Sofie Ye
December 10, 2014
Course:
Supervisor:
Figure 1: Quantum Dots with gradually stepping emission from violet to deep
red are being produced in a kg scale at PlasmaChem GmbH From: Wikimedia Commons.
(2012) Quantum Dots. Retrieved 9 December, 2014.
Contents
1 Introduction
2 Theory
2.1 Surface eects . . . . . . . . .
2.2 Quantum confinement eects .
2.2.1 The density of states .
2.2.2 The band gap . . . . .
2.3 Quantum dots . . . . . . . . .
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3 Production
3.1 Colloidal synthesis . . . . . . . . . . .
3.1.1 General outline . . . . . . . . .
3.1.2 The organic-inorganic interface
3.1.3 Kinetic size control . . . . . . .
3.1.4 Kinetic shape control . . . . . .
3.2 Passivation . . . . . . . . . . . . . . .
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4 Applications
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4.1 Biological imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.2 Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
References
13
Introduction
In a review published in the journal Chemical Society Reviews, March 2006, Professor Roduner pointed out that We might still want to think, though, that gold
is gold, platinum is platinum and CdS is CdS, but we slowly have to get used to
the fact that this is also not true... (Roduner, [1]). By these words he wanted to
emphasize the fact that many materials exhibit new properties when going from
bulk sizes, down to sizes of the nanoscale. There are no distinct boundaries for the
so called nanoscopic scale but in most cases it is considered to include materials
with a size of 1-100 nm [2] (in this review, the size is assumed to be the length
or the diameter of the material or particle).
The study of matter at the nanoscale is referred to as nanotechnology. This
term was first introduced in 1986 by Drexler [3] but the concept had been brought
up already in the late 50s by the physicist Richard Feynman, who in a famous
lecture with the title Theres Plenty of Room at the Bottom, asked What would
happen if we could arrange the atoms one by one the way we want them? (Feynman, [4]). This phrase provides us with a definition of nanotechnology as the manipulation of individual atoms, molecules etc. at the nanoscopic scale. However,
this branch of science also includes the applications of so called nanomaterials.
As mentioned earlier in this section, nanomaterials are usually built up by units
of sizes between 1 and 100 nm and in accordance with this, a crystal with at least
one dimension confined to these limits is said to be a nanocrystal.
More specifically, structures confined to the mentioned nanoscale in only one
dimension are called quantum wells, while those confined in two directions are
thought of as quantum wires. In this review, the case where a nanocrystal is
confined in all three spatial dimensions will be studied. Materials of this type have
been given a bunch of names (colloidal particle, pseudo/artificial atom, quantum
sphere, nanoparticle, nanocluster etc. [6]), however the most used one is no-doubt
quantum dots. Figure 2 depicts the density of states (see section 2.2.1) as function
of the dimensionally confined structures named above.
Due to the highly tunable optical and electrical properties of quantum dots,
they are of great interest to many researchers of today. The application fields
are many and for example, they have been or are used in the development of
solar cells [7], biological imaging [8] and light emitting diodes (LEDs) [9]. In
this review, the basics of quantum dots and how they can be synthesized, will be
covered. Furthermore, some of their interesting applications are brought up.
Theory
2.1
Surface eects
Consider the atoms in the bulk and those at the surface of a cluster, it is quite
obvious that they will posess dierent properties since they are situated in rather
dierent environments. A surface atom has a lower coordination number (fewer
neigbours) than an atom in the bulk and thus, it is less stabilised and has a higher
anity to create bonds to e.g. adsorbate molecules.
Figure 3: The increase of the surface-to-volume ratio with smaller volume. The
numbers at the corners of the cubes represents the side length in length units and
the first row of numbers below the cubes shows the surface area in area units. The
second row gives the volume of each cube in volume units and in the last row, the
resulting surface-to-volume ratios are given (in length units). From: The McGraw-Hill
Companies, inc. (2001) Biology Retrieved 8 December, 2014. New York City: Author.
As can be seen in Figure 3, a small cluster (or particle) will have a larger fraction
of surface atoms than a large one and since surface atoms are less stabilised than
those of the bulk, small clusters have lower melting points than large ones. A
striking example of this is in the case of gold where it has been observed that the
melting point for particles of the size 2.5 nm is about 400 K lower than that of
the bulk [11]. Another property dependening on the so called surface-to-volume
ratio is the catalytic activity. In this case, it has been proved that a small gold
cluster, having a higher number of low coordinated surface atoms comparing to a
large cluster, is more reactive and has a higher catalytic activity [12].
2.2
Discrete atoms have well-defined atomic orbitals of certain energies. Each orbital
has a characteristic wave function and can be combined to, as a first step, form
molecular orbitals (MOs). Also these, are rather well-defined concerning energy
and thus, have individual wave functions. At this point the energy dierence between successive energy levels is still distinguishable. Nonetheless, as more atoms
are added, the dierence between adjacent energy states decreases and eventually,
this leads to the formation of so called bands. In other words, a band is just a
way of describing a huge amount of energy states so tightly packed that there is
no reason to even try disjuncting them.
The number of energy states divided by the energy interval covered by a band,
is called the denisty of states (DOS). And so, it is also possible to to describe the
progress of the electronic structure when going from a discrete atom to a large
crystal as an increase of the DOS.
A nanocrystal can be thought of as being the transfer structure when going
from an unlimited crystal to individual molecules or atoms. Consequently, its
electronic structure lies somewhere in between the continuous band of a typical
crystal and the discrete DOS for separated molecules/atoms [14], see Figure 4.
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(a) Metal
(b) Semiconductor
Figure 4: The DOS in a metal (a) and a semiconductor (b), respectively. The
variation of the electronic structures in their corresponding bulk, nanocrystal and
atomic/molecular form are shown. From: Alivisatos, A. P. (1996) Perspectives on the Physical
Chemistry of Semiconductor Nanocrystals. Retrieved 9 December, 2014.
2.2.2
Not all of the energy states are filled with electrons and a special name, the band
gap, has been assigned to the energy dierence between that of the highest occupied
MO (HOMO) and that of the lowest unoccupied MO (LUMO). In band theory, the
energy states lower than the HOMO are considered to be part of the valence band,
while those of energies higher than the LUMO are said to constitute the conduction
band. The band gap is usually given in eV and depending on its magnitude, a solid
is considered to be a metal, semiconductor or insulator, see Figure 5.
2.3
Quantum dots
In the process where a material goes from a smaller to a larger size, i.e. when
becoming more bulk-like, the center of a band will appear before the edges. That
is to say, the energy states in the middle of a soon-to-be band adopt to the new
band structure before the edges does. This is illutrated for a metal in Figure 4a
and for a semiconductor in Figure 4b.
Both Figure 4b and 5, shows that the Fermi level of a metal lies in the center of
a band while that of a semiconductor is located in the middle of a band gap (this
is true for an undoped semiconductor). Therefore, the Fermi level of a metal is
almost not aected at all when going from bulk to nanocrystal (since the changes
are most significant at the edges and not in the middle). The Fermi level of a
semiconductor though, will be highly influenced by the changes at the band edges.
This explains why the optical and electrical properties of nanocrystals made from
semiconductors (quantum dots) are aected to a much greater extent than those
made from metals, when tuning their size and thus, band gap.
The inversely proportional relationship between the size of a quantum dot
and the size of its band gap, can be proved by performing several spectroscopic
experiments [1]. By considering the fact that a smaller particle will be have a larger
portion of atom-like behaviour comparing to a larger particle, it is reasonable to
assume that a smaller particle will also have a larger band gap (more separated
energy levels). The same reasoning holds for the opposite case a larger particle
behaving more like bulk material, will have a smaller band gap, see Figure 6a.
Figure 6: (a) The particle size eect on the band gap. (b) Fluorescence of CdSeCdS core-shell nanoparticles with a diameter of 1.7 nm to about 6 nm. From: Roduner,
E. (2006) Size matters: why nanomaterials are dierent. Retrieved 9 December, 2014.
For electrons of the discrete energies in the vicinity of the HOMO in a quantum
dot to overcome the band gap and reach one of the discrete energy levels above
the LUMO, quantised amounts of energy are required. The larger the band gap,
the higher the energy needed to overcome it.
High-energy, or high-frequency, wavelengths are short and thus appear as being
blueish and low-energy, or low-frequency, wavelengths are long and reddish.
Thence, by changing the particle size from smaller to larger, it is possible to tune
the fluorescence of the quantum dots between blue and red [1], see Figure 6b.
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Production
Quantum dots can be made through several methods such as epitaxial growth,
optical litography and colloidal synthesis. In epitaxial growth, a crystalline layer
is deposited on a crystalline substrate [15] and in litography, which has some
similarities to common photography, light is used to forward a pattern from a
photomask onto a light-sensitive so called resist [16]. Colloidal synthesis is the
method which is most related to this course (Colloidal and Surface Chemistry),
which is why it is going to be studied in more detail.
3.1
Colloidal synthesis
The products of this particular synthesis are called colloidal nanocrystals, or in the
case of nanocrystals made from semiconductors, colloidal quantum dots. These are
grown from solution and are typically inorganic particles coated by a stabilising
layer of organic surfactants. The synthesis is based on the introduction of inorganic
precursors to a hot solution containing organic surfactants.
Colloidal synthesis is a great tool for chemists today. By oering the possibility
to regulate parameters like composition; size; shape; surface properties; and crystal
structure (through changing, for example, temperature and/or monomer concentration [17]), it indirectly enables design of the electronic and optical properties of
quantum dots.
3.1.1
General outline
Three main ingredients are needed in order to perform a plain colloidal synthesis:
precursors, organic surfactants and solvents. To start the crystal formation, an
initial thermolysis is required. This is easily done by simply combining the three
components in some kind of container and add heat. When the temperature is
high enough (n.b. low-temperature synthesis is also feasible [18]) for the precursor
to chemically transform into reactive monomers, the nucleation takes place. The
nucleation is, according to IUPAC [19], defined as the inital step of a process in
which a new phase is to be formed.
After the thermal decomposition of precursors in the formation of new nuclei,
the latter will start to grow by including additional free monomers in the solution
to their assembly. Only if the formed nanoparticles are able to simultaneously
rearrange and anneal during the formation, crystalline solids will be formed. Thus,
the outcome of the process is highly dependent on choosing a proper temperature
which allows rearrangement of atoms but at the same time, permits annealing
within the growing crystal.
3.1.2
The interface between the inorganic nanocrystal and the organic shell of surfactants
is, according to Yin and Alivisatos [17], of great interest to many researchers. But
why? Well, consider the adhesive energy between the organic surfactants and the
inorganic nanocrystal. This energy has to be in a range where the exhange of
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Figure 7 illustrates the relation between the growth rate of a nanocrystal and its
size. The dashed line divides the graph in two parts; a left side describing what
happens to small clusters; and a right side showing the destiny of large clusters.
By studying these curves, it is possible to see a small nanocrystal which posess a
high surface-to-volume ratio making it quite unstable, has a negativ growth rate
in a low monomer concentration (blue curve). Another observation is that larger
crystals, which are more stable (having a smaller surface-to-volume ratio) have
positive growth rates in both low and high monomer concentration.
The critical size is the particle size when the growth rate is zero. At this point,
the nanocrystal can be thought of as being quite pleased with itself and hence,
does not grow nor shrink.
The rather vague but still existing peak of the blue curve arises from the fact
that larger crystals need a lot more monomers than smaller crystals, in order to
be able to grow even larger. Thus, the growth rate eventually slows down and
reaches a maximum value.
A slow growth rate is favoured by low monomer concentrations. In this case, the
critical size is a bit larger than that in a solution of high monomer concentration
and thus, there is a higher probability that it will be in the same range as the
nanocrystals present in the solution. Due to the eect of Ostwald ripening,
when small particles shrink and deposit themselves on larger ones, a broad size
9
3.2
Passivation
excitons. Since excitons are the charge carriers of quantum dots, the trapping of
them will degrade both electrical and optical properties.
To prevent this negative eect of surface recombination, passivation is applied.
This is done by covering the quantum dot with a material that has a higher band
gap. Thereby, the orbitals of the surface atoms are saturated and the energy levels
within the forbidden gap will be eliminated [1], see Figure 8 for a schematic picture. Encapsulated quantum dots are often referred to as core/shell quantum dots.
In general, they are composed by semiconductors of type IIVI, IVVI and IIV, where the
roman numbers indicate in which groups (n.b.
old group numbers, thus III is actually 13) of
the periodic table the combined materials are
found. Combinations that have been widely
studied are CdSe/ZnS, CdS/HgS, InAs/CdSe
and CdS/CdSe [21].
At the moment, there seems to be a worldwide agreement among researchers about inorganic coatings being much more beneficial than
organic ones. Almost two decades ago, Hines Figure 8: Illustration describing
and Guyot-Sionnest [22], managed to show that the concept of passivation.
by coating a CdSe colloidal quantum dot with
a shell of ZnS, they could measure a photoluminiscence quantum yield of 50%
comparing to 5-15% for organic shells. The quantum yield improvement has
later been proved to be a persistent trend for inorganic passivation. This is very
promising since the shell also acts like a shield, protecting the core from being
damaged through interactions with the surrounding medium [20]. Figure 9 shows
a simple illustration of a core/shell colloidal quantum dot. Note that even though
the inorganic shell is applied after the synthesis of the colloidal quantum dot (having a layer of surfactants surrounding it), the inorganic coating will be in between
the core and the surfactants.
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Applications
Due to their size-tunable electric and optical properties, quantum dots are today
used in a wide range of applications from biological imaging [8], light emitting
diodes (LEDs) [9] and solution processed lasers [20], to photovoltaics [20] like solar
cells [7]. Short descriptions of how quantum dots are used in biological imaging
and solar cells are given below.
4.1
Biological imaging
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4.2
Solar Cells
Quantum dots are used in the production of so called quantum-dot-sensitized solar cells (QDSC, where the organic molecular dye in a typical dye-sensitized solar
cell (DSSC) has simply been exhanged to semiconductor nanocrystals. The quantum dots are the light harvester and these solar cells have already shown nice
results with eciencies of about 10% for all solid nano-devices using lead halide
perovskite [7].
References
[1] Roduner, E. Chem. Soc. Rev. 2006, 35 (7), 583-592.
[2] Roduner, E. Nanoscopic Materials: Size-Dependent Phenomena ; Royal Society of Chemistry: Cambridge, 2006.
[3] Wikipedia. Nanotechnology. [Online] December 8, 2014. Available on internet:
http://en.wikipedia.org/wiki/Nanotechnology (accessed Dec 9, 2014)
[4] Feynman, R. P. Eng. Sci. 1960, 23 (5), 22-36.
[5] Guyot-Sionnest, P. C. R. Physique 2008, 9, 777-787.
[6] Eychmller, A. J. Phys. Chem. B 2000, 104 (28), 6514-6528.
[7] Fuente, M. S.; Snchez, R. S.; Gonzlez-Pedro, V.; Boix, S. G. M.; Rincn,
M. E.; Bisquert, J.; Mora-Ser, I. J. Phys. Chem. Lett. 2013, 4, 1519-1525.
[8] Gao, X.; Ciu, Y.; Levenson, R. M.; Chung, L. W. K.; Nie, S. Nature Biotechnology 2004, 22 (8), 969-076.
[9] Colvin, V. L.; Schlamp, M. C.; Alivisatos, A. P. Nature 1994, 370, 354-357.
[10] Alivisatos, A. P. Science 1996, 271 (5251), 933-937.
[11] Koga, K.; Ikeshoji, T.; Sugawara, K. Phys. Rev. Lett. 2004, 92 (11), 115507.
[12] Hvolbk, B.; Janssens, T. V. W.; Clausen, B.; Falsig, H.; Christensen, C. H.;
Nrskov, J. K. Nano Today 2007, 2 (4), 14-18.
[13] Buhro, W. E.; Colvin, V. K. Nature Materials 2003, 2, 138-139.
[14] Alivisatos, A. P. J. Phys. Chem. 1996, 100 (31), 13226-13239.
[15] Wikipedia. Epitaxy. [Online] November 23, 2014. Available on internet: http:
//en.wikipedia.org/wiki/Epitaxy (accessed Dec 9, 2014)
[16] Wikipedia. Photolitography. [Online] November 29, 2014. Available on internet: http://en.wikipedia.org/wiki/Photolitography (accessed Dec 9,
2014)
[17] Yin, Y.; Alivisatos, A. P. Nature 2005, 437 (7059), 664-670.
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[18] Siy, J. T.; Brauser, E. M.; Bartl, M. H. Chem. Commun. 2011, 47, 364-366.
[19] IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book").
Compiled by McNaught, A. D.; Wilkinson, A. Blackwell Scientific Publications, Oxford (1997).
[20] Kim, J. Y.; Voznyy, O.; Zhitomirsky, D.; Sargent, E. H. Adv. Mater. 2013,
25, 4986-5010.
[21] Reiss, P.; Protire, M.; Li, L. Small 2009, 5 (2), 154-168.
[22] Hines, M. A.; Guyot-Sionnest, P. J. Phys. Chem. 1996, 100, 469-471.
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