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The Fuss About Quantum Dots (Photonics Spectra | Jan 2008 | Features)

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The Fuss About Quantum Dots
What are quantum dots, and why are they important to today’s technology? Here’s a tutorial on the basics.

Sjoerd Hoogland, University of Toronto It is hard to think about a life without semiconductor technology: The entire global information and communications infrastructure is based on semiconductors, and in every one of these applications, size matters. To create computer chips that operate at ever-increasing speeds, engineers must search for ways to decrease device size. One promising way of doing this is to replace electronic semiconductor devices with photonic ones, such as quantum dots. Quantum dots exhibit unique characteristics, including size-tunability of their emission wavelength, an ultranarrow emission bandwidth, and a peak emission wavelength that is insensitive to temperature. These characteristics are tied to the fact that quantum dots exhibit discrete atomlike energy states because of the three-dimensional quantum confinement. Quantum dots also can serve as the gain media in lasers, in which case the laser threshold is decreased dramatically compared with lasers with quantum confinement in fewer than three dimensions (e.g., quantum wells). But what happens to the optical properties of semiconductors when their size is reduced to the scale of quantum dots? What confines carriers in all three dimensions, and what are the methods used today to accomplish this? This article will address the most popular systems of epitaxially grown quantum dots, which have yielded lasers that are commercially available, and it will examine colloidal quantum dot nanocrystals synthesized chemically through the organo-metallic route. Semiconductor properties The crystal structure of a solid restricts the movement of carriers. In a semiconductor material, the outer electrons of the atoms are delocalized over the entire crystal, with the periodicity of the crystal structure limiting their movement. For a certain electron energy, the carrier is allowed to move in one direction, but its motion in a different direction is restricted as a result of destructive interaction from the atomic lattice. This dependence of the electron energy on the momentum of the carrier results in a structure of energy bands where the carrier can exist. Semiconductors distinguish themselves from other materials by having an energy gap between the highest occupied energy band (the valence band) and the lowest unoccupied energy band (the conduction band). The bandgap of a semiconductor is measured between the top of the valence band and the bottom of the conduction band and is called direct if these extrema coincide in momentum (e.g., GaAs) and is called Article indirect if they do not (Si). Optical-emitting transitions are most likely to occur in direct-bandgap materials. In the real world, the semiconductor crystal is finite, which puts restrictions on the allowed wave vectors within the energy bands, resulting in a set of discrete states available in each band with a wave vector separation determined by the size of the semiconductor. As a practical matter, the states in a macrosize chunk of semiconductor are so closely spaced that the conduction and valence bands appear to be continua. The number of these states per unit volume in an energy band is described by the density of states. Because no available states exist within the bandgap, the density of states is measured from the bottom of the conduction band and the top of the valence band from which it is, for a bulk semiconductor, a continuously increasing function with carrier energy (Figure 1a).
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QR = quantum wire. These graphics represent the active region (top). this distribution is widespread. Articles Products Companies Calendar Register Log In The magnitude is determined by the effective mass of the carrier. Alternatively.. electrons can be actively excited to the conduction band. (d = dimension(s) of quantum structure. In a bulk semiconductor. the wave vector separation between allowed states in the direction of the quantum well is greatly enlarged. the temperature-dependent carrier distribution also makes the laser threshold temperature-dependent. in one dimension M ore (i. When the size of the well becomes comparable to the de Broglie wavelength of the carrier. the smaller the effective mass Reference of the carrier. the effective bandgap — are tunable by adjusting the well dimensions.e. compared with www. The small width of the well results in the restriction of the carrier movement in the direction perpendicular to the well. the energy separation between the resonances becomes large enough to form a discrete energy spectrum. The wave functions of carriers at these allowed energies are standing waves. Toward artificial atoms A quantum well can be formed by introducing a very thin layer of semiconductor whose bandgap is less than that of the surrounding semiconductor (Figure 2). A carrier is confined within the potential well when it has an energy of Ee1 or Ee2 for electrons and Eh1. a quantum wire) (c) and in three dimensions (i. Moreover. Quantum confinement in a quantum well is realized by sandwiching a lower bandgap material (II) between two larger bandgap materials (I and III). bulk material) (a).com/Article.e.. Figure 2.e.. as shown. Because the emission spectrum depends on the distribution and number of available transitions. electrons can be excited thermally to the conduction band.. a quantum well) (b). In semiconductors. leaving holes in the valence band. These unfavorable optical properties of bulk semiconductors can be overcome by confining carriers to dimensions approximating the de Broglie wavelength of the carriers. whose position is temperature-dependent. Charge carriers in this potential well can survive only when their energies correspond to wave functions that satisfy the boundary conditions for a standing wave. Eh2 for holes. QW = quantum well. in two dimensions (i. a quantum dot) (d).9/29/13 The Fuss About Quantum Dots (Photonics Spectra | Jan 2008 | Features) Discuss Related Figure 1. The overall carrier distribution in a semiconductor thus is a function of both the density of states and of the temperature-dependent FermiDirac distribution. Because the width of the quantum well typically is several orders of magnitude smaller than the dimensions of the bulk semiconductor crystal. which is undesirable for stable lasing operation. hence. The excited carriers will thermalize very quickly to the bottom of the conduction band (electrons) and to the top of the valence band (holes) by losing energy through carrier-carrier and carrier-phonon scattering. which is a measure of the degree of Downloads curvature of the energy band around the extrema — the larger the curvature. causing the discrete energy spectrum. by absorbing a photon with energy larger than the semiconductor bandgap. the energies allowed in the well — and.e. the larger the wave vector separation between states. Because these wave functions depend on the quantum well dimensions. QD = quantum dot). a bulk semiconductor exhibits a temperature-sensitive emission spectrum.photonics. k = momentum. the smaller the density of states. allowed states in momentum space (middle) and density of states (bottom) for confinement in no dimensions (i. with a small number of carriers right near the edge of the conduction and valence bands and with a peak that is situated above (below) the conduction (valence) band.aspx?AID=31908 2/6 . The probability of finding an excited carrier at a certain energy in a semiconductor at thermal equilibrium is described by temperature-dependent Fermi-Dirac statistics. for example.

Therefore. In addition. as shown in the bottom panel of Figure 1b. However. as well as the lowest transparency threshold. excited electrons can relax down to the bottom of the conduction band by losing energy through carrier-carrier and carrier-phonon interactions. and so quantum dots with strong quantum confinement should not be expected to emit light from the normal transition across the bandgap. In most semiconductors. eliminating the possibility of bulklike carrier motion. thus yielding a two-dimensional density of states: At each allowed energy. As a result. with the peak emission wavelength more stable around the quantum-confined transition energies. Such shape is analogous to atomic energy levels. the interaction length is shorter than the dimensions of the quantum dot. This shape results in a less temperature-sensitive carrier distribution than in bulk material. the probability for a carrier in a higher energetic state to lose its energy to a lower energetic state through these interactions becomes very low. just as in bulk material. In this case. resulting in widely spaced energy states.photonics. When taking the degree of confinement to the maximum by creating a quantum dot. this phonon bottleneck has not been observed experimentally. the emitted light spectrum has a narrower bandwidth. thus breaking up the exciton and making the transition energy independent of the quantum dot size. compared with the size of the quantum dot. Therefore. thus yielding a dense distribution of states in plane parallel to the well (Figure 1b. This could be explained by the fact that fabricated quantum dots still are imperfect 3-D quantum-confined systems. In this case. a phonon bottleneck occurs when the spacing between energy states is much larger than these interaction energies — as is the case in strong quantum confinement.com/Article. the excited electron and hole are forced to exist very close to each other. the peak material gain is increased. The degree of quantum confinement is determined by the interaction length over which the bond between an electron and a hole extends in an exciton. The Fuss About Quantum Dots (Photonics Spectra | Jan 2008 | Features) All these improvements in the optical properties arise from quantum confinement of carriers in only one dimension. The quantum dot sizes can be so small that the energy spacing between the allowed states in the conduction and valence bands is large enough to cause a so-called phonon bottleneck. How-ever. a sharp increase of the density states occurs. However. Epitaxially grown quantum dots www. middle panel). 3-D quantum confinement ensures not only temperature insensitivity of the emission wavelength but also the narrowest emission and gain bandwidths. the carriers are restricted in their motion in all three dimensions. the binding energy and oscillator strengths are increased. resulting in very closely spaced quantum-confined energy states. and the transparency threshold is decreased. An excited electron and hole can interact with each other through Coulomb attractions. In this case. creating a quasiparticle called an exciton. In the strong quantum-confinement regime. causing large Coulomb interactions between them. because of the increased number of carriers near the transition energy. middle). the quantum dot seems more bulklike because the electron and hole can separate beyond the exciton interaction length. In quantum-confined systems. the quantum dot size is smaller than the electron hole interaction length.aspx?AID=31908 3/6 . In weak quantum confinement. therefore. and the excitons can exist at room temperature. excitons have a very low probability of existing in a bulk semiconductor at room temperature. the binding energy required to create one is much smaller than the thermal energy.9/29/13 the bulk case (Figure 1a. electrons cannot relax to the bottom of the conduction band. at each allowed quantum-confined level. and therefore quantum dots also are known as artificial atoms. This leads to a truly discrete density of states exhibiting delta functions at the allowed energy states (Figure 1d). carrier movement parallel to the well is unrestricted. the overall density of states is determined by the wave vectors parallel to the well. However. The number of charge carriers accumulated at the working transition is enlarged greatly at the expense of the higher-energy parasitic states of the continuum. and particularly in a quantum dot.

Postsynthesis. Figure 3. with ligand molecules bound to its surface. On the other hand. However. forming islands of material on top of the surviving few monolayers. resulting in a lower efficiency in the radiative recombination in the semiconductor. In a Stranski-Krastanow quantum dot. the random nucleation of the quantum dots has a downside: There is limited control of the quantum dot’s size. to stop them from aggregating and to avoid any unsatisfied bonds of the surface atoms that could become trapping sites for excited carriers. In addition. but their large asymmetry in shape results in an imperfect delta function-shaped density of states. The energy separation between allowed states for these types of quantum dots is very large compared with the phonon energies. the reaction temperature and the duration of the reaction determine the final size of the colloids.9/29/13 The Fuss About Quantum Dots (Photonics Spectra | Jan 2008 | Features) Epitaxial growth of one material on top of another with a different lattice constant causes strain. quantum dots (a). only several monolayers can survive the strain. They are chemically synthesized.aspx?AID=31908 4/6 . The synthesized spheroidal nanocrystal quantum dots remain in solution because the surfaces are passivated by organic molecules (Figure 3b). In a colloidal quantum dot. while lasing operation has been demonstrated with ultralow thresholds and highly reduced temperature sensitivity of the emission wavelength. Any additional layers are strained to the point that they break apart. Emission from Stranski-Krastanow quantum dots has been realized from the nearinfrared to more than 2 μm. Binding the ligands on the surface of the colloidal quantum dots avoids such trap states by satisfying the unsatisfied bonds of the atoms on the surface of the colloids. Commercial quantum dot lasers made from III-V semiconductor material systems now are available. The quantum dots’ small height allows for size-tunability of the bandgap. Some colloid material systems also can be overcoated by a different semiconductor material that has properties to improve surface passivation. When this lattice mismatch is 5 to 10 percent. such as binding the colloids to specific molecular species to use the emissive dots as biological markers. the Stranski-Krastanow method is the one most often used to create quantum dots.com/Article. ensuring strong confinement of carriers and enabling bandgap tunability by varying the size of the dot. Colloidal quantum dots Colloidal nanocrystal quantum dots are an attractive alternative to epitaxial self-assembled dots. which act as life preservers to keep the colloids in solution and to prevent them from aggregating. for example. to optimize the carrier density to obtain a population inversion. The high crystalline quality that Stranski-Krastanow growth produces gives high radiative efficiencies. but the small size distribution gives rise to a continuous absorption spectrum in which only the lowest allowed transitions are clearly observable. The true strong confinement regime ensures large separation between allowed energy levels. the core is a semiconductor sphere several nanometers across.photonics. The most widely used colloidal quantum dots consist of II-VI semiconductors. called ligands. The ligands typically contain long carbon chains to keep the dots in solution. www. typically through an organometallic reaction route without the need of ultrahighvacuum equipment or dangerous gases. with a size distribution of typically less than 10 percent. the size of the quantum dots is small (several nanometers) compared with the exciton radius (several tens of nanometers). even at room temperature. but no phonon bottleneck has been observed. Because of its simplicity. They are suspended in an organic solvent so that they are castable from solution — for example. so the emission spectrum of the ensemble is broader than the ultranarrow emission spectrum of a single quantum dot. where cadmium-based materials provide operation in the visible spectrum and lead-chalcogenides in the near-infrared. Unsatisfied bonds on the surface of semiconductors are sources for excited carriers to be trapped. the strain caused by the large lattice mismatch between the substrate and the wetting layer material results in a contraction of the wetting layer material to form small islands. Typically.) This so-called Stranski-Krastanow growth method of self-assembled nanometer-size islands typically yields pyramid-shaped quantum dots with dimensions on the order of tens of nanometers for the base and several nanometers for the height (Figure 3a). by spincoating — onto any substrate without lattice matching. careful choice of the overcoating material and its thickness could alter the electron and hole interaction strength. The concentration of the reaction chemicals. the ligands can be replaced with molecules that have specific end groups that serve a particular purpose. the large range of lattice mismatch allows for the growth of new material systems on common substrates. (The surviving monolayers are referred to as the “wetting” layer.

semiconductor technology . Feature Artic les. e-mail: sjoerd.ca. POPULAR TOPICS More Feature Articles Bright Lights in the Bio(photonics)sphere STED M icroscopy: A New Chapter in Light Imaging CW Lasers Boost Resolution for M icroscopy Smartphones Set to Revolutionize the M edical World … Conference to Explore Laser-based Weather Control Graphene on Chip Closing the Gap with Germanium Tunable Polymer Could M ake Truly White OLED South Africans Develop ‘Digital Laser’ Bioimaging Laser Branches Out to Bomb Detection Recommended by You May Also Like Gun Laser Presented at FEL Conference Vitara UBB Femtosecond Laser Nanomagnets could sharpen M R images Tunable Polymer Could M ake Truly White OLED STED M icroscopy: A New Chapter in Light Imaging Bioengineers Aim for ‘Visual Cortex on Silicon’ More News By Category Business Handheld Lidar System Creates 3-D Image of Leaning Tower of Pisa Sunshield for NASA Telescope Ready for M anufacturing Lasers & Light Sources Light-Emitting Diodes Tunable Laser Technology Optical Components Filters Beryllium M irrors Products 12100 Series Polarizing M icroscope OSA205 Optical Spectrum Analyzer Research & Technology University of Calgary Launches Institute for Quantum Science and Technology THz Sensor to Detect Viruses Before Outbreaks Biophotonics Zeiss M editec Expands Intrabeam Uses Sarfus M apping Nanoscale M icroscopy Green Photonics Laser Spectroscopy Overcomes M easurement Challenge LumiM ap Electroluminescence System Photonic s. ARTICLE DISCUSSION You must be Logged In to comment on this article.c om Photonic s BioPhotonic s Photonic s Photonic s Photonic s e-New sletters Subsc riptions Advertising www.com/Article. Subject: Body: Submit Tags: photonic s . quantum dots .aspx?AID=31908 5/6 .photonics.hoogland@utoronto.9/29/13 Meet the author The Fuss About Quantum Dots (Photonics Spectra | Jan 2008 | Features) Sjoerd Hoogland works for a privately held venture and was a postdoctoral fellow at the University of Toronto when he prepared this article. Please Log In or Register.

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