Quantum dots in solar cells

IH 2654

Nanoelectronics

Quantum Dots in Solar Cells

Nabeel Aslam

Yashar Hormozon

Dated: 2009-11-02

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Quantum dots in solar cells

Quantum Dots in Solar Cells

Introduction: The project which is prearranged to us based on Quantum Dots in solar cells. In the project we tried to divulge how
quantum dots are made by different techniques and which method is good for the production of quantum dots in solar cells. We also
discussed the method of putting Quantum Dots in solar cells. There are number of different quantum dots available of different materials.
But here we had described only core CdSe quantum dot.

Background: The quantum Dots are the semiconductor nanocrystals. The size of these nanocrystals should be analogous to the size of
the Bohar exciton radius. It is fundamentally the 3- dimensional confinement of the electrons or holes. The properties of the quantum dots
are size reliant. Due to decrease in size (up to Bohar exciton radius) energy levels become detached. These energy levels are tunable. This
tune ability in energy levels of quantum dots makes them very engrossed and functional for different application. The variation in the band
gap makes it very prominent in optical and biomedical application. In our project we have described quantum dots applications in solar
cells. The exploit of quantum dots in solar cells make them resourceful and cheap. (1)

Fig 1: The energy discreetness and 3-D confinement

Methods: Now in these days the CdSe quantum dots have become very promising nanocrystals due to its absorption and
photoluminescence properties. A very important property of CdSe quantum dots is the covering of whole spectra of UV and Visible light
due to change in its size. The following fig which given below depicts the clear cut view of the above statement. (2)

Fig 2: Different sizes have different emission.

Microwave Synthesis of CdSe Quantum Dots: It is a very good technique of making CdSe quantum dots. In making of solution
base quantum dots we need heat to decompose the precursors for making quantum dots. Question arises how heat is provided to solution
in microwave technique? The following figure gives very clear cut picture of this mechanism.
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Quantum dots in solar cells

Fig 3: Dipolar polarization mechanism

As we know that the microwave has two components, electric component and magnetic component.For microwave mechanism the
solution should contain either polar or ionic compounds. For example in the case of Polar molecules, which have partial positive and partial
negative poles, when microwaves pass through the solution the electric vector tends to attract the positive or negative end of the polar
molecules but the frequency is so mush high (2.45GHz) that the molecules do not follow the frequency of the microwave. They start
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rotating. During rotation they collide with each other very fast. This process produces tremendous heat about 300 C for 300W at 2.45GHz.
The rotational energy is converted into thermal energy. In the case of ions the translational energy of ions is converted into heat energy.
(3)

Experimental details:

Cd-Precursor:

 CdO (.666g)
 Oleic acid (7mL)
 ODE (8mL)
Making of Cd-Precusor:
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 Heated the above 3 species at 160 C
 Keep the solution for 2 hours.
 Collect only 5mL for experiment
Se-Precusor:

 Se Powder (.394g)
 TOP (8.65mL)
 ODE (6.35)
Making of Se-Precursor:
o
 Heated the above 3 species at 200 C
 Keep the solution for 2 hours.
 Collect only 5mL for experiment

Fig 3: Reaction vessel for precursor and QD’s preparation

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Quantum dots in solar cells

After making the Cd and Se precursors they were mix together.

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 Took 5mL OF Cd-Precursor and heated at 270 C
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 At 270 C inserted the Se-Precursor very quickly into the Cd-Precursor.
 Put 3mL Olylammine after 5 minutes to enhance the capping ability.
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 Then temperature is allowed to drop down till 190 C.
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 Again increased the temperature and tried to keep it at 210 C throughout the growth.
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 Took the samples from the solution at different time intervals at 210 C.
 Keep the solutions stirring until the temperature cool down?
 Inserted the Ethanol in solution get the QD’s by putting it in Centrifuge machine. (4)
Let us look at the chemistry behind the whole procedure.

Chemistry of behind the mechanism:

CdO(S) + Oleic Acid(aq) + ODE(aq) Cd-OA(aq) + H2O

Se(S) + TOP(aq) TOPSe(aq)

Cd-OA(aq) + TOPSe(aq) + ODE(aq) CdSe(s) + TOPO(aq)+ (OA)2O(aq)

Precursor Organic Surfactant non-coordinating Solvent

Cd-Precursor (Group II) Oleic Acid ODE

and and (1-Octadecene)

Se-Precursor (Group VI) Oleylamine

Table 1: Three major components

After making the Cd and Se precursors they are put into the microwave and provided the heat for reaction. The set up is given below.

Fig 8: The microwave set up

Discussion: As I have described above that this set up is only different in a way of providing heat to chemical reaction. But in this
mechanism we need initially very high temperature to start the reaction. It is because first we want to get very high activation energy to
start reaction. After that we get the nucleation step by cooling it little bit. The nucleation energy is less than the activation energy. Then the
system is cooled down to have growth. In this process it a very big problem to have very good control over the cooling process. But the
very important thing is the homogenous heat throughout the reaction. This thing make the very narrow size distributed CdSe quantum
dots. The following fig gives very good picture about the energies. (5)

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Quantum dots in solar cells

Fig 9: The pathway for CdSe quantum Dots

The way of heating the solution is very interesting. As we know that the microwave has two components, electric component and magnetic
component. Similarly the solution contains some polar molecules or ions. The polar molecules have polarities (Partial +ve and partial –ve)
ends. The electric vector of the microwave tends to attract and repel. But the frequency of the microwaves is so much high that that
remain unable to read the positive and negative cycles of the wave so they start oscillating with very high frequency. During this process
they colloid with each other and produce heat. This heat provides the energies for the Cd and Se precursors break and combine. Similarly if
the solution is ionic then they try to oscillate tro and fro. It is also another way of providing heat.
In our case the TOPSe is the polar precursor which provides the heat and absorbs the microwave. So there should be one part of the
solution which should be in position to absorb the heat. But with that we need one non absorbing solvent to control the extra heat in the
solution. In our case we have used ODE which is non polar (non-absorbing) solution. So in this way we can cool the solution and can get
well control over growth. (5)

Results:
In this case I only study the two very important techniques. The UV-Vis and PL-Emission spectra our discussed.

Fig 10: The Absorption and emission spectra for CdSe QD’s in microwave

These are three graphs which are taken for the analysis of three factors which are very important in this case. In the first graph the power
and time are kept constant but temperature is changed. At different temperatures we have different growth. The peak of the emission is
going to broadening. So by increasing the temperature the QY is not good in this case. But in the 2nd case time is varying but temperature
and power are kept constant. In this case there is not very difference in the QY of the CdSe quantum dots. But power seems to be not very
big difference. (5)

Advantages:

Well control on particle size and particle size distribution.

Easy to handle in the experiment.
Non toxic chemicals are used in this method.
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Quantum dots in solar cells

Very small scale particles can be made (2.4nm-8nm).

Very fast method for the preparation of DQ’s.(less than 2 0min).
The QY’s is up to 74%.
Good control on the Nucleation rate.
Optimizing the defects and dislocations.
Due to time saving issue it is very much favorable for bulk production.
Disadvantages:

Slow rate of cooling.

Domination of Ostwald repining due to absence of MW power.
Additives or pressurization can accelerate the growth.

Principles of Solar cells: Solar cells are based on semiconductor p-n junctions under illumination. Light generates electron-hole pairs
on both sides of the junction, in the n-type emitter and in the p-type bases. The generated electrons and holes then diffuse to the junction
and are separated by the built-in electric field at the p-n junction, because of the staggered structure of the band gap (6). Thus connecting
each side of the junction produces electric current [Figure 11].

Figure 11

The maximum thermodynamic conversion efficiency for a single band gap solar cell is about 31% (7). But charge carriers recombination and
heat loss caused by electron-phonon scattering and relaxation of carriers at the band edges (bottom of conduction band for electrons and
top of the valance band for holes) limits this conversion efficiency. When a photon with an energy larger than the band gap is absorbed it
produces hot carriers which have effective temperatures as large as 3000K and then they are cooled down by electron phonon scattering
and give their energy to the semiconductor lattice (7) [Figure 12].

Figure 12

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Quantum dots in solar cells

To avoid this heat loss, solar cells should be engineered by a method in which each photon is absorbed by its corresponding material with a
band gap close to its energy. Moreover recombination of charge carriers should be prevented as much as possible(7).

Another approach is to utilize hot carriers before their relaxation at band edges by carrier-phonon scattering.

There are two ways to do it:

1. Extraction of hot carriers from photo converter before cooling down. This method results in better photocurrent. This process
needs high rates of carrier separation, transport and interfacial transfer in comparison with cooling rate (7).

2. Using the hot carriers to produce another electron hole pair by impact ionization. This method results in better photo voltage. In
this case the rate of impact ionization should be higher than cooling rate. (7) [Figure13].

Figure 13

In recent years it has been revealed that Quantum confinements can significantly affect the relaxation dynamics of hot carriers.

Application of QDs in solar cells: The tunable band gaps of QDs and controllability of hot carriers relaxation have made them
tempting in solar cell applications (7). Hence, three different QD solar cell configurations have been proposed. 1. Quantum dot arrays in p-
i-n cells, 2. Quantum dos dispersed in organic semiconductor polymer matrices and 3. Quantum dot-sensitized nanocrystaline solar cell

Figure 14

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Quantum dots in solar cells

Quantum dot arrays in p-i-n cells: In this configuration QDs are located in the intrinsic region of a p-i-n structure and form a superlattice.
This superlattice structure leads to formation of miniband states. These minibands are expected to facilitate transport of hot carriers and
prevent them from relaxation at edges and finally cause increased photocurrent. They can also make impact ionization easier by providing
new states and increase photo voltage. But these two cannot occur at the same time for a carrier [Figure 14(a)] (7) .

Quantum dots dispersed in organic semiconductor polymer matrices: Here, QDs are dispersed in a hole conducting polymer and
photogenerated holes are conducted to the electrical contact by this polymer. And diffused electrons in QD network are collected by an
electrical contact [Figure 14(c)] (7) . Unfortunately, this configuration has had low conversion efficiencies in initial attempts. In order to
increase the conversion efficiency, a polycrystaline layer can be used as an electron conducting phase. Thus electron and holes are
injected into their respective transport medium after photoexcitation of the QDs (7).

Quantum dot-sensitized nanocrystaline solar cell: This method is a modification of promising dye-sensitization of
nanocrystaline . In this method 10-30 nm size nanoparticles are sintered into a highly porous nanocrystaline film with a
thickness of 10-20 µm. Then dye molecules are chemisorbed to the surface of nanoparticles (7). nanoparticles are large band
gap semiconductors which absorb UV light, however, they are used because they have a large surface area and many smaller dye
molecules can be linked to a large particle. Furthermore conduction band is usually lower than the conduction band of the dye
molecule and it can provide staggered band structure for solar cell (8).

In QD-sensitized cells, short-band-gap QDs (CdS, PbS, Bi2S3, CdSe and InP) are substituted for dye molecules. They are absorbed from a
colloidal solution or produced in situ (7). The advantage of QDs versus dye molecules are the tunability of optical properties and slow hot
carriers cooling rate [Figure 14(b)]. Further modifications are also done by using bifunctional linker molecules. Such modification has been
done by Robel et al (8), using bifunctional linker molecules (HOOC-R-SH) with carboxylate and thiol functional groups. These linker
molecules provide better binding between CdSe QDs to . They also conduct electrons from QDs to particles [Figure 15]. The
maximum photon to charge conversion efficiency reported for this assembly is 12% (8).

Figure 15

“ Colloids were first prepared by hydrolyzing titanium isopropoxide in a glacial acetic acid solution followed by autoclaving the
suspension at 497 K for 12 h. The suspension was sonicated whereupon a known amount was applied to the conducting glass plates
(referred as OTE) and dried. After annealing these electrodes at 673 K, the weight of the film was determined. The average thickness of the
film was subsequently determined from the weight, density, and area of the film. Thicker films were obtained by carrying out
repeated applications of the suspension followed by drying” (8).

“The films, stored in an oven (373 K), were subsequently dipped into a solution of acetonitrile containing carboxy alkane thiols
(thiolacetic acid [TAA], mercaptopropionic acid [MPA], and mercaptohexadecanoic [MDA]). The films were kept immersed for 4 h.
Resulting films, functionalized with these bifunctional surface modifiers, were then washed with both acetonitrile and toluene and
transferred to a glass vial containing a suspension of CdSe QDs in toluene. The electrodes were kept immersed in the CdSe solution for
approximately 12 h. Figure 9 shows the sequence of steps followed. The resulting film is referred to as /L/CdSe films (L) TAA, MPA,
and MDA)” (8). Figure 16 is a scheme of this procces.

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Quantum dots in solar cells

Figure 16

Figure17 shows that both MDA and MPA linkers can provide better coverage of CdSe QDs on the and lead to more photocurrent and It
is justified by shorter chains of these molecules (8).

Figure17

In the next step the effects of the morphology of nanomaterials have been investigated (9). Figure 18 shows two different
investigated morphologies, nanoparticles and nanotubes (9).

Figure 18

Figure 19 shows photon to electron conversion efficiency of different sizes of CdSe QDs in these two structures. At the first glance at this
figure one can conclude that more conversion efficiency is achieved by using nanotubes. It is possibly because of the more
susceptibility of electrons to loss at grain boundaries in nanoparticles.

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Quantum dots in solar cells

nanoparticles nanotubes

Figure 19

And the other important point in figure 18 is that smaller QDs can produce more photocurrent in respect to bigger QDs. It happens because
QD band gap becomes larger as its size is decreased; it means that the difference between the conduction edge of QD and conduction edge
of is increased. And the higher difference means the more recombination prevention and more photocurrent (9) [Figure 20].

Figure 20

But smaller nanoparticles absorb less light than larger nanoparticles. This problem might be solved by constructing rainbow solar cells. In
rainbow solar cells an ordered assembly of QDs with different sizes will be used.

One suggested method to solve this problem is application of nanotubes as holder for QDs and putting QDs inside nanotube array in
respect to their size (Smaller ones on the top and larger ones at the bottom) [Figure 21] (9). As white light enters the cell, smaller QDs
absorb smaller wavelengths and larger wavelengths pass through the initial layer and are absorbed by the next larger QDs, and so on. This
structure can make one able to apply both higher photocurrent of smaller QDs and higher photo absorption of larger QDs simultaneously.
However, more experiments should be done to investigate its effectiveness on improving the photo current.

Figure 21

Conclusion: In this report focus was mainly on CdSe quantum dots, because they have tunable band gaps in the range of the visible light
and many research have been done and are being done on them. Microwave synthesis of CdSe QDs was introduced as a very good method
for production of these QDs with a very high yield and excellent size distribution. Principles of Solar Cells were discussed briefly to
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Quantum dots in solar cells
investigate how one can utilize QDs to improve the efficiency of them. Then different proposed assemblies for utilization of QDs in solar
cells were generally introduced. Among these assemblies Quantum dot-sensitized nanocrystaline solar cell were discussed more
detailed, because it is a modification of promising dye-sensitized nanocrystaline solar cell which has resulted in up to 12% efficiency.
Investigations showed that using bifunctional linker molecules can improve bounding between QDs and nanocrystals. The
morphology of nanocrystals also takes an important part in electrons conduction. It has been revealed that nanotubes can
provide better photocurrent due to less loss in the boundaries. Finally, rainbow solar cell has been suggested to couple higher conversion
efficiency of smaller QDs and higher photo absorption of larger QDs.

Refferences
1. B.E.A. Saleh, M.C. Teich. Fundamentals of photonics. New Jersy : John Wiley, 2007.

2. [Online] Evident Technologies, 2008. http://www.evidenttech.com/quantum-dots-explained.html.

3. C. Oliver Kappe, Doris Dallinger, and S. Shaun Murphree. Practical Microwave synthesis for organic chemists: Strategies
,Instrumens, and protocols. s.l. : Wiley VCH Verlag GmbH & Co. KGaA, Weinheim, 2009. 978-3-527-32097-4.

4. Synthisis of high quality Zinc blende CdSe nanocrystals. Mona B. Dino Tonti, Awos Al-salman, Abdelkarim Cemseddine and
Majed Chergui. s.l. : Physical chemistry letters, 2005, Vol. 109.

5. Microwave synthesis of CdSe and CdTe nanocrystals in non-absorbing Alkanes. Strous., Aaron L.Washington II and Geoffrey
F. s.l. : J.AM.CHEM. SOC, 2008, Vol. 130.

6. Davies, JH. The Physics of Low-Dimensional Semiconductors. An Introduction. Cambridge : Cambridge University Press, 1998.
ISBN 978-0-521-48491-6.

7. Quantum dot solar cells. Nozik, A.J. s.l. : Physica E, 2002, Vol. 14.

8. Quantum Dot Solar Cells. Harvesting Light Energy with CdSe. Istva´n Robel, Vaidyanathan Subramanian,Masaru Kuno. 7,
s.l. : J. AM. CHEM. SOC, 2006, Vol. 128.

9. Quantum Dot Solar Cells. Tuning Photoresponse through. Anusorn Kongkanand, Kevin Tvrdy, Kensuke Takechi, Masaru
Kuno, and Prashant V. Kamat. 12, s.l. : J. Am. Chem. Soc., 2008, Vol. 130.

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