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INTRODUCTION TO PHOTOVOLTAIC
AND PHOTOELECTROCHEMISTRY
Photovoltaic (or PV) systems convert light energy into electricity. The term
photo is a stem from the Greek phos, which means light. Volt is named
for Alessandro Volta (1745-1827), a pioneer in the study of electricity. Photovoltaics, then, could literally mean light-electricity. Photovoltaics (PV) is a
method of generating electrical power by converting solar radiation into direct
current electricity (converts sunlight into electricity).
IUPAC definition of Photoelectrochemistry: A term applied to a hybrid field
of chemistry employing techniques which combine photochemical and electrochemical methods for the study of the oxidation-reduction chemistry of the ground or
excited states of molecules or ions. In general, it is the chemistry resulting from the
interaction of light with electrochemical systems. (See also photoelectrochemical,
photogalvanic, photovoltaic cell)
1.1
Photovoltaic History
The first photovoltaic observation: A. E. Becquerel discovered the first photovoltaic effect, the operating principle of the solar cell, in 1839.1
1.1.1
Some milestones
The origin of photovoltaic effect started from the observation at the solid-liquid
interface of a photoelectrochemical cell called the Becquerel effect[1] as a
coincidence, just like many other discoveries in the science history. Forty years
later, photovoltaic effect was observed by Adams and Day[2]. In parallel with
the technology progress of photography, photoelectric effect remained a focus
of scientific interest, though this phenomenon was not well understood till the
1
A. E. Becquerel, (1839). Memoire sur les effets electriques produits sous linfluence des
rayons solaires. Comptes Rendus 9: 561
modern era of photochemistry in 1954 when Brattain and Garrett presented the
electrochemistry on Ge electrode by controlling the semiconductor properties
and light illumination[3]. The pioneering work of Ge was rapidly followed up
with other semiconductor electrodes such as Si, CdS, ZnS, CdSe, ZnO, TiO2 ,
SrTiO3 Ta2 O5 ... etc[4]. The fundamental was established by Gerischer on the
work of kinetics and energetics of electron transfer across the semiconductorelectrolyte junction and the characteristics of the space charge layer at the semiconductor surface in contiguous to the semiconductor-electrolyte interface. In
brief, the junction is formed between a semiconductor and another phase initially with difference of Fermi level between them. The majority carrier, upon
contact, will transfer through the interface to equalize the Fermi level and establish a thermodynamic equilibrium which generate a potential barrier at the
interface. Based on the new equilibrium, phenomenon of current rectifying
diode behavior and photovoltaic response upon illumination will prevail at the
junction. Some valuable reviews and books describe well the history and fundamentals of this type of photoelectrochemical photovoltaic cells [4, 5, 6, 7, 8].
The first solid state photovoltaic effect with Se was discovered by Willoughby
Smith in 1873[9]. In 1876, R. E. Day, W. G. Adams found that illuminating a
junction between selenium and platinum also has a photovoltaic effect, and an
EMF (Electromotive force) is produced. These two discoveries were a foundation for the first selenium solar cell construction, which was built in 1877[2].
Charles Fritts first described them in detail in 1883. This effect is the basis for
the modern solar cell. The silicon solar cell has remained essentially dominating the market since it was invented in 1954 by three American researchers,
Gerald Pearson, Calvin Fuller and Daryl Chapin, who designed a silicon solar
cell capable of a six percent energy conversion efficiency with direct sunlight
at Bell Labs[10]. A comprehensive account on solar cell history can be found
1.2
1.2.1
(1.1)
The reserves which have accumulated over millions of years will go up in the air
in a time of only hundred years!!! However, the elimination of energy is not yet
a major problem. A much worse issue will be the alternation of the atmosphere
and climate change as a result of the product of combustion. These effects last
long and have profound impact on our life and environment.
1.3
Some Facts
1. Current global energy consumption rate : 13 1012 W
(13T W )
And ....
Figure 1.9: Area required for various energy supplies to satisfy the US demand
10
1.4
1.4.1
11
12
From http://pv.energytrend.com.tw/
13
14
1.5. Radiation
1.5
15
Radiation
1.5.1
Blackbody Radiation
An object that absorbs all radiation incident upon it, regardless of the frequency,
is consider as a blackbody. An blackbody can be approximated by a hollow
object with a very small hole leading to its interior (Fig. 1.15). Any radiation
strikes the hole enters the cavity where it is trapped until being absorbed. At
equilibrium, radiation emitted must equal radiation absorbed. Therefore, the
body that emits the maximum amount also absorbs the maximum amountwhich
should look black. Practically, a blackbody is constructed by opening a small
hole on a large cavity.
(, T ) =
(f rom
standing
wave
in
cavity)
(1.2)
16
Equation 1.2 is the energy density of radiation per unit frequency interval in a
cavity of temperature T . It is not directly observable. The directly observable
quantity is the spectral radiance (, T ), that is, the energy radiating from a
unit area of the hole per unit frequency range.
1
2 2
(, T ) = c(, T ) = 2 kB T
4
c
(1.3)
The Rayleigh-Jeans distribution fits the low-frequency behavior of the experimental energy density very well. However, as the frequency increases, the
spectral irradiance increases, the total irradiation energy is infinite (so called
ultraviolet catastrophe). This contradicts the experimental fact that the total
blackbody radiation is finite, and the spectral density has a maximum. Max
Planck found an empirical formula that fits accurately the experimental data
using the energy quantum and Maxwell-Boltzmann statistics. He assumed
that the energy of radiation with frequency can only take integer multiples of a basic value h. The probability of finding a state with energy nh
is exp( nh/kB T ). Then, the average value of energy of a given component of
radiation with frequency is
P1
nh e nh/kB T
P1
= n=0
=
nh/kB T
n=0 e
(1.4)
Replacing the kB T in Equation 1.2, with Equation 1.4, Max Planck found
an empirical formula that fits accurately the experimental data:
(, T ) =
2 2
h
h/k T
2
b
c
e
(1.5)
1.5. Radiation
17
Initially, Max Planck believed that the quantization of energy is only a mathematical trick to reconcile his empirically obtained formula with the knowledge
of physics known at that time. The profound significance of the concept of
quantization of radiation and the meaning of Plancks constant were discovered
by Albert Einstein in his interpretation of the photoelectric effect, which is the
conceptual foundation of solar cells.
() d =
8h
3 d
c3 eh/kT 1
(1.6)
34
(J s).
18
e = (, T )A
where e is the power emitted per unit area per unit frequency by a heated
object. A is the fraction of the incident power absorbed per unit area per
unit frequency by the heated object, and (, T ) is a universal function for all
materials that depends only on frequency and temperature. A blackbody that
absorbs all the electromagnetic radiation falling on it would have A = 1 for all
frequency and so Kirchhoffs theorem for a blackbody becomes
(1.8)
e = (, T )
Stefan found experimentally the that the total power per unit area emitted
at all frequencies by a hot object, U (T ), was proportional to the fourth power
of its absolute temperature.
U (T ) =
U (T ) =
Z
Z
(1.9)
e d = T 4
0
1
0
2 2
h
h/k T
2
b
c
e
d =
(1.10)
where U is the power per unit area emitted at the surface of the blackbody, T is
the absolute temperature of the body, and
given by = 5.67 10
(W m
K 4 ).
1.5. Radiation
19
suns radius with Rs =7.0 108 m. The average Sun-Earth distance R= 1.5
1011 m. The power per unit area from the Sun (for all frequencies) is measured at
the Earth to be 1400 W/m2 . Assume that the Sun is a blackbody.
20
max
max
= const
max
stating that
1.5. Radiation
1.5.2
Solar Radiation
21
22
Figure 1.18: The earths orbital around the sun and the position of the earths
axis at various seasons over a year
1.5. Radiation
23
24
1.5. Radiation
25
26
1.5. Radiation
27
Air Mass
The Air Mass is the ratio of path length which light travels through the atmosphere normalized to the shortest possible path length (that is, when the sun is
directly overhead). The Air Mass quantifies the reduction in the power of light
as it passes through the atmosphere. The Air Mass is defined as:
AM f actor =
(1.11)
28
1.5. Radiation
29
30
(Re = 6370km)
( = 5.67 10 8 W/m2 K 2 )
For steady-state condition, IE,abs = IE,emi , we have the mean temperature of the
earth Te = 275K.
Green House effect : A great part of the energy emitted from the earth surface is
absorbed by the atmosphere and re-emitted back to the earth. This warm up the
atmosphere and rise the temperature. From Fig1.30, we have the relation of
1
IE,earth = IE,sun + IE,atm
2
Figure 1.30: Balance of the absorbed and emitted energy current on the surface
of the earth.(From P. W
urfel)
What is the temperature ( Tegh =?) with such greenhouse effect
gh
0.5IE,atm = IE,sun this leads to IE,earth
= 2IE,sun = 2IE,abs = 2IE,emi = 8Re 2 Te 4
gh
Since IE,earth
= 4Re 2 Tegh
Tegh = 54 C
we have
Tegh = 2Te 4
1.5. Radiation
31
32
1.5.3
Solar Spectrum
N umber of photon
second area
1.6
33
Basics in Photovoltaics
Figure 1.36: Comparison of photoelectric effect (left) and a photovoltaic device (right). The photovoltaic device needs certain spatial asymmetry such as
selective contact to drive excited charges to external circuit.
34
35
Figure 1.39: I-V characteristics of a solar cell under dark and illumination
FF =
(1.12)
n=
(1.13)
36
Figure 1.43: Equivalent circuit of a solar cell with series and shunt resistance
Iph = Is [exp(
qv
)
kt
1]
Il
photocurrent equation
(1.14)
37
High Rs and low Rsh will kill the performance of a solar cells.
Figure 1.44: Effects of series (a) and shunt resistance (b) in a solar cell.
A STUDY OF DYE SENSITIZED SOLAR CELLS UNDER INDOOR AND LOW LEVEL OUTDOOR
LIGHTING: COMPARISON TO ORGANIC AND INORGANIC THIN FILM SOLAR CELLS AND METHODS
TO ADDRESS MAXIMUM POWER POINT TRACKING
ABSTRACT: With increasing applications in consumer electronics such as smart phones, laptops and tablet PCs, the
need for pervasive computing with a requirement of lower power consumption is increasing every day, This opens the
door for energy harvesting that could charge the batteries in these devices to keep them continually functioning in
some useful state. There has been a lot of attention on flexible thin film solar cells, such as dye sensitized (DSSC),
organic and inorganic, given their low cost and improving efficiency. Such cells are suitable for these applications
both under outdoor and indoor conditions due to their larger spectral response. Understanding the behavior of solar
cells such as DSSC under indoor light conditions along with power management algorithms to extract maximize the
collected energy is vital for consumer electronics applications. This analysis is compared to organic and inorganic
thin film solar cells.
Keywords: Dye-sensitized, Spectral response, Shading, Power Conditioning.
1
MEASUREMENT SETUP
MPP ALGORITHMS
(1)
(2)
ADDITIONAL COMPONENTS
8.1 Illustrations
8.3 References
[1] B. Atwood, B. Warneke, K. S. J. Pister, Proceedings
of 14th Annual International Conference on
Microelectromechanical Sytsems, (2001) 357.
[2] S. Chalasani, J. M. Conrad, Southeastcon IEEE,
Vol. III (2008) 442.
[3] J. Colomer-Farrarons, P. Miribel-Catala, A. SaizVela, J. Samitier, IEEE Transactions on Industrial
Electronics, Vol. 58, (2011) 4250.
[4] B. ORegan, M. Grtzel, Nature 335 (1991) 737
[5] M. Grtzel, Journal of Photochemistry and
Photobiology C: Photochemistry Reviews, Vol. 4
(2003) 145.
[6] N.Femia, D.Granozio, G.Petrone, G.Spaguuolo,
M.Vitelli, IEEE Trans. Aerosp. Electron. Syst., Vol.
2 (2006).
[7] D.P.Hohm, M.E.Ropp, Proc. Photovoltaic Specialist
Conference (2000) 1699.
[8] R. Faranda, S. Leva, V. Maugeri, Power and Energy
Society General Meeting - Conversion and Delivery
of Electrical Energy in the 21st Century, IEEE,
(2008) 1.
43
44
45
46
47
48
1.7
Basics of Photoelectrochemistry
49
50
51
52
1.8
1.8.1
53
54
55
Figure 1.67: Basic structure of a crystalline Si solar cell (150 - 300 um)
56
Figure 1.71: Buried-contact, surface texture and back surface field design
57
Figure 1.72: Special design of a sc-Si PERL solar cell with inverted pyramids
and bilateral area parallel point contacts back surface field architecture
1.8.2
58
Figure 1.75:
Wronski effect
Process of Staebler-
59
60
1.8.3
61
62
1.9
Further Readings:
63
64
BIBLIOGRAPHY
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BIBLIOGRAPHY