11.3: Semiconductor Quantum Dots

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One of the most fascinating and well-studied mesoscopic effects occurs with semiconductor particles of various shapes when one or more of their dimensions is in the range of a few nanometers. These so-called "quantum dots" (0D), "quantum rods" (1D) and "nanosheets" (2D) acquire striking new electronic and optical properties.

Atomic resolution image of a CdSe nanoparticle.

The synthesis of semiconductor quantum dots, which is discussed in more detail below, is sufficiently well controlled to give essentially perfect crystals of a few thousand atoms, something that is statistically impossible in a macroscopic crystal. An image of such a crystal is shown at the right. In the synthesis, these crystals can be capped with an epitaxial layer of ligands or by a shell of a wider bandgap semiconductor (such as ZnS in the case of CdSe), so that the inner core is effectively a quantum well. Electron-hole pairs formed by excitation of the core semiconductor are confined there and cannot reach the external surface of the particle, where they might otherwise be trapped and recombine thermally. Consequently, the quantum yield for bandgap emission of semiconductor quantum dots is typically high, giving rise to the bright emission colors shown at the right for CdSe particles of different sizes. Because of their strong and narrow emission bands, quantum dots are of interest as luminescent tags for biological imaging applications, and also as light absorbers and emitters in solar cells and LEDs.

From right to left, the particles increase in size and move from red to orange to yellow to green, and then blue.

Emission colors of CdSe nanoparticles of different sizes. Smaller particles emit blue light because the exciton energy increases as the size decreases.

The size-dependence of the emission color comes primarily from a particle-in-a-box effect. The electron and hole that are created when the quantum dot absorbs light are bound together as an exciton by the confines of the "box". Louis Brus used first-order perturbation theory to determine that the bandgap of a semiconductor quantum dot is given approximately by:^[4]

\[E_{gap} = E_{gap, bulk} + \frac{h^{2}}{8 \mu R^{2}} - \frac{1.8e^{2}}{4R \pi \varepsilon \varepsilon_{0}} + \dots\]

where R is the particle radius, µ is the electron-hole reduced mass (1/µ = 1/m_e* + 1/m_h*), m_e* and m_h* are the electron and hole effective masses, and ε is the dielectric constant of the semiconductor. In this equation, the first term after the bulk bandgap is the kinetic energy due to confinement of the exciton, and the second term represents the electrostatic attractive energy between the confined electron and hole. Because the energy is a function of R², it can be widely tuned across the visible spectrum by changing the size of the quantum dot.