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at low temperatures
Honours Thesis
Mathew Guenette
This study examines the operation of photovoltaic solar cells at low tempertaures(T < 300K). The
efficiency at which a GaAs solar cell converts light into electrical power was measured as a function
of temperature. The efficiency was found to increase as temperature decreased and then begin to
plateau at T ∼ 100K. These results can be explained by a decrease in energy loss from emission
of radiation(radiative recombination) and most importantly a decrease in the activity of electronic
defects in the solar cell (Shockley-Read-Hall recombination). Computer simulations showed that the
relative contribution of radiative and Shockley-Read-Hall recombination increases towards the ideal
radiative regime at low temperatures providing an environment which can be considered to be free
of parasitic losses due to Shockley-Read-Hall recombination however experimentally this was found
not to be the case due to the complex behaviour of Shockley-Read-Hall capture cross section with
temperature.
1
Acknowledgements
Type acknowledgements here.
All Matlab code written by myself and all computer simulations run by myself except for computer
simulation of radiative efficiency in section 3.3 done with N.J. Ekins-Daukes.
Building of experimental setup and all experimental measurements as outlined in sections 4 and 5
were done by myself.
Signed .........................................
Date:
Contents
1 Introduction 4
4 Experimental setup 21
4.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.2 In the vacuum chamber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.2.1 Temperature sensor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.2.2 Heater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.2.3 Sample solar cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.3 Outside the vacuum chamber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.3.1 Cryogenic system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.3.2 Temperature Controller . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.3.3 Variable light source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.3.4 I-V source measure unit . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.4 Photogenerated current . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2
Contents 3
5 Results 27
5.1 Current-Voltage and power measurements . . . . . . . . . . . . . . . . . . . . . . . 27
5.2 Variation of capture cross section with temperature . . . . . . . . . . . . . . . . . . 28
5.3 Temperature vs efficiency with varying capture cross section . . . . . . . . . . . . . 29
5.4 Uncertainties with power conversion efficiency . . . . . . . . . . . . . . . . . . . . 30
5.4.1 Theoretical uncertainty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.4.2 Experimental uncertainty . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
5.5 Dark I-V curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6 Conclusion 35
A Matlab Code 36
References 46
Chapter 1
Introduction
In the past extensive studies have been performed to test how the power conversion efficiency of pho-
tovoltaic solar cells changes with increased temperature however none have considered operation at
low temperature. This is primarily due to the energy required for cooling far outweighing any benefits
from increase of efficiency. This regime is interesting as it is hypothesised electronic defects will
effectively become ’frozen out’ and the only efficiency losses will come from emission of radiation,
which is thermodynamically unavoidable. This provides an environment in which solar cells can op-
erate in the ideal radiative limit and a testing ground for new solar cell device concepts such as the
intermediate band solar cell[1] which currently do not operate efficiently at room temperature.
This thesis is organised into 6 chapters. Chapter 2 is a survey of the literature on the subject of
photovoltaic solar cells and provides most of the background and theory necessary for this thesis.
Chapter 3 discusses the theory and computer model used to predict the behaviour of solar cells and
contains the results from several computer simulations. Chapter 4 outlines the experimental setup
and equipment used to measure efficiency. Chapter 5 gives the results of the experiment and discusses
how the results correlate with theory. Chapter 6 concludes the thesis and discusses possible associated
future work.
4
Chapter 2
2π E2
n(E, T, µ) = ²(E) (2.1)
c2 h3 e E−µ
kT − 1
where n is the photon flux as a function of energy E, ² is the emissivity,µ is the photon chemical
potential and T is the temperature. For a blackbody, ² = 1 for all energies and µ = 0. The total
energy density from the sun can be obtained by multiplying the photon flux by the photon energy, E,
and integrating over all energies to obtain the Stefan-Boltzmann law.
Z ∞
En(E, T )dE = σT 4 (2.2)
0
When T = Tsun = 6000K equation 2.1 describes the photon flux at the surface of the sun and
equation 2.2 describes the energy density at the surface of the sun. On Earth we receive sunlight from
5
Chapter 2. Survey of the literature 6
Figure 2.1 Extraterrestrial AM0 or 6000K blackbody spectrum (solid line) compared with terrestrial AM1.5
spectrum(Dashed line).
the solar disc subtending only a fraction of the hemisphere visible to the solar cell thus a dilution
factor of fω = 2.16 × 10−5 [6] must be included to calculate the photon flux and energy density on
Earth.
Ework 4 TA 1 TA 4
≡ ηL = 1 − ( − ) (2.3)
Eabs 3 TS 3 TS 4
This is only dependant on the temperature difference between the Sun and the absorber with
ηL = 93.3% for TA = 300K and approaching 100% as TA approaches 0K.
Chapter 2. Survey of the literature 7
Figure 2.2 A general absorber showing energy and entropy absorbed from the sun, radiated back to the sun
and dumped to a reservoir, resulting in useful work.
The Landsberg efficiency is the efficiency limit for a general absorber and does not consider the
realistic unavoidable entropy generation upon photon absorption[10]. When this is considered the
efficiency at 300K drops to 86%.
Figure 2.3 (a) Radiative generation in a semiconductor solar cell. (1) Transparent for incoming photon
with E < Eg .(2) Incoming photon with E = Eg will have enough energy to excite an electron across the
band-gap.(3) Incoming photon with energy E > Eg will excite an electron high into the conduction band
and quickly relax to the band gap edge(b)Radiative and non-radiative recombination in a semiconductor solar
cell.(4) Electron drops to across the band-gap and emits a photon. (5) SRH recombination, electrons and holes
recombine via defects
Ec + Ev 3kT mh
Ef = + ln (2.4)
2 4 me
where Ec and Ev are the energy levels of the conduction and valence bands respectively, k is
Boltzmann’s constant, T is the temperature and mh and me are the effective masses of the holes and
electrons respectively[13]. At room temperatures and lower the second term is small hence the Fermi
energy lies very close to the centre of the band gap.
When an impurity is introduced to an intrinsic semiconductor the Fermi energy must shift to
ensure charge neutrality. When a donor state is introduced with an energy level close to the conduction
band (n-type), the Fermi energy will shift towards the conduction band. When a acceptor state is
introduced with an energy close to the valence band(p-type), the Fermi energy will shift down towards
the valence band.
A single Fermi level is sufficient to describe a solar cell in equilibrium however when the cell
is illuminated and/or a voltage bias is applied it is no longer in equilibrium. Quasi-Fermi levels
Chapter 2. Survey of the literature 9
Figure 2.4 Energy levels for a p-n junction. (a) In equilibrium (b)With an applied bias resulting in a separation
of quasi-Fermi levels µ
describe the occupancy of the conduction and valence band individually when the electron and hole
populations are in respective equilibrium, but not in equilibrium with each other. The dashed lines
on figure 2.3 indicate the quasi-Fermi levels of the conduction and valence band with an applied bias
V. The separation of the quasi-Fermi levels is µ which is equal to the applied bias V at the terminals
when E is measured in electron-volts[5].
2πm∗h kTcell 3
Nv is the density of states in the valence band Nv = 2( h2
)2 and m∗e and m∗h are the effective
electron and hole masses respectively.
Figure 2.5 Idealised I-V curves for a solar cell in the dark(Green) and in the light(Red) indicating Jsc , Voc ,
the voltage and current for maximum power Vop and Jop and the associated rectangle of maximum power.
A typical idealised current-voltage (I-V) curve for a p-n junction solar cell in the dark and light is
shown in figure 2.5. The dark current curve (green) shows only the recombination effects in a solar
cell as no radiation is incident on the cell to produce generation effects. The light current curve (red)
is the same shape as the dark current curve but offset by a factor of Jsc . Jsc is the short circuit current,
defined to be the current when the applied bias is zero, it can be interpreted as the photogenerated
current resulting from illumination of the cell. Voc is the open circuit voltage, the voltage at which
there is zero current. Voc can be interpreted as the voltage at which the photogenerated current matches
and cancels out the recombination current.
The maximum power output of a solar cell occurs at some optimum applied bias Vop and a corre-
sponding current Jop . The fill factor is defined to be
Vop Jop
FF = (2.12)
Voc Jsc
The efficiency of a solar cell under incident power density Pin is defined as
Vop Jop
η= (2.13)
Pin
gap will be transparent to all but the highest energy photons. A cell with a relatively low band-gap will
have more electrons excited across the band gap but they will have less energy. Using the principle of
detailed balance Shockley and Queisser calculated the efficiency limits for different band-gaps[17].
The Shockley-Queisser calculation ignores all parasitic losses such as Shockley-Read-Hall recombi-
nation, leaving only radiative recombination, as required by the second law of thermodynamics[18].
The net power output for such a cell will be the difference between the current generated from the sun
and the current lost from radiative recombination multiplied by the applied voltage
Z ∞ Z ∞
efω 2π E2 e2π E2
P (Eg , V ) = V × ( 2 3 E−V dE − 2 3
E−V dE) (2.15)
ch e kTSun
Eg −1 ch
Eg e kTcell − 1
Finding Vop to maximise power output is done numerically for different band-gaps, the most ef-
ficient band-gap being approximately 1.3eV with an efficiency of η ≈ 30%. The efficiency is calcu-
lated by dividing the maximum power output by the power input from the sun given by the Stefan-
Boltzmann law multiplied by the dilution factor fω = 2.16e − 5.
P (Eg , Vop
η= 4
(2.16)
fω σTsun
The results from Shockley and Queisser are summarised in figure 2.6 (a). The Shockley-Queisser
limit for a terrestrial AM1.5 spectrum is shown in figure 2.6 (b) with the best experimental results[19]
for single junction devices shown as red dots. The optimum band gap for the AM1.5 spectrum is
approximately 1.4eV which corresponds closely to the band-gap of 1.42eV for GaAs.
eW qV
JSRH (V ) = σvth Nt ni e 2kTcell (2.17)
2
1
For example good GaAs cells are not SRH dominant at the operating voltage, the main recombination mechanism is
radiative recombination. This will be explored in the next chapter
Chapter 2. Survey of the literature 13
Figure 2.6 (a)The Shockley-Queisser efficiency limit for a single-junction cell published in the original Shock-
ley and Queisser paper in 1961[17] for an AM0 incident spectrum (6000K blackbody), including the best exper-
imental efficiency for Silicon cells in 1961 and a semi-empirical curve thought to be the efficiency limit before
the Shockley-Queisser paper was published(b)The Shockley-Queisser limit with an AM1.5 incident spectrum,
best experimental results for single junction devices are shown as red dots.Image (b) from N.J. Ekins-Daukes
where e is the charge of an electron, W is the depletion layer width given by equation 2.5,q σ is the
capture cross sectional area, vth is the thermal RMS velocity of an electron given by vth = 3kT cell
m∗e
, Nt is the trap density, ni is the intrinsic density of states given by equation 2.6 and V is the applied
bias. The capture cross section is the probability of an electron or holer being captured in a defect
state expressed as an area.
The only terms which cannot be calculated easily are the capture cross section and the trap density
which generally must be measured using capacitance spectroscopy[21, 22] or deep-level transient
spectroscopy[23].
The photogenerated current is given by equation 2.9 and is calculated in the model by numerically
integrating from the band gap, Eg to 10eV 1 using the trapezium rule method with Tsun = 6000K.
The recombination current calculation consists of two parts dependant on the bias voltage, ra-
diative and non-radiative SRH recombination. Radiative recombination is calculated by numerically
integrating equation 2.11 from Eg to 10eV for a bias voltage range of 0 to 0.99Eg . SRH recombina-
tion is calculated by simply evaluating equation 2.17 over the same bias voltage range. The net current
can then be plotted as a function of voltage. The power of the solar cell as a function of voltage can be
calculated by multiplying the current curve by the voltage. The maximum power can easily be found
from this curve and divided by the power input to find the efficiency.
14
Chapter 3. Theoretical model and computer simulation 15
The results are interesting to conceptually show a trend for increasing efficiencies with decreasing
temperatures however could not be considered to be a theoretical prediction for real solar cells as
SRH recombination has not been included. Increased efficiency is not particularly surprising as the
photogenerated current will not change with cell temperature for a fixed band gap however radiative
recombination is strongly dependant on temperature with decreased recombination occurring at lower
temperatures. What is surprising though is the fact that the band gap at which the peak efficiency
occurs shifts with temperature, however only slightly from approximately 1.3eV at 300K towards
1.2eV at 50K.
Figure 3.1 Shockley-Queisser calculation at 300K and 50K for band gap Eg = 1.42eV (a) Current-Voltage
curve. Note this curve is of the same form as the one shown in figure 2.5, current density is simply measured in
the opposite direction. (b) Power curve
Chapter 3. Theoretical model and computer simulation 16
Figure 3.2 Temperature dependant Shockley-Queisser type calculation, shows a general trend for increasing
efficiencies with decreasing temperatures. 300K - Blue (Lowest), 200K - Green (2nd lowest), 100K - Red
(2nd highest) and 50K - Light Blue (Highest)
Jrad
(3.1)
Jrad + JSRH
and provides a measurement of the relative contributions of radia-
tive and SRH recombination. High radiative efficiency is desirable as
it means there is negligible parasitic current losses and recombination Figure 3.3 Photon recycling,
is predominantly radiative. emitted photons internally re-
The dark current of a good 24.4% efficient GaAs cell[25] is shown flected off the front surface then
in figure 3.4 along with calculated radiative and SRH recombination absorbed into the substrate
components.
Chapter 3. Theoretical model and computer simulation 17
The SRH recombination component was calculated using equation 2.17 as in the previous section.
For simplicity the capture cross section, trap density, effective mass and band-gap were taken to be
independent of temperature, the validity of these assumptions will be examined in future sections. A
trap density of Nt = 4.5 × 1014 cm−3 was required to fit the non-radiative component with a capture
cross section of σ = 1 × 10−16 cm2 and a cell temperature of 307K was required to fit the radiative
component.
Under the illumination of one sun this cell has Jsc = 27.6 mA/m2 as indicated by the dashed line
in figure 3.4. The radiative efficiency is calculated at the corresponding Voc point giving this cell a
high radiative efficiency of 88%.
The radiative efficiency of this cell is plotted in figure 3.5(a) as a function of temperature along
with calculations for a GaAs cell with a much larger trap density Nt = 1 × 1016 cm−3 . Jsc was taken
to be the same for both cells, at all temperatures.
It is clear that both cells display an increasing radiative efficiency with decreasing temperature,
the cell with the larger trap density showing a more dramatic increase.
The power conversion efficiency of the two cells are shown in figure 3.5(b). The larger trap
density is a considerable problem at room temperature but becomes insignificant at low temperatures
converging with the low trap density cell. These results indicate that the low temperature regime is
effectively a environment where defects in the cell are ’frozen out’ and the cell can operate in the ideal
radiative limit.
Voc = 0.845 V. Once again Jsc was fixed to 25.9 mA/cm−2 and and the trap density which predicted
the same Voc was found to be Nt = 4 ± 0.1 × 1018 cm−3 . The model predicted an efficiency of
17.1 ± 0.4% whereas the record is 16.5 ± 0.5%.
Although within errors the inconsistency between the measured efficiency and the efficiency pre-
dicted by the model is due to the model incorrectly predicting the fill factor of the cell. This comes
from not correctly predicting the rate of change between the voltage and the recombination current.
The motivation for this is to find a reasonable value for Nt for a good quality solar cell (GaAs)
and a poor quality solar cell (CdTe). Band-Gap vs efficiency for a good cell, Nt = 4 × 1018 cm−3
and a poor cell, Nt = 1 × 1016 cm−3 are illustrated in figure 3.6 along with a mediocre quality cell,
Nt = 2 × 1017 cm−3 and a cell with a extremely low trap density, Nt = 4.5 × 1014 cm−3 .
The interesting and somewhat surprising result from this simulation is that the band gap where
peak efficiency occurs is dependant on the trap density. The very low trap density of Nt = 4.5 ×
1014 cm−3 approaches the Shockley-Queisser efficiency curve as expected, with the optimum band
gap being approximately 1.3eV . The highest trap density of Nt = 4.5 × 1018 cm−3 corresponds to an
optimum band gap of approximately 1.7eV . These results suggest that if the intention is to purposely
make a cheap solar cell suffering from high rates of SRH recombination it might be better focusing
on materials with higher band gaps around the 1.7eV range rather than the band gaps traditionally
thought to produce the highest efficiencies predicted by the Shockley-Queisser efficiency curve.
In the SRH calculation the data for effective electron and hole mass used was that of GaAs,
∗
me = 0.45m0 and m∗e = 0.067m0 where m0 is the mass of the electron. The permittivity of GaAs
was also used ²s = 13.1²0 .
Chapter 3. Theoretical model and computer simulation 19
Figure 3.4 Dark current data of a good GaAs cell[25]. Dashed line refers to Jsc under AM1.5 illumination.
Image from N.J. Ekins-Daukes
Figure 3.5 (a) Radiative efficiency and (b) power conversion efficiency as a function of temperature for two
GaAs cells, Nt = 4.5 × 1014 cm−3 and Nt = 1 × 1016 cm−3
Chapter 3. Theoretical model and computer simulation 20
Figure 3.6 Shockley-Queisser type calculation including SRH recombination, shows a general trend for in-
creasing optimum band gap with increaasing trap density, capture cross section kept constant at σ = 1 × 10−16
cm−2 . Nt = 4.5 × 1014 cm−3 - Blue (Highest), Nt = 1 × 1016 cm−3 - Green (2nd highest), Nt = 2 × 1017 cm−3
- Red (2nd Lowest) and Nt = 4.5 × 1018 cm−3 - Light Blue (Lowest)
Chapter 4
Experimental setup
4.1 Overview
Figure 4.1 (a) Schematic of experimental setup (b) Photograph of experimental setup
The experimental setup is shown in figure 4.1. The sample solar cell is held by a cryostat in
a specifically designed mount inside the vacuum chamber. The vacuum is necessary to insulate the
sample and reach very low temperatures efficiently. It was discovered no diffusion pump was required,
only a rotary pump was necessary to reach temperatures as low as ∼ 10K using the cryogenic system.
A nichrome wire heater and diode temperature sensor were attached to the mount in the vacuum
chamber which were controlled by the temperature controller. The I-V source / measure unit was
21
Chapter 4. Experimental setup 22
used via the laptop to measure the current-voltage characteristics of the sample. The sample was
illuminated by the variable light source via an optic fibre with a collimator through diffusing glass.
These components will be discussed in more detail in the next sections.
Figure 4.2 (a) Schematic of inside the chamber (b) Photograph of inside the chamber
The vacuum chamber is shown in figure 4.2. Substantial work was done in building the experi-
ment. A new temperature sensor with a 4-point measurement system was installed. The heater failed
several times throughout the course of the experiment and needed to be rewired after cooling the
system one or two times. Plugs required to connect to the sample solar cell were constructed and
connected via a 4-point measurement to the I-V source / measure unit. A specific size mount was
designed to hold the sample solar cell and fit the cryostat, the design of the mount can be found in
Appendix B.
resistance(∼ 5Ω). The temperature sensor was clamped down to the base of the mount with a spring
loaded screw, the spring is required to compensate for any thermal contraction that occurs during
cooling to avoid crushing the diode.
4.2.2 Heater
The heater consisted of ∼ 1.5m Nichrome 32 AWG wire wrapped around the base of the mount with
a total resistance ∼ 50Ω which gives maximum heating capacity from the temperature controller. The
heater is required to stabilise the temperature by counteracting the cryogenic system which provides
cooling at a constant rate.
Figure 4.3 (a) Schematic of sample cell, cell is 1mm in diameter, the black region indicating the shading of
the cell from the metal cap (b) Photograph of 6 sample cells
The sample solar cell used in this experiment was QT1405R, designed by the Department of
Physics at Imperial College, London. It is a GaAs pn junction grown by metal organic chemical
vapour deposition (MOCVD) with parameters as specified on the growth profile
- Dielectric Constant ²s = 13.18²0
- Band Gap Eg = 1.424 eV
- Refractive index n = 3.660
- P-type doping NA = 2 × 1018 cm−3
- N-type doping ND = 2 × 1017 cm−3
Chapter 4. Experimental setup 24
The spectrum of this light source is different from the spectrum of the sun and hence this exper-
iment is not capable of accurately measuring the efficiency under one sun illumination. The light
source is a tungsten halogen light bulb producing a 3200K blackbody spectrum whereas the sun
produces a ∼ 6000K blackbody spectrum. However this experiment is primarily concerned with
measuring the relative change in efficiency at with temperature and it is not a requirement we know
what the efficiency under one sun illumination as long as we have the same illumination source for all
temperatures.
αT 2
Eg (T ) = Eg (0) − (4.2)
T +β
where Eg (0) = 1.52eV, α = 5.4×10−4 and β = 204 for GaAS[13]. Band gap decreases with with
increased temperature is due to thermal expansion of the lattice in the semiconductor. An increase in
interatomic spacing decreases the potential of the electron and consequently the band gap.
Under constant illumination the photogenerated current in a cell is going to change with temper-
ature due to the temperature dependance of the band gap. To further complicate the situation in this
experiment the location of the solar cell is going to change due to the thermal contraction of the mount
at low temperatures making it very difficult to experimentally keep the same level of illumination on
the cell. It was decided for simplicity to keep Jsc constant by adjusting the position and intensity of
the light source for each measurement.
It is known that under illumination of 1000 W m− 2 at 300K the QT1405R cell has a Jsc of
63 ± 0.5µA[29]. It was found that the lamp used in the experimental setup could not produce enough
power at low temperatures to create such a Jsc however it could easily produce Jsc of 21µA for all
cell temperatures, equivalent to illumination under 10003
W m− 2 or 2.6 × 10−4 W over the front of the
Chapter 4. Experimental setup 26
cell(including shading). Jsc varied slightly for measurements at different temperatures between the
range 21 ± 1µA, this was taken into account when the power conversion efficiency was calculated.
Chapter 5
Results
Figure 5.1 (a) Theoretical and experimental I-V curve of Q1405R at 300K (b) Theoretical and experimental
power curve of Q1405R at 300 ± 1K. There is an error of ±1K for the experimental curve.
27
Chapter 5. Results 28
However at lower temperatures the model underestimated the recombination current leading to an
overestimate of the volatge at a particular current as evident in figure 5.2. At 200K the discrepancy
is moderate yet beyond experimental error and at 50K the discrepancy is large. The magnitude of
the error is revealed in figure 5.3 where the experimental and theoretical efficiency as a function of
temperature is shown. Experimental efficiency as a function of temperature shows a very strong linear
relationship at temperatures greater than ∼ 100K and then begins to plateau at lower temperatures.
Good agreement is obtained at 300K where the fitting parameters were established but a signifi-
cant deviation from the theoretical curve towards lower efficiencies at low temperatures is observed
experimentally. These results indicate that the fitting parameters have some temperature dependance.
Figure 5.2 (a) Theoretical and experimental I-V curve of Q1405R at 200 ± 1K and (b)50 ± 5K. Theory keeps
σ constant with temperature.
Figure 5.3 Experimental and Theoretical efficiency Vs temperature. Theory keeps σ constant with temperature
level traps in GaAs and GaP[30]. No information is known about the defect levels in QT1405R and
thus attempting to theoretically model how σ changes with temperature was not possible.
Nt = 1.75 × 1016 cm−3 was kept constant and σ was used as a fitting parameter for each curve
such that σ was varied until the experimental Voc matched the theoretical Voc . A plot of fitted capture
cross section vs inverse temperature is shown in figure 5.4 (b). The shape of the capture cross section
bears resemblance to the shape of the deep level defect ’A’ in figure 5.4 lending credibility to this
method of approximating σ(T ) and suggesting that the unknown deep level defect ’A’ may be the
dominant defect present in QT1405R. Measuring the capture cross section of defects in solar cell can
be performed using capacitance spectroscopy and deep level transient spectroscopy techniques[23]
though this was not done due to complexity and time restraints.
Figure 5.4 (a)Capture cross section vs Inverse temperature for a number of defects in GaAs and GaP. n denotes
electron capture whilst p denotes hole capture. A and B are common but unidentified deep level defects Image
from C.H. Henry and D.V. Lang[30]. (b) Inverse temperature vs fitted capture cross section for QT1405R.
ure 5.5 shows much better agreement between theory and experiment in the range 150K . T < 300K
but still displays significant variation at the lowest measured temperatures (T . 150K). The most
likely explanation behind this deviation between experiment and theory is due to a reduction in elec-
tron density at low temperatures where free electrons and holes return to their respective donor and
acceptor impurity states.[13]. Electron density can be considered to be constant in the range between
approximately 150K and 500K and equal to the donor impurity concentration, ND . However when
the thermal energy of the lattice is not high enough to ionize the donor impurities, the electron den-
sity decreases dramatically with temperature and is less than the donor impurity concentration, this is
known as the’freeze out region’. Incorporating this theoretically into calculations of I-V curves would
require a model and computer package with a higher degree of sophistication and is beyond the scope
of this thesis.
For completeness the full set of experimental I-V curves and their corresponding theoretical curves
are in appendix C.
Figure 5.5 Experimental and Theoretical efficiency Vs temperature. Theory varies σ with temperature.
half the difference in the σ value needed to match the points on either side of J=0.
The values of σ and associated error is summarised in appendix C.
The error associated with the temperature of the cell varies for different temperatures and is deter-
mined by the inability to keep the temperature stable during measurement.
Experimental uncertainty data is summarised in figure C.2 in Appendix C.
(a) 300K dark I-V curve (b) 175K dark I-V curve
Figure 5.6 Dark I-V curves for QT1405R at 300K, 175k and 100K. The dashed line represents the cell’s Jsc
Chapter 5. Results 34
Figure 5.7 Radiative efficiency of QTQ1405R as a function of temperature, a sharp decrease is observed at
T < 100K due to the sharp increase in capture cross section shown on the secondary axis
Chapter 6
Conclusion
The power conversion efficiency of a photovoltaic solar cell was predicted to increase as the tem-
perature of the cell was decreased due to a reduction in radiative and non-radiative recombination. A
simple matlab model for calculatin I-V curves and efficiency theoretically predicted how the efficiency
varied with temperature.
Experimental results revealed that the efficiency of our sample GaAs solar cell increased con-
sistently with decreasing temperature however discrepancies between theory and experiment were
apparent. This was due to the complex behaviour of the capture cross section for non-radiative re-
combination with temperature.
Capture cross section was adjusted to vary with temperature showing significantly improved
agreement between theory and experimental yet still large discrepancies at the lowest temperatures.
The most likely reason for this is the thermal energy of the lattice not providing enough energy to
ionise donor and acceptor impurity atoms decreasing the electron density of the semiconductor.
The experimental radiative efficiency of the cell was found to be approximately constant above
100K and dropping dramatically at lower temperatures to almost zero. These results indicate that the
sample cell did not become radiatively efficient at low temperatures with parasitic SRH recombination
still the dominant recombination process in the cell. The decrease in experimental radiative efficiency
contradicted computer simulations again due to the complex behaviour of the capture cross section
with temperature. It was concluded that the low temperature environment is generally not a reliable
testing ground for new solar cell design concepts such as the intermediate band cell unless the capture
cross section for the defects present in a particular cell are known to decrease with temperature.
Future work associated with this project would be to employ a more sophisticated computer model
for increased accuracy in predicting I-V curves and understand how the electron density varies at low
temperatures. The low current measurements on the dark I-V curves could be improved by better
wiring and shielding of wires from interference in the cryostat. By improving the bonding of wires
to the solar cell increased currents could be used in the cell without the risk of melting the bond
wires thus being able to push the cell into the radiative regime at high voltages. In this work the
capture cross section and trap density are used as fitting parameters having only values relative to
each other. Capacitance spectroscopy and deep level transient spectroscopy techniques would allow
accurate measurement of both parameters as a function of temperature.
35
Appendix A
Matlab Code
%Everything in electronvolts
T=300 %temp of cell
36
Appendix A. Matlab Code 37
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%Shockley-Read-Hall current expression%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
V=linspace(0,0.99*eg,1000); const=((q*w*sigma*vth*nt*ni)/2);
JSRH=const*exp((V)/(2*k*T));
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%Calculate photgenerated current from the Sun
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
e=linspace(eg,20,1000); n=1:1:1000;
JSC=trapz(e,J);
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%calculate radiative recombination%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
for j=1:1000;
v= j*0.99*(eg)/1000;
m = 1:1:1000;
en=linspace(eg,20,1000);
energy(m)=en;
Appendix A. Matlab Code 38
planck(m)=((26.2*q*2*pi)/(cˆ2*hˆ3)*en.ˆ2)./(exp((en-v)/(k*T))-1);
bias(j)=v;
end
[a,b]=min(yep);
JSC=yi(b)
f=6.3e-5/JSC;
[maxpowers,maxplace]=max(yp);
[maxpower,maxt]=max(power);
Eff=100*maxpower*f/(A*1000)
%plotting stuff
%Light curves
figure(3) plot(bias,current,yv,yi,’*’) title([’Light I-V curve at
’,int2str(T),’\pm1K’]) xlabel(’Applied Bias (V)’); ylabel(’Current
(A)’); legend(’Theoretical’,’Experimental’) ylim([0 0.3e-4]) xlim([0
1.5])
%dark curves
figure(9)
semilogy(bias,JSRH2,bias,int2,bias,dark,expV2,expI2,’*’)%yv,yi,’*’)
title([’Dark I-V curve at ’,int2str(T),’\pm1K’]) xlabel(’Applied
Bias (V)’); ylabel(’Current (A)’);
legend(’Theoretical SRH’,’Theoretical radiative’,
’Theoretical SRH + radiative’,’Experimental’)%,’dark shifted by JSC’)
%power curves
figure(4)
plot(bias,power,yv,yp,’*’)%,expV2,pow3)
title([’Power curve at ’,int2str(T),’\pm1K’]) xlabel(’Applied Bias
(V)’); ylabel(’Power (W)’);
legend(’Theoretical’,’Experimental’)%,’dark shifted by JSC’)
ylim([0 0.4e-4]) xlim([0 1.5])
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
Appendix B
Designs of mount and cover plate for sample solar cell, material is copper.
40
Appendix B. Solar Cell Mount Designs 41
Appendix C
42
Appendix C. Capture Cross Section Data and I-V curves 43
Temperature (K) Position Error (%) Measurement Error (%) Total Error (%)
300 ± 1 ±0.6 ±0.8 ±1
275 ± 1 ±0.7 ±0.8 ±1
250 ± 1 ±0.8 ±0.8 ±1
225 ± 1 ±0.1 ±0.8 ±0.8
200 ± 1 ±0.4 ±0.8 ±0.9
175 ± 2 ±0.5 ±0.8 ±0.9
150 ± 5 ±0.3 ±0.8 ±0.9
125 ± 5 ±0.1 ±0.8 ±0.8
100 ± 5 ±0.5 ±0.8 ±0.9
75 ± 5 ±0.1 ±0.8 ±0.8
50 ± 5 ±0.2 ±0.8 ±0.8
Figure C.1 Table showing the experimental error associated with Temperature, the position of the maxi-
mum power point, measurement of the maximum power point and total combined error for power conversion
efficiency
Figure C.2 I-V curves for temperatures between 175K and 300K
Appendix C. Capture Cross Section Data and I-V curves 45
(e) 50K
Figure C.3 I-V curves for temperatures between 50K and 175K
References
46
References 47