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PROPERTIES OF INDIVIDUAL NANOPARTICLES
4.3. SEMICONDUCTING NANOPARTICLES
4.3.1. Optical Properties
Because of their role in quantum dots, nanoparticles made of the elements, which are
normal constituents of semiconductors, have been the subject of much study, with
particular emphasis on their electronic properties. The title of this section, “semiconducting nanoparticles,” is somewhat misleading. Nanoparticles made of cadmium, germanium, or silicon are not themselves semiconductors. A nanoparticle of
Si,, can be made by laser evaporation of a Si substrate in the region of a helium gas
pulse. The beam of neutral clusters is photolyzed by a UV laser producing ionized
clusters whose mass to charge ratio is then measured in a mass spectrometer. The
most striking property of nanoparticles made of semiconducting elements is the
pronounced changes in their optical properties compared to those of the bulk
material. There is a significant shift in the optical absorption spectra toward the blue
(shorter wavelength) as the particle size is reduced.
In a bulk semiconductor a bound electron-hole pair, called an exciton, can be
produced by a photon having an energy greater than that of the band gap of the
material. The band gap is the energy separation between the top filled energy level of
the valence band and the nearest unfilled level in the conduction band above it. The
photon excites an electron from the filled band to the unfilled band above. The result
is a hole in the otherwise filled valence band, which corresponds to an electron with
an effective positive charge. Because of the Coulomb attraction between the positive
hole and the negative electron, a bound pair, called an exciton, is formed that can
move through the lattice. The separation between the hole and the electron is many
lattice parameters. The existence of the exciton has a strong influence on the
electronic properties of the semiconductor and its optical absorption. The exciton
can be modeled as a hydrogen-like atom and has energy levels with relative spacings
analogous to the energy levels of the hydrogen atom but with lower actual energies,
as explained in Section 2.3.3. Light-induced transitions between these hydrogenlike energy levels produce a series of optical absorptions that can be labeled by the
principal quantum numbers of the hydrogen energy levels. Figure 4.19 presents the
optical absorption spectra of cuprous oxide (Cu20), showing the absorption spectra
due to the exciton. We are particularly interested in what happens when the s u e of
the nanoparticle becomes smaller than or comparable to the radius of the orbit of
the electron-hole pair. There are two situations, called the weak-conjinement and the
strong-conjnement regimes. In the weak regime the particle radius is larger than the
radius of the electron-hole pair, but the range of motion of the exciton is limited,
which causes a blue shift of the absorption spectrum. When the radius of the particle
is smaller than the orbital radius of the electron-hole pair, the motion of the electron
and the hole become independent, and the exciton does not exist. The hole and the
electron have their own set of energy levels. Here there is also a blue shift, and the
emergence of a new set of absorption lines. Figure 4.20 shows the optical absorption
spectra of a CdSe nanoparticle at two different sizes measured at 10 K. One can see
that the lowest energy absorption region, referred to as the absorption edge, is
PROPERTIES OF INDIVIDUAL NANOPARTICLES
4.3. SEMICONDUCTING NANOPARTICLES
4.3.1. Optical Properties
Because of their role in quantum dots, nanoparticles made of the elements, which are
normal constituents of semiconductors, have been the subject of much study, with
particular emphasis on their electronic properties. The title of this section, “semiconducting nanoparticles,” is somewhat misleading. Nanoparticles made of cadmium, germanium, or silicon are not themselves semiconductors. A nanoparticle of
Si,, can be made by laser evaporation of a Si substrate in the region of a helium gas
pulse. The beam of neutral clusters is photolyzed by a UV laser producing ionized
clusters whose mass to charge ratio is then measured in a mass spectrometer. The
most striking property of nanoparticles made of semiconducting elements is the
pronounced changes in their optical properties compared to those of the bulk
material. There is a significant shift in the optical absorption spectra toward the blue
(shorter wavelength) as the particle size is reduced.
In a bulk semiconductor a bound electron-hole pair, called an exciton, can be
produced by a photon having an energy greater than that of the band gap of the
material. The band gap is the energy separation between the top filled energy level of
the valence band and the nearest unfilled level in the conduction band above it. The
photon excites an electron from the filled band to the unfilled band above. The result
is a hole in the otherwise filled valence band, which corresponds to an electron with
an effective positive charge. Because of the Coulomb attraction between the positive
hole and the negative electron, a bound pair, called an exciton, is formed that can
move through the lattice. The separation between the hole and the electron is many
lattice parameters. The existence of the exciton has a strong influence on the
electronic properties of the semiconductor and its optical absorption. The exciton
can be modeled as a hydrogen-like atom and has energy levels with relative spacings
analogous to the energy levels of the hydrogen atom but with lower actual energies,
as explained in Section 2.3.3. Light-induced transitions between these hydrogenlike energy levels produce a series of optical absorptions that can be labeled by the
principal quantum numbers of the hydrogen energy levels. Figure 4.19 presents the
optical absorption spectra of cuprous oxide (Cu20), showing the absorption spectra
due to the exciton. We are particularly interested in what happens when the s u e of
the nanoparticle becomes smaller than or comparable to the radius of the orbit of
the electron-hole pair. There are two situations, called the weak-conjinement and the
strong-conjnement regimes. In the weak regime the particle radius is larger than the
radius of the electron-hole pair, but the range of motion of the exciton is limited,
which causes a blue shift of the absorption spectrum. When the radius of the particle
is smaller than the orbital radius of the electron-hole pair, the motion of the electron
and the hole become independent, and the exciton does not exist. The hole and the
electron have their own set of energy levels. Here there is also a blue shift, and the
emergence of a new set of absorption lines. Figure 4.20 shows the optical absorption
spectra of a CdSe nanoparticle at two different sizes measured at 10 K. One can see
that the lowest energy absorption region, referred to as the absorption edge, is