28/10/2014

Why does band gap energy of quantum dots vary with its size?

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Lappeenranta University of Technology

Why does band gap energy of quantum dots vary with

its size?
Why does band gap energy of quantum dots vary with its size?
TOPICS
Solid State Physics

Photocatalysis

Quantum Dots

Physical Chemistry

Nano-catalysis

Oct 6, 2013

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Daniel Patrick Weller Saginaw Valley State University

Quantum confinement effects take over when we shrink an object to the
size-scale of an emergent phenomenon. As we shrink a semiconducting
particle (such as quantum dots), the size of the particle approaches the
size of the electron-hole distance known as the Bohr radius. CdSe has a
Bohr radius of 56 Angstroms, for example. For a 3D spherical particle, we
consider the energy of a "particle in a box" (as chemists see it), or the
energy of a particle in a "infinite potential well" (as physicists like to think
of it), to describe the band gap energy.

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E_n=(h^2 n^2)/(8 m_c R^2)

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This is the band gap energy for a spherical box (same lengths in all 3
dimensions), n is energy level, h is planck's constant, m_c is the effective
mass of a point charge, and R is the radius of our box (or the size of the
particle). We see from this that as our particle increases in size, the band
gap energy decreases. Therefore, as size varies in QDs, the energy
changes because the exciton in the QDs behaves like a "particle in a
box."
Oct 6, 2013

Suchand Sandeep C. S. Delft University Of Technology

Hello Dmytro,
The image below shows the change in band gap with change in size of a
QD. All of them are the same material (CdSe in this case), with varying
size. The emission (as well as absorption) wavelength changes with the
size, and that is why they have different colours.

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An atom-like spectra is rarely seen in the case of QDs, as the typical QDs
reported have 2- 50 nm size, which contains 10000 + atoms per QD and
the spectra is no longer atom-like. Also these QDs need to be highly
monodisperse to get sharp spectral features.
You can probably find atomic like spectra reported for very small clusters
(mostly in gas phase) in the literature.
In a nutshell, you need vary small and highly monodisperse particles to
observe atom-like spectra.

http://www.researchgate.net/post/Why_does_band_gap_energy_of_quantum_dots_vary_with_its_size2

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28/10/2014

Why does band gap energy of quantum dots vary with its size?
Oct 8, 2013

ALL ANSWERS (11)

Daniel Patrick Weller Saginaw Valley State University

Quantum confinement effects take over when we shrink an object to the
size-scale of an emergent phenomenon. As we shrink a semiconducting
particle (such as quantum dots), the size of the particle approaches the
size of the electron-hole distance known as the Bohr radius. CdSe has a
Bohr radius of 56 Angstroms, for example. For a 3D spherical particle, we
consider the energy of a "particle in a box" (as chemists see it), or the
energy of a particle in a "infinite potential well" (as physicists like to think
of it), to describe the band gap energy.
E_n=(h^2 n^2)/(8 m_c R^2)
This is the band gap energy for a spherical box (same lengths in all 3
dimensions), n is energy level, h is planck's constant, m_c is the effective
mass of a point charge, and R is the radius of our box (or the size of the
particle). We see from this that as our particle increases in size, the band
gap energy decreases. Therefore, as size varies in QDs, the energy
changes because the exciton in the QDs behaves like a "particle in a
box."
Oct 6, 2013

Sagar Ganguli Indian Institute of Science Education and Research

Kolkata
For bulk material, we do not have discrete energy states. But, as the
particle becomes smaller, the energy levels become discrete.
Now if you imagine a quantum dot according to "a particle in a box"
concept, then, you know that the energy gap between different energy
states is inversely proportional to the square of the length of the box. For
a quantum dot, the length of the box is actually its size. So, with decrease
in size (i.e., with decrease in the length of the box), the energy gap will
increase and with increase in size the reverse will happen.
This is primarily the reason behind the dependence of the band gap
energy of quantum dots on its size.
Oct 7, 2013

Dmytro Solonenko Technische Universitt Chemnitz

All these definitions from books don't approach to real understanding. Has
anyone ever seen linear spectra ("atom-like" spectra) for QD? I haven't
Oct 7, 2013

Suchand Sandeep C. S. Delft University Of Technology

Hello Dmytro,
The image below shows the change in band gap with change in size of a
QD. All of them are the same material (CdSe in this case), with varying
size. The emission (as well as absorption) wavelength changes with the
size, and that is why they have different colours.
http://www.umt.edu/ethics/Debating%20Science%20Program/ODC/imx/Fl
uorescence_of_CdSe-CdS.jpg
An atom-like spectra is rarely seen in the case of QDs, as the typical QDs
reported have 2- 50 nm size, which contains 10000 + atoms per QD and
the spectra is no longer atom-like. Also these QDs need to be highly
monodisperse to get sharp spectral features.
You can probably find atomic like spectra reported for very small clusters

http://www.researchgate.net/post/Why_does_band_gap_energy_of_quantum_dots_vary_with_its_size2

2/3

28/10/2014

Why does band gap energy of quantum dots vary with its size?
(mostly in gas phase) in the literature.
In a nutshell, you need vary small and highly monodisperse particles to
observe atom-like spectra.
Oct 8, 2013

Tim Gould Griffith University

As the particles get smaller, you also need to take more care of surface
effects. The spectra of small quantum dots is quite well known from theory
(albeit inexactly). Look up papers on "jellium sphere"s by John Perdew
and others.
Oct 8, 2013

Sridhar Sampath Lappeenranta University of Technology

Is it possible to prepare quantum dots with different color (different sizes)
for TiO2?
Oct 9, 2013

Susana Lpez Ayala Nano Coating technologies, Mxico

Quantum size effect in TiO2 nanoparticles. Does it exist?
Oct 9, 2013

Sridhar Sampath Lappeenranta University of Technology

To Susana Lpez Ayala
Band gap energy of TiO2 is too wide to absorb visible light.so I think
Quantum size effect in TiO2 nanoparticles doesnt exist .
Oct 10, 2013

Susana Lpez Ayala Nano Coating technologies, Mxico

it seems that if there is, at least this article suggests
Self-ordered TiO2 quantum dot array prepared via
anodic oxidation.
Drbohlavova et al. Nanoscale Research Letters 2012, 7:123
Oct 10, 2013

Jayakrishna Khatei Technion - Israel Institute of Technology

Since TiO2 band gap does not lie in visible region you will not observe
size dependent tunable visible emissions but there is certainly quantum
confinement effect once the size approaches Bohr exciton radius limit.
This will be reflected in their optical absorption spectra.
Oct 12, 2013

Amir Zada Abdul Wali Khan University Mardan

The band gap energy of any semiconductor is given by
E = hc/
As for nanoparticles depends on size, the band gap energy increases as
decreases.
Jan 13, 2014

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