Raymond A. Adomaitis
Department of Chemical & Biomolecular Engineering and
Institute for Systems Research
University of Maryland
College Park, MD 20742
adomaiti@umd.edu
c Copyright by
Raymond A. Adomaitis
2 The Sun 15
2.1 Blackbody radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.1.1 AM0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1.2 Numerical integration of spectral irradiance . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2 Atmospheric absorption effects on spectral irradiance . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.1 AM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.2 Direct versus diffuse radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.3 The projection effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.3.1 Optimal panel tilt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.3.2 Integrating projection and absorption effects . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.3.3 3D modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.4 Insolation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.5 Cloud cover . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.5.1 Insolation data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
1
CONTENTS 2
Energy conversion, such as that which is concerned with converting solar radiant energy to electrical, chemical,
or kinetic energy is a key topic in these lecture notes, so starting with a review of the basics of energy, power, and
radiant intensity unit definitions makes sense. To put these issues in context, consider Fig. 1.1 where a typical
silicon solar cell is illustrated. The basic questions we seek to answer include
1. How do we relate photon energy and flux to the electrical power produced by the PV cell?
2. How do we develop mathematical models describing the internal currents and total electrical power produced
by PV cells?
3. How do we engineer the PV cell components to optimize cell performance?
4. How do we expand our fundamental knowledge of solidstate PV devices to electrochemical and biological
systems?
Let us now consider Fig. 1.2 where the electric power demand of approximately 30 million Californians [CaISO]
is plotted for a 24hour period. When we examine the power production potential of wind, solar, and other
renewable resources, we observe a number of important phenomena:
1. The renewable energy sources can introduce a high degree of dynamic (in time) variability in the power
supply resulting from wind variations and passing clouds that reduce the intensity of the solar radiation
reaching the solar panels.
2. The temporal variations have multiple timescales, introducing higherfrequency fluctuations with time scales
measured in seconds or minutes and diurnal variations that take place over the day.
3. There is a strong incentive to include energy storage elements in the overall design to reduce the power
fluctuations and to allow for peak power delivery at the 5 pm demand peak.
To compensate for the variations introduced by solar and wind power sources, some type of an energy storage
system is used to help match power production levels to demand; see the right plot of Fig. 1.2 where the difference
between production and demand is plotted. The increasing use of renewable power sources complicates the energy
picture and requires the integration of a number of energy generation, conversion, and storage technologies.
7
CHAPTER 1. ENERGY  UNITS AND BASIC CONCEPTS 8
hυ
e
n0 
n1
n2 + h+ e ntype
+ + +
    emitter Figure 1.1: The architecture of a typical Si
PV cell.
h+ e Ie,sc
h+ e
ptype
Ih,sc base
h+ e
+
2500 09/02/13 45000 09/02/13
geothermal demand
wind scaled renewables
2000 solar 40000
1500 35000
MW
MW
1000 30000
500 25000
0 5 10 15 20 20000 5 10 15 20
time of day time of day
Figure 1.2: Renewable energy production (left) and overall electricity demand (right) in California during a 24 hour period
in late summer 2013 [CaISO].
of PV cells is considered. The study of thermodynamics is crucial to rigorously assessing the efficiency of the solar
energy devices described later and provides a quantitative means of comparing competing technologies.
We now define the following terminology and conventions:
• Isolated systems are closed and also do not allow energy transport across the system boundaries.
• Heat is energy in transit between a system and its surroundings or between two systems, driven by the
temperature difference between the two. Heat energy has units of J (Joules) and symbol Q; Q > 0 will
denote heat flowing into the system.
• Intensive properties do not depend on the total amount of material present; examples include temperature
T , pressure P, and molar quantities such as molar volume V (unless we specify bymass).
• Extensive properties do depend on the quantity of material, such as volume V t or mass m. Note the use
of the t superscript.
1.2 SI units
There are seven base SI units; all other units are derived from combinations of these quantities. Some of these
we know and deal with on a daily basis such as
m, kg, s
that require no additional introduction. We are also familiar with the notion of temperature, though we be less
so with its actual definition. Kelvin, the unit of temperature is 1/273.16 of the thermodynamic temperature of the
triple point of water [NISTkelvin]. Recall the Gibbs phase rule in which the thermodynamic degrees of freedom
(d.o.f .) are related to the number of components c and phases π: d.o.f . = c − π + 2. Therefore, for the one
component of water with three phases, d.o.f . = 0 and so the temperature and pressure are both uniquely defined
at the triple point.
For the fifth base unit, a mole is defined as the number of atoms or molecules equal to the number of atoms in
12 g of carbon12. Of course, this is equal to Avogadro’s number NA = 6.02214179 × 1023 .
Because of our focus on solar energy issues, we must also consider the remaining two base SI units. Electric
current has a base SI unit of amperes (A) defined by the current that produces a prescribed amount of force per
unit length between two parallel conductors at a specified separation. With n as the number of electrical charges,
current I is defined as
dn
I =
dt
and has units amperes (A) where 1 A = 1 C/s. The coulomb (C) is a unit of electrical charge and corresponds to
We distinguish between conventional current which is the flow of positive charges (this unfortunate convention
is due to Benjamin Franklin) and electron current which to many makes more physical sense. If I is constant,
the total charge transferred due to the current is
Z t
q= I dt.
t0
A typical candle radiates approximately 1 cd of radiant power. Solid angles are measured with the dimensionless
unit of steradian (sr), defined by the quotient of a spherical cap area S and the square of the radius r of the
sphere defining that spherical cap
S
solid angle ω = 2 steradians.
r
To visualize the steradian, think of the angle created by a solid cone where the base consists of the spherical cap
surface S. If that area is chosen so that S = r 2 , the solid cone corresponds to 1 sr. One can also compare the
steradian to the more familiar unit of angular measurement, the radian. Given that the surface area of a sphere
is 4πr 2 , we see that a sphere measures 4π sr (compare to 2π radians for a full circle). Therefore, a light source
that isotropically radiates 1 candela (power/solid angle) produces 4π lumens of total luminous power. As such,
1 lm = 1 cd·sr = (1/683.002) W. To understand this in more concrete terms, examine a representative package
of light bulbs, e.g., Fig. 1.3 or the LCD projector brightness ratings for representative displays.
Taking into account the area over which the luminous flux falls, we define 1 lux (lx) = 1 lm m−2 where
cd· sr
1 lx = 1 .
m2
One must be careful in converting from candela to lux when the area in question is a flat surface, such as with an
optical sensor element. To summarize, the overarching concept connecting all of these units is that measure of
luminous intensity (candela, lumen) are values associated with the light source, while the flux (lux) can depend
on the distance to the luminous source, the geometry of the surface onto which it falls, and the nature of the
light (diffuse or direct).
Luminous efficiency ηL is defined by the fraction of chemical or electrical energy that is converted to visible light.
Therefore, ηL = 1 (100% luminous efficiency) corresponds to 683.002 lm/W.
We can convert the frequency ν of light to wavelength λ using the speed of light in a vacuum as c = 299, 792, 458
m/s and so
c 2.998 × 108 m/s (109 nm/m)
λ= = = 555 nm.
ν 5.4 × 1014 s−1
This corresponds to green visible light and is the wavelength to which the human eye is most sensitive. This
brings up an important point: the units of candela, lumen, luminous efficiency, and others just described are most
useful for lighting (photometry) applications, where only the visible portion of the spectrum is important. These
measures require the use of a luminosity function y (λ) to model the human eye’s spectral sensitivity to light.
Therefore, a light source with some total spectral power distribution Eλ0 (λ) in W/m (note that the unit of m
CHAPTER 1. ENERGY  UNITS AND BASIC CONCEPTS 11
corresponds to wavelength) emits visible light with an intensity defined by the inner product
Z∞
lm
683.002 y (λ)Eλ0 (λ) dλ lumens.
W
0
The luminosity function y (λ) is defined by several standards and takes the form of a Gaussianlike distribution
centered, for example, at λ = 555 nm for daylight conditions.
Because photovoltaic and solar thermal systems can make use of the infrared and ultraviolet portions of the
spectrum, we will find that these units generally will not be used in our calculations. More appropriate measures
of solar radiant intensity (in radiometry units) such as irradiance and insolation will be defined in detail in the
next chapter.
We will use the convention that work done by a system has negative values and work done on a system as positive.
Energy has the same units as work. Let us consider Newton’s Second Law F = ma which can be rearranged to
produce
du
dw = F dz = ma dz = m dz
dt
but the velocity u is defined by
Z u1 2
u02
dz u1
= u so dw = mu du thus w = m u du = m − .
dt u0 2 2
The calculation above immediately illustrates that kinetic energy EK = w > 0 if u1 > u0 which is consistent with
our sign convention. Likewise, we have the potential energy EP associated with mass m and gravitational field g
dw = F dz = mg dz so w = EP = mg (z1 − z0 )
−2π 2 mq 4
En =
h2 n2
CHAPTER 1. ENERGY  UNITS AND BASIC CONCEPTS 12
voltage drop
voltage rise
A B
Figure 1.4: An electrical element.
+ 
I
where q is the unit electron charge, m is electron mass, n = 1, 2, 3, ... is the principle quantum number, and h is
Planck’s constant (in appropriate units). Given that the ground state corresponds to n = 1, the energy required
to move an electron from the ground state to some excited state nE > 1 is
" #
2
−2π 2 mq 4 1
∆En = −1 >0
h2 nE
and so work is done on the electron. When the electron falls back to its ground state and emits a photon with
energy Ep = hν, we note ∆E < 0 and so work is done by the electron.
Finally, power is energy per unit time and so has units J/s or W.
J
1V=1 .
C
We will make frequent use of the electron volt (eV) which is a unit of work:
1 eV = 1.6022 × 10−19 J
We also define elementary charge as the electric charge of a signal proton, thus
e or q = 1.6022 × 10−19 C
and is a positive quantity. The Faraday constant F , which is commonly used in electrochemical calculations,
corresponds to the total charge of one mole NA of elementary charges so
F
e= .
NA
In Fig. 1.4, node A has a potential of V volts (V) higher than node B. This corresponds to a voltage drop in the
direction A→B and a voltage rise for B→A. We can now ask if energy is supplied to or supplied by the element
(think resistor versus a battery). Following the definition of [Johnson, Hilburn, Johnson, 1978] (page 8):
“If a positive [conventional] current enters a positive terminal, then an external force must be driving
the current and is thus supplying or delivering energy to the element. The element is absorbing energy
in this case.”
CHAPTER 1. ENERGY  UNITS AND BASIC CONCEPTS 13
I I
A +
voltage drop
+
Figure 1.5: An elementary electrical circuit.

B 
Whether this energy accumulates or dissipates will be examined more carefully in the transient energy balance
chapter, but for now if we take one system to be the nh charge carriers, the work w done by/on the charge carriers
is determined by the voltage drop/rise through the device (the other system). As we saw before w > 0 when work
is done on a system. Because nh > 0 (positive conventional current) between A and B in Fig. 1.4 and because
the charge carriers experience a voltage difference −V
w = (−V )nh
implies w < 0 and so work is done by the charge carriers carriers at the following rate
dw dnh J C
= power = V = VI = watts.
dt dt C s
Therefore, if in Fig. 1.4, V = −5 V and I = 2 A, p = −10 W is the rate of work done by the charge carriers. By
the conservation of energy (to be discussed in more detail later), the charge carriers may transfer up to p = 10
W to the electrical element.
In Fig. 1.5 a voltage source connected to terminals A and B is depicted. Closing the circuit with the resistor
shown and using Ohm’s law
V = RI
we find
V V
R= : = Ω Ohms.
I A
In this case, the conventional current enters at a higher potential (voltage), and so positive charge carriers pass
from high to low potential implying w = (−V )I and so again, work is done by the charge carriers to the resistor.
The power dissipated by the resistor is
V2 J2 /C2
p = VI = (RI )I = RI 2 = = =W
R J·s/C2
We note that in Fig. 1.5 the battery cathode is where the conventional current flows out of the device, and so it
is the (+) terminal at A. In a device that produces power, the cathode is positive (+); for a device that consumes
power (such as the resistor), the cathode is the (−) terminal. The anode corresponds the the (−) terminal at B.
Finally, the conductance is defined as the inverse of resistance
1 A
G= : = 0 mho
R V
and so I = GV .
at some specific location within a circuit or circuit element. Therefore, considering Fig. 1.4, the voltage difference
between the terminals A and B are related to the difference in Fermi levels by
µA − µB
VA − VB = − .
e
In this case, we observe that it requires more energy to “insert” an electron into node B relative to node A and
that election current must flow from right to left. A voltmeter connected to nodes A and B effectively measures
the difference in electron chemical potential by its voltage reading.
2. Describe how the total energy and peak power dissipated in an earthquake is determined.
3. Create a short list of luminous efficiencies ηL for incandescent, halogen, compact fluorescent, and LEDbased
light bulbs available at your local hardware or drug store.
4. Compute to 5 significant figures the number of photons/sec corresponding to 1 lumen (1 lm) of a monochro
matic light source with wavelength λ = 555.17 nm.
5. What is the mean electrical power production rates of the US and China? Report your results in TW and
cite your sources of information.
References
[CaISO] California ISO http://www.caiso.com/outlook/SystemStatus.html
[Johnson, Hilburn, Johnson, 1978] Johnson, D. E., J. L. Hilburn, and J. R. Johnson, Basic Electric Circuit
Analysis, PrenticeHall, 1978.
[NISTkelvin] From the NIST website http://physics.nist.gov/cuu/Units/kelvin.html
Chapter 2
The Sun
Our goal in this chapter is to investigate the solar spectrum, how one calculates the intensity of solar irradiance at
the Earth’s surface, both at peak intensity and hourly, how we use NREL (National Renewable Energy Laboratory)
spectral irradiance tables and insolation maps, and how those maps compare to values produced by our integrated
irradiance calculations.
Ep = hν
using Planck’s constant h. Introducing the Boltzmann constant1 kB and recalling that a blackbody is characterized
by its ability to absorb all radiation that falls on it, the spectral irradiance of the blackbody is given by Planck’s
law:
2πhc 2 W
Eeλ (λ, T ) = with units (2.1)
m3
hc
λ5 exp −1
λkB T
which describes the spectral distribution of light emitted by a blackbody at temperature T . The units in the
denominator should be thought of in terms of m2 m, where the first factor m2 corresponds to the surface area
of the blackbody and the second unit of length corresponds to the wavelength of the emitted light. We will
frequently write the units of (2.1) as Wm−2 nm−1 to represent the wavelength in terms of the more commonly
used units of nm.
Before proceeding, we note that for smaller values of temperature T and for values of λ → 0, that the exponential
term in the denominator grows infinitely large and at a rate greater than λ5 , resulting in Eeλ → 0 as λ → 0.
The size of the exponential term, however, can become difficult to compute for small values of λ, and so one can
multiply the numerator and denominator by exp (−hc/λkB T ) to improve the reliability of this computation.
The effective temperature of the Sun’s photosphere is TS = 5777 K; the surface area of the sun’s photosphere
is AS = 6.0786 × 1018 m2 , and the area of a sphere corresponding to the mean radius of Earth’s orbit (one
1 Note how the Boltzmann constant is related to the gas constant Rg by Avogadro’s number NA through Rg = kB NA .
15
CHAPTER 2. THE SUN 16
0.5
astronomical unit, or 1.496 × 1011 m) is AAu = 2.8124 × 1023 m2 . Therefore, the effective solar spectral
irradiance at this location in the solar system is
AS 1m W
EE λ (λ, TS ) = Eeλ (λ, TS ) .
AAu 109 nm m2 ·nm
We plot this function in Fig. 2.1 along with the lines indicating the wavelengths of red λ = 700 nm, green λ = 555
nm, and violet λ = 400 nm, the first and last being the approximate limits of the visible spectrum.
The total power per unit area between wavelengths λ0 and λ1 defines irradiance and is computed by
Z λ1
EE (TS , λ0 , λ1 ) = EE λ (λ, TS )dλ
λ0
and so we can compute the ultraviolet, visible, infrared components as well as the total irradiance (be sure to
note the difference between irradiance and the wavelengthdependent spectral irradiance) as
the last of which is a good approximation to the measured solar constant Esc
W
Esc = 1366 , (2.2)
m2
a quantity also equivalent to the direct irradiance at the Earth’s surface if none of the radiation was absorbed
or scattered by the Earth’s atmosphere.
Computing the integral of (2.1) over λ ∈ (0, ∞) gives the StefanBoltzmann equation:
Z ∞
W
Eeλ (λ, T )dλ = σT 4 2
0 m
CHAPTER 2. THE SUN 17
with
2π 5 k 4 W
σ= = 5.670400 × 10−8
15c 2 h3 m2 ·K4
which gives the total power per unit area radiated by a blackbody object. We will make use of this relation in
later radiant heat transfer calculations. As a quick reality check, we compute
As W
σ(5777 K)4 = 1365.1 2
AAu m
which is very close to the correct value of the solar constant.
Finally, we observe the peak intensity of the Planck distribution for T = 5777 K occurs at a wavelength λpeak of
value slightly greater than 500 nm (in the green portion of the spectrum). The true peak value can be computed
using Wien’s displacement law
2.8978 × 106 nm K
λpeak = (2.3)
T
with T in K. Therefore, for T = 5777 K we find λpeak = 502 nm.
Of course it can be clearly observed from (2.3) that the wavelength of the peak intensity grows with decreasing
T ; a hot object glowing yellow will shift to orange and then to red as it cools. Using (2.1) we can also show
that the irradiance distribution as a whole also shrinks with decreasing T by computing the ratio of two spectral
irradiance distributions for two different temperatures T0 and T1 :
hc
exp −1
Eeλ (λ, T0 ) λkB T1
= < 1 for T1 > T0 .
Eeλ (λ, T1 ) hc
exp −1
λkB T0
Therefore, the blackbody spectral irradiance curve corresponding to the hotter T1 must lie above that correspond
ing to T0 for every value of λ, meaning that the cooler body must have a lower irradiance (obtained by integrating
the spectral irradiance over 0 < λ < ∞) and so emit less radiant energy. Likewise, when the spectral irradiance
peak shifts to the right for lower temperature values, the peak will never cross through irradiance distributions
corresponding to higher temperatures.
2.1.1 AM0
The US National Renewable Energy Laboratory (NREL) provides an online, experimentally measured reference
solar spectral irradiance data ASTM G173 [NRELdata]. The data corresponding to the true spectral irradiance
(AM0) at the top of the atmosphere at mean EarthSun distance are plotted in Fig. 2.1.
AM0
2.0 AM1.5
AM1.5 direct
AM1.5 diffuse
1.5
EE W/(m2 nm)
0.5
1. Absorption of portions of the spectrum by water vapor, CO2 and other green house gases (mostly in the
infrared region) and by ozone (in the visible and ultraviolet portion of the spectrum);
2. Scattering of (mainly blue) light by dust and ice particles in the atmosphere, giving rise to direct and
diffuse components;
3. Absorption and scattering by clouds.
The first two effects can be measured, and standardized tables corresponding to passage of the sun’s radiant energy
through the equivalent of 1.5 clear atmospheres (AM1.5: the equivalent of 1.5 air masses) also are available from
NREL [NRELdata]. The NREL data corresponding to AM0, AM1.5 global, and AM1.5 direct are plotted in
Fig. 2.2; the graph corresponding to AM1.5 diffuse is computed as the difference between AM1.5 global and
AM1.5 direct. We note that AM1.5 has become a standard method of characterizing spectral irradiance for the
design of photovoltaic systems.
2.2.1 AM
Before proceeding, we must make the concept and value of AM clearer. On page 6 of [Wenham, et al.(2007)],
the air mass (AM) is the Earth’s atmosphere is approximated by
1
AM = (2.4)
cos ζ
where ζ is the zenith angle which is defined as the angle made between a line segment extending between the
Earth and sun and local vertical, e.g., ζ = 0 when the sun is directly overhead and ζ = π/2 when the sun is on
the horizon. More will be said on ζ in Section 2.3.
The approximation (2.4) is justified by the small relative thickness of the Earth’s atmosphere relative to its radius:
RE = 6370 km while the internationally accepted definition of space is an altitude of LA = 100 km. Therefore, in
the limit of small ζ values, the distance L a ray of light must travel through the atmosphere can be calculated by
L cos ζ = LA
and so AM = L/LA = 1/ cos ζ.
CHAPTER 2. THE SUN 19
Therefore, we see that AM = 1.5 corresponds to 48o , a reasonable approximation to the mean value of the zenith
angle through the day, resulting in AM1.5 as the standard by which PV cell performance is measured.
Atmospheric pressure and density are strong functions of altitude z. To approximate the effect air density has on
AM, we make use of equation (2.29) of [Rekioua and Matagne(2012)] to find
0.89z
AM = for z < 3 km (2.5)
cos ζ
where z is given in km. This correlation is useful for most locations we encounter, but alternative correlation
must be used for higher elevations, such as those encountered by solarpowered aircraft.
• The direct irradiance corresponds to light which travels on a straight line from the sun. When the surface
of the collector is normal to the incident direct radiation, this component is called direct normal irradiance.
Distinguishing the direct (normal or otherwise) component from the diffuse radiation is important because
the direct irradiance is the only portion that can be used in concentrating solar systems.
• Diffuse radiation is that component scattered by our atmosphere and is weakly directionally dependent. It,
for example, is the only component illuminating solar panels in the shade. There is no diffuse component
in space (but reflections from planets and other objects can be important).
• The global irradiance simply is the sum of the direct and diffuse contributions.
We can integrate the direct and diffuse spectral irradiance components shown in Fig. 2.2 to find the irradiance
values listed in the center column of Table 2.1.
NREL irradiance, W/m2 Model W/m2
EAM0 1348 ED⊥ (AM = 0) 1366
EAM1,global  EG⊥ (AM = 1) 1107
EAM1.5,global 1000 EG⊥ (AM = 1.5) 1002
EAM1.5,direct 900 ED⊥ (AM = 1.5) 903
EAM1.5,diffuse 100 EF (AM = 1.5) 99
Table 2.1: Integrated values of true irradiance versus our modeled values computed using (2.6) and (2.9).
The integrated NREL data of Table 2.1 shows that 10% of the global irradiance is contributed by the diffuse
component of the total irradiance. We also pause to take note that a good round number to keep in mind is that
at sea level under clear conditions and with a solar panel positioned normal to the Sun’s rays, one can expect a
global solar irradiance of approximately 1 kW/m2 , defining an absolute maximum solar power generation rate.
In the right columns of Table 2.1, the numerical AM values of 0, 1, and 1.5 can be used to approximate the
reduction of the direct normal irradiance ED⊥ (on a surface oriented such that its face is normal to the Sun’s
rays) by atmospheric absorbance with the model described by a slightly modified2 form of the model presented in
[Wenham, et al.(2007)]:
0.678 W
ED⊥ = Esc × 0.73(AM ) (2.6)
m2
2 We changed the model coefficient from the value 0.7 in the cited work to 0.73 to produce a better match with the NREL data.
CHAPTER 2. THE SUN 20
Day: 0 Day: 91
WDC ArcC
TCan ArcC WDC
Eq TCan
TCap ecliptic Eq ecliptic
TCap
AntC
Axis AntC
Axis
ArcC ArcC
WDC
TCan
WDC
TCan ecliptic Eq ecliptic
Eq TCap
TCap
AntC Axis AntC
Axis
Figure 2.3: Earth at winter solstice (top left), spring equinox (top right), summer solstice (bottom left), and fall equinox
(bottom right). In all cases, the Sun is to the left.
where Esc is the solar constant given by (2.2). The global normal irradiance EG⊥ includes the radiation scattered
by the Earth’s atmosphere but ultimately reaches the Earth’s surface through the diffuse radiation mode. As we
saw earlier, 10% of the global normal irradiance corresponds to the diffuse component EF (we assume for now
that EF is independent of solar panel orientation) Therefore, we approximate the diffuse irradiance as
EF = 0.1EG⊥ (2.7)
ED⊥ h 0.678
i
so EG⊥ = ED⊥ + EF = = 1.11 Esc × 0.73(AM ) (2.8)
0.9h i
0.678
⊥
and EF = 0.11ED = 0.11 Esc × 0.73(AM ) (2.9)
for a surface aligned normal to the Sun’s rays. Note that we use the parentheses in the exponent of 0.73 to
emphasize that AM is first raised to 0.678 and that 0.73 then is raised to the resulting value.
n θtilt
τ
φ
φ z
sun y
ζ latitude
δ
θ=0 sun
x
equator δ λ
ecliptic: z=0
Figure 2.4: Geometry of the Earth relative to the ecliptic in 2D (left) and in 3D (right). The equatorial plane defines the
ring shown at right.
amount of light at this latitude if the normal to the panel pointed directly upward. Given the 23.44o tilt of our
planet, we can conclude that
1. The Tropic of Cancer and Capricorn lie 23.44o north and south, respectively, of the equator;
2. The Arctic and Antarctic Circles lie 90o − 23.44o north and south, respectively, of the equator.
Declination is defined as the angle between the sunearth line segment and the equatorial plane. We can
approximate this tilt of the equator at solar noon relative to the ecliptic plane as
o 2πtd
δ(td ) = 23.44 cos (2.10)
365
where td ∈ [0, 365] is the date of interest in terms of the number of days after the winter solstice (e.g., td = 11 for
1 January 2014). This results in the winter and summer solstices and spring and fall equinoxes shown in Fig. 2.3.
Latitude φ is defined in terms of degrees north or south of the equator (lines of longitude λ are denoted as E
and W of the prime meridian and will be used later in this chapter). Defining θn as the angle made by a vector
~n normal to the earth’s surface from the earth’s center to the solar panel located at φ, at solar noon one can see
directly from the geometry portrayed in Fig. 2.4 that
ζ =φ+δ (2.11)
where we define ζ as the zenith angle, described previously as the angle between the sunearth vector and ~n, or
in other words, the position of the sun relative to what appears as directly vertical.
Before concluding this section we make note of the sign convention used for the declination δ and and latitude
φ; in both cases, positive values denote degrees north of the equator, so δ < 0 during the latespring, summer,
and early fall, and φ > 0 for locations in the northern hemisphere. We denote latitude of locations in the
southern hemisphere in terms of degrees S, or for the sake of our calculations, negative degrees N. A short table
of representative city latitudes is given in Table 2.5.
CHAPTER 2. THE SUN 22
irradiance W/m2
600
400
200
00 5 10 15 20
time
Figure 2.6: 1 degreeoffreedom optimal tilt of a solar panel located in Washington, DC (left). Irradiance profiles
corresponding to the optimal tilt (right).
Plotting θtilt,op (td ), we observe that the optimal panel tilt value in midwinter is θtilt,op = 62.32o and θtilt,op =
15.44o in summer in Washington, DC. We see an immediate use of the winter value as that which would be best
for a remote power application in which a minimal level of energy was required on a daily basis through the winter.
We note that the average of these two maximum values equals θtilt,op,avg = 38.88o , precisely our latitude of
interest. This gives a good general design rule for fixed solar panels.
For a panel with θtilt degrees of tilt to the South Pole, it is not difficult to see that the angle ζtilt between a vector
n~p normal to and pointing out of the panel front surface to the sunearth line is
Think of ζtilt as the zenith angle experienced by a person standing on the solar panel surface, immune to gravity
and standing normal to the panel surface. In this case
1. As before, AM = 0.89z / cos ζ for z < 3 km because the attenuation effect of the Earth’s atmosphere does
not depend on the solar panel tilt angle;
2. EF does not change because of our assumption that it is independent of panel orientation.
CHAPTER 2. THE SUN 23
Therefore, for a panel located at latitude φ, tilted at angle θtilt towards the equator, and at solar noon
h 0.678
i h 0.678
i
EG = Esc × 0.73(AM ) cos ζtilt + 0.11 Esc × 0.73(AM )
h 0.678
i
= Esc × 0.73(AM ) (0.11 + cos ζtilt ) (2.13)
2.3.3 3D modeling
For a more accurate method of computing the Sun’s position relative to a point on Earth we must use a fully
3dimensional model. Based on the geometry shown in Fig. 2.4, we define
φ = latitude, λ = longitude.
If the Earth’s axis of rotation is aligned along the z vector in Fig. 2.4, we can convert from spherical to cartesian
coordinates
xo = RE sin φ cos λ
yo = RE sin φ sin λ
zo = RE cos φ
using the Earth’s radius RE and where we use the rotation matrix below to rotate the x and z points by the
Earth’s axial tilt δ(td ) (2.10) around the y axis (the negative values −δ(td ) are needed for the orientation depicted
in Fig. 2.4 because counterclockwise rotations result for positive angles):
x cos −δ(td ) − sin −δ(td ) xo cos δ(td ) sin δ(td ) xo
= =
z sin −δ(td ) cos −δ(td ) zo − sin δ(td ) cos δ(td ) zo
so
As seen in Fig. 2.7, we can now plot the lines of latitude on the surface of the globe tilted in the correct manner.
If ~x , ~y , and ~z are the basis vectors in three dimensional space and x, y , and z the magnitudes along these
directions, the vector normal to a point on the surface of the Earth is
Because both vectors are normalized, using the vector dot product we can compute
Figure 2.7: Circles of latitude marked in increments of 10o ; Washington, DC is shown in red.
600 Daily clear/cloudy insolation = 2.92/1.20 kWh/m2 /day 1200 Daily clear/cloudy insolation = 9.03/2.29 kWh/m2 /day
global global
direct direct
500 cloudy 1000 cloudy
diffuse diffuse
mean global mean global
400 800
irradiance W/m2
irradiance W/m2
300 600
200 400
100 200
00 5 10 15 20 00 5 10 15 20
time time
Figure 2.8: Mean and quarterhourly irradiance values corresponding to Washington, DC, onto a plate tangent to the
Earth’s surface on January 15 (left) and July 15 (right).
Given the irradiance model (2.13) applicable to horizontal surfaces, we find our final model for global irradiance
with respect to a panel tangent to the Earth’s surface becomes
1200
EG  sea level
EG  corrected
1000
800
Figure 2.9: Solar irradiance curves correspond
irradiance W/m2
600
ing to June 1 for a solar panel with zero tilt lo
cated in Guadalajara, MX. The two curves illus
trate irradiance calculated at sea level and the
400
correct elevation.
200
00 5 10 15 20
time
Tilted surfaces
For a surface tilted θtilt degrees to the South Pole, the normal vector of the tilted panel is computed using an
additional set of points (xtilt , ytilt , ztilt ) computed using (2.142.16) but with RE and φ replaced with
respectively. We compute the projection effect on the direct irradiance component using
1
cos ζtilt = −~s · ~ntilt with ~ntilt = [x − xtilt , y − ytilt , z − ztilt ].
RE
giving the following function for global irradiance that now includes the effect of θtilt :
h 0.678 0.678
i W
EG (td , φ, λ, θtilt ) = H(cos ζtilt )Esc × 0.73(AM ) cos ζtilt + 0.11Esc × 0.73(AM ) H(cos ζ) (2.19)
m2
where the case H(cos ζtilt ) < 0 and H(cos ζ) > 0 corresponds to a panel in daylight but tilted so that it is in the
shade and only illuminated by the diffuse component.
2.4 Insolation
Insolation is solar irradiance integrated over a specific time period, and so has units of energy/(unit area) such
as J/m2 , or more typically in solar energy applications kW hr m−2 day−1 ). Given our irradiance model (2.18) for
EG (td , φ, λ), we can translate points of differing longitude λ into hourly (or finer) intervals:
24λ
t=
360
and so if t = [0, 1, 2, ... , 24] represent the hours in one day and EG (td , φ, t) the irradiance at those times during
the day, the resulting insolation E is computed as
Z 24
E (td , φ) = EG (td , φ, t) dt. (2.20)
0
Numerical values corresponding to midJanuary and midJuly are listed in Fig. 2.8.
CHAPTER 2. THE SUN 26
• a sunny day corresponds to 30% or less of cloud cover, resulting in the full, unobstructed direct and diffuse
components of irradiance. Under these conditions, ED , EF and EG are defined by the values computed
using (2.18) or (2.19).
• cloudy or foggy days where we will assume no direct component of irradiance, only diffuse corresponding
to EG = EF = 0.2ED⊥ , in which ED⊥ is evaluated with (2.6), i.e., the direct irradiance taking AM into
account, but independent of panel tilt. This model is based on the arguments described on page 20 of
[Wenham, et al.(2007)]).
• and partly cloudy days where 40 to 70% of the sunlight is obstructed by clouds and where we assume the
global irradiance is computed as the average of full sun and fully cloudy values.
http://rredc.nrel.gov/solar/old_data/nsrdb/19611990/redbook/atlas/
for a flat plate collector for an average day in January and July, we find for the state of Maryland the figure for
the average daily insolation values
kW hr kW hr
2 in January, 5.5 in July
m2 day m2 day
We can compare these to our computed figures of
2.92(8 + 4) + 1.20(15 + 4) kW hr 9.03(9 + 6) + 2.29(10 + 6) kW hr
= 1.87 2 in January, = 5.55 2 in July
31 m day 31 m day
demonstrating the excellent predictive capabilities of our irradiance model insolation results depicted in Fig. 2.8
when they are combined with measured cloudiness data listed in Table 2.2.
CHAPTER 2. THE SUN 27
Alaska
Average Daily Solar Radiation Per Month
JANUARY
Hawaii
3.69
3.93
4.03
3.75
Hawaii, Puerto Rico, and
Guam are not shaded.
4.28 4.43
Collector Orientation This map shows the general trends in the amount of solar radiation received in the
United States and its territories. It is a spatial interpolation of solar radiation values
derived from the 19611990 National Solar Radiation Data Base (NSRDB). The dots kWh/m2/day
on the map represent the 239 sites of the NSRDB.
10 to 14
Flatplate collector facing south on a Maps of average values are produced by averaging all 30 years of data for each site.
horizontal surface: This map shows Maps of maximum and minimum values are composites of specific months and years 8 to 10
how much solar radiation is received for which each site achieved its maximum or minimum amounts of solar radiation. 7 to 8
by a horizontal surface such as a Though useful for identifying general trends, this map should be used with caution for 6 to 7
solar pond. sitespecific resource evaluations because variations in solar radiation not reflected in
the maps can exist, introducing uncertainty into resource estimates. 5 to 6
Maps are not drawn to scale. 4 to 5
3 to 4
*NREL 2 to 3
0 to 2
none
National Renewable Energy Laboratory
Resource Assessment Program FT00A01313
3. Using the ASTM AM1.5 global spectral irradiance data provided by NREL and splitting the spectrum at
λ = 1127 nm, numerically integrate each portion of the spectrum and report the irradiance for each in
W/m2 .
4. 10 m2 of PV panels operating at 12% efficiency are mounted on a southfacing roof with a pitch of 6 in
12 (i.e., 6 m of vertical rise for 12 m of horizontal distance). Determine the peak potential electrical power
production (in W) for clear and cloudy days during the spring/fall equinoxes and summer/winter solstices
if the house is located in Beijing.
5. Compute the maximum power produced by a 1 m2 solar panel tilted 10o south located at a latitude of 20o
N during the spring equinox and summer solstice on cloudy and clear days. Be sure to show your explicit
calculations for AM and the direct and diffuse irradiances.
6. You have purchased a solar simulator to test solar cells in the lab. The lamp temperature is rated as
CHAPTER 2. THE SUN 28
Alaska
Average Daily Solar Radiation Per Month
JULY
Hawaii
6.00
6.62
6.67
5.20
Hawaii, Puerto Rico, and
Guam are not shaded.
6.09 5.09
Collector Orientation This map shows the general trends in the amount of solar radiation received in the
United States and its territories. It is a spatial interpolation of solar radiation values
derived from the 19611990 National Solar Radiation Data Base (NSRDB). The dots kWh/m2/day
on the map represent the 239 sites of the NSRDB.
10 to 14
Flatplate collector facing south on a Maps of average values are produced by averaging all 30 years of data for each site.
horizontal surface: This map shows Maps of maximum and minimum values are composites of specific months and years 8 to 10
how much solar radiation is received for which each site achieved its maximum or minimum amounts of solar radiation. 7 to 8
by a horizontal surface such as a Though useful for identifying general trends, this map should be used with caution for 6 to 7
solar pond. sitespecific resource evaluations because variations in solar radiation not reflected in
the maps can exist, introducing uncertainty into resource estimates. 5 to 6
Maps are not drawn to scale. 4 to 5
3 to 4
*NREL 2 to 3
0 to 2
none
National Renewable Energy Laboratory
Resource Assessment Program FT00A07319
T = 5000 K. Compute the fraction of the spectral irradiance in the visible portion of the spectrum (400 ≤
λ ≤ 700 nm).
7. For the system described in the previous problem, compute the number of photons within the visible portion
of the spectrum out of a total of 100 photons distributed over the Planck distribution.
8. Describe in two to three sentences why the factor AS /AAU is used in conjunction with the Planck distribution
to approximate EE λ at AM0 conditions.
9. As we will see in Chapter 11, plants absorb light in the wavelength ranges of 550 < λ < 700 nm and
λ < 480 nm. If eight photons are required to produce one molecule of O2 , estimate the molar production
rate of O2 by 1 m2 of leaf surface area under AM1.5 conditions. Report your result in mol/hr.
10. Compute a plot of insolation (in units kW hr m−2 day−1 ) vs. latitude valid on the summer solstice for (a) a
panel mounted flat to the ground, and (b) a panel mounted with tilt optimized for solar noon at the panel’s
particular latitude. Describe the differences you find between the two cases.
References
[NRELdata] NREL spectral irradiance data http://rredc.nrel.gov/solar/spectra/am1.5/
[Rekioua and Matagne(2012)] Rekioua, D. and E. Matagne, Optimization of Photovoltaic Power Systems,
Springer 2012.
CHAPTER 2. THE SUN 29
Recall our previous thermodynamically precise definitions of a system, its surroundings, and the differences between
open and closed systems. At this point we would like to develop the energy balance modeling concepts needed to
understand the interconnection of solar and conventional energy production systems, the consumers of electrical
power, and various means of storing excess energy.
load
(lamp)
power
controller
PV panel storage
(battery)
Figure 3.1: A highlevel view of a representative solar energy balance for an integrated energy production and storage
system.
A simple, but nontrivial, example of these concepts is illustrated in Fig. 3.1 where a stand alone PVpowered
street lamp is shown. What makes this system nontrivial is the dynamic interconnection of the components and
the solar source itself. The basic characteristics of this system are listed in Table 3.1 and will be used in a number
of the following example calculations. For example, given the definition of luminous efficiency ηL in Section 1.2,
we can immediate compute the luminous output of the streetlamp as
lm
683 (30 W)(0.148) = 3030 lm
W
which demonstrates the considerable advantage (approximately 10×) of solidstate over incandescent lighting (see
Fig. 1.3).
30
CHAPTER 3. TRANSIENT ENERGY BALANCES 31
Component Specifications
PV panel polySi cells; η = 0.15 efficiency; A = 1 m2 total panel PV cell area; θtilt = 50o S
Battery voltage: 12 V; capacity: 120 Ah
Lamp assembly LED lamps with ηL = 0.148; total power consumption: 30 W
Table 3.1: Components and their specifications for the commercial PV street lamp.
• A system is at steady state when it no longer changes with time; in many cases it can be determined by
t → ∞ or by setting the timederivative terms d/dt to zero;
• Equilibrium is the condition found as t → ∞; we note that equilibrium can be a steady or nonsteady state.
• Instantaneous conditions correspond to a ”snapshot” in time;
• Transient states depend on time and can have derivatives or integrals with respect to time; these systems
sometimes are divided into forced and autonomous systems;
• Spatially distributed states are a function of position, generally have derivatives or integrals with respect
to position, and can be transient in nature.
δ = 23.44o
ζ = 62.32o = 1.0877 radians
ζtilt = 12.32o = 0.2150 radians
are computed using (2.10), (2.11), and (2.12), respectively. The atmosphere equivalents AM is evaluated using
ζ and (2.4) gives
1
AM = = 2.15
cos(1.0877)
giving a peak global irradiance computed using (2.13) as
h 0.678
i
EG = Esc × 0.73(AM ) (0.11 + cos ζtilt ) = 875 W/m2
CHAPTER 3. TRANSIENT ENERGY BALANCES 32
which, of course, gives the total power of the solar flux incident to the panel surface as PI = 875 W. Therefore,
with an efficiency of 15%, the peak power produced by this panel is PA = −131 W.
System B consists of the combination of the streetlamp (the load) and the battery storage system. If the lamp is
on at solar noon, we can write our instantaneous power balance as
implies that PB,storage = 101 W to the battery storage system if the lamp is operating during the peak power
produced during the day.
11 833.4
400 12 874.6
300 13 833.4
14 710.9
200
15 508.3
100 16 208.5
00 5 10 15 20 17 0.0
time, hrs
Figure 3.2: Global effective irradiance for a PV panel tilted at 50o over the day 21 December 2014 (left); daytime global
irradiance values EG (t) (right).
We use of Earth irradiance model (2.18) on the date td = 0 to compute the hourly global irradiance EG (t) for
the tilted PV panel described above; a plot of the data and the hourly values themselves are shown and tabulated
in Fig. 3.2. Using the trapezoidal quadrature rule described in Section 12.2 the total energy that can be collected
over the day is the daily insolation E , defined by (2.20) and can be simply approximated by the trapezoidal rule:
Accounting for the panel efficiency, the total energy EA generated over the day by the panel
The streetlamp will consume EB =(24 h)(3600 s/h)(30 J/s) = 2.59 MJ of energy/day if continuously lit. There
fore, we can power the lamp continuously with our 1 m2 tilted panel during the winter solstice with a bit of extra
energy left at the end of the day if we store the excess energy produced during the day to power the lamp at
night.
the night. Additionally, we would like plot the battery charge level over the course of a day to determine the
effectiveness with which the battery storage is used.
To begin this analysis we define C as the level of electrical energy charge in the battery system (in J), and a new
system is created to account for the charge stored in the battery. We note that the true capacity of the battery
system Ccap is found from Table 3.1 by integrating 120 A × 12 V over one hour:
The rate of change of charge of charge in this new battery system is determined by the energy balance
dC
= power received from the panel − power to the street lamp
dt
subject to the initial state of the battery charge C (t = 0) = C0 . For this example, we consider the initial state to
be the battery charge at midnight (t = 0) of the day (td ) we are modeling. Under these assumptions,
dC
= 0.15EG (t) − 30 W lamp
dt
Z t
or after integrating C (t) = C0 + 0.15 EG (t 0 )dt 0 − (30 W)t.
0
We know 0 < C0 < Ccap and so we consider the case where C0 = 1 MJ. Using an explicit Euler integration
numerical method (see Section 12.4) we find the results plotted in Fig. 3.3. Note how the battery is charged
when solar energy production rates climb above the power consumption of the bulbs. To implement the Euler
method, we first rewrite the battery charge model as
The minimum battery capacity of 1.94 MJ that we computed is nearly three times the actual capacity of this
system. Of course it is not unreasonable to overspecify the storage system as this will allow for the build up of
sufficient charge to compensate for a string of cloudy days. Other issues to consider before moving on to other
examples of modeling energy system dynamics is how quickly this simple system can turn into a complex dynamic
optimization problem. For example, one can size the components and design the power system controller to adjust
the duration of the periods during which the street lamp is lit with input from the state of the battery charge and
the power generation rate of the panel.
0
20
40
Panel power, W
60
80
100
120
1400 5 10 15 20 Figure 3.3: State of battery
2.5 charge over the course of the
day.
2.0
Battery charge, MJ
1.5
1.0 min battery capacity
0.5
0.00 5 10 15 20
time, hrs
The molar and total internal energies U and U t , respectively, of a system are the energy associated with
the kinetic, vibrational, and chemical bond energy of the molecules making up the system. It is important to
distinguish internal energy from the kinetic and potential energy associated with the entirety of the system itself.
We note that for an ideal gas the internal energy is only a function of the gas temperature.
The general energy balance for a system consisting of some fixed volume Vst with a boundary into which a stream
flows from the surroundings with properties
where Q̇ t and Ẇst denote total heat input and shaft work/unit time.
Returning to our control volume as the system, we see that because this fluid can be thought to enter the control
volume, the W t above is the same as the work done on the control volume system. This means
net work rate done by flows through boundary = [ṁin Pin Vin ] − [ṁout Pout Vout ].
Defining
results in
dmU
= ṁin U + u 2 /2 + zg in − ṁout U + u 2 /2 + zg out + [ṁPV ]in − [ṁPV ]out + Q̇ t + Ẇst
dt
Because specific enthalpy H is defined by
H = U + PV
dmU
= ṁin H + u 2 /2 + zg in − ṁout H + u 2 /2 + zg out + Q̇ t + Ẇst
(3.1)
dt
subject to initial condition U(t = 0) = U o and, potentially, a timedependent total mass m.
Because the water is essentially incompressible Cp ≈ Cv ; we further assume the heat capacity is not a function of
temperature and take Cp = Cv = 4.2 kJ/kg/K. These definitions lead to
dT
mCp = A(928 W/m2 )
dt
A(928 W/m2 )
T = T (0) + t
mCp
CHAPTER 3. TRANSIENT ENERGY BALANCES 36
so given the initial condition T = 20o C, we can compute the reflector projected1 area as
or a circular reflector of radius r = 0.48 m, a reasonable size. Of course, the system should be overdesigned to
account for reflector nonidealities.
Question: What elements are missing from this model? Answer: A partial list includes
1. Heat loss to the environment, including reflection from the water container walls;
2. Energy absorption/imperfect focusing of the reflector;
Adding these model features would improve the model accuracy, but also would make it nonlinear, and so most
likely require an iterative numerical solution procedures (e.g., Newton’s method).
EG
.
m, Hout
.
m, Hin
Figure 3.4: A rooftop solar thermosiphon water heating system (left) and a diagram illustrating its operation (right).
Consider an energy balance on the thermosiphon water heater shown in Fig. 3.4. The system in this case is the
water in the tank and solar collector, and the inflow/outflow pipes are the boundary for mass flow. Assuming the
total mass m in the tank is constant, ṁin = ṁout = ṁ.
The operating principle of the system is simple: because water at 20o C expands as a function of temperature
according to
−4 3 3 1 ∂V
α = 2.07 × 10 m /m /K =
V ∂T P
the heated water rises in the solar collector into the hotwater reservoir (note that α, the thermal expansion
coefficient, becomes negative between 0 and 3o C). To model the water temperature dynamics, we first observe
1 We define the projected area as the area of a shadow cast by the reflector onto a surface normal to the sun’s rays; this area will
.
Qt
.
m, Hin, Tin
T, m
Figure 3.5: The lumped approximation of the thermosiphon hot water
heater system.
.
m, Hout, Tout = T
that no work is done on the tank and so Ẇst = 0; we also can neglect changes in fluid kinetic and potential
energy. These simplifications result in
dU
m = ṁHin − ṁHout + Q̇ t = ṁ[Hin − Hout ] + Q̇ t
dt
The inlet, outlet, and tank temperatures are Tin , Tout , and T , respectively. If we consider T to represent the
mean water temperature, we can approximate Tout = T . This effectively reduces the problem to the lumped
formulation illustrated in Fig. 3.5.
Given all the assumptions of this example, we can now write dU = Cv dT and
Z T
Hout − Hin = Cp dT = Cp (T − Tin )
Tin
dT ṁ Q̇ t
= (Tin − T ) +
dt m mCp
dT Q̇ t
=
dt mCp
mCp
t = (T − T o )
Q̇ t
(200 kg)(4200 J/kg/K)
= (40 K)
3600 W
= 9333 s = 2 hr 35 min
After reaching 50o C, how long does it take to reach 95% of its steady state value with ṁ = 10 kg/min?
CHAPTER 3. TRANSIENT ENERGY BALANCES 38
At steady state
ṁ Q̇ t
0 = (Tin − Tstst ) +
m mCp
Q̇ t
Tstst = Tin +
ṁCp
(3600 W)(60 s/min)
= 10o C +
(10 kg/min)(4200 J/kg/K)
= 15.1o C
e −ṁt/m = 0.05
m
t = − ln(0.05)
ṁ
= 60 min
or 14 min for the system to reach 50% of equilibrium.
Given the volume of the reservoir corresponds to 1011 kg of water, we see that it would be emptied in 16 h, not
unreasonable for this application.
Phase Density g/cm3 Atomic mass g/mol Molar density mol/m3 Melting pt o C
Na 0.927 22.990 40322 98
S 1.82 32.066 56758 115
The batteries generally have a cylindrical geometry; as seen in Fig. 3.7 a key feature is the solid alumina electrolyte
that separates the two molten phases and conducts the Na+ ions. During discharge, the following overall reaction
takes place
1
Na + xS → Na2 S2x Ecell = 2 V
2
and so one electron travels through the external circuit for every Na atom involved in the reaction above. The
question we would like to address in this section is
How much S and Na are needed to match the Ludington pumped storage facility, a facility with an
energy storage capacity of 30 GWh?
CHAPTER 3. TRANSIENT ENERGY BALANCES 40
anode
molten Na
e
solid
alumina Na+ load Figure 3.7: Simplified schematic of a sodiumsulfur battery
during the discharge phase.
electrolyte
S and Na2Sx
I
cathode
Recalling that voltage V corresponds to J/C and with Vcell = 2 V, and the Faraday constant F = 9.64853 × 104
C mol−1 , the number of moles of Na required can be found as
1.08 × 1014 J 1
nNa = = 5.597 × 108 mol Na
2V F
t
Using the densities of Table 3.2 and taking x = 2, we find a minimum total battery volume Vbatt of the Na and
S phases as
t
Vbatt = 33601 m3 or a cube with side length 32.2 m
which while large, is significantly smaller than the pumpedwater facility.
2. Consider the standalone streetlamp system described in the beginning of this chapter. Repeat the calcula
tions, but use a threeday basis in which the first day is perfectly clear while the second is cloudy and the
third is perfectly clear again. What conclusions can we reach regarding the battery storage capabilities of
this system?
CHAPTER 3. TRANSIENT ENERGY BALANCES 41
3. The state of Maryland has set a goal of generating 20% of its electricity using instate renewable resources
by 2022 [MDrenewables]. Write a short summary of the stated objectives taking care to note the solar
component of the renewable energy portfolio. Estimate the magnitude of the solar energy infrastructure
necessary to achieve this goal.
4. The enthalpy of combustion of methane is given as −802.36 kJ/mol CH4 at 25o C and 1 atm. Compute
the rate of methane consumed by a power plant for each 100 W of electrical power produced. Assume the
plant is 35% efficient and a loss of 20% in transmission of electrical power to the end user.
5. A single photon of wavelength λ = 550 nm is absorbed by 1 gm of water. What is the temperature rise
assuming CP = 4.2 J/(g·K) and the all of the photon energy is dissipated as heat within the water?
6. I estimate the lights in my campus office consume a total of 45 W of power. How much energy is saved
when I turn off the lights for 1 hour assuming
(a) it is a hot summer day with an outside temperature of 35 C, an indoor temperature of 25 C
(b) the minimum work required by an air conditioning (AC) system is
TH − TC
AC work = [heat to be removed]
TC
7. The potential for a largescale PV installation in the lower peninsula of Michigan is to be examined. The PV
panels are 17% efficient and will be mounted with a fixed tilt corresponding to their latitude. The Ludington
pumpedstorage facility will be used so that the PV power can be supplied at a roughly continuous rate
over the 24hr day. What is the maximum area (in m2 ) of solar panels that can be used in this situation so
that the limits of the storage facility are not exceeded?
References
[Geankopolis (1978)] Geankopolis, C. J. Transport Processes and Unit Operations, Allyn and Bacon, Inc., 1978.
[MDrenewables] http://www.statestat.maryland.gov/GDUenergy.asp
[Smith, Van Ness, Abbott (2005)] Smith, J. M., H. C. Van Ness, and M. M. Abbott Introduction to Chemical
Engineering Thermodynamics, 7th Ed., McGrawHill’s Chemical Engineering Series, 2005.
[Wenham, et al. (2007)] Wenham, S. R., M. A. Green, M. E. Watt, and R. Corkish, Applied Photovoltaics, 2nd
Ed., Earthscan, UK, 2007.
Chapter 4
Figure 4.1: A portion of the periodic table of elements with semiconductors shown shaded in gray; metals are to the left
of the semiconductor range and nonmetals to the right.
What is interesting is that virtually all these materials are clustered in the region of the periodic table containing
semiconductors, with nearby metals and electrically insulating materials rounding out the list. Therefore, to
understand what takes place electronically within a solar cell, we begin with a closer look at band structure of
solid materials.
Recall that electrons can only inhabit discrete energy levels; these may be filled, partially full, or empty (Fig. 4.2).
As we bring atoms together, the valence electrons interact to form bonds and the energies associated with these
bonding orbitals take on a discrete structure as a result of the Pauli exclusion principle, which dictates no two
electrons can have identical sets of quantum numbers1 As atoms bond to form a crystal, the number of molecular
orbitals that can be created grows, forming a band structure when a large number of atoms (e.g., 1023 ) make up
the crystal.
1 For electrons we have n the electron shell (energy level), l the subshell (the s, p, d, etc. orbital), m the orbital (e.g., which of
l
the 3 p orbitals), and ms the spin (always one of two states).
42
CHAPTER 4. THE PHYSICS OF PV DEVICES 43
These bands are characterized by band edges and whether they are filled or empty. The regions between are
the forbidden gaps. In cases where the topmost band containing electrons is completely filled, the material is
nonconductive unless an electron is promoted to a higherenergy conduction band, leaving a hole in the valence
band. Electric current can flow as a result of either, or both, charge carriers. Charge cannot be transferred within
a filled band  there simply are no unoccupied energy levels within the band for charges to go to. However, when
bands are only partially filled, as in the case of metals, even a small applied electric field is sufficient to raise an
electron to a nearby unoccupied state, resulting in an electrical current.
We note that in metals, semiconductors, and insulators, the distinction between the last two is somewhat artificial
 the commonly accepted limit for semiconductor band gap is 4 eV.
Finally, we note that compound semiconductors can be formed by combination of elements, such as the IIIV
compounds AlN, GaN, and InP.
electron energy
band edges
Figure 4.2: Energy levels of an individual atom (left), finite number of discrete states for a small number n of atoms
(center left) band structure of a conductor (center right) and of an insulator (right).
∆G = ∆H − T ∆S
∂(nG )
µ=
∂n P,T
and so because spontaneous processes require a reduction in ∆G , variations in Fermi level can drive electrons
from energetically favorable states to those that are less so.
CHAPTER 4. THE PHYSICS OF PV DEVICES 44
1.0
300 K
500 K
0.8
For silicon, the band gap is 1.1 eV; we can plot the function to observe how electrons are promoted to the
conduction band at higher temperatures in a semiconductor (Fig. 4.1.1).
For a semiconductor with Ef , Ec , and Ev marking the Fermi level, conducting band bottom, and valence band
top edges, respectively, and with me∗ and mh∗ as the effective electron and hole masses, we can compute the
number density of the electrons ne with energies above Ec and holes nh with energies below Ev in an intrinsic
semiconductor by
3/2
2πme∗ kB T
Ef − Ec
ne = 2 exp
h2 kB T
3/2
2πmh∗ kB T
Ev − Ef
nh = 2 exp .
h2 kB T
Setting ne = nh in an uncharged semiconductor, we can then compute
Ec + Ev 3kB T Ec + Ev
Ef = + ln (mh∗ /me∗ ) ≈ = Ei
2 4 2
The intrinsic carrier concentration ni then is defined by the geometrical mean ni2 = ne nh . For silicon, ni =
1.45 × 1010 charges/cm3 at 300 K [Middleman and Hochberg (1993)]. We observe that the intrinsic carrier
concentration increases with temperature, resulting in electrical conductivity for semiconductors that increases
with temperature:
3/2 VG
ni = no T exp −
2VT
where VG is the band gap and VT = kB T /q the thermal voltage.
Before we move on from this discussion, we list the following Fermilevel facts:
• The Fermi level corresponds to the thermodynamic work necessary to add an electron to a system; it thus
defines the electron chemical potential;
• As seen in the calculation above, the Fermi level for intrinsic semiconductors is approximately midway
through the forbidden gap;
• The previous fact does not imply there are electrons within the gap because there are no available states
within the forbidden gap of a defectfree intrinsic semiconductor;
• The “spreading” of the Fermi distribution explains why the conductivity of a semiconductor increases with
temperature;
• The Fermi level for a metal is found where the conduction and valence bands overlap.
Si Si Si Si Si
Si Si Si Si Si
CHAPTER 4. THE PHYSICS OF PV DEVICES 45
4.1.2 Doping
Si Si Si Si Si Si Si Si Si Si
The band structure of intrinsic semiconductors can be modified by doping, a means of introducing new energy
Si Si Si Si Si Si Si P Si Si
levels into the forbidden gap. In the discussion that follows, we will focus on substitutional doping, as opposed to
Si toSicases
interstitial doping and will also limit our analysis Siwhere
Si the
Sidopant concentration
Si Si Si level Si is Si
relatively small
(typically true) so that the dopant atoms do not interact.
Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si
Si Si Si Si Si Si Si P Si Si Si Si B Si Si
Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si
Figure 4.4: Lewis structure of crystalline Si (left); ntype Si resulting from phosphorous doping (center), and ptype from
Si Si
boron doping (right). Si Si Si Si Si Si Si Si
The location Si SinewPstates
of the Si relative
Si to theSi band
Si edges
B of Si theSiforbidden gap depends on the nature of the
dopant atoms. Consider, for example, the Si crystal shown in Fig. 4.4. Si is a column IV element meaning it
Si electrons.
has four valence Si Si PSi Si
(phosphorous) Si Si SiV element;
is a column Si Si four of its valence electrons can bond with
the Si neighbors, leaving an unbound electron (while still remaining neutral). This single electron inhabits an
energy level close to the bottom edge of the conduction band (see Fig. 4.5 and the ionization value tabulated
in Fig. 4.1.2), requiring little extra energy to excite the extra electron of the new state to the conduction band.
Si Si Si Si Si
Therefore, addition of dopant atoms results in an increase in electrical conductivity of the material, in this case an
ntype semiconductor
Si Si where B Si electrons
Si are the majority carriers. In this context, the P atoms act an an electron
donor; after ionization, the positively charged P remains fixed within the Si crystal while the e− charge is free
Si way,
to move. In this Si weSican Si Si why electrons are the majority carrier and are found in the conduction
understand
band of ntype semiconductors.
The number density of P atoms within the Si is given by ND atoms/cm3 or sites/cm3 . The number density of
atoms in a pure Si crystal is approximately 5 × 1022 atoms/cm3 . We compare this density to typical dopant
densities of 1010 to 1020 atoms/cm3 [Middleman and Hochberg (1993)].
CB CB CB
band gap
electron energy
hole energy
Ef Efn Efp
VB VB VB
Figure 4.5: Energy levels and band structures for an intrinsic semiconductor (left), ntype (center) and ptype (right).
We are familiar with electrons, but may be uncomfortable with the concept of holes. Roughly
1. Holes mark the position in an atom lattice normally occupied by an electron and so has positive charge e;
CHAPTER 4. THE PHYSICS OF PV DEVICES 46
2. Holes can move in response to an electric field, resulting in conduction through the em valence band of a
material;
3. Holes can be assigned an effective mass mh∗ , useful for quantifying the mobility of these charge carriers.
With these concepts in mind, consider doping the Si with B (boron), a column III element. In this case, three
valence electrons are available to bond. This gives rise to a broken bond in the crystal, creating a new energy level
slightly above the valence band. Analogous to the previous doping case, a small amount of energy is necessary
to excite an electron from the valence band to this new energy level. Another way to look at this is a small
increase in hole energy (as seen in Fig. 4.5, oriented in the direction opposite of electron energy) is required to
promote it to the valence band. This is a ptype semiconductor, in which holes are the majority carrier found
within the valence band (c.f. electrons in the CB for ntype materials). We note that boron is widely used as
a ptype dopant in electronic devices instead of silicon’s neighbor aluminum because of the lower diffusivity and
higher solubility of B in Si relative to Al [Middleman and Hochberg (1993)]. As with ntype dopant, the number
density of acceptor sites in the Si is given as NA sites/cm3 .
The important notion here is that for the n and ptype semiconductors described, the Fermi level of the doped
material is shifted from the approximate center of the forbidden gap towards the conduction band of the majority
carrier (see Fig. 4.5). For an extrinsic ntype semiconductor
ND
Ef = Ei + kB T ln
ni
a relationship valid for with 1011 < ND < 1018 cm−3 for Si. Of course a similar relationship can be derived for
ptype materials [Leck (1967)].
where n are the charge carrier number densities (commonly in cm−3 for semiconductors), q is unit charge in C,
and µ is charge carrier mobility. For Si
nneg = npos
ne + NA = nh + ND .
ne = nh + ND ≈ ND
ni2
ne nh = ni2 and so nh =
ND
For a ptype semiconductor, ND = 0, therefore
nh = ne + NA ≈ NA
ni2
ne nh = ni2 and so ne = .
NA
Therefore, given the charge carrier number densities ne and nh and the charge carrier mobilities, µe and µh listed
above, the specific conductivity σ can be computed using (4.1).
4.2 Junctions
Recall p and ntype semiconductors, their band edges and Fermi levels; these are depicted in Fig. 4.7. A crucial
point is that both pieces of semiconductor are electrically neutral when they are separate. As a “thought”
experiment, we bring them in contact to form a double layer inside the depletion region.
When the doped semiconductors are separate, the ntype and ptype have different Fermi levels. When joined,
the materials must come to equilibrium, forcing the Fermi levels to become equal.
ptype ntype E
holes electrons
depletion
region
CB
CB CB
qVbi
electron energy
 CB
hole energy
Ef +
 +
VB +
VB VB
VB
Figure 4.7: p and ntype semiconductors before (left) and after (right) they are brought into contact.
The electric field is electric force per unit charge E = F /q. The direction of the field is taken as the direction
of force acting on a positive charge. Electric field has units N/C or V/m.
CHAPTER 4. THE PHYSICS OF PV DEVICES 48
The effect of this is band bending, resulting in the builtin potential Vb . Recall 1 V=1 J/C, so energy is (unit
charge)×(Voltage). When the ptype and ntype semiconductors are brought into contact, the conduction and
valence bands (which were identical because both correspond to Si) of the ptype material effectively shifts upward
in electron energy qVb relative to the ntype. This seems counterintuitive, in that the electrons, when migrating
across from the ntype to ptype material during the formation of the spacecharge region, are moving uphill in
terms of energy. While energetically unfavorable, this process is entropically favorable. The process is analogous
to the normal diffusion of gases when a partition separating two gas species is removed.
The work function Φ is defined by the energy required to remove an electron from the Fermi level of a material
to vacuum. After the n and ptype semiconductors with work functions Φn and Φp are brought into contact and
their Fermi levels equilibrate, the builtin voltage of the junction is simply
qVbi = Φp − Φn .
The builtin voltage can be explicitly computed as [Middleman and Hochberg (1993)]
kB T NA ND
Vbi = ln + ln
q ni ni
where V is the applied voltage (bias) and is the electric permittivity of the semiconductor.
When the junction is at equilibrium, no net current flows. However, there is quite a bit still going on. Thermally
generated or drift currents Ihdrift and Iedrift result from excitation the minority carriers: electrons are thermally
excited into the conduction band on the pside of the junction and holes are promoted into the valence band on
the nside. These minority carriers diffuse through their respective quasineutral regions of the junction, and if
they reach the junction before they recombine, are swept through the junction by the electric field, generating
currents Iedrift and Ihdrift , respectively.
The recombination or diffusion currents Iediff and Ihdiff , are due to the majority carriers (holes on the pside,
electrons on the nside). This process, as described earlier, is due to the relatively large concentration of these
carriers on their respective sides of the junction, and can cross the barrier due to entropic effects.
Overall, this leaves us with the saturation current across the junction:
because Ihdiff + Iediff is positive and
diff
Ih + Iediff = − Ihdrift + Iedrift
at zero bias.
We note that in this notation positive conventional current flows from left to right, and positive electron current
flows right to left.
In summary,
• Iedrift : created on the pside by thermal excitation, and forced to the nside by the electric field;
• Iediff : majority carriers of the nside, driven by a concentration gradient across the barrier  similar to what
happens when the materials are first brought into contact;
• The degree to which the CB and VB are shifted, qVb , is typically less than the band gap of the undoped
semiconductor.
CHAPTER 4. THE PHYSICS OF PV DEVICES 49
E E E
  ++  + +
p   ++ ++ n p  +
+ n p + n
++ +
e  + +  e
Iediff
Iediff
Ie drift Iedrift Iedrift
electron energy
hole energy
Ihdrift
Ihdrift Ihdrift
Ih diff Ihdiff
Figure 4.8: Generation and recombination currents in an unbiased, forwardbiased, and reversebiased pn junction.
Parameters for the diode equation are Io = 1 mA, β = 2, and T = 300 K.
Forward bias
A forward bias (attaching a positive electrode to the pside of the junction) of magnitude V reduces the barrier
height by qV
In this case, the total current has a large positive value (see Fig. 4.8)
I ≈ Ihdiff + Iediff .
CHAPTER 4. THE PHYSICS OF PV DEVICES 50
Reverse bias
A reverse bias (attaching a positive electrode to the nside of the junction) of magnitude V  increases the barrier
height by −qV
In this case, the total dark current is consists mainly of the thermally generated current and so
where Io is the limiting value of current described earlier for high negative bias values, kB is the Boltzmann
constant, and β is the nonideality factor, described in the next section. The electric circuit symbol for a diode is
shown in Fig. 4.9; the diode equation is given by (4.2).
E
 +
p  +
+ n Figure 4.9: The pn junction and corresponding symbol for a
+ diode. We recall that electron current flows out of the anode
+ 
E c ch
ν= , λ= = = 1127 nm
h ν E
The value above is consistent with Fig. 2.8 of [Wenham, et al. (2007)].
The key idea is simple: photogenerated (minority) carriers in both the the n and ptype sections behave much
like the thermally generated Ihdrift , Iedrift versions of these carriers.
E E
 +
+  ++ n
p  +n p
+ 
Iediff
hole energy
hv Ieph Ieph
hv
Ihdiff
Ihph Ihdrift
Ihdiff
Figure 4.10: PV cell currents under short circuit (left) and open circuit conditions (center). These points are marked by
the circle and square markers, respectively, in the plot of the PV diode equation (right). For this example, Iph = −10Io
taken from Fig. 4.8, as are the other model parameters.
As seen in Fig. 4.10, the total photocurrent the sum of the electron and conventional photocurrents is
Based on the sign convention described earlier, for the short circuit case, the conventional current is negative
because it flows to the right of the cell. This means under illumination, electrons flow out from the ntype end of
the junction, travel around the external circuit, and recombine with holes on the pside of the cell.
CHAPTER 4. THE PHYSICS OF PV DEVICES 52
The photo and dark currents add linearly in our idealized analysis, and so the voltagecurrent equation for the
solar cell now is a simple modification of the diode equation
qV
I = −Iph + Io exp −1 . (4.3)
βkB T
3. Create a plot of the depletion zone width (in nm) as a function of NA and ND in cm−3 . Assume the external
bias is V = 0.
4. Compute the minority and majority charge carrier concentrations for n and ptype doped Si for a) NA = 1015 ,
ND = 0 cm−3 ; b) NA = 0, ND = 1015 cm−3 ; c) NA = 1015 , ND = 1016 cm−3 .
5. Compute the builtin voltage Vbi and depletion zone width WD of a junction formed from materials in part
(a) and (b) of the previous problem.
6. Estimate the fraction of ionized P and B atoms in lightly doped Si over the temperature range 250 ≤ T ≤
350 K.
References
[Gray (2003)] Gray, J. I., Chapter 3: The physics of the solar cell. In Handbook of Photovoltaic Science and
Engineering, A. Luque and S. Hegedus (Ed.), John Wiley & Sons, Ltd, 2003.
[Leck (1967)] Leck, J. H., Theory of Semiconductor Junction Devices, Pergamon Press, 1967.
[Middleman and Hochberg (1993)] Middleman, S. and A. K. Hochberg, Process Engineering Analysis in
Semiconductor Device Fabrication, McGrawHill, Inc., 1993.
[Wenham, et al. (2007)] Wenham, S. R., M. A. Green, M. E. Watt, and R. Corkish, Applied Photovoltaics, 2nd
Ed., Earthscan, UK, 2007.
Chapter 5
PV cell design is generally split between thinfilm (aSi, CIGS, CdTe) and Sisubstrate cells. Let us consider the
entire manufacturing process for creating multicrystalline silicon (mcSi) solar cells, starting with the production
of the Si substrates that form the base of the PV cell; additional details can be found in the overviews by
[Ceccaroli and Lohne (2003)] and [Ranjan et al. (2011)].
The first step of the process is SiO2 reduction in which lumpy quartz (see Fig. 5.1) is converted to metallurgical
grade Si. The primary reaction
SiO2 (s) + 2C(s) → Si(l) + 2CO(g)
takes place in a carbon electrode arc furnace at approximately 2200 K (compare this to 2000 K, the melting point
of quartz). Additional reactions compete with the Si production in the furnace, such as those producing SiC.
Figure 5.1: An atypical sample of lumpy quartz found outside the Geological
Museum of China, Beijing.
53
CHAPTER 5. PV CELL ARCHITECTURE AND MANUFACTURING METHODS 54
Iron, boron, and aluminum remain as some of the impurities in the metallurgicalgrade Si. Silicon hydrochlorination
is the first step to removing these impurities. The reactions take place in a fluidizedbed reactor at approximately
300o C, with the primary reaction
Si + 3HCl → H2 + SiHCl3 .
Additional chlorosilanes (e.g. SiCl4 , SiH2 Cl2 ) are produced, as well as other chlorinated impurities.
Step 3: Distillation
compound SiH4 SiH3 Cl SiH2 Cl2 SiHCl3 SiCl4 FeCl3 AlCl3 BCl3
boiling pt (o C) 112.3 30.4 8.3 31.5 57.6 316  12.7
melting pt (o C)       190 
Our desired product is SiHCl3 , silicon chloride hydride. Given the wide separation of boiling points, it is a relatively
simple matter to design two sequential distillation columns capable of producing the desired product stream.
Step 4: Chemical vapor deposition
Purified chlorosilane → Si
As the final purification step, electronic grade silicon (EGS) is produced in the Siemens CVD process and the
equilibrium reaction
SiHCl3 (g) + H2 (g) ↔ Si(s) + 3HCl(g)
Note this is CVD because of the gasphase precursors and the solid film that is deposited; this reaction is the
reverse of the (exothermic) hydrochlorination reaction, and so high temperatures (1400 K) are needed to shift
the reaction above to the right.
[HCl]3 −∆G o
= exp = K (T )
[SiHCl3 ][H2 ] RT
200300 hours of deposition are required to produce EG polycrystalline silicon.
Step 5C: Single crystal growth
The polycrystalline Si is remelted (melting point: 1687 K) and then grown into a single crystal (and further
purified) via
1. The Czochralski method, in which an ingot (1 m long and 15 cm in diameter) is pulled from molten Si
forming a single cylindrical crystal; impurities tend to stay in the melt;
2. The floatzone process, where the cylindrical ingot is heated by a moving heater zone, allowing the Si to
melt and recrystallize; the segregation coefficients of impurities are < 1, meaning they prefer to remain in
the melted region, and so are swept from the crystal with each zone pass.
CHAPTER 5. PV CELL ARCHITECTURE AND MANUFACTURING METHODS 55
In each process, a small quantity of boron is added to melt to create the ptype substrates.
Step 5M: Multicrystalline Si ingots
Multicrystalline Si ingots then are created from a combination of polycrystalline Si and waste EGS from the
semiconductor industry. Molten Si is pored into crucibles and solidification takes place from the bottom up.
Small, mostly vertical crystals (grains) are formed during the solidification process; this directionality is important
to the operation of the final solar cell. For ptype Si, a small amount of boron is added to the molten Si prior to
pouring the mixture into the crucible.
For silicon ingot formation a technique called “monocasting” appear to be a promising development. In this
case, a monocrystalline ingot is cast (not pulled, such as in the Czochralski process). This is a much faster and
therefore less expensive process. Typically portions of the ingot are still multicrystalline, but large sections are
monocrystalline. Better casting process control will improve monocrystalline yield and subsequently will have a
significant influence on the industry.
Step 6: Wafering
(Multi)crystalline Si → Wafers
In the final wafering process, a wire saw is used to slice the Si ingots into ≈ 180 µm thick wafers. Many parallel
cutting wires and an SiC cutting solution is used in the process, where the cuts are made perpendicular to the
long crystal grains, resulting in the rectangular wafers distinctive to mcSi cells. Kerf losses and surface roughness
are important considerations in the wafering operation [Koch et al. (2003)].
top contacts
antireflective coating
ntype silicon
ptype Si
back contact
Figure 5.2: Completed Si solar cell. We note that the ntype layer normally forms the top (sunfacing) surface of a solar
cell because it has a higher surface quality relative to ptype Si. The top layer is called the emitter (thickness ≈ 1 µm),
the bottom (substrate) is called the base, with current thickness of 100 µm.
At this point we have the Si substrates that will be transformed into the finished Si cells (Fig. 5.2); we recall the
basic diode equation model to make a conceptual connection between the photocurrent source term −Iph and the
junction of the model to the physical features of the complete PV cell:
qV
I = −Iph + Io exp −1 . (5.1)
βkB T
Given the model and final cell structure, we now examine the individual PV manufacturing steps and make note
where additional nonidealities might be introduced.
ptype Si
Step 7: Surface finishing/texturing Chemical etches are used to smooth wire saw marks. Likewise KOH or
NaOH solutions can be used to texture the surface to decrease light reflection; the micronsized pyramid shaped
surface results in a higher probability that a reflected photon encounters another portion of the cell surface.
Step 8: Phosphorous diffusion To create the ntype layer, a phosphorous precursor (for example, gasphase
P2 H2 , liquid POCl3 , or solidsource precursor P2 O3 ) is used with a furnace operating at 900 o C to diffuse the P
into the Si; this diffusion can be modeled simply by
∂[P] ∂ 2 [P]
=D
∂t ∂z 2
subject to a constant concentration boundary condition at the wafer surfaces; note that all sides of the wafer
become doped.
Step 9: Edge isolation The wafer edge doping is removed to prevent short circuits through the PV device,
resulting in low shunt resistance.
Step 10: AR deposition Reflectance loss for bare Si in air can be as high as 30%. Antireflection coatings can
reduce losses below 10%; for mSi with texturing, the combination reduces reflection to < 1%. AR coatings
typically consisting of CVD titanium dioxide or PECVD silicon nitride. The thickness of these coatings is set to
the wavelengthdependent optimal value Material refractive index is important and AR coating compositions are
chosen to give a refractive index between the values of glass and silicon.
It will be shown in a later chapter of these notes that reflectance loss for bare Si in air can be as high as
30%. Antireflection (AR) coatings reduce losses below 10%, and potentially to < 1% when combined with the
texturing described earlier [?]. AR coatings typically consist of CVD titanium dioxide or PECVD silicon nitride.
The thickness of the coatings is set to the wavelengthdependent optimal value such as
λ
d= .
4
CHAPTER 5. PV CELL ARCHITECTURE AND MANUFACTURING METHODS 57
Material refractive index is important and AR coating compositions are chosen to give a refractive index between
the values of glass (or air) and silicon.
Step 11: Front contact printing A silver paste mixture in an organic binder is used in a screenprinting process
to produce the front contacts. Line widths are ≈top
50 contacts
µm and the design [?] of the contact pattern is nontrivial.
Front contact shading can account for up to 10% loss of cell surface area.
antireflective
Step 12: Back contact The back contact is deposited as a metal paste containing silvercoating
and aluminum, the
latter to produce an ohmic contact with the ptype Si layer. ntype silicon
ptype Si
Step 13: Firing With the front/back contacts applied, the final assembly is fired to remove the contact organic
binders and to drive the Al contacts through the ntype back layer into the player and the front contacts through
back contact
the AR film. This thermal process also can profoundly affect other characteristics of the cell performance.
Step 14: Wiring and sealing the panel A set of cells connected by series wiring is shown in Fig. 5.4; module
packaging is describe in Ch. 5 of [?]; additional details on cell wiring will be covered in later in these notes.
• Previously, Si single crystals or multicrystalline material was used both for the PV cell structural support
(substrate) and to form the junction. Typical cells were ≈ 300 µm thick;
• Now we consider thin films O(1 µm) thick deposited onto an essentially inert substrate for support  obvious
advantage: less active material required.
3. Polycrystalline, structures of O(1 µ m); nanocrystalline materials also can be grown with processes otherwise
used to deposit amorphous films;
4. Amorphous, faster growth rates from gasphase precursors, lower temperature processes, can mostly preserve
stoichiometry.
Overall, the first two morphologies are relevant to cSi and mSi cells discussed in the previous chapter; the poly
and nanocrystalline and amorphous materials are more relevant to thinfilm cells.
reactor roof
reactor outlet
precursor gas phase reactions
reactor inlet
diffusion diffusion
substrate (wafer)
thermal
energy
cmcm
Figure 5.5: Twin CVD reactor system (left) and a schematic diagram of one reactor with major chemical species
transport and reaction phenomena noted (right).
5.4 Amorphous Si
Consider the differences between the regular structure of cSi and aSi illustrated below. The H passivation and
amorphous structure are crucial to understanding the behavior of PV cells manufactured using these films:
• The chemical structure has much in common with crystalline Si, e.g., generally 4 bonds per Si atom;
• H atoms remove (passivate) dangling bonds which would otherwise encourage recombination;
CHAPTER 5. PV CELL ARCHITECTURE AND MANUFACTURING METHODS 59
Figure 5.6: Fivewafer planetary reactor system (left) and stalled wafer thickness profile illustrating the strong
depletion effect in these reactors (right).
Figure 5.7: Applied Materials aSi PECVD production line (left) and an enlarged view of one reactor (right).
• Band gap depends on H fraction: Ebg = 1.6  1.8 eV for 5  20 at. % H [Archer and Hill (2001)];
• aSiGe:H up to 60 at% Ge resulting in Ebg = 1.3 eV;
• Disorder may be one factor in much greater absorptivity.
1. Superstrate designs where the sunlight passes through the glass substrate first; this is a good design for
buildingintegrated PV applications where the glass is exposed to the outdoors environment;
2. Substrate designs where the glass substrate or other substrate is at the bottom of the cell; this is a good
design when opaque substrates are to be used (e.g., stainless steel in rolltoroll processes).
Both cases are characterized by a pin junction (pintrinsicn), seen in Fig. 5.9. The large undoped (intrinsic)
i aSi:H layer is where most photons are absorbed; the electrons and holes then migrate to the n and players,
respectively. This device architecture is used because the heavily doped n and ptype layers result in high
recombination rates, and so they are made as thin as possible to minimize charge carrier residence times in these
regions.
CHAPTER 5. PV CELL ARCHITECTURE AND MANUFACTURING METHODS 60
 e +
TCO, SnO2
+
glass  +
+ p aSi:H
TCO, SnO2  hv
+
p aSi:H
i aSi:H
i aSi:H
n aSi:H  +
contact

n aSi:H  +
 glass
h+
contact  +
Superstrate design Substrate design p aSi:H i aSi:H n aSi:H
Figure 5.9: Amorphous Si PV cell designs (left and center); band structure for single junction aSi:H cell (right).
In [Adomaitis (2010)], an approach to empirical model development for a plasmaenhanced chemical vapor depo
sition (PECVD) reactor used to deposit amorphous hydrogenated silicon (aSi:H) films of transparent conducting
oxidecoated glass substrates in an industrial manufacturing system is described. Experiment design, response
surface modeling, analysis of variance, model use for process optimization, and inversion of the models to compute
process operating conditions corresponding to a specified set of film qualities are all described in that work. In the
industrial PECVD system considered, three process operating parameters were identified as potentially important
CHAPTER 5. PV CELL ARCHITECTURE AND MANUFACTURING METHODS 61
to influencing film quality: the H2 /SiH4 dilution ratio (D), reactor total pressure (P), and RF discharge power
(W ).
RT ET
1 1
W
PECVD ilayer deposition rate
(left) and final aSi:H PV cell ef
0 0
1 1 ficiency (right). Higher values are
0.5 0.5 indicated in red.
0 −1 0 −1
−0.5 −0.5
0 0
−0.5 0.5 −0.5 0.5
D P D P
RB EB
As seen in Fig. 5.10, the disposition rate (left plot) and final solar cell efficiency (right) are found to be strongly
1 1
influenced by the three operating parameters; in these plots, red corresponds to higher values of the growth rate
and cell efficiency, while blue denotes lower values. Of course, our objective it to maximize both. In these plots
we 0.5
spot a number of important trends.0.5In terms of deposition rate, we see that the film grows more quickly
W
with decreasing dilution ratio D and with increasing pressure P; while more difficult to see, film growth rate also
0 0
increases,
1 but at a lesser rate, with RF power 1 W . These observations all make physical sense in terms of the
chemical
0.5 vapor deposition process. Regarding 0.5 cell efficiency, that characteristic also increases with decreasing
0 −1 0 −1
dilution rate D; pressure0 P has−0.5 no effect and cell efficiency increases
0
−0.5 with decreasing RF power, the opposite of
−0.5 0.5 −0.5 0.5
growth rate.
D ThereforeP the optimal operating conditions
D areP low dilution ratio, high pressure, and a power level
that balances the overall manufacturing process economics with final product value.
5.5 CIGS
CuInSe2 is inherently a ptype semiconductor; partial substitution of Ga for In increases the CuInx Ga1−x Se2 band
gap from 1.02 eV to 1.1 to 1.2 eV, allowing the CIGS films to be made into efficient PV devices as seen in
Fig. 5.11. The band structure has a unique conductionband offset that varies with processing conditions and
with the composition of the this buffer layer; regardless, this ntype film generally is depleted of its majority charge
carriers and so is vital to forming the pn junction of the cell. Currently (as of December 2013) Samsung holds
the largesubstrate commercial CIGS panel efficiency record of 15.7%. Cells fabricated on smaller substrates and
researchonly (c.f., commercial panels) CIGS cells have reached a record efficiency of 20.8% [Wesoff(2013)].
Substrate: The PV devices can be constructed on a wide range of flexible and rigid substrates. In
many cases, a sodalime glass substrate is used because of its low cost and similar thermal expansion
coefficient as the CIGS film; borosilicate glass has lower coefficient of expansion and so leads to
cracks when cooling. The Na, K, and Ca oxide impurities in the substrate contribute positively to
the performance of the PV cell [Shafarman and Stolt(2003)]. However, all subsequent processing is
limited by the Tsoftening ≈ 550o C for sodalime glass.
Back contact: The Mo back contact is created by DC sputtering. This step is relatively straightfor
ward, though adhesion of the contact layer to the substrate can be an issue.
Absorber: Coevaporation is a widely used method in manufacturing the CuInx Ga1−x Se2 absorber
layer. In this process, the elements, or elementcontaining precursors, are evaporated in a parallel
CHAPTER 5. PV CELL ARCHITECTURE AND MANUFACTURING METHODS 62
e
ZnO:Al

nCdS  +
hv
pCu(In,Ga)Se2  +
 +
Mo contact
+ h+
+
n ZnO:Al
soda glass 
 +
Substrate design n CdS
p Cu(In,Ga)Sn2
Figure 5.11: Representative CIGS cell design (left), corresponding electrostatic band structure (center), and a
monolithically interconnected CIGS cell module (right)
fashion and are ballistically transported to the substrates for deposition. [Zachmann et al.(2009)]
used coevaporation of Cu, In, and Ga as a part of the process to create a flexible CIGS film sup
ported on polyimide. [Xu et al.(2012)] used coevaporation from a single source with powders of the
elemental components in nominal composition (Cu25, In12.5, Ga12.5, and Se50). The powders
were evaporated using an electron beam and the composition of the film was controlled by varying
the beam current. [Jung et al.(2010)] deposited CIGS thin films on Mo/sodalime glass in a three
stage method to study the effects of Ga composition on the films properties.
Alternatively, a twostep process can be used where the Cu, In, and Ga are first deposited, potentially
as thin separate layers, followed by a hightemperature annealing step in a Se atmosphere.
Buffer layer: A chemical bath deposition process is used to produce the undoped ntype CdS and
makes use of an alkaline aqueous solution containing the Cd and S precursors as well as a complexing
agent. Deposition times typically are several minutes. Pseudoepitaxial growth at the interface suggests
that the Cu(InGa)Se2 surface promotes the initial reaction and results from the small lattice mismatch
between the two layers.
Top contact: A transparent conducting oxide (TCO) such as Aldoped ZnO is deposited by an ALD
or atmospheric CVD process using water and diethylzinc as precursors for both processes.
5.6 CdTe
e
glass  +

TCO, SnO2
hv
+
nCdS
 +
pCdTe  +
 + SnO2  ITO
back contact
+ h+
 +
Superstrate
(preferred) design p CdTe n CdS
Figure 5.12: Representative CdTe cell design (left) and corresponding band structure (right).
We see that in this design, light enters the cell from the top, through the glass and TCO layer. This configuration
is consistent with the general design rule concerning the arrangement of the device semiconductor layers according
to decreasing bandgap in the direction light takes through the device: in this case, the topmost layer is SnO2 with
Ebg = 2.5 to 3 eV, CdS with Ebg = 2.42 eV, and CdTe with Ebg = 1.44 eV.
5.7 Summary
Thinfilm PV cells are developing rapidly and have great potential; taken from [Archer and Hill (2001)], the
following efficiencies have been reported for commercial modules:
3. Write a sentence or two describing the role these junctions play in thinfilm and crystalline Si solar cells:
(1) ohmic junction; (2) Schottky junction; (3) homojunction; (4) heterojunction; (5) tunnel junction; (6)
rectifying junction; (7) nonrectifying junction.
4. The absorption coefficient of crystalline Si is α = 105 m−1 for light with wavelength λ = 800 nm. What
fraction of light at this wavelength is absorbed within the first 1 µm of the top surface of an Si solar cell if
absorbance is modeled by αe −αz where z = 0 represents the top surface of the PV cell.
5. Given the P diffusion coefficient 6.5 × 10−13 cm2 /s, a surface equilibrium P concentration [P]o = 1020
cm−3 and a boron doped Si substrate with NA = 1015 cm−3 , compute the diffusion time (in s) required to
create a junction with depth 1 µm. Plot the resulting [P] profile.
6. List typical thicknesses for the base layers making up an aSi, CdTe, and CIGS PV cell. Be sure to cite
sources.
References
[Adomaitis (2010)] Adomaitis, R. A., Notes on response surface modeling for a thinfilm solar cell
manufacturing application. Unpublished technical document.
[Archer and Hill (2001)] Archer, M. D. and R. Hill, Ed. Clean Energy from Photovoltatics 2001, Imperial
College Press, pp. 202203.
[Ceccaroli and Lohne (2003)] Ceccaroli, B. and O. Lohne, Chapter 5: Solar grade silicon feedstock. In Handbook
of Photovoltaic Science and Engineering, A. Luque and S. Hegedus (Ed.), John Wiley & Sons, Ltd (2003).
[Holmqvist(2013)] Holmqvist, A., Modelbased Analysis and design of Atomic Layer Deposition Processes, PhD
Thesis, Lund University (2013).
CHAPTER 5. PV CELL ARCHITECTURE AND MANUFACTURING METHODS 65
[Jung et al.(2010)] Jung, S., S. J. Ahn, J. H. Yun, J. Gwak, D. Kim, and K. Yoon, Effects of Ga contents on
properties of CIGS thin films and solar cells fabricated by coevaporation technique, Current Applied
Physics, 10 990996 (2010).
[Koch et al. (2003)] Koch, W., A. L. Endrös, D. Franke, C Haßler, J. P. Kalejs, and H. J. Möller, Chapter 6:
Bulk crystal growth and wafering. In Handbook of Photovoltaic Science and Engineering, A. Luque and S.
Hegedus (Ed.), John Wiley & Sons, Ltd (2003).
[Ranjan et al. (2011)] Ranjan, S., S. Balaji, R. A. Panella, and B. E. Ydstie, Silicon solar cell production. Comp.
& Chem. Enging 35 14391453 (2011) .
[Salehi et al. (2010)] Salehi, H., M. Aryadoust, and M. Farbod, Electronic and structural properties of tin
dioxide in cubic phase. Iranian J. Sci. Tech., Trans. A 34 131138 (2010).
[Shafarman and Stolt(2003)] Shafarman, W. N and L. Stolt, Chapter 13: Cu(inGa)Se2 Solar Cells, In Handbook
of Photovoltaic Science and Engineering, A. Luque and S. Hegedus (Ed.), John Wiley & Sons, Ltd (2003).
[van Delft et al.(2012)] van Delft J. A., D. GarciaAlonso, and W. M. M. Kessels, Atomic layer deposition for
photovoltaics: Applications and prospects for solar cell manufacturing, Semicond. Sci. Tech. 27 074002
(2012).
[Wesoff(2013)] Wesoff, E., Samsung now the new CIGS solar module efficiency record holder, Greentech Media,
December (2013).
[Xu et al.(2012)] Xu, C., H. Zhang, J. Parry, S. Perera, G. Long, and H. Zeng, A single source threestage
evaporation approach to CIGS absorber layer for thin film solar cells, Solar Energy Materials and Solar
Cells, 117 357362 (2012).
[Zachmann et al.(2009)] Zachmann, H., S. Heinker, A. Brauna, A. V. Mudryi, V. F. Gremenok, A. V.
Ivaniukovich, and M. V. Yakushev, Characterisation of Cu(In,Ga)Se2 based thin film solar cells on
polyimide, Thin Solid Films, 517 22092212 (2009).
Chapter 6
As part of the Gemstone program, a group of undergraduate students at the University of Maryland has worked on
a number of solar energy concepts, constructing panels and preparing to test concepts in concentrating systems.
Consider, for example, the panel they constructed (Fig. 6.1, left) consisting of 30, 8 × 15 cm2 multicrystalline Si
cells, wired in series. This gives a total active cell area of Ac = 0.012 m2 per cell and Ap = 0.36 m2 for the panel.
external load
A

voltage drop
R V
+
B
I
Figure 6.1: Gemstone teambuilt solar panel (left) and the panel and external test circuit (right).
The students conducted a sequence of experiments from about noon to 1pm on September 22, 2010, in which
the voltage (V ) across a selection of resistors R forming an external circuit to the panel (Fig. 6.1, right) was
measured across the AB terminals shown. A subset of the data1 are listed in Table 6.1.
The results are shown in the top left plot of Fig. 6.2. The current I flowing through the external circuit was
1 Scaled by dividing by the total number of cells N = 30 that are wired in series.
Table 6.1: Experimentally measured voltage versus external load resistance, scaled in such a way to represent a
singlejunction PV cell.
66
CHAPTER 6. PV CELL POWER AND THE EQUIVALENT CIRCUIT MODEL 67
V2
P = IV =
Rex
and as displayed in Fig. 6.2, top right, it is important to to keep in mind that the net power produced by the solar
cell is equivalent in magnitude but opposite in sign to that which is dissipated by the resistor.
0.5
0.45
0.4
0.4
0.35
P (W)
Vex (V)
0.3
0.3
0.25
0.2 0.2
0.15
0.1 0.1
0.5 1 1.5 2 2.5 3 0.1 0.2 0.3 0.4
R (Ohms) Vex
ex
800
2
global irradiance EG, W/m2
600
1.5
Iex (A)
400
1
200
0.5
0
0.1 0.2 0.3 0.4 0 5 10 15 20
Vex (V) hour
Figure 6.2: Measured solar cell voltage versus external circuit resistance (top left), current vs. voltage (bottom left),
power versus voltage (top right) and irradiance for a horizontal solar panel on Sept 22, 2010.
Finally, in Fig. 6.2 bottom right, we plot the global irradiance for the day of the experiment (at zero degrees tilt).
Given that the experiments took place at about the time of maximum irradiance (818 W/m2 × 0.012 m2 = 9.74
W for the active cell area), the maximum cell efficiency η is
0.54 W
η= ≈ 5.5%
9.74 W
The main question we now try to answer is: how does this panel perform relative to the maximum theoretical
efficiency, and how do we begin to understand inherent versus specific device inefficiencies?
CHAPTER 6. PV CELL POWER AND THE EQUIVALENT CIRCUIT MODEL 68
h!
(a)
e
n0 (b) 
n1
n2 h+ e
Ie,ph
ntype
+ + + + (c) +
    h+ e 
h+ e ptype
(b)
Ih,ph h+ e
+
Figure 6.3: PV cell photocurrent and recombination sites.
actual e A

V = voltage drop
ntype
I R
Iph ptype Idiode
+
I<0 B
Figure 6.4: PV cell and external load equivalent circuit.
As described in the previous chapter, the photocurrent consists of the flow of electrons and holes created by
photons interacting with the semiconductor making up the PV cell; this additional current Iph flows parallel to
but opposite in direction of the diode (Fig. 6.4). Recall the PV cell singlediode model (4.3), we adopt the
conventional current sign convention illustrated in Fig. 6.4 to find
qV
I = Idiode − Iph = Io exp − 1 − Iph
βkB T
with Iph , Io ≥ 0.
CHAPTER 6. PV CELL POWER AND THE EQUIVALENT CIRCUIT MODEL 69
1.5 0.4
2.0 0.2
2.50.0 0.1 0.2 0.3 0.4 0.5 0.00.0 0.1 0.2 0.3 0.4 0.5
2.5 V V
2.0
current (A)
1.5
1.0
Iph
0.5 Idiode
0.00.0 0.1 0.2 0.3 0.4 0.5
V
Figure 6.5: Diode plus photocurrent model for the Gemstone data; note how Isc = Idiode at V = Voc .
Plots of the cases for β = 1 and β = 2 are shown in Fig. 6.5. As we would expect, the fit of the model is good
at the open and shortcircuit cases; the modeldata mismatch in the midsection of the data is poor, however,
indicating our diode+photocurrent model (6.1) may be missing some elements; these will be discussed next and
in later chapters.
CHAPTER 6. PV CELL POWER AND THE EQUIVALENT CIRCUIT MODEL 70
Differentiating the power equation above with respect to V and setting the result equal to zero results in a
nonlinear equation for Vmp
qVmp qVmp q
g (Vmp ) = Iph + Io 1 − exp − Vmp Io exp =0 (6.3)
βkB T βkB T βkB T
which must be solved numerically for Vmp . We can simplify equation (6.3) using
Iph qVoc
= exp −1
Io βkB T
to find equation (3.4) of [Wenham, et al. (2007)]:
qVoc qVmp qVmp q
0 = exp − exp − Vmp exp
βkB T βkB T βkB T βkB T
qVoc − qVmp q
= exp − 1 − Vmp
βkB T βkB T
βkB T q
therefore Vmp = Voc − ln 1 + Vmp . (6.4)
q βkB T
It is clear from the equation above that Vmp < Voc . For T = 300 K we find that
kB T
= 0.0259 V
q
and so equation (6.4) can be safely used in an iterative manner to find Vmp , starting with an initial guess
0
Vmp ≈ Voc where superscript i = 0, 1, 2, ... indicates iteration index:
i+1 βkB T i q
Vmp = Voc − ln 1 + Vmp . (6.5)
q βkB T
There are other approaches to computing solutions to equation (6.3). One of the most efficient is to use Newton’s
method, which consists of the following steps:
0 0
1. Estimate a solution to (6.3) by choosing a value 0 ≤ Vmp ≤ Voc (such as before Vmp = Voc or the mean
0
value of the expected voltage range Vmp = Voc /2);
g i = g (Vmp
i
)
where i is the iteration number (i = 0 for the initial guess, i = 1 for the first iteration, etc.)
3. The objective of the Newton procedure is to compute solutions to the problem
∂g
0 = gi + i+1 i
Vmp − Vmp
∂Vmp V i
mp
CHAPTER 6. PV CELL POWER AND THE EQUIVALENT CIRCUIT MODEL 71
Iteration number i 0 1 2 3 4 5 6 7
Iterated equation (6.5) 0.5 0.4221 0.4263 0.4260 0.4260 0.4260 0.4260 0.4260
Newton procedure 0.5 0.4766 0.4551 0.4381 0.4286 0.4262 0.4260 0.4260
Table 6.2: Computations of Vmp (in Volts) using the iterative (eqn 6.5) and Newtonbased methods.
i+1
and so a more refined solution estimate Vmp is computed using
i+1 i gi
Vmp = Vmp −
[∂g /∂Vmp ]V i
mp
with 2
∂g qVmp q qVmp q
= −2Io exp − Vmp Io exp
∂Vmp βkB T βkB T βkB T βkB T
i+1
4. We increment i = i + 1 and return to step 2 and continue to iterate until the difference between Vmp and
i
Vmp is infinitesimally small (with a sufficiently good initial solution estimate, the procedure should converge
in as few as six iterations). This difference is called the update u i and is defined as
gi
u i = Vmp
i+1 i
− Vmp =−
[∂g /∂Vmp ]V i
mp
We compare the two techniques in Table 6.2 for the case Isc = 2.25 A and Voc = 0.5 V to see that the iterative
technique actually can outperform the Newton procedure for this choice of parameter values and initial estimate
for Vmp . This does not render the Newton procedure useless, however, as we will see in the later section on series
and shunt resistances.
Of course, we use Vmp to then find Imp and Pmp directly from the diode model and the definition of power.
• Series resistance: results from the inherent resistance of the PV cell itself to charge carrier flow, from the
resistance of interfaces between the cell and metal contacts, and from the resistance of the metal contacts
themselves. Denoted RS , the optimal value of this resistance is zero.
• Shunt resistance: results primarily from manufacturing defects, allowing current to flow through the PV
cell or around its edges (recall the edge isolation step after P diffusion in crystalline PV cell manufacturing).
Denoted Rsh the ideal value approaches positive infinity.
V = voltage drop
Iph ntype Idiode Rs
1. We know Iph and Io and wish to compute the resulting Isc , Voc and points on the I versus V curve for
Rs > 0 and/or finite Rsh . This situation can be thought of as having a pristine cell with known performance
undergo some transformation introducing parasitic resistances, degrading the performance of the cell.
2. We know Isc , Voc and either the values of the parasitic resistances, or the values of I for one or more values
of V ∈ (0, Voc ).
with the initial guess for Voc the value found for ideal conditions. From this equation we observe that Rs has
no effect on the value of Voc because no current flows through the resistor corresponding to Rs . Likewise, under
short circuit conditions we find an equation that can be used immediately in an iterative manner and that should
perform well as Rs → 0:
−Isc Rs Isc Rs
Isc = −Iph + Io exp q −1 − (6.8)
βkB T Rsh
with an initial guess of Isc = Iph . It is important to stress, however, that this iterative equation works only in the
limit of small values of Rs ; for midsize and large values, a Newton procedure must be employed with
−Isc Rs Isc Rs
g (Isc ) = −Isc − Iph + Io exp q −1 −
βkB T Rsh
−Isc Rs Rs Rs
dg /dIsc = −1 − Io exp q q −
βkB T βkB T Rsh
The current I that flows through the external circuit is plotted as a function of V ∈ [0, Voc ] using (6.6). Again, a
nonlinear procedure (e.g., Newton’s method) must be used to solve for I as a function of V , where for this case
we wish to find the root of h(I ) = 0 where
V + IRs V − IRs
h(I ) = −I − Iph + Io exp q −1 +
βkB T Rsh
V − IRs Rs Rs
dh/dI = −1 − Io exp q q −
βkB T βkB T Rsh
given a vector of values V ∈ [0, Voc ] where Voc is found using (6.7) or another Newton procedure.
An alternative, noniterative approach for plotting I versus V is to recall the diode equation
qV
Idiode = Io exp −1
βkB T
and employ Kirchhoff’s current law to find
I = −Iph + Idiode + Ish
where Ish corresponds to the current flowing through the shunt resistor. We observe that the voltage across both
the diode and the shunt resistor are equal with value
Vdiode = V − IRs . (6.9)
The definition of Vdiode then can be used in (6.6) to obtain the explicit equation for I as a function of Vdiode
Vdiode Vdiode
I = −Iph + Io exp q −1 + (6.10)
βkB T Rsh
Vdiode
= −Iph + Idiode +
Rsh
= −Iph + Idiode + Ish which checks.
Therefore, the following procedure can be developed to compute I versus V given values of Iph and Io :
so adding the two conditions gives an equation that can be solved for Io :
−Isc Rs qVoc Isc Rs − Voc
Isc = Io exp q − exp −
βkB T βkB T Rsh
0.0
Rs =0.08
Rs =0
0.5 data
1.0
I (A)
2.0
and so the power dissipated by the load is P = IV . As before, we differentiate P with respect to V to find the
peak value
∂P ∂I
=I +V (6.11)
∂V ∂V
∂I qIo /βkB T
with = . (6.12)
∂V exp [−q(V − IRs )/βkB T ] + qIo Rs /βkB T
Substituting (6.12) into (6.11), setting the result equal to zero, and making use of the opencircuit conditions
Iph qVoc
= exp −1
Io βkB T
0
Using Vmp,diode = Voc we observe the following excellent convergence behavior of the algorithm
i 0 1 2 3 4 5
i
Vmp,diode 0.5 0.4681 0.4567 0.4528 0.4516 0.4513
i
Imp  0.0 1.5938 1.8293 1.8879 1.9041
to find for the Gemstone data the results shown in Fig. 6.8.
Finally, we compute the photocurrent produced per unit area as
2.25 A
= 18.75 mA/cm2
120 cm3
and compare that to [Krogstrup, et al. (2013)] where a stateoftheart research nanostructured solar cell produced
a full order of magnitude greater current density.
1.0
Rs =0.08
Rs =0
0.8 data
Pmp
parameter value
0.6 Io 8.97 × 10−9 A
Iph 2.25 A
P (W)
Vmp 0.299 V
0.4 Imp 1.90 A
Pmp 0.57 W
0.2
Figure 6.8: Power dissipated by the external load (P) versus V for a PV cell with parasitic series resistance Rs = 0.08 Ω.
To derive a generally applicable method for computing Pmp , we recall that the maximum power point is defined
by (6.11) and so
dP dI
= −Imp − Vmp =0
dV mp dV mp
Rs 1
0 = −Imp 1 + ΓRs + − Vmp Γ +
Rsh Rsh
where we must differentiate (6.6) and solve the result for dI /dV to find
1
Γ+
dI Rsh
=
dV Imp ,Vmp
Rs
1 + ΓRs +
Rsh
with
Vmp − Imp Rs q
Γ = Io exp q .
βkB T βkB T
We note that dI /dV > 0, which makes sense given all of the I versus V curves we have seen so far. To find the
maximum power point we must find the solution vector
Vmp
x=
Imp
that satisfies the following pair of equations consisting of our zeroderivative condition and the diode equation
(6.6) itself
Rs 1
−I mp 1 + ΓR s + − V mp Γ +
Rsh Rsh
g (x)
f= = .
h(x)
Vmp − Imp Rs Vmp − Imp Rs
−Imp − Iph + Io exp q −1 +
βkB T Rsh
CHAPTER 6. PV CELL POWER AND THE EQUIVALENT CIRCUIT MODEL 77
A NewtonRaphson procedure then is used to solve the coupled set of nonlinear equations such that
xi+1 = xi − [J(xi )]−1 f(xi )
where the iteration number now is denoted using the subscript i and with Jacobian array elements
1
Γ+
∂g Rsh (1 + ΓRs + Rs /Rsh )(−Γq/βkB T ) + (Γ + 1/Rsh )(ΓRs q/βkB T )
J1,1 = = + Vmp
∂Vmp Rs (1 + ΓRs + Rs /Rsh )2
1 + ΓRs +
Rsh
∂g (1 + ΓRs + Rs /Rsh )(−Γq/βkB T ) + (Γ + 1/Rsh )(ΓRs q/βkB T )
J1,2 = = 1 + Rs Vmp
∂Imp (1 + ΓRs + Rs /Rsh )2
∂h
J2,1 = = −Γ − 1/Rsh
∂Vmp
∂h
J2,2 = = −1 − Rs Γ − Rs /Rsh
∂Imp
While somewhat complicated, the procedure converges quickly to accurate values of Vmp and Imp .
case Voc (V) Isc (A) Pmp (W) Vmp (V) Imp (A) FF
1 0.505 2.6
2 0.645 3.65
3 0.623 3.15
4 0.775 3.37
CHAPTER 6. PV CELL POWER AND THE EQUIVALENT CIRCUIT MODEL 78
2. We collect the following data from a solar cell using a sequence of resistors with relatively low resistance
values:
Rex (Ohms) 0.033 0.067 0.102
V (V) 0.075 0.149 0.220
Estimate the value of Isc by fitting a linear function of the form I = aV +b to the data using linear regression
and extrapolating to V = 0.
3. We collect the following data from a solar cell using a sequence of resistors with relatively high resistance
values:
Rex (Ohms) 0.667 0.733 1.000 3.333
V (V) 0.445 0.448 0.457 0.483
Estimate the value of Voc by fitting a linear function of the form V = aI + b to the data using linear
regression and extrapolating to I = 0.
4. Using the values of Voc and Isc determined in two previous problems, plot the resulting I versus V curves
all for β = 1. Then determine the maximum power point Pmp and the corresponding values of Vmp , Imp
and FF .
5. For singlediode PV cell model, the maximum power Pmp is computed using (6.2). Differentiating this
equation above with respect to V and setting the result equal to zero results in a nonlinear equation
for Vmp given by (6.3) which must be solved numerically. For this HW assignment, develop a numerical
procedure (in Excel, MATLAB, Python or any other computing environment/language) that allows you to
(a) Take as input values of Voc (in V), Isc (in A), β and T (K) and compute Io ;
(b) Plot the I versus V curve and the P (power) versus V curve;
(c) Compute Pmp , Vmp and Imp , marking these points on the current and power curves.
6. Given the ideal (β = 1) solar cell diode equation
qV
I = −Iph + Io exp −1
kB T
for open circuit voltage Voc = 0.6 V and short circuit current Isc = 10 A,
(a) Determine the photocurrent and dark saturation current parameter values for the model;
(b) Estimate to two significant figures the maximum power (in W) and corresponding voltage Vmp .
7. A PV cell with Voc = 0.5 V and Isc = −5 A under conditions of Rsh → ∞ and Rs = 0 is mounted in an
outdoor location. Weathering of the electrodes causes the series resistance to increase from 0 on the day
the cell is installed to Rs = 3 × 10−5 t Ω where t is the number of days after the installation. Plot graphs
of the peak cell power and corresponding Vmp for 0 ≤ t ≤ 1000 days.
8. A PV cell with Voc = 0.6 V and Isc = −10 A has been manufactured with the perfect characteristics
Rsh → ∞, Rs = 0, and β = 1. The cell over time develops faults corresponding to Rsh = 10 and Rs = 0.02
Ω. Assuming β remains unchanged,
(a) Plot I and power as a function of V making use of the procedure described in class whereby I first is
computed as a function of Vdiode and then is transformed into a function of V .
(b) What are the relevant ranges of V and Vdiode for this problem?
(c) Report the maximum power to two significant digits.
CHAPTER 6. PV CELL POWER AND THE EQUIVALENT CIRCUIT MODEL 79
9. Given the student PV panel measured performance of Voc = 0.5 V and Isc = −2.25 A, what is the efficiency
at T = 298 K if the panel measurements were actually taken at 50o C?
10. A PV panel made up of cSi cells is found to have Io = 4.2 × 10−10 A m−2 , Iph = 30 A m−2 , Rs = 0,
Rsh → ∞, and β = 1.
(a) Plot I and P versus V ; determine Voc , Isc , Vmp , Imp , and Pmp at T = 298 K.
(b) Compute panel temperature T when the panel is mounted horizontally with a significant air gap
between the panel and the roof. For your thermal energy balance only, assume that EG = 850 W/m2 ,
that 35% of the incoming irradiance is reflected, and that 85% of what remains is absorbed by the
PV cell as heat. The panel/air heat transfer coefficient is h = 20 Wm−2 K−1 . Take the ambient
temperature to be 300 K.
Major clue: Heat transfer to each of the panel sides is Q = Ah(Tamb − T ) W where A is the area of
one side of the panel, T is the panel temperature, and Tamb is ambient temperature.
(c) Evaluate Pmp at your calculated PV cell temperature Tcell in K.
References
[Kano (1998)] Kano, K., Semiconductor Devices, Prentice Hall (1998).
[Krogstrup, et al. (2013)] Krogstrup, P, Jorgensen, H. I., Heiss, M., Demichel, O., Holm, J. V., Aagesen, M.,
Nygard, J. and Fontcuberta i Morral, A. Singlenanowire solar cells beyond the ShockleyQueisser limit,
Nature Photonics, DOI: 10.1038/NPHOTON.2013.32 (2013).
[Möller (1993)] Möller, H. J., Semiconductors for Solar Cells, Artech House, (1993).
[Wenham, et al. (2007)] Wenham, S. R., M. A. Green, M. E. Watt, and R. Corkish, Applied Photovoltaics, 2nd
Ed., Earthscan, UK, (2007).
Chapter 7
Figure 7.1: Scaled (for a global irradiance of 1000 W/m2 ) solar flux intensity spectrum. Only photons with
wavelength shorter than λ = 1107 nm (indicated by the vertical line) are absorbed by the Si solar cell.
80
CHAPTER 7. EXTERNAL AND INTERNAL QUANTUM EFFICIENCY 81
We recall the silicon the band gap of Ebg = 1.12 eV and that the energy of a single photon is Ep = hν where
h is Planck’s constant (h = 4.136 × 10−15 eV·s) and that the speed of light is c = 2.998 × 1017 nm/s and so
converting Si band gap to the corresponding photon wavelength:
E c hc
ν= , λ= = = 1107 nm
h ν E
which gives the cutoff point in the spectrum, above which photons have insufficient energy to promote an electron
from the valance to conduction band.
Therefore, photons with wavelength λ = 1107 nm have precisely the right amount of energy to create an elec
tron/hole pair in the Si solar cell. Photons corresponding to shorter wavelengths have more than sufficient energy
to do this, as seen in Fig. 7.2.
Ep  1.12 eV
CB
Ep = h!
1.12 eV
VB
Figure 7.2: A closer look at how electrons are promoted from the valence to conduction band in Si, illustrating
the energy loss (hν − 1.12 eV) by photons with wavelength less than 1107 nm (left). The resulting usable spectral
irradiance EE λ,u versus the spectral irradiance EE λ scaled to 1000 W/m2 is shown at right.
so if we consider a given value of global irradiance EG in W/m2 at some fixed wavelength λ, provided
hc (eV·s)(nm/s)
λ ≤ λbg = =
Ebg eV
we will have
photons EG power flux W/m2
= = = .
s·m2 hc/λ energy/photon (J·s)(nm/s)/(nm·photon)
where, of course, h has units consistent with Ebg . We summarize our results as follows
Z∞ Z∞ Z∞
Ebg ∗
EG ,u = SR(λ)EE λ (λ) dλ = SR (λ)EQE (λ)EE λ (λ) dλ = EE λ,u (λ) dλ (W/m2 )
q
λ=0 λ=0 λ=0
Z∞
Igen = SR(λ)EE λ (λ) dλ (A/m2 )
λ=0
These results illustrating EE λ,u are plotted in Fig. 7.2. The conclusion we reach from this analysis is that we can
compute the true theoretical maximum power EG ,u that can be generated by a 1.12 eV band gap Si solar cell by
integrating EE λ,u over the usable portion of the spectrum:
Z 1107
EG ,u = EE λ,u (λ) dλ = 490.7 W/m2
λ=0
noting that the upper limit of integration can be either λbg = 1107 nm or λbg = ∞ because EE λ,u = 0 for
λ > λbg by definition. This gives the theoretical maximum efficiency of a Si solar cell as
490.7 W/m2
ηSi,max = = 49.1%
1000 W/m2
This provides us with another, and potentially better, way of assessing the efficiency of the Gemstone team panel:
by using the ratio of the observed maximum panel power and the theoretically usable flux, we can state that the
panel achieves the following percentage of its maximum theoretical efficiency for a single junction cell:
0.54 W
ηof theo = = 11.2%.
(490.7 W/m )(818/1000)(0.012 m2 )
2
Figure 7.3: Maximum theoretical efficiency as a function of semiconductor band gap under AM1.5 conditions.
glass 1.2
+ 1.0
TCO (SnO2) 0.8
p aSi:H 0.6
0.4
0.2
i aSi:H
200 400 600 800 1000 1200 1400
1.2 EE ,u,top
i aSiGe:H 1.0 EE ,u,bot
0.8
0.6
n aSi:H 0.4
contact
 0.2
200 400 600 800 1000 1200 1400
Tandem device (nm)
Figure 7.4: Multi (tandem) junction aSi cell design (left) and spectral irradiance curves (right) indicating the
maximum usable spectral irradiance for the upper and lower layers shown in green and red, respectively.
We also note that a transparent conducting oxide (TCO) layer of tin oxide (SnO2 ) has been deposited above
CHAPTER 7. EXTERNAL AND INTERNAL QUANTUM EFFICIENCY 85
Given the AM1.5 spectral irradiance EE λ normalized to 1 kW/m2 , we can compute the fraction of each portion
of the spectrum that is absorbed by each of the three layers. If we assume the TCO to be transparent to all
wavelengths above λbg ,TCO
Z λbg ,TCO
ITCO = EE λ dλ
λ=0
= 16.1 W/m2
therefore, less than 2% of the total incident power is absorbed by the TCO film. We can then move on to
computing the fraction of light remaining that can be effectively converted to electronhole pairs by
Z λbg ,aSi
1 ∗
ηmax,aSi = SRaSi (λ)EE λ dλ
1000 W/m2 λbg ,TCO
= 0.361
Z λbg ,aSiGe
1 ∗
ηmax,aSiGe = SRaSiGe (λ)EE λ dλ
1000 W/m2 λbg ,aSi
= 0.192
and so the maximum total potential efficiency of this tandem junction cell is
a substantial improvement over the singlejunction aSi and aSiGe cells (where the absorption of the SnO2 layer
remains for the sake of direct comparison) of
respectively. While the improvement in potential performance is notable, the improvement is partially offset by
increased resistance across the tunnel junction and through the cell itself. However, we note that the most efficient
PV cells that currently exist are multijunction devices; a summary is shown in Fig. 7.5
We take note of two important features in this diagram
1. cSi solar cells have improved from 13 to 25% over 25 years, but are a long way from the 49.1% potential
efficiency we computed (note that mcSi cells are limited to slightly over 20%);
2. Both in multijunction and cSi solar cells, significant improvement is observed when concentrated solar
radiation is used.
which must be solved numerically for Vmp . Again, we can simplify equation (7.2) using
XIph qVoc βkB T XIph
= exp −1 and Voc = ln +1
Io βkB T q Io
but with Voc corresponding to the concentrating system. Computing the maximum power point for our system
we find
X 0.2 1 2
Vmp (V) 0.387 0.426 0.443
Imp (A) 0.422 2.121 4.252
Pmp  (W) 0.163 0.904 1.884
Pmp /X 0.816 0.904 0.942
As expected, the power increases with solar concentrating ratio, be we also observe the efficiency likewise increases.
1.6 AM1.5
AM1.5u
1.4 h < h crit
crit
1.2
0.4
0.2
Figure 7.6: Splitting the spectrum into its thermally and PVuseful components.
To address the loss of the thermal portion of the irradiance spectrum (λ > λcrit ), we propose the hybrid thinfilm
PV/concentrating thermal solar system illustrated in Fig. 7.7. The key idea behind this approach is to coat the
reflecting surface with a thinfilm PV layer; this PV cell will generate electricity directly from the λ ≤ λcrit portion
of the spectrum and will be transparent to the longerwavelength portion of the spectrum. The IR portion of the
spectrum then could be focused on a thermal collector for solar heating or generating electricity, such as by using
a Stirling engine.
waste
heat I load
The challenges posed by such as system include engineering the thinfilm PV/reflector (Ebg ), systems integration,
optimization, and (static) concentrator design. However, the potential benefits of this technology include efficient
combined power + heating or power + water desalination applications. More information on these technologies
can be found in [Charalambousa, et al., (2007)] and [Mittelman, Kribus, and Dayan (2007)].
CHAPTER 7. EXTERNAL AND INTERNAL QUANTUM EFFICIENCY 88
x = 1.33 x =0
Si N Si N
N H H Si N H
Si Si Si Si
H
N Si Si Si H Figure 7.8: SiAmorphousSi
SiNx :H
H Si Si H N
N corresponding to a stoichiometric
N
Si Si Si N H Si Si
Si Si Si N
N H H Si Si Si films (left) and
N the limitingH case of
H N N H Si H N N H
Si Si N Si Si Si Si Si a pure amorphous Si film
N (right).
Si
N Si Si H Si
N Si
H N N HH N
H N
N H H
N
0.65
n1 = + 1.3 (7.3)
x
Of course (7.3) becomes invalid in the limit of pure amorphous Si (x → 0) where the true index of refraction is
between 3.5 and 4 [Janai, et al., (1979)].
AR film band gap has been shown to decrease with increasing Si content from 5.3 eV for a stoichiometric film to
1.8 eV for amorphous Si. Assuming a linear relationship, [Adomaitis and Schwarm (2013)] found
I
h!
r01
(a) r12
e
n0 n0
n1
(b) 
n1
n2 n2 h+ e
w
Ie,ph
ntype
+ + + + (c) +T
    h+ e 
h+filmeregion
Figure 7.9: An enlargement of the AR  ptype
(left) and thinfilm reflectance (right)
(b)
Ih,ph h+ e
n0 and reflects off the surface of material with n1 ,
2 2
+
2
s s 2
n0 n0
n0 cos θi − n1 1 − sin θi n0 1 − − n1 cos θi
sin θi
n1 n1
rs =
s 2 ,
rp = s
2
n0 n0
n0 cos θi + n1 1 − sin θi n0 1 − sin θi + n1 cos θi
n1 n1
where the total reflectance r is simply the mean of the two components
rp + rs
r= .
2
For θi = 0 the Fresnel equations reduce to
2
n1 − n0
rs = rp = .
n1 + n0
Returning to the AR film of Fig. 7.9, we can write the singleinterface reflectances [Melles Griot (2009)] as
2 2
n1 − n0 n2 − n1
r01 = , r12 =
n1 + n0 n2 + n1
(see Fig. 7.9 for an enlargement of the AR film region). At this point it is interesting to consider the (idealized)
case where no film exists; under these conditions n0 = 1 and n2 = 3.85 (for Si) and so
2 2
n2 − n0 3.85 − 1
r02 = = = 35% reflectance.
n2 + n0 4.85
While this, at first, may appear to be a high value, we note that this case corresponds to a polished Si surface
with no surface oxide coating and no P doping.
To determine the overall reflectivity, the first and secondsurface reflected wave phase difference is defined by
2π
φd = n1 (2w )
λ
CHAPTER 7. EXTERNAL AND INTERNAL QUANTUM EFFICIENCY 90
Figure 7.10: Reflectance r as a function of λ for the case x = 1 and w = 200 nm.
where we incorporate the factor 2 to account for the length of the path light incident to the AR film of thickness w
takes through the film and back after being reflected at the ARSi interface1 . Setting φd = π results in maximum
destructive interference of light at wavelength λ corresponding to a film thickness equivalent to one quarter of
the wavelength λ divided by the refractive index of the AR film n1 :
λ
w= .
4n1 (x)
The final form of total reflectance is
2 2
r̂01 + r̂12 + 2r̂01 r̂12 cos φd
r (w , x, λ) = 2 2 + 2r̂ r̂ cos φ (7.5)
1 + r̂01 r̂12 01 12 d
with
n1 − n0 n2 − n1
r̂01 = , r̂12 =
n1 + n0 n2 + n1
a model for reflectance that is valid in the limit of w → 0 (proof is left to the reader). For our silicon nitride AR
film
n0 = 1 for air
n1 = 0.65/x + 1.3 for SiNx :H
n2 = 3.85 for Si
An example of the reflectance as a function of wavelength for a film with thickness w = 200 nm and composition
x = 1 (n1 = 1.95) is shown in Fig. 7.10. For this relatively thick film, we observe the 1/4 wavelength minimum
at λ = 1560 nm. Within the visible and UV portions of the spectrum we find minima at λ = 520, 312, 223 nm
and more values at higher frequencies.
Therefore
1 − a(λ) = 1 − H(λ − λa ) = 1 − IQE (Ebg ,1 )
where H is the Heaviside function.
Contact shading is proportional to the area covered by the front surface contact; we will use a constant value
of s = 0.1 (10%) unless otherwise noted.
where the Ebg preceding the integral has units of eV and SR ∗ is dimensionless. To determine cell peak power
requires knowing Voc ; an approximation is described in the following section.
We note that a number of other issues remain to be discussed, including (1) reduction of reflections using surface
roughening by etching; (2) modeling the AR film over these roughened surfaces; (3) front surface contact layout
optimization; (4) buried and laseretched contact designs; and (5) backsurface roughening.
4n2
T kB T Ωemit
Voc = Ebg 1 − − ln + ln 2 − ln(QE )
Tsun q Ωsun X
CHAPTER 7. EXTERNAL AND INTERNAL QUANTUM EFFICIENCY 92
1.6
EE
EE ,u
1.4 (1r)EE ,u
(1s)(1r)EE ,u
1.2
power W/(m2 nm)
1.0
0.8
0.6
0.4
0.2
Figure 7.11: Spectral irradiance and the effects of spectral responsivity SR ∗ , reflectance, AR film absorbance,
and contact shading. We note that [1 − a(λ)] does not appreciably affect the useful power because the lower
spectral cutoff wavelength λbg = 280 nm for the AR film is essentially completely below the power spectrum in
this example.
where in our interpretation Ebg is in eV and kB in J/K, Ωemit and Ωsun are the solid angles of photons radiated
and absorbed (in steradians), n is the PV semiconductor refractive index, X is the solar concentration ratio and
QE is the emission quantum efficiency. After simplifying to
kB T 4n22
T
Voc = Ebg 1 − − ln ,
Tsun q X
using the refractive index of Si, and setting X = 1, the effective Voc is computed and plotted in Fig. 7.12.
While the reduction of Voc relative to Ebg appears small in Fig. 7.12, when combined with the diode model, the
effect of maximum efficiency is significant. Computing
−1
qVoc
Io = Iph,max exp −1
kB T
and then using the (ideal) diode model to determine Pmp , the resulting maximum theoretical singlejunction PV
cell efficiency for one sun under AM1.5 conditions is shown in Fig. 7.13. We see that the maximum efficacy now
is 36.8% and that there is a slight shift to the higher Ebg materials, making the maximum theoretical efficiency
of CdTe cells competitive with cSi.
CHAPTER 7. EXTERNAL AND INTERNAL QUANTUM EFFICIENCY 93
Figure 7.13: Maximum theoretical efficiency as a function of semiconductor band gap under AM1.5 conditions; curve
corresponding to Pmp is shown in red.
7. For a single interface with n0 = 1 and n1 = 3.85, determine the total reflectance when the incident radiation
is normal and 45o to the surface.
8. Using the singlefilm reflectance equation (7.5) and n0 = 1, n2 = 4
(a) Determine the optimal values for n1 and w for an Si cell using the AM1.5 spectrum.
(b) What is the limit of (7.5) for w → 0?
(c) For n1 = 2 and w = 100 nm, determine the location of the reflectance minima for 0 < λ < 2000 nm.
What is the physical interpretation of the minima?
9. Recall the section in this chapter where a concentrating solar system design was discussed which effectively
split the AM1.5 spectrum into the IR and visible/UV components and then used the spectrum fractions in
thermal and PV systems, respectively. If the thermal portion is to be used as the heat source for a 25%
efficient Stirling engine, what is the optimal PV band gap? To solve the problem, create a plot of overall
efficiency vs. Ebg .
10. The star Betelgeuse in the constellation Orion has a surface temperature of 3500 K and therefore is cool
relative to our Sun. Someone claiming to be from that star’s planetary system would like to evaluate the
potential for generating solar energy using a singlejunction PV cell under conditions of zero atmospheric
absorption. For this problem,
(a) Assume the spectral irradiance is approximated by Planck’s distribution normalized to 1 kW/m2 over
λ ∈ [200, 4000] nm; plot the spectral irradiance and estimate the wavelength corresponding to peak
irradiance.
(b) Assuming ideal internal and external quantum efficiencies, compute the maximum fraction of the 1
kW/m2 irradiance that can be converted to useful power for PV cell semiconductor band gap values
Ebg = 0.75, 1, 1.25, and 1.5 eV.
(c) Estimate to two significant figures the optimal band gap value (in eV) and the peak theoretical efficiency
at that value; do not simply interpolate between two values of (b).
References
[Adomaitis and Schwarm (2013)] Adomaitis, R. A. and A. Schwarm, Systems and control challenges in
photovoltaic manufacturing processes – A modeling strategy for passivation and antireflection films,
Computers & Chemical Engineering 51 6576 (2013).
[Charalambousa, et al., (2007)] Charalambousa, P. G., G. G. Maidmenta, S. A. Kalogiroub, and K.
Yiakoumettia, Photovoltaic thermal (PV/T) collectors: A review, Applied Thermal Engineering 27 275286
(2007).
[Janai, et al., (1979)] Janai, M., D. D. Allred, D. C. Booth, and B. O. Seraphin, Optical properties and
structure of amorphous silicon films prepared by CVD, Solar Energy Materials 1 1127 (1979).
[Mittelman, Kribus, and Dayan (2007)] Mittelman, G., A. Kribus, and A. Dayan, Solar cooling with
concentrating photovoltaic/thermal (CPVT) systems, Energy Conversion and Management 48 24812490
(2007).
[Gray (2003)] Gray, J. I., Chapter 3: The physics of the solar cell. In Handbook of Photovoltaic Science and
Engineering, A. Luque and S. Hegedus (Ed.), John Wiley & Sons, Ltd (2003).
[Krogstrup, et al., (2013)] Krogstrup, P. and coworkers, Singlenanowire solar cells beyond the
ShockleyQueisser limit, Nature Photonics DOI: 10.1038/NPHOTON.2013.32 (2013).
CHAPTER 7. EXTERNAL AND INTERNAL QUANTUM EFFICIENCY 95
[Schockley and Queisser (1961)] Shockley, W. and H. J. Queisser Detailed balance limit of efficiency of pn
junction solar cells, J. Appl. Phys. 32 510519 (1961).
[Melles Griot (2009)] Melles Griot, Technical Guide, Vol. 2, Ch 5 (2009).
Chapter 8
In our previous discussions, V denoted both the voltage rise across the PV cell as well as the voltage drop though
the external load. Because we now will consider cases of multiple cells wired together, a modified interpretation
of Vi on a percell basis will be required and is shown in Fig. 8.1.
A
 
Vi = voltage drop
Vi Ii
ptype Rsh Ish
+ +
B
Ii < 0
Figure 8.1: Notation used to represent a single solar cell.
The two simplest multicell configurations are shown in Fig. 8.1. Before we proceed with the analysis, we recall
Kirchhoff’s Current and Voltage Laws [Johnson et. al (1978)]:
Let us begin with the case of two identical cells mounted in parallel, connected to an external circuit consisting
of a resistor with resistance R. We denote the currents I1 , I2 and voltages V1 and V2 as those corresponding to
cells 1 and 2, respectively, and V as the voltage difference across the external load of Fig. 8.1. Making use of
Kirchhoff’s Laws we find:
96
CHAPTER 8. CELL AND PANEL INTERCONNECTIONS 97

V/N 1 I
Figure 8.2: Two identi
V1 1 V2 2 V V cal cells arranged in par
I1 I2 R R allel (M = 2, left) and
series (N = 2, right).
2
+ I/M I
+ I
1. Given that the conventional current of each cell is denoted downward (hence negative in our sign convention),
at the lower node where the two cells connect we have I = I1 + I2 , therefore the total current I to the
external load is the sum of the individual cells.
2. There are three unique closed circuit paths in this case: it is easy to see under these circumstances that the
voltage rise (from the top to bottom) of each cell V −!, V2 and the voltage drop across the external load
V all are equal.
Now consider the case of two identical cells mounted in series (Fig. 8.1, right), again connected to an external
circuit consisting of a resistor of resistance R Ω. In this case, Kirchhoff’s Laws give the following relationships
between the individual cell characteristics and the twocell string performance:
1. Because any point in the loop is effectively a node, the current must be constant through the circuit, and
so I = I1 = I2 ;
2. There is only one loop in this circuits and so V1 + V2 = V .
N
M
where it is important to stress that I and V correspond to those values measured for the entire array, not a
representative cell in the array.
For the case Rs = 0 and Rsh → ∞, we can immediately write the array open circuit voltage Voc and array
shortcircuit current Isc as:
NβkB T Iph
Voc = ln +1
q Io
Isc = −MIph .
For cases where Rs 6= 0 and Rsh finite, we must use a Newton or other iterative procedure to compute the solutions
to the nonlinear equations defining Voc , Isc , and I (V ).
glass superstrate
TCO
aSi:H
metal
Figure 8.4: Integral interconnected panel design for a superstrate thinfilm PV cell array.
Another appealing aspect of aSi:H panels is their utility in Building Integrated Photovoltaics (BIPV). An excellent
overview is given by [Schade (2004)] but will not be described further in these notes.
CHAPTER 8. CELL AND PANEL INTERCONNECTIONS 99
Figure 8.5: A commercial cSi solar panel (left) and panel performance specifications (right).
Consider the commercial cSi PV panel shown in Fig. 8.5. The panel consists of 36 monocrystalline Si solar cells
mounted on an aluminum backing plate and the overall panel is sealed for outdoor use. We read off the following
performance data from the cSi PV panel:
We note Pmp = 30 W is given, but this data point is redundant because Vmp and Imp are listed on the panel
specifications.
Because Voc = 21.6 V for the 36 cells of this panel and because we know that individual junction Voc values are
normally between 0.5 and 1 V, we can assume (and verify by visual inspection) that all 36 cells in this panel are
wired into a single series string. Recalling the PV array modeling equation (8.1) this gives N = 36 cells mounted
in series and M = 1. Given these are highquality commercial cells, we will initially assume Rs to be small but
nonzero (on a percell basis), Rsh is large but finite, and β = 1. We note the panel specifications were determined
under AM1.5 conditions at T = 298 K.
These assumptions and observations lead to the panel modeling equation:
V /N − IRs V /N − IRs
I = −Iph + Io exp q −1 + . (8.2)
kB T Rsh
The model has the four unknowns: Iph , Io , Rs , and Rsh having fixed β = 1. We use the panel open and
shortcircuit data as well as the maximum power data to define these parameters in (8.2):
qIsc Rs Isc Rs
Isc = −Iph + Io exp −1 −
kB T Rsh
qVoc Voc
0 = −Iph + Io exp −1 +
NkB T NRsh
which gives
Isc + Isc Rs /Rsh + Voc /(NRsh )
Io =
qIsc Rs qVoc
exp − exp
kB T NkB T
CHAPTER 8. CELL AND PANEL INTERCONNECTIONS 100
0.0
computed
0.5 mp specs
mp computed
Voc specs
I (A)
1.0
Isc specs
1.5
0 5 10 15 20
30
25
computed
mp specs
20 mp computed
P (W)
15
10
5
00 5 10 15 20
V (Volts)
Figure 8.6: cSi PV panel current (top) and power (bottom) as a function of external voltage V .

 V1 1 I Figure 8.7: Two iden
V1 1 V2 2 V + V tical cells arranged in
I1 I2 R R parallel (left) and se
ries (right) where the
+ V2 2 damage/shaded cells are
I shown as red.
To compute I1 and I2 we will use a Newton procedure to compute the two currents directly as a function of V
instead of the procedure based on using Vdiode ; we chose this approach to simplify the numerical calculation of
I = I1 + I2 in that the Newtonbased procedure guarantees the values of V used to compute I1 and I2 will match.
Of course, the alternative is to define Vdiode,1 = V − I1 Rs and Vdiode,2 = V − I2 Rs to compute I1 and I2 followed
by interpolation of one set of current values to the voltage values of the other prior to computing the sum.
Results are shown in Fig. 8.8, where the four subplots illustrate current I (top plots) and power P (bottom plots)
as a function of external voltage V . The plots in the left column of the figure correspond to two cells wired in
parallel. We observe that the fully illuminated pair of cells produce approximately twice the current (as expected)
and twice the overall power. However, examining the results for the full 36 cell panel with all cells wired in
parallel, we see that the overall impact of a single shaded cell is diminished as the number of illuminated cells
grows relative to the shaded cells. Therefore, an important conclusion can be drawn from this result: for a long
string of parallel cells or solar panels, one dark cell/panel in a string of many illuminated cells/panels results in
little performance degradation.
0.0 0
0.5 10
1.0 20
1.5 30
2.0
I (A)
2.5 40
3.0 50
3.5 60
4.00.0 0.1 0.2 0.3 0.4 0.5 700.0 0.1 0.2 0.3 0.4 0.5
2.0 30
25
1.5
20
P (W)
1.0 15
10
0.5
5
0.00.0 0.1 0.2 0.3 0.4 0.5 00.0 0.1 0.2 0.3 0.4 0.5
V (Volts) V (Volts)
Figure 8.8: Current (top) and power (bottom) versus voltage for two cells arranged in parallel (left) and 36 cells in parallel
(right). Cases where all cells are illuminated are shown as the dotted blue curves; cases with a single shaded cell is shown
in red.
For cases where Isc Rs  is small, Vsc,1 can be found using a Newton procedure (as opposed to the NewtonRaphson
necessary to compute Vsc,1 and Isc simultaneously) to find that Isc is exceedingly small in this situation and that
Vsc,2 ≈ −Voc,1 meaning that what little power is produced by cell 1 is dissipated in the darkened cell in this
situation.
CHAPTER 8. CELL AND PANEL INTERCONNECTIONS 103
To compute I versus V for the twocell system for V ∈ [0, Voc ], Kirchhoff’s Laws give V = V1 +V2 and I1 = I2 = I ,
and so
V1 − IRs V1 − IRs
I = −Iph,1 + Io exp q −1 + (8.3)
βkB T Rsh
V2 − IRs V2 − IRs
= Io exp q −1 + (8.4)
βkB T Rsh
V − V1 − IRs V − V1 − IRs
= Io exp q −1 + (8.5)
βkB T Rsh
This give two equations (8.3,8.5) and 2 unknowns, I and V1 , the latter which can be determined using a Newton
Raphson technique.
0.0 0.0
0.5 0.5
1.0 1.0
I (A)
1.5 1.5
15
0.04
10
0.02 5
0.00 00
0.0 0.2 0.4 0.6 0.8 1.0 5 10 15 20
V (Volts) V (Volts)
Figure 8.9: Current (top) and power (bottom) versus voltage for two cells arranged in parallel (left) and 36 cells in parallel
(right). Cases where all cells are illuminated are shown as the dotted blue curves; cases with a single shaded cell is shown
in red.
A plot of power and current versus voltage is given in Fig. 8.9 for the serieswired case, comparing the fully
illuminated and singleshaded cell performance curves. What is striking is how severe the performance loss is with
a single shaded cell: nearly all the twocell PV string power is dissipated in the shaded cell, and for the case of 36
cells with one shaded, we observe that the total power output is reduced to 10 W, onethird the power of the fully
illuminated panel. We note that because so much power is potentially dissipated by the shaded cell, significant
heating and ultimate damage of the shaded cell can result.
0.5
I (A)
1.0
1.5
0 5 10 15 20
30
25
20
P (W)
15
10
5
00 5 10 15 20
V (V)
0.5
I (A)
1.0
1.5
of this model prediction, a set of experiments was performed to assess the performance of the panel shown in
Fig. 8.5. With the panel positioned at optimal tilt on a day when the global irradiance at solar noon corresponded
to EG ≈ 1000 W/m2 , the fully exposed panel data plotted in Fig. 8.10 was recorded and shown to be in good
agreement with our model predictions. Likewise, data corresponding to a single shaded cell showed the remarkable
agreement between the observations and the performance loss predictions.
 I
V 1 I 2
Vex
+ Vex
Rex
Rex
I 2 V 3 I
Iex Iex
4
battery DC
bank load
charge
controller
= AC
~ load
inverter
building AC
= load
~
inverter utility
grid
Figure 8.12: Standalone (top) and and gridconnected PV (bottom) systems. After Figs 15.8 and 15.9 of
[Archer and Hill (2001)].
The components of standalone and gridconnected PV systems are shown in Fig. 8.12. There are a number of
excellent sources of information on the practical aspects of PV system design, some of which are listed in the
references of this chapter. We will only briefly discuss the elements of systems design and several general design
rules.
• As a general design rule, peak installed power should be 5 times the nominal load; this rule is taken from
from page 124 of [Wenham and coauthors (2007)].
• Panel tilt should be set at the local latitude for gridconnected systems and latitude plus 15 degrees for
standalone systems if possible [Balfour, Shaw, and Jarosek (2013)]. Of course, panels in the northern
CHAPTER 8. CELL AND PANEL INTERCONNECTIONS 106
hemisphere are tilted south and are tilted north in the southern hemisphere.
• The DC bus of a typical domestic PV installation is designed for 1248 VDC, with 48 VDC as the most
common [Balfour, Shaw, and Jarosek (2013)]. We compare that voltage to utility scale PV production
production where the DC bus operates at 200600 VDC (page 184 of [Markvart (1994)]).
• Inverters are a critical component to an integrated system. Inverters convert the DC current produced by
the PV panels and/or battery storage to AC. Inverters are characterized by the AC current they produce:
whether they produce AC as a sine wave or a modified square wave, the former being more desirable. The
operation of a simple inverter capable of producing a square wave is shown in Fig. 8.13.
Iph  +
ntype
ptype Id
+ +
I

• Power controllers are crucial to the operation of the overall PV installation. Power controllers mainly
function to regulate the minimum and maximum voltage produced by the solar panels. Certain controllers
include maximum power tracking algorithm, effectively adjusting the voltage drop of the panel load to allow
the panels to operate as close as possible to Pmp ; the controller basically acts as a DC to DC transformer
in this operation. Power system controllers also are required to allow operation parallel to the grid in grid
connected systems; in domestic applications, this operation is called net metering whereby the PV owner
sells excess power to the electrical utility.
• Battery storage is sized such that 2 to 15 days of nominal power can be provided under cloudy conditions.
Battery capacity is measured in A·hr; battery voltages commonly are 12 and 24 V. We note that solar panels
generally are designed with Vmp in increments of 18 V; this is to account for the voltage drop across the
blocking diode, the 2.8 V loss due to operation to 60o C, and the 1 V loss through the power regulator
[Wenham and coauthors (2007)], and that at least 2 V of overvoltage is required to charge a 12 V battery.
• The balance of system (BOC) refers to the remaining wiring, metering, grounding, and other elements
completing the PV installation.
A very readable article describing the home installation of a complete PV system can be found in [Murphy (2008)].
Compute and plot the hourly total power production on July 20 of this year assuming (a) a totally clear
day; (b) a totally cloudy day. Each panel has 72 cells wired in series.
2. We have the responsibility of designing a PV system for a remote medical clinic. The following define the
design specifications:
(a) the system is to continuously power a 150 W refrigerator, 50 W of security lighting through the night,
and 1200 W·hrs of miscellaneous load throughout the day
(b) all loads require 220 V AC power provided by a 48VDC to 220 VAC inverter which is 80% efficient
(c) 12V DC, 200 amphr batteries are to be purchased
(d) panels similar to those of the previous problem are to be used
(e) the country is located 8.5o N latitude and is mostly sunny
(f) diesel generator backup for cloudy days already exists
What is your recommended design in terms of the number and wiring arrangement of the panels, batteries,
and inverter? Draw a diagram illustrating your design.
3. Consider three identical PV cells with the following characteristics under standard AM1.5 conditions: Iph =
2.5 A, Io = 9 × 10−9 A, β = 1, Rs = 0, Rsh = 10 Ω, and T = 300 K. If the cells are wired in series,
(a) Compute Vmp , Imp , and Pmp for the string of three;
(b) Repeat the calculation when the middle cell receives 800 W/m2 compared to the two others which
continue to receive 1000 W/m2 .
4. Consider a tandem (2junction) thin film PV cell with total surface area of 10 × 10 cm2 . If one layer
of the cell is composed of aSi:H, what is the optimal band gap of the other semiconductor? For your
calculations, assume all Rs = 0 and Rsh = 10 Ω for each junction. Assume the tunnel junction separating
the semiconductors has zero resistance. Plot I and P versus V for your optimized design.
References
[Archer and Hill (2001)] Archer, M. D. and R. Hill, Clean Electricity from Photovoltaics, Imperial College Press,
2001.
[Balfour, Shaw, and Jarosek (2013)] Balfour, J. M. Shaw, and S. Jarosek, Introduction to Photovoltaics, Jones
& Bartlett Learning, 2013.
[Johnson et. al (1978)] Johnson, D. E., J. L. Hilburn, and J. R. Johnson, Basic Electric Circuit Analysis,
Prentice Hall, NJ, 1978.
[Wenham and coauthors (2007)] Wenham, S. R., M. A. Green, M. E. Watt, and R. Corkish, Applied
Photovoltaics, 2nd Ed., Earthscan, UK, 2007.
[Worder and ZuercherMartinson(2009)] Worder, J. and M. ZuercherMartinson, How inverters work,
SOLARPRO, 6885, AprilMay 2009.
Chapter 9
In all PV cell architectures considered to this point, photons are absorbed by a semiconductor creating an electron
hole pair from the promotion of a valence electron the conduction band. To prevent loss of the potential energy in
crease produced in this process, charges are separated by a semiconductor/semiconductor or semiconductor/metal
junction where minority carriers are swept through the junction by the builtin electric field. In this chapter, we
begin to explore other types of charge carrier generation and separation mechanisms. Specifically, we consider
the thinfilm dyesensitized solar cell (DSSC), often referred to as the Grätzel cell [O’Regan and Grätzel (1991)].
This PV cell is based on very different charge generation and separation mechanisms:
1. Photons are absorbed by a lightsensitive dye, promoting an electron from the dye molecule highest occupied
molecular orbital (HOMO) to the lowest unoccupied molecule orbital (LUMO)
2. The excited electron then is injected into the conduction band of a largeband gap semiconductor such as
TIO2 as the charge separation mechanism
TiO2 dye
anode
cathode
electrolyte
load
e
These dyesensitized solar cells have a number of advantages [Hardin et. al (2012)]; for example, they can be
constructed from relatively inexpensive raw materials, can be made into flexible cells with plastic substrates, have
108
CHAPTER 9. DYE SENSITIZED CELLS 109
demonstrated efficiencies of up to 12.8%, and they perform well in lowlight conditions. Doityourself kits have
even been published illustrating how working cells can be made using ingredients of suntan lotion and blackberry
juice [Appleyard (2006)].
A schematic of a typic cell is shown in Fig. 9.1 and the major cell components are described as follows. We
first recall that conventional current flows into the anode of an electrical device. The anode of a DSSC is
transparent to most of the incoming solar radiation and consists of a TCO (transparent conducting oxide) coated
glass or plastic substrate onto which a 10 µm coating of nanostructured TiO2 is deposited. The TiO2 particles
are approximately 10 nm in diameter and so form a high surface area layer (1000× compared to a flat surface)
onto which a monolayer of light absorbing dye is deposited.
The electrolyte consists typically of iodide (I− , and I−
3 ) (note that iodine is I and I2 ) in an organic solvent. The
purpose of the electrolyte is to provide a mechanism by which the dye is regenerated and to create an electric
contact with the counter electrode (the cathode). The cathode, also generally made to be transparent, supports
a platinum or carbon conducting layer.
To help make these concepts clear, consider the classic copperzinc electrochemical experiment – the Daniell
galvanic cell – consisting of the two halfreactions described above. Adding the oxidation and reduction reactions
1 In the sense of Gibb’s free energy at standard solution conditions.
CHAPTER 9. DYE SENSITIZED CELLS 110
gives
o
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Ecell = 1.1 V (9.1)
o o o o o
where Ecell = Ecathode + Eanode = 1.1 V gives the voltage of the battery cell. Because ECu 2+ > EZn2+ , the forward
reaction above is favored over the reverse, resulting in the metal Zn electrode dissolving (oxidizing) from the Zn
anode (anode = conventional current in). Another way to view (9.1) is that it is spontaneous in the direction
o
indicated because Ecell > 0.
Zn anode Cu cathode
load
e
An alternative view of the charge transport through this electrochemical system is presented in Fig. 9.2 from
the perspective of the electrons involved in the reactions. As stated earlier, the valence electrons of Zn have a
higher energy relative to those of Cu, and so the overall reaction cycle can be thought of as starting with the
Zn oxidation reaction, releasing Zn2+ to the electrolyte solution and 2e− to the Zn anode. In this diagram, we
represent the Fermi level of the anode as being lower in energy relative to the Zn2+ /Zn redox couple, indicating
the driving potential for this forward reaction.
The electrons produced by this reaction travel through the external circuit and the external load which results in
a voltage drop in the electrons. The electrons enter the Cu cathode at a reduced voltage and then are consumed
in the Cu2+ reduction reaction, resulting in metallic Cu deposition on the cathode. Of course there must be a
corresponding positive ion current in the electrolyte to maintain electrical neutrality of each electrode. Note that
the standard potential for the Cu2+ /Cu redox couple is written in terms of the Cu oxidation reaction to maintain
consistency with the potential of the Zn2+ /Zn redox couple – recall that the energy levels represent the relative
energies required to extract the electrons from each metal.
Before returning to the DSSC, we propose the following thought experiment involving varying the resistance R
of the external load: as R → 0, the Fermi levels of each electrode should approach a common value between the
potentials of the two redox couples. This should result in maximum driving force for each halfreaction, resulting
in a high reaction rate and zero useful external work. Likewise, increasing R → ∞ should move each electrode
Fermi level towards the corresponding redox couple potential. Because each halfreaction approaches equilibrium
under these conditions, the overall reaction stops and again, no useful external work is produced. Therefore, much
like PV cells, the optimal power output of a battery appears to be governed by the external load.
its ground state D to D∗ . The dyes are typically composed of a ruthenium complex; the dye concentration on the
TiO2 nanoparticles is approximately 0.51 dye molecules/nm2 and the dye absorbs from λ = 780 nm and lower
wavelengths [Hardin et. al (2012)].
D *, D + e injection
ECB
overpotential
EF
V
I3 /I
dye regen Figure 9.3: Band diagram
D overpotential of the DSSC illustrating the
I3 useful voltage V produced
by this PV cell.
EVB I
load
e
Rather the returning to its ground state by fluorescence, the dye molecule can transfer the excited electron to
the conduction band of its TiO2 substrate. Recall that TiO2 is an ntype semiconductor with Ebg = 3 eV. The
electron then can migrate through the TiO2 nanoparticles to the TCO anode, after which it can travel through
the external circuit and load to perform useful work, finally returning to the cell at the counter electrode (the
cathode).
The dye molecule, having transferred its charge to the TiO2 is regenerated by driving the following oxidation
reaction at the interface of the dye and electrolyte
3I− → I−
3 + 2e
−
The I−
3 species then diffuses through the electrolyte and when it reaches the counter electrode, undergoes the
reduction reaction
I− −
3 + 2e → 3I
−
Overall the iodide reactions do no net chemical work (as opposed to the photoelectrochemical cells described
in Chapter 10) and simply act as charge transfer mechanisms. Just as with the galvanic cell, the overpotential
required to inject electrons into the TiO2 conduction band and to drive the dye regeneration reaction at finite
rates results in a useful external voltage V being less than the energy required to excite the dye molecule. We
can write the overall chemical reactions as
D → D∗
D∗ → e − + D +
2D+ + 3I− → 2D + I−
3
I− −
3 + 2e → 3I
−
where the first three reactions take place at the anode and the final reaction at the cathode.
CHAPTER 9. DYE SENSITIZED CELLS 112
V = voltage drop
Iph ntype Idiode R3 R1 Rh
Rh : ITO resistance
R1 : charge transfer at Pt electrode
R3 : electrolyte resistance
and so Rs = R3 + R1 + Rh
The second major difference is in the diode nonideality factor β: for the dye sensitized cell, values of β ≥ 2 can
result from recombination of e − and I−
3 from the TiO2 surface.
Finally, we note that this model applies only to DC operating conditions; this is important because dyesensitized
cell parameters are frequently determined by applying an alternating external potential.
References
[Appleyard (2006)] Appleyard, S. J., Simple photovoltaic cells for exploring solar energy concepts. Physics
Education 41 409419 (2006).
[Hardin et. al (2012)] Hardin, B. E. , H. J. Snaith, and M. D. McGehee, The renaissance of dyesensitized solar
cells. Nature Photonics 6 162169 (2012).
Photoelectrochemical systems
hc/λ"
V
I
counter electrode
ions
Consider the electrochemical system illustrated in Fig. 10.1. Sunlight enters through the top of the cell and falls
on a semiconductor electrode. As with the solidstate PV cells we are familiar with, an electron/hole pair is
formed and subsequently separated by a junction. However, rather than doing external work, the photon energy is
used to drive an electrochemical reaction in the electrolyte solution. In this chapter, we will study the similarities
between this system and the PV cells we considered to this point, and will address the following questions:
1. What is the nature of the junction that separates the e− /h+ charges?
2. How do p and ntype working electrodes differ in terms of system behavior?
3. What are the chemical reactions that take place and how are they driven by the sunlight?
4. What gases are produced at the electrodes?
5. What is the nature of the electrolyte, e.g., is it an acid or base, and does the pH matter?
114
CHAPTER 10. PHOTOELECTROCHEMICAL SYSTEMS 115
2H2 O → 2H2 + O2
To start, we consider doing so not by solar energy but by an electrolysis process where direct current from an
external source is used to drive the reaction shown above. An externally applied voltage bias provides the driving
force to pull electrons from the anode through the external circuit, and then to return them to the cell through
the cathode to enable the reactions there. The product of that bias voltage and external current determines the
total applied power.
o
Later in this chapter we will show that the minimum cell potential required for this reaction is Ecell = −1.23 V,
noting the large difference from the positive cell voltage of 1.1 V for the Daniell cell (Fig. 9.2) described previously.
With ∆G o as the change in Gibbs free energy under standard conditions, we write
∆G o = −nFEcell
o
n = moles of electrons
F = Faraday constant = 96485 C/e− mole
o
Ecell = cell potential, V
Positive ∆G o indicates nonspontaneous reaction and the minimum work required to split one mole of water;
again, we compare this to the Daniell cell which produces electrical current spontaneously.
o
Given the minimum cell potential of Ecell = −1.23 V, we can argue that in the context of solar energydriven
reactions that photons with energy less than 1.23 eV cannot be used for water splitting reactions. This energy
corresponds to photons with wavelength
hc 1239.8eV nm
λ= o = = 1008 nm
Ecell 1.23 eV
indicating that (a) most of the visible spectrum of sunlight has the theoretical potential be used to drive the
PEC water splitting reactions, and (b) a semiconductor with Ebg ≥ 1.23 eV is necessary for the PEC reactions to
proceed in a singlejunction device.
10.1.1 Electrolyte pH
One of the questions posed at the outset of this chapter relates to the role electrolyte pH plays in the overall water
splitting process. As a quick review, recall that pure water partly dissociates into H+ and OH− ions according to
the equilibrium relationship
[H+ ][OH− ]
= Keq
[H2 O]
where the equilibrium constant Keq has units mol/l (molar, or M). Under normal laboratory conditions [H2 O] =
55.5 mol/l and so
Kw = 55.5Keq = [H+ ][OH− ]
CHAPTER 10. PHOTOELECTROCHEMICAL SYSTEMS 116
where Kw = 10−14 mol2 /l2 . This means [H+ ]=[OH− ] = 10−7 mol/l in pure water, resulting in a pH of
Given that HCl is an acid (proton donor) and a strong one at that (because it essentially fully dissociates in
water), a 1 M solution of HCl will have pH=0. For a 1 M NaOH (a strong base and proton acceptor) solution in
water
Kw
[H+ ] = = 10−14 mol/l
[OH− ]
resulting in pH=14.
Electrolyte conductivity
Pure water is a relatively poor conductor of electricity, and one important aspect of electrolyte pH is its role
in determining its charge carrriers, the electrolyte conduction mechanisms, and the mobility of those carriers
[Memming (2001)]. For example, one factor necessary to compute the overall conductivity of an electrolyte is the
combination of charged species mobility and the concentrations of the species themselves. Consider, for example,
the two cases illustrated in Fig. 10.2. For a basic solution, negative charges are transported through a hopping
mechanism where a hydroxyl ion OH− removes a proton from a nearby water molecule, transferring its negative
charge to that molecule. In an analogous manner, hydronium ions (H3 O− ) transfer a proton to a neighboring
water molecule, thus transporting the positive charge though the electrolyte.
e
O2 H2
H H H
Figure 10.2: The charge jumping mech
OH O H O H O H O H O anism at work in an aqueous electrolyte,
shown for the basic (top) and acidic (bot
H H tom) cases.
base
acid
H H H H
H O H O H O H O H H+
+
To qualify this conduction mechanism, electric ion mobility data below (from page 460 of [Levine (1978)]) corre
spond to 25o C, 1 atm of pressure, and are extrapolated to infinite dilution.
Multiplying each value by a representative electric field value, e.g., 10 V/cm, shows the relatively slow pace by
which ion charge is transferred through the electrolyte. From this we conclude that concentrated electrolyte
solutions will be required for practical PEC devices.
CHAPTER 10. PHOTOELECTROCHEMICAL SYSTEMS 117
At this point we have extensively discussed the concept of the Fermi level EF in the context of semiconductors and
metals. Otherwise known as electron chemical potential µe , it is characterized by the energy level corresponding
to a 0.5 probability of electron occupation, or the highest occupied energy state in the limit of T → 0 K.
• For a semiconductor, EF = f (EVB , ECB , T ) and, of course, also is a function of acceptor and donor concen
trations NA and ND in the case of doped semiconductors.
• For an electrolyte, EF ,redox = f (Eredox ) = f (pH), so the pH of the electrolyte plays a critical role in
) Ox + e− the electrochemical potential
determining the solution Fermi level. For the redox reaction Re *
[Ox ]
µe,redox = µored − µoox − RT ln
[Re ]
and so the chemical potential decreases with increasing oxidized species concentration [Memming (2001)].
In the case of Ox = H− this would result in decreasing electrochemical potential with decreasing pH.
• Reminiscent of the thought experiment involving semiconductor band structures and the band bending that
results when a junction is formed (Fig. 4.7), when a semiconductor and electrolyte are brought into contact,
the Fermi levels equilibrate and a junction is formed.
When EF < EF ,redox (a basic electrolyte) When EF > EF ,redox (acidic electrolyte)
• electrons move from the electrolyte into the • holes build up at the semiconductor edge
semiconductor forming the depletion region; nearest the electrolyte;
• the EVB and ECB bend downwards inside the • anions (negatively charged species) in the
semiconductor until EF = EF ,redox . electrolyte migrate to the surface to balance
the positive charges forming the accumula
tion region;
These two situations are depicted in Fig. 10.3 where the band bending corresponding to a basic solution is shown
at left and in an acidic solution, right. In the latter situation, if an electron is promoted to the conduction band,
the hole becomes available to drive an oxidation reaction at the electrode/electrolyte interface. The electron,
however, would be required to traverse the full width of the semiconductor  being the minority carrier, it will
encounter substantial resistance and likely undergo recombination, reducing the effectiveness of the cell. This
results in the preferred combination of ptype semiconductor with a basic solution where a reduction reaction
takes place.
We observe the PEC cell in operation in Fig. 10.4, where an electron is promoted to the conduction band in
the semiconductor, while the majority carriers (holes) migrate through the semiconductor to the electrode. The
reduction reaction takes place at the photocathode, resulting in OH− ions which migrate through the electrolyte
CHAPTER 10. PHOTOELECTROCHEMICAL SYSTEMS 118
ECB ECB
+ +
Figure 10.3: ptype depletion region (left) and
+ + accumulation (right) regions. PEC operation un
+ ERedox + ERedox der conditions where a depletion region exists is
EF EF the more common case.
+ +
EVB EVB
electrolyte electrolyte
ptype ptype
semicond semicond
to the counter electrode where the oxidation reaction takes place. Electrons involved in the anode reactions at
the liquid/semiconductor interface then are replenished by those traveling through the external circuit. In our
archetype PV cell, we recall that some resistance across an external load is required to generate useful electrical
work from the cell shown in Fig. 6.3. In the PV cell, a short (external) circuit results in no useful work. However,
an external short circuit forces the PEC cell to maximize useful chemical work.
e
e
2H2O + 2e 2OH + H2
OH 
1.23 V Figure 10.4: ptype PEC cell operation in a basic elec
EF,Redox trolyte.
hc/λ"
Surface reactions
The details of the surface reaction are important because of the strong dependency the reaction rates demonstrate
with different surfaces. Typically catalysts are required to produce effective reaction rates. The watersplitting
reaction details also are an important first step in understanding other photocatalyzed reactions. For the case of
an ptype semiconductor in a basic electrolyte, we can write the oxidation reactions that take place at the anode
as OXB the the reduction reactions at the cathode as REB .
S S S S S
S S S S S
CHAPTER 10. PHOTOELECTROCHEMICAL SYSTEMS 119
The anode and cathode reactions are summarized as follows; when the two half reaction potentials are added,
the cell potential is found be 1.23 V, the value discussed earlier in this chapter.
When EF > EF ,redox (e.g., an acidic electrolyte) When EF < EF ,redox (basic electrolyte)
• electrons move from the semiconductor into • electrons build up at the semiconductor edge
the electrolyte forming the depletion region; nearest the electrolyte;
• the EVB and ECB bend upwards inside the • cations (positively charges species) in the
semiconductor until EF = EF ,redox . electrolyte migrate to the surface to balance
the negative charges;
ECB ECB
+ +
EF ERedox EF ERedox
+ + Figure 10.5: ntype depletion region (left) and
accumulation (right) regions. As with the ptype
+ + semiconductor, the more common configurations
result in a junction featuring a depletion region.
+ +
EVB EVB
electrolyte electrolyte
ntype ntype
semicond semicond
These two situations are depicted in Fig. 10.5 where the band bending corresponding to an acidic solution is
shown at left and in a basic solution, right. In the latter situation, if an electron is promoted to the conduction
band, it becomes available to drive a reduction reaction at the electrode/electrolyte interface. The hole, however,
would be required to traverse the full width of the semiconductor  being the minority carrier, it will encounter
substantial resistance and likely undergo recombination, reducing the effectiveness of the cell. This results in the
preferred combination of ntype semiconductor with a acidic solution where an oxidation reaction takes place.
We observe the PEC cell in operation in Fig. 10.6, where an electron is promoted to the conduction band in the
semiconductor, while the minority carriers (holes) drift through the depletion zone to semiconductor/electrolyte
CHAPTER 10. PHOTOELECTROCHEMICAL SYSTEMS 120
interface. The electrons, as majority carriers, migrate through the semiconductor to the electrode. The oxidation
reaction takes place at the photoanode, resulting in H+ ions which migrate through the electrolyte to the counter
electrode where the reduction reaction takes place. Electrons generated in the anode travel to the counter
electrode through the external circuit.
e
e
2H+ + 2e ! H2
1.23 V
EF,Redox Figure 10.6: ntype PEC cell operation in an acidic
electrolyte.
H+
hc/λ"
Surface reactions
For the case of an ntype semiconductor in an acidic electrolyte, we can write the oxidation reactions that take
place at the anode as OXA the the reduction reactions at the cathode as REA .
OXA : H2 O + S → OH + H+ + e− OH → O + H+ + e− O+O → 2S + O2
S S S S S
REA : H+ + S → H+ H+ + e− → H H+H → 2S + H2
S S S S S
The anode and cathode reactions are summarized as follows; when the two have reaction potentials are added,
the cell potential again is found be 1.23 V.
Because we are operating under (external) shortcircuit conditions, the maximum theoretical current is deter
mined in exactly the same manner as with Iph,max for a PV cell: first we compute λbg for the titanium dioxide
semiconductor as
λbg = 413 nm
and then
Z∞
Iph = SR(λ)EE λ dλ
λ=0
Z λbg
EE λ
= q dλ
0 hc/λ
= 18.68 A/m2
At this point in the analysis we must ask “Is this a lot?” Or “Are we certain we have an energy balance?”
10.5 Nonidealities
We make note of some of the many nonidealities that limit the effective performance of these PEC systems. These
include
• Recombination: where electrons and holes may recombine within the semiconductor because of limited
charge carrier mobility and faults in the semiconductor, reducing the rate of the redox reactions.
• Electrolyte redox competition
– For ntype semiconductors, electrolyte cations may be reduced (instead of H+ ) and electrolyte anions
may be oxidized (instead of H2 O being split to (1/2)O2 , 2H+ , and 2e− );
CHAPTER 10. PHOTOELECTROCHEMICAL SYSTEMS 122
– For ptype semiconductors, electrolyte cations may be reduced at the photocathode in place of the
2H2 O + 2e− → H2 + 2OH− reaction, and electrolyte anions may be oxidized (instead of OH− reacting
to form O2 , water and e− ).
• Electrode degradation In some cases, the semiconductor itself may be oxidized or reduced instead of the
water or electrolyte anions or cations.
2. Consider the ptype semiconductor Cu2 O (Ebg = 2.1 eV) with an active electrode surface area of 10 m2 in a
PEC system operating at ambient conditions with an AM1.5 spectral irradiance normalized to 1000 W/m2 .
Assuming ideal conditions, determine the maximum possible molar flow rates (mol/sec) of the H2 and O2
produced as well as the water needed to replenish the system.
References
[Fujishima and Honda(1972)] Fujishima, A. K. Honda, Electrochemical photolysis of water at a semiconductor
electrode. Nature, 238 pp. 3738 (1972).
The DSSC and PEC devices discussed in the two previous chapters demonstrated photon absorption and charge
separation mechanisms that were new, but not entirely different from those that govern the solidstate PV devices
making up the majority of this text. We now turn our attention to photosynthesis, with the ultimate goal of
estimating the efficiency of natural photosynthesis processes as a means of comparing natural photosynthesis and
biofuel production to the PV systems we have studied.
11.1 Photosynthesis
The overall photosynthesis reaction is referred to as carbon fixation, the conversion of carbon dioxide to sugars
such as glucose:
hν
6CO2 (g) + 6H2 O(l) → (CH2 O)6 (aq) + 6O2 (g) (11.1)
o
The standard Gibbs energy of glucose formation by the reaction above is ∆G298 = 2880 kJ/mol (page 224 of
o
[Akins and DePaula (2002)]); for liquid water we have the Gibbs energy of formation ∆G298 = −237.1 kJ/mol
o
and for gaseous CO2 ∆G298 = −394.4 kJ/mol (pp. 686687 of [Smith et al. (2005)]). Of course, work (energy)
can be produced by the reverse reaction; an objective of this chapter is to determine the solar energy required
to produce energystoring molecules such as sugars and alcohols, and to give an estimate of the efficiency of
photosynthesis.
Carbon fixation is a redox reaction, and so (i) electron transfer is involved and (ii) energy is required to drive
the process because of the positive ∆G of (11.1). It is easy to show the reaction above is a redox reaction: 4
electrons are needed to reduce CO2 to the carbohydrate1 . Of course the reverse reaction is oxidation of sugar to
water and CO2 .
Before we proceed to our more quantitative analysis, we consider the following prehistory facts: photosynthesis
in early life on our planet (3.5 billion year ago) converted H2 and H2 S to bioproducts; one half billion years after
that, watersplitting photosynthesis led to the O2 in our atmosphere.
Modern photosynthesis is a twostage process
1. Light reactions capture solar energy and create ATP and NADPH, described by the Zscheme; these
reactions are mostly unaffected by temperature, and the light reactions are responsible for splitting water
in the photosynthesis process;
1 Definition: Carbohydrates are hydrates of carbon with general formula Cm (H2 O)n .
123
CHAPTER 11. PHOTOSYNTHESIS AND THE EFFICIENCY OF BIOETHANOL PRODUCTION 124
2. Light independent reactions convert CO2 to sugar. The reaction rate of this process increases with
temperature and these reactions form the CalvinBenson Cycle, consuming CO2 , ATP, NADPH and H+ to
generate a 3carbon carbohydrate, ADP, NADP+ , and water.
It is interesting to note that the rate of the carbonfixing reactions increases initially with solar irradiation (which
makes sense), reaches a plateau near the peak irradiance of 1 kW/m2 , and then decreases, though some sources
cite a 100 W/m2 plateau [Hall and Rao (1991)] (page 26).
11.1.1 Chlorophyll
There are two types of chlorophyll in green plants: chlorophyll a and chlorophyll b. Typically, the ratio of
chlorophyll a molecules to b is three to one. The function of chlorophyll a is to drive the water splitting reaction;
chlorophyll b also absorbs sunlight, but transfers its energy efficiently to chlorophyll a, expanding the spectral
range over which plants can absorb light.
2
second singlet
heat
1 green
first singlet
480 nm 550 nm 700 nm
hν"
energy available for
chemical work Figure 11.1: Chlorophyll excitation and ground states.
ground state
Plants absorb light between 550 and 700 nm, and for λ < 480 nm. It is the gap in between that results in the
green coloration of most plants. We note the sodium doublet (at 589 and 589.6 nm) falls within the absorption
range, resulting in the efficient use of sodium vapor lights for indoor plant growth (Fig. 11.1).
The molecule of chlorophyll a has at its center an Mg atom surrounded by a structure containing 10 CC conjugated
double bonds that are delocalized, switching between resonance structures. Generally, the higher the number of
double bonds in a system, the lower the energy required to form an excited state by a photon.
In Fig. 11.1, we observe two excited chlorophyll states denoted as the first and second singlets; the second
corresponds to and energy level accessible by the higherenergy photons (λ < 480 nm). This state will relax to
the first singlet releasing heat; the first singlet also can be accessed directly from photons in the lowerenergy
fraction of the absorption spectrum. The energy associated with excitation to the first singlet can drive the light
reactions of photosynthesis (described next) or, much like a direct band gap semiconductor, release the energy
via fluorescence with a peak intensity of λ = 685 nm [Hall and Rao (1991)] (page 63).
2e
2hν
λ=700 nm
NADP+ + H+ + 2e ! NADPH

e transport
2e rxns
2hν PS I Figure 11.2: The photosyn
reaction center
λ=680 nm thesis ”Z” scheme, sonamed
because of the ”Z” shape of
the energy levels.
PS II
reaction center
To understand how plants have engineered their lightharvesting capabilities, recall the discrete energy levels of
molecules as compared to the band structure of crystalline materials (Fig. 4.2). The lightharvesting complexes
inside chloroplasts are tightly packed crystalline structures composed of bundles of different pigments, each capable
of absorbing photons of higher energy relative to the chlorophyll center. These additional pigments (responsible for
fall colors in trees?), as part of the antenna proteins, essentially transfer their absorbed energy to the chlorophyll,
widening the spectral range over which the lightharvesting structure can absorb sunlight.
Photosystem II is a chemical complex with a chlorophyll a molecule at its center and absorbs light of wavelength
680 nm or less, hence the notation P680 or PS II. Photosystem I can absorb light of wavelength 700 nm or less
and is denoted P700 or PS I. We note that the reaction center of PS I also has chlorophyll a at its center.
The energycarrying molecules ATP and NADPH are generated by the light reactions and subsequently provide
the energy source for the carbonfixing reactions. NADPH is a reducing agent; when it is produced it leaves the
chlorophyll of PS I in a positively charged (oxidized) state.
where the NADPH is a sufficiently strong reducing agent to reduce CO2 and to ultimately create glucose.
11.3 Efficiency
Examining the literature, the efficiency of photosynthesis is listed as being anything from 0.1 to nearly 10%. But
what does this mean?
To begin our analysis, we begin with the water splitting reaction in the first step of the Zscheme and recall the
overall cell potential E o = −1.23 eV and so photons of wavelength λmax ≤ 1008 nm are required to split the
water molecule.
• Integrating the AM1.5 spectrum from 0 to 480 nm for both photosystems and from 550 to 680 nm for PSII
and to 700 nm for PSI, the mean maximum theoretical efficiencies are found to be
where SR ∗ is computed using λ = 1008 nm as the equivalent of λbg . Thus, the limiting efficiency is taken
as the mean ηPS = 19%
• 70% quantum efficiency reduces η = 13.3%
• dark reaction losses, including 32% efficiency in conversion to glucose gives η = 4.3%
• and 40% of glucose is consumed by the plant itself
2
AM1.5
PS I
1.5 PS II
W/m2/nm
0.5
0
200 400 600 800 1000 1200 1400
nm
Figure 11.3: The AM1.5 spectrum and the portion used by photosynthesis.
Overall, we obtain a final estimate of photosynthesis efficiency of converting sunlight at AM1.5 conditions to
harvestable glucose as η = 2.6%.
1. All calculations will be performed for a 1 hectare area (10000 m2  the size of a cricket field, or about 2.5
US acres)
CHAPTER 11. PHOTOSYNTHESIS AND THE EFFICIENCY OF BIOETHANOL PRODUCTION 127
2. Glucose will be produced by corn grown in Iowa, assuming a latitude of 42.5o N and a growing season from
early May to midOctober (approximately 160 days)
3. We will omit energy costs due to irrigation, human work, transportation, and application of pesticides and
herbicides
4. That days during the corn growth period are a 50/50 mix of full sun and full clouds
11.4.1 A PV farm
To begin, we compute the total amount of solar energy that falls on our one hectare plot to determine an upper
limit on the energy that can be harvested during the 160 day growing cycle. To carry out this calculation, we use
our solar toolbox sodtware starting with day 120 after the winter solstice, randomly choosing whether the day is
cloudy or clear according to our assumed 50/50 distribution. A plot of the hourly global irradiance EG is shown
in Fig. 11.4.
Figure 11.4: Iowa global irradiance EG over the corn growing season.
Integrating the hourly EG data over the full 160 days, we find the total solar energy Esolar ,tot as
280
10000 m2
Z
Esolar ,tot = EG (t)dt
hectare 120
= (10000)(2.97 × 109 J/m2 ) = 2.97 × 1013 J/hectare
We take a relatively conservative estimate that a PV farm would convert 10% of this energy to electricity, resulting
in a total PV energy production of
So far this looks promising given that these energy requirements are significantly lower that the power input from
the sun. Note that for fertilizer
3H2 + N2 ↔ 2NH3
with H2 produced from methane reforming, partial oxidation, or electrolysis; all constitute energy and carbon
inputs.
The resulting annual corn production rate cited by [Pimental and Patzek (2005)] for this farming operating is
In producing 99.5% pure ethanol, the following utility costs from [Pimental and Patzek (2005)] for ethanol distil
lation are used; based on the rate of ethanol production Retoh , we convert the utility costs to the same basis as
the corn production energy inputs:
The final step requires that we compute the energy content of the product ethanol. For this, we assume that it
is used in the most efficient form of the combustion reaction (e.g., using a fuel cell)
7
C2 H5 OH(l) + O2 → 2CO2 + 3H2 O(g )
2
and so the maximum work that can be extracted is
o
∆G298 = 2(−394000) + 3(−229000) − (−175000) = −1.3 × 106 J/mole ethanol
Given ethanol’s molecular mass of MW = 46.07 g/mol and density of ρ = 0.789 kg/l, our ethanol energy
equivalent is
1000 o
Eetoh = ρRetoh ∆G298 = −7.14 × 104 MJ/hectare
MW
We summarize our findings in the following table
CHAPTER 11. PHOTOSYNTHESIS AND THE EFFICIENCY OF BIOETHANOL PRODUCTION 129
In conclusion
• The total energy input (not including the sun!) necessary to produce fuelgrade ethanol essentially equals
the ethanol’s fuel value itself;
• Numerous energy inputs were omitted, but other factors, such as the dry distiller’s grain: 33% of corn (page
68 of [Pimental and Patzek (2005)], constitute an additional source of revenue for the overall production
process;
• Much can be done in optimizing the water/ethanol separation process;
• Because of its high oxygen content, we should consider biomass as a potentially more significant value as
a feedstock for chemical production instead of as a liquid fuel.
References
[Akins and DePaula (2002)] Akins, P. W. and J. DePaula, Physical Chemistry, 7th ed., Oxford University Press,
2002.
[Hall and Rao (1991)] Hall D. O. and K. K. Rao, Photosynthesis, 6th ed., Cambridge University Press, 1991.
[Pimental and Patzek (2005)] Pimentel, D. and T. W. Patzek, Ethanol production using corn, switchgrass, and
wood; biodiesel production using soybean and sunflower, Natural Resources Research 14 (1). pp. 6576,
2005.
[Smith et al. (2005)] Smith, J. M, H. C. Van Ness, and M. M. Abbott, Introduction to Chemical Engineering
Thermodynamics, 7th ed., McGrawHill Chemical Engineering Series, 2005.
Chapter 12
In this chapter we summarize the main numerical techniques used in our solar energy calculations.
We have the following values of f (x) within the interval of integration, including the two endpoints
[x0 , x1 , x2 , ... , xN ].
Given these data, we can compute an approximation to the definite integral (12.1) as
130
CHAPTER 12. ELEMENTARY NUMERICAL METHODS 131
If we consider xn = x(tn ) to be a point on the exact solution to the differential equation, we can write the Taylor’s
series approximation to the timedependent behavior of x (the exact solution) in the neighborhood of xn as
1 d 2 x
dx
x(t) = x(tn ) + (t − t n ) + (t − tn )2 + h.o.t.
dt tn 2 dt 2 tn
1 2 d 2 x
dx
x(tn+1 ) = x(tn ) + ∆t + ∆t 2 + h.o.t.
dt tn 2 dt tn
1 2 dg (x)
= x(tn ) + ∆t g (xn ) + ∆t + h.o.t.
2 dt tn
and so subtracting the results from one step of the Euler integrator and retaining only terms of order ∆2t or less
CHAPTER 12. ELEMENTARY NUMERICAL METHODS 132
gives an estimate of the error dn+1 generated by one step of the Euler integrator:
This means halving the step size decreases the local error by a factor of 1/4, however, twice as many steps are
required to integrate the system over the original time step and so if we assume errors accumulate in an additive
manner over short time intervals, we see the net effect of halving the step size when using the Euler method is to
halve the error. This is why the Euler method is called a first order method, even though it is accurate to order
2.
The following points also should be noted:
• The Euler method works for sets of equations by simply employing vector notation:
• The method works with mixed algebraic/ODE systems provided the AEs are solved at each time step for
some subset y the state variables:
zn+1 = zn + ∆t g(zn , yn )
f(zn , yn ) = 0
subject to z0 ;
• Stability issues set an upper practical limit on the time step sizes for most numerical integration techniques,
because instabilities can cause “runaway” to infinitely large global errors in systems which in reality display
bounded, longtime behavior.
g (x; p) = 0
We now solve for solutions xs using the iterative Newton’s method for a specified set of parameters p. If x 0 is
our guess for a solution, a more refined solution x 1 can be computed using the Taylor’s series of g evaluated at
the current solution estimate x 0 :
1 d 2 g
1 0 dg 1 0
g (x ) ≈ g (x ) + (x − x ) + (x 1 − x 0 )2 + h.o.t.
dx x 0 2! dx 2 x 0
CHAPTER 12. ELEMENTARY NUMERICAL METHODS 133
where h.o.t. refers to order three and higher derivative terms. To compute the more refined solution estimate
x 1 , a linear curve gL (x) tangent to g (x) at the current solution estimate g (x 0 ) is defined from the Taylor’s series
expansion by
0 dg
gL (x) = g (x ) + (x − x 0 ).
dx x 0
We see that gL (x) is a linear approximation to the true g (x), but one that can be solved explicitly for the value
of x where the function crosses zero; therefore, setting the right side of the equation above equal to zero and
solving for the corresponding x = x 1 gives
g (x 0 )
x1 = x0 − .
dg /dxx 0
Produced by this computation is a (hopefully) better estimate x 1 of a true solution to g (x) = 0; the word
hopefully is used because the actual convergence behavior of the Newton procedure can be difficult to predict.
We can continue to refine the solution estimate by replacing the previous estimate x 0 with the newer estimate x 1
and then repeating the procedure until a sufficiently accurate solution is reached.
g 0 (x) = g 0 (r ) + g 00 (r ).
g (x 0 )
x1 = x0 −
g 0 (x 0 )
g (x 0 )
x1 − r = x0 − r − 0 0
g (x )
0 g 0 (r ) + 12 (0 )2 g 00 (r )
1 = 0 −
g 0 (r ) + 0 g 00 (r )
0 g 0 (r ) + (0 )2 g 00 (r ) − 0 g 0 (r ) − 21 (0 )2 g 00 (r )
=
g 0 (r ) + 0 g 00 (r )
1 0 2 00
2 ( ) g (r )
=
g (r ) + 0 g 00 (r )
0
which normally will be sufficiently accurate if C 0  < 1 because, for example, if C 0  = 0.5
63
6 = 0.5 (0.5) = 5.4 × 10−20
which is less than roundoff error. It is important to point out, however, that choosing initial guesses based on
C 0  < 1 do not necessarily have to converge to the fixed points used to calculate the values of C .
The analysis above illustrates the quadratic convergence behavior of the Newton method when the estimate of
the solution approaches the true value. Because the next value of the error 1 is proportional to the square of
the previous error 0 , the accuracy of the solution estimates improves with each iteration in such a way that the
number of accurate digits doubles with each iteration, i.e., if 0 = 0.001, then 1 = 0.00001 in the neighborhood
of the converged solution. We note that explicit computation of g 0 and g 00 may be used to gain further insight
into the true accuracy of the solution.
12.5.2 NewtonRaphson
Now consider a representative set of nonlinear algebraic equations
h1 (x, y )
h(z) = (12.4)
h2 (x, y )
∂ 2 h1
0 0 ∂h1 0 ∂h1
h1 (x, y ) ≈ h1 (x , y ) + (x − x ) + (y − y 0 ) + (x − x 0 )(y − y 0 ) + ...
∂x x 0 ,y 0 ∂y x 0 ,y 0 ∂x∂y x 0 ,y 0
∂ 2 h2
∂h2 ∂h2
h2 (x, y ) ≈ h2 (x 0 , y 0 ) + (x − x 0
) + (y − y 0 ) + (x − x 0 )(y − y 0 ) + ...
∂x 0 0x ,y ∂y 0 0x ,y ∂x∂y 0 0
x ,y
Of course, we do not actually invert the Jacobian J; instead, we use the Gaussian elimination (or similar) procedure
described in the linear systems chapter to solve
J0 u1 = −h(z0 ) with u1 = z1 − z0
for the update vector u, which is used to compute the refined solution estimate z1 from
z1 = z0 + u1 .
CHAPTER 12. ELEMENTARY NUMERICAL METHODS 135
The perturbation δ used in the forward finite difference calculation actually varies according to the magnitude of
the variable zj to which the variation of the residuals are being computed; following [Kelly (2003)]:
√
δj = max [zj , 1]
References
[Kelly (2003)] Kelly, C. T. Solving Nonlinear Equations with Newton’s Method SIAM Press (2003).
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