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Full download Ternary Quantum Dots: Synthesis, Properties, and Applications (Woodhead Publishing Series in Electronic and Optical Materials) 1st Edition Oluwatobi Samuel Oluwafemi file pdf all chapter on 2024
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TERNARY QUANTUM DOTS
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Woodhead Publishing Series in
Electronic and Optical Materials
SUNDARARAJAN PARANI
Department of Chemical Sciences, University of Johannesburg,
Doornfontein Campus, Doornfontein, South Africa
An imprint of Elsevier
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The Officers’ Mess Business Centre, Royston Road, Duxford, CB22 4QH, United Kingdom
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Publisher (other than as may be noted herein).
Notices
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broaden our understanding, changes in research methods, professional practices, or medical
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any liability for any injury and/or damage to persons or property as a matter of products liability,
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Library of Congress Cataloging-in-Publication Data
A catalog record for this book is available from the Library of Congress
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A catalogue record for this book is available from the British Library
ISBN: 978-0-12-818303-8 (print)
ISBN: 978-0-12-818304-5 (online)
Preface ix
v
vi Contents
Index 265
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Preface
ix
x Preface
ħ2 ε
rBohr ¼ (1.2)
e2 μ
Conducon band
e e
` e
hν Bandgap
h
h h
Bulk Confined
Bohr exciton Exciton
radius in zero dimensional
(A) Valence band (B) QDs
Fig. 1.3 (A) Illustration of exciton and Bohr exciton radius (rBohr) and (B) quantum con-
finement in QDs.
4 Ternary quantum dots
where ħ is the reduced Plank constant, μ is the reduced mass of the exciton
and defined by the relation μ1 ¼ (m∗e )1 + (m∗h)1, me and mh are the effec-
tive masses of electron and hole respectively, e is the charge of electron, and ε
is the dielectric constant. Annexure lists the Bohr exciton radius and bandgap
energy for the selected binary and ternary bulk semiconductors [5, 6].
Fig. 1.4 Illustration of size dependent variation of bandgap of QDs in comparison with
the bandgap of bulk and single molecule.
band gap and optical properties. For instance, the bandgap of smaller QDs is
higher and when it is excited, it emits blue color whereas the bigger crystals
are with low bandgap which emit red color after excitation (Fig. 1.5).
Because of the strong confinement, the quantized energy levels of QDs
shows similarities with the that of atoms/molecule and hence they are often
represented as artificial atoms.
Fluorescence
2.3 nm 5.5 nm
Par cle Size
Fig. 1.5 Representative image of size dependent fluorescence of quantum dots (CdSe/
ZnS). Adapted with the permission from B.O. Dabbousi, J. Rodriguez-Viejo, F.V. Mikulec, J.R.
Heine, H. Mattoussi, R. Ober, K.F. Jensen, M.G. Bawendi. (CdSe) ZnS core-shell quantum dots:
synthesis and characterization of a size series of highly luminescent nanocrystallites. J. Phys.
Chem. B 101(46) (1997) 9463–9475. Copyright (1997) American Chemical Society.
by Brus [22]. The first term with 1/R2 denotes the quantum localization
energy which is the sum of the confinement energy of electron and hole.
The second term with 1/R represents the Coulombic interaction between
electron and hole. The coefficient A is 1.79 for the 1Se-1Sh electronic tran-
sition state and has values between 1.6 and 1.9 for other electronic transition
states. The third energy term in the Eq. (1.3) was introduced by Kayanuma
[23] and is usually negligible but it can become significant for a semiconduc-
tor with a smaller dielectric constant. For bulk crystals, the influence of the
particle size on its bandgap is fully negligible as there is no confinement of
charge carriers. Accordingly, all the terms involving R can be omitted and
hence E simply becomes equal to Eb. However, for QD nanocrystals, as
mentioned earlier, the bandgap is highly dependent on their size and so their
electronic transitions. As the bandgap decreases with the increase in the size
of QDs, both absorption and emission spectra of the QDs will be red-shifted
as depicted in the Fig. 1.6A, B and D.
The relationship between the bandgap and the particle size can also be
derived empirically. The bandgap Eg energy (eV) can be experimentally cal-
culated from the absorption wavelength (λ, nm) of first excitonic transition
(1Se-1Sh) using absorption spectroscopy according to the Eq. (1.4)
Fig. 1.6 Representative figures showing (A) size dependent absorption spectra and, (B) fluorescence spectra, (C) bandgap determination
from Tauc’s plot, and (D) size dependent bandgap of CdSe (CS) QDs of various sizes from 2.5 to 5.2 nm [24].
8 Ternary quantum dots
hc
E¼ (1.4)
λ
where h is the plank constant, c is the speed of light.
However, Tauc’s plot is widely used to calculate the bandgap with more
accuracy using the Tauc’s relationship given below
n
αhv ¼ A hv Eg (1.5)
where α is the absorption coefficient, A is the Tauc constant, hv is the photon
energy, n is the parameter which is ½ for direct bandgap and 2 for indirect
bandgap. The extrapolation of the linear region of the plot of (αhv)1/n vs hv
to α ¼0 yields the bandgap (Fig. 1.6C).
On the other hand, average particle size can be calculated from XRD
patterns using the Scherrer equation given below:
Kλ
D¼ (1.6)
β cosθ
where D is the crystallite size, K is a shape factor which typically 0.9 for
spherical particles, λ is the wavelength of the X-rays, β is the width (full-
width at half-maximum) of the X-ray diffraction peak in radians and θ is
the Bragg angle [25]. Moreover, the exact size of the crystals and their dis-
tribution can be obtained by analyzing the samples using high resolution
transmission electron microscope (HRTEM).
Based on the correlation of above analyses, the empirical relationship
between the particle diameter (D) and the first excitonic absorption peak
(λ) or bandgap (Eg) for some of the QDs have been determined in good
approximation and given in the Table 1.1. In addition, particle size can
be used to calculate molar extinction co-efficient, an important parameter
to determine the concentration of the QDs using Beer Lambert law.
It must be noted that the above relations are only the fitting functions of
experimental data which are valid only for particular range of sizes as
described in the experiments.
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jotkin kummalliset laitteet, jotka ruiskivat vettä ja pitivät sen täytistä
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jo pienikarjaisetkin sen hankkineen. Meilläkin tässä on jo kymmenen
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