell the millions of people afflicted with cancer and other devastating conditions that we are canceling the development of all bioengineered treatments because there is a risk that these same technologies may someday be used for malevolent purposes?".

Prey

Main article: Prey (novel)

Prey is a 2002 novel by Michael Crichton which features an artificial swarm of nanorobots which develop intelligence and threaten their human inventors. The novel generated concern within the nanotechnology community that the novel could negatively affect public perception of nanotechnology by creating fear of a similar scenario in real life.

Drexler–Smalley debate

Main article: Drexler–Smalley debate on molecular nanotechnology

Richard Smalley, best known for co-discovering the soccer ball-shaped “buckyball” molecule and a leading advocate of nanotechnology and its many applications, was an outspoken critic of the idea of molecular assemblers, as advocated by Eric Drexler. In 2001 he introduced scientific objections to them attacking the notion of universal assemblers in a 2001 Scientific American article, leading to a rebuttal later that year from Drexler and colleagues, and eventually to an exchange of open letters in 2003.

Smalley criticized Drexler's work on nanotechnology as naive, arguing that chemistry is extremely complicated, reactions are hard to control, and that a universal assembler is science fiction. Smalley believed that such assemblers were not physically possible and introduced scientific objections to them. His two principal technical objections, which he had termed the “fat fingers problem" and the "sticky fingers problem”, argued against the feasibility of molecular assemblers being able to precisely select and place individual atoms. He also believed that Drexler’s speculations about apocalyptic dangers of molecular assemblers threaten the public support for development of nanotechnology.

Smalley first argued that "fat fingers" made MNT impossible. He later argued that nanomachines would have to resemble chemical enzymes more than Drexler's assemblers and could only work in water. He believed these would exclude the possibility of "molecular assemblers" that worked by precision picking and placing of individual atoms. Also, Smalley argued that nearly all of modern chemistry involves reactions that take place in a solvent (usually water), because the small molecules of a solvent contribute many things, such as lowering binding energies for transition states. Since nearly all known chemistry requires a solvent, Smalley felt that Drexler's proposal to use a high vacuum environment was not feasible.

Smalley also believed that Drexler's speculations about apocalyptic dangers of self-replicating machines that have been equated with "molecular assemblers" would threaten the public support for development of nanotechnology. To address the debate between Drexler and Smalley regarding molecular assemblers Chemical & Engineering News published a point-counterpoint consisting of an exchange of letters that addressed the issues.

Drexler and coworkers responded to these two issues in a 2001 publication. Drexler and colleagues noted that Drexler never proposed universal assemblers able to make absolutely anything, but instead proposed more limited assemblers able to make a very wide variety of things. They challenged the relevance of Smalley's arguments to the more specific proposals advanced in Nanosystems. Drexler maintained that both were straw man arguments, and in the case of enzymes, Prof. Klibanov wrote in 1994, "...using an enzyme in organic solvents eliminates several obstacles..." Drexler also addresses this in Nanosystems by showing mathematically that well designed catalysts can provide the effects of a solvent and can fundamentally be made even more efficient than a solvent/enzyme reaction could ever be. Drexler had difficulty in getting Smalley to respond, but in December 2003, Chemical & Engineering News carried a 4-part debate.

Ray Kurzweil spends four pages in his book 'The Singularity Is Near' to showing that Richard Smalley's arguments are not valid, and disputing them point by point. Kurzweil ends by stating that Drexler's visions are very practicable and even happening already.

Royal Society report on the implications of nanotechnology

Further information: Studies on the implications of nanotechnology

The Royal Society and Royal Academy of Engineering's 2004 report on the implications of nanoscience and nanotechnologies was inspired by Prince Charles' concerns about nanotechnology, including molecular manufacturing. However, the report spent almost no time on molecular manufacturing. In fact, the word "Drexler" appears only once in the body of the report (in passing), and "molecular manufacturing" or "molecular nanotechnology" not at all. The report covers various risks of nanoscale technologies, such as nanoparticle toxicology. It also provides a useful overview of several nanoscale fields. The report contains an annex (appendix) on grey goo, which cites a weaker variation of Richard Smalley's contested argument against molecular manufacturing. It concludes that there is no evidence that autonomous, self replicating nanomachines will be developed in the foreseeable future, and suggests that regulators should be more concerned with issues of nanoparticle toxicology.

Initial commercial applications

Further information: List of nanotechnology applications

The early 2000s saw the beginnings of the use of nanotechnology in commercial products, although most applications are limited to the bulk use of passive nanomaterials. Examples include titanium dioxide and zinc oxide nanoparticles in sunscreen, cosmetics and some food products; silver nanoparticles in food packaging, clothing, disinfectants and household appliances such as Silver Nano; carbon nanotubes for stain-resistant textiles; and cerium oxide as a fuel catalyst. As of March 10, 2011, the Project on Emerging Nanotechnologies estimated that over 1300 manufacturer-identified nanotech products are publicly available, with new ones hitting the market at a pace of 3–4 per week.

The National Science Foundation funded researcher David Berube to study the field of nanotechnology. His findings are published in the monograph Nano-Hype: The Truth Behind the Nanotechnology Buzz. This study concludes that much of what is sold as “nanotechnology” is in fact a recasting of straightforward materials science, which is leading to a “nanotech industry built solely on selling nanotubes, nanowires, and the like” which will “end up with a few suppliers selling low margin products in huge volumes." Further applications which require actual manipulation or arrangement of nanoscale components await further research. Though technologies branded with the term 'nano' are sometimes little related to and fall far short of the most ambitious and transformative technological goals of the sort in molecular manufacturing proposals, the term still connotes such ideas. According to Berube, there may be a danger that a "nano bubble" will form, or is forming already, from the use of the term by scientists and entrepreneurs to garner funding, regardless of interest in the transformative possibilities of more ambitious and far-sighted work.

Commercial nanoelectronic semiconductor device fabrication began in the 2010s. In 2013, SK Hynix began commercial mass-production of a 16 nm process, TSMC began production of a 16 nm FinFET process, and Samsung Electronics began production of a 10 nm process. TSMC began production of a 7 nm process in 2017, and Samsung began production of a 5 nm process in 2018. In 2019, Samsung announced plans for the commercial production of a 3 nm GAAFET process by 2021.