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USF Tampa Graduate Theses and Dissertations USF Graduate Theses and Dissertations

November 2024

Performance Optimization and Application of p-type Transparent

Semiconductors in the CdTe Solar Cells
Md Zahangir Alom
University of South Florida

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Performance Optimization and Application of p-type Transparent Semiconductors

in the CdTe Solar Cells

by

Md Zahangir Alom

A dissertation submitted in partial fulfillment

of the requirements for the degree of
Doctor of Philosophy
Department of Electrical Engineering
College of Engineering
University of South Florida

Major Professor: Chris Ferekides, Ph.D.

Andrew Hoff, Ph.D.
Arash Takshi, Ph.D.
Abla Zayed, Ph.D.
Yusuf Emirov, Ph.D.

Date of Approval:
November 14, 2024

Keywords: semiconductor, bandgap, spin coating, annealing, composition

Copyright © 2024, Md Zahangir Alom

 Dedication

To my respected parents, grandparents, wife, sisters, teachers and my beloved country

people in Bangladesh.
 Acknowledgments

First, I want to thank the almighty Allah for His blessings, help, and mercies on me. I am

so grateful to Him that I can not express it. I never thought that I could do a PhD and here I am,

writing my dissertation. I always trust Allah’s plan. If you have complete faith in Him, your life

will be full of blessings no matter what is happening around you.

Secondly, I want to thank my parents, sisters, and wife for their endless support. Without

them, I am nobody. I can never forget my parent’s sacrifice for my well-being. They are my

superheroes. They supported and allowed me to do whatever I liked. My sisters also inspired me

and helped to create an excellent family-friendly environment. For the last couple of years, I

have had endless support from my wife, which is very rare. I am grateful and fortunate to have

her in my life. She is such a good person and life partner. I am blessed to have her in my life.

I am also very grateful to all my teachers. The ethical standards they set for me have

made me a better human being. I also want to show my gratitude to all my friends, seniors, and

juniors who helped me to become a better person both academically and professionally.

I am also very grateful to my major professor, Dr. Chris Ferekides, for his continuous

help and support and for allowing me to work under his supervision. I want to thank Vasilios

Palekis, Sheikh Tawsif Elahi, and Wei Wang for their help in my research. Most of my research

works are supported by the National Science Foundation (NSF), the Department of Energy

(DOE), and the National Renewable Energy Laboratories (NREL). I am also grateful to them for

allowing me to work on these projects.

 Table of Contents

List of Tables ................................................................................................................................. iv

List of Figures ................................................................................................................................ vi

List of Acronyms .............................................................................................................................x

Abstract .......................................................................................................................................... xi

Chapter 1: Introduction ....................................................................................................................1

1.1 PV Technologies ............................................................................................................2
1.1.1 Wafer Technology ..........................................................................................2
1.1.2 Thin Film Technology ....................................................................................3
1.1.3 Emerging Thin Film Technology....................................................................3
1.2 Advantages of CdTe ......................................................................................................4

Chapter 2: Semiconductors and Solar Cells.....................................................................................6

2.1 Semiconductors ..............................................................................................................6
2.2 pn Junction .....................................................................................................................7
2.2.1 pn Heterojunction............................................................................................8
2.3 Solar Cell Operation ......................................................................................................8
2.3.1 p-type CdTe Solar Cell Operation ..................................................................9
2.3.2 n-type CdTe Solar Cell Operation ................................................................10
2.4 Solar Cell Terminologies .............................................................................................10
2.5 Photo Conversion Efficiency .......................................................................................12
2.6 Solar Spectrum and Quantum Efficiency ....................................................................13

Chapter 3: Evolution of the CdTe Solar Cells ...............................................................................15

3.1 CdTe Solar Cells Development History ......................................................................15
3.2 CdTe Solar Cells Present and Future ...........................................................................16
3.3 CST (CdSeXTe1-X) Layer Optimization and Doping ...................................................17
3.4 n-type CdTe Solar Cells and Challenges .....................................................................21
3.5 CuSCN Properties ........................................................................................................24
3.6 CuI Properties ..............................................................................................................25
3.7 Interface Passivation Layer ..........................................................................................26
3.8 Objective of This Study ...............................................................................................28

Chapter 4: Experimental Details ....................................................................................................29

4.1 Device Architecture of p-type CST/CdTe Solar Cells .................................................29
4.1.1 Substrate ........................................................................................................30

i
 4.1.2 Transparent Conducting Oxides (TCOs) ......................................................30
4.1.3 Buffer Layer ..................................................................................................30
4.1.4 Window Layer ..............................................................................................31
4.1.5 CST (CdSeXTe1-X) Absorber Layer ..............................................................31
4.1.6 CdTe Absorber Layer ...................................................................................32
4.1.7 CdCl2 Heat Treatment ...................................................................................32
4.1.8 Back Contact Formation ...............................................................................32
4.1.9 Experimental Process ....................................................................................33
4.1.10 CST (CdSeXTe1-X) Source with Different Se Compositions .......................34
4.1.11 Spin Coating Process ..................................................................................35
4.1.12 CuSCN Spin Coating ..................................................................................36
4.1.13 CuI Spin Coating.........................................................................................38
4.2 Device Architecture of n-type CdTe Solar Cells .........................................................39
4.2.1 Experimental Process ....................................................................................39
4.2.2 EVT Process..................................................................................................40

Chapter 5: Experimental Measurements ........................................................................................41

5.1 Current Voltage (I-V) Measurement ............................................................................41
5.2 Spectral Response (SR) Measurement .........................................................................41
5.3 Capacitance-Voltage (C-V) Measurement ...................................................................42
5.4 X-ray Diffraction (XRD) .............................................................................................42
5.5 Scanning Electron Microscope (SEM) ........................................................................42

Chapter 6: Optimization of p-type CST/CdTe Solar Cells ............................................................44

6.1 Effect of CdS Thickness ..............................................................................................44
6.2 Effect of CdCl2 Annealing Temperatures ....................................................................46
6.3 Effect of Selenium (Se) Composition of the CST (CdSexTe1-x) Layer ........................47
6.4 Effect of As (Arsenic) Doped CST (CdSexTe1-x) on the Cell Performance ................50
6.5 Effect of CST (CdSeXTe1-X) Layer Thickness on the Performance .............................53
6.6 Summary of Chapter 6 .................................................................................................54

Chapter 7: p-type CST/CdTe Solar Cells with Transparent Back Contact ....................................56
7.1 p-type CdTe Solar Cells with CuI Transparent Back Contact .....................................57
7.2 p-type CST/CdTe Solar Cells with CuI Transparent Back Contact ............................62
7.3 p-type CdTe Solar Cells with CuSCN Transparent Back Contact ..............................63
7.4 p-type CST/CdTe Solar Cells with CuSCN Transparent Back Contact ......................66
7.5 Summary of Chapter 7 .................................................................................................67

Chapter 8: n-type CdTe Solar Cells with Transparent p-type Heterojunction Partner ..................69
8.1 CuI as p-type Heterojunction Partner ..........................................................................71
8.1.1 Effect of CuI Annealing Temperature ..........................................................72
8.2 CuI as an Interfacial Layer ...........................................................................................73
8.3 CuSCN as p-type Heterojunction Partner ....................................................................75
8.3.1 Effect of CuSCN Thickness ..........................................................................76
8.3.2 Effect of CuSCN Annealing Temperature ....................................................77
8.3.3 Effect of CuSCN Annealing Time ................................................................78

ii
 8.3.4 Effect of CuSCN Doping ..............................................................................79
8.4 Effect of n-type CdTe Doping .....................................................................................80
8.5 CuSCN as an Interfacial Layer ....................................................................................81
8.6 Surface Treatment ........................................................................................................83
8.7 Al2O3 as an Interface Passivation Layer ......................................................................84
8.8 Summary of Chapter 8 .................................................................................................85

Chapter 9: Conclusions and Future Opportunities .........................................................................87

9.1 Conclusions ..................................................................................................................87
9.2 Future Opportunities ....................................................................................................89

References ......................................................................................................................................90

Appendix A: Copyright Permissions ...........................................................................................105

A.1 Permission for Figure 10 ...........................................................................................105
A.2 Permission for Figure 11 ...........................................................................................106
A.3 Permission for Figures 28, 29, 30, 31 .......................................................................107
A.4 Permission for Figures 22, 23, 24, 25, 26, 27 ...........................................................108

iii
 List of Tables

Table 1.1 Levelized cost of energy (LCOE) for all generation resources entering
service by 2025. .......................................................................................................2

Table 3.1 CdTe solar cell efficiency trend from the literature ...............................................17

Table 3.2 CdTe doping level achieved for the single and polycrystalline cells.....................19

Table 3.3 Bandgap, electron affinity, ΔEC, ΔEV, doping, and lattice constant of
various p-type heterojunction partners...................................................................22

Table 4.1 CuSCN solvents with their boiling point. ..............................................................37

Table 6.1 VOC, FF, and JSC of CdTe solar cells at different CdS thicknesses ........................45

Table 6.2 VOC, FF, and JSC of CdTe solar cells at different CdCl2 annealing
temperatures. ..........................................................................................................46

Table 6.3 VOC, FF, and JSC of 0.25-1.00 µm CST thickness at 410 and 430°C
heat treatment for 27% Se composition. ................................................................53

Table 7.1 VOC, FF, and JSC of p-type CdTe solar cells with different back
contacts. .................................................................................................................58

Table 7.2 VOC, FF, and JSC of p-type CdTe solar cells at different CuI
thicknesses. ............................................................................................................59

Table 7.3 VOC, FF, and JSC of p-type CdTe solar cells at different annealing
temperatures. ..........................................................................................................60

Table 7.4 VOC, FF, and JSC of p-type CST/CdTe solar cells with CuI ...................................62

Table 7.5 VOC, FF, and JSC of p-type CdTe solar cells with different back
contacts ..................................................................................................................64

Table 7.6 VOC, FF, and JSC of p-type CdTe solar cells with CuSCN at different
annealing temperatures. .........................................................................................65

Table 7.7 VOC, FF, and JSC of p-type CST/CdTe solar cells with CuSCN. ...........................66

iv
Table 8.1 VOC, FF, and JSC of n-type CdTe with CuI and ZnTe:Cu
heterojunction partner ............................................................................................71

Table 8.2 VOC, FF, and JSC of n-type CdTe with CuI as an interfacial layer .........................74

Table 8.3 VOC, FF, and JSC of n-type CdTe with CuSCN as p-type
heterojunction partner. ...........................................................................................75

Table 8.4 VOC, FF, and JSC of n-type CdTe with CuSCN as p-type
heterojunction partner. ...........................................................................................76

Table 8.5 VOC, FF, and JSC of n-type CdTe with CuSCN as p-type
heterojunction partner. ...........................................................................................78

Table 8.6 VOC, FF, and JSC of n-type CdTe at different CdTe doping levels ........................81

Table 8.7 VOC, FF, and JSC of n-type CdTe with CuSCN as an interfacial layer...................82

Table 8.8 Effect of Br etching on the n-type CdTe solar cell performance. ..........................83

v
 List of Figures

Figure 1 The reported best cell efficiency table of recent years by the National
Renewable Energy Laboratory (NREL). .................................................................5

Figure 2 pn junction under no (left), reverse (middle), and forward bias (right) ...................7

Figure 3 Band diagram of n-type CdS/p-type CdTe ..............................................................9

Figure 4 Band diagram of n-type CdTe/p-type heterojunction partner ................................10

Figure 5 Solar cell equivalent circuit ...................................................................................11

Figure 6 Dark and light I-V of a solar cell. ..........................................................................13

Figure 7 “AM 1.5 Global” spectra for solar cell characterization........................................14

Figure 8 Past, present, and future device structure for the CdTe solar cells (from
First Solar) .............................................................................................................20

Figure 9 Simulated I-V of n-type CdTe solar cells at bandgap 1.10 (top left), 2.10
(top right), 2.70 (bottom left), and 3.00 eV (bottom right) of p-type
heterojunction partners at different ΔEV ................................................................23

Figure 10 Modeling band diagram of CdTe solar cells with CuSCN ....................................25

Figure 11 CdTe TRPL data with TiO2, Ta2O5, SiO2, and Al2O3 front interface
passivation layers ...................................................................................................27

Figure 12 p-type CST /CdTe solar cells structure ..................................................................29

Figure 13 CSS deposition chamber ........................................................................................34

Figure 14 Se composition at different source temperatures ...................................................35

Figure 15 Spin coater .............................................................................................................36

Figure 16 CuSCN in NH4OH (left) and DMSO (right) solvent .............................................37

Figure 17 CuI in Acetonitrile solvent .....................................................................................38

vi
Figure 18 Plain glass (left), glass with CuSCN film (middle) and CuI film
(right) .....................................................................................................................39

Figure 19 n-type CdTe solar cells structure ...........................................................................39

Figure 20 Schematic diagram of the EVT deposition system ................................................40

Figure 21 CdS thickness effect in the spectral response. .......................................................45

Figure 22 Monochromatic I-V measurement at 410 (left) and 430°C (right)

CdCl2 annealing temperature .................................................................................46

Figure 23 XRD data of CdTe, CdSe, and CST films at various Se compositions .................47

Figure 24 (111) peak of CdTe, CST, and CdSe films ............................................................48

Figure 25 VOC and bandgap as different Se compositions .....................................................48

Figure 26 JSC and FF as different Se compositions ................................................................49

Figure 27 Experimental (left) Vs. simulated (right) J-V at 27 and 40% Se ...........................50

Figure 28 VOC vs. Se composition for undoped (left) and As-doped (right)
CST/CdTe cells ......................................................................................................50

Figure 29 Jsc vs. Se composition for undoped (left) and As-doped (right)
CST/CdTe cells ......................................................................................................51

Figure 30 Bandgap vs. Se composition for undoped (left) and As-doped (right)
CST/CdTe cells ......................................................................................................52

Figure 31 Net p-doping vs. Se composition for undoped (left) and As-doped
(right) CST/CdTe cells ...........................................................................................52

Figure 32 Summary of all CST/CdTe cells with 0.50 µm CST thickness .............................54

Figure 33 Standard (left) and bifacial (right) p-type CST/CdTe solar cells ...........................56

Figure 34 XRD data of CuI powder .......................................................................................57

Figure 35 Tauc plot of CuI film .............................................................................................57

Figure 36 Light J-V and SR of p-type CdTe solar cells with different back
contacts ..................................................................................................................58

vii
Figure 37 Light JV and SR of p-type CdTe solar cells at different CuI
thicknesses .............................................................................................................60

Figure 38 Light J-V and SR of p-type CdTe solar cells at different CuI
annealing temperatures ..........................................................................................61

Figure 39 C-V measurements at different CuI annealing temperatures .................................61

Figure 40 Different illuminated light J-V of p-type CST/CdTe solar cells with
CuI..........................................................................................................................63

Figure 41 XRD data of CuSCN powder .................................................................................63

Figure 42 Light J-V and SR of p-type CdTe cells with different back contacts ....................64

Figure 43 Light J-V and SR of p-type CdTe solar cells with CuSCN ...................................65

Figure 44 C-V measurements at different CuSCN annealing temperatures ..........................66

Figure 45 Different illuminated light J-V of p-type CST/CdTe solar cells with
CuSCN ...................................................................................................................67

Figure 46 SEM images of CdTe at different Cd/Te (0.5-top left, 0.7- top right,
1- bottom left, 2- bottom right) ratios ....................................................................70

Figure 47 CdTe normalized XRD at different Cd/Te ratios ...................................................70

Figure 48 n-type CdTe with CuI and ZnTe: Cu as p-type heterojunction partner .................71

Figure 49 n-type CdTe with CuI at different annealing temperatures ...................................72

Figure 50 Spectral response of n-type CdTe with CuI at different annealing

temperatures ...........................................................................................................73

Figure 51 Spectral response of n-type CdTe with CuI as an interfacial layer........................74

Figure 52 Light J-V and SR of n-type CdTe with CuSCN as p-type partner.........................75

Figure 53 Light J-V and SR of n-type CdTe with CuSCN as p-type

heterojunction partner ............................................................................................77

Figure 54 n-type CdTe with CuSCN at 100-200°C annealing temperatures .........................77

Figure 55 n-type CdTe with CuSCN at different annealing times .........................................79

Figure 56 n-type CdTe with different CuSCN doping levels .................................................80

viii
Figure 57 Net n-type CdTe doping vs. In vapor concentration ..............................................80

Figure 58 Light J-V and SR of n-CdTe/p-CuSCN at different CdTe doping ........................81

Figure 59 Light J-V and SR of n-type CdTe with CuSCN as an interfacial layer .................82

Figure 60 Effect of the interface recombination velocity on the JSC ......................................83

Figure 61 Effect of the Br etching on the light J-V and SR ...................................................84

Figure 62 Effect of Al2O3 annealing temperature on the VOC and JSC ...................................85

ix
 List of Acronyms

Acronym Definition
VOC Open Circuit Voltage
JSC Short Circuit Current Density
FF Fill Factor
η Efficiency
∆EV Valance Band Offset
∆EC Conduction Band Offset
µm Micrometer
CuI Copper Iodide
CuSCN Copper Thiocyanide
Cu Copper
Br Bromine
As Arsenic
CST CdSeXTe1-X
SR Spectral Response

x
 Abstract

CdTe thin-film solar cells are one of the major interests in the solar industry for their

favorable properties. For example, CdTe has a near-ideal bandgap (1.45 eV) for absorption of the

solar spectrum, and a high absorption coefficient ( ̴ 105 cm-1) and can capture 99% of light with

only 2 µm of film thickness. Moreover, CdTe can be doped both n and p-type. Additionally, low

production costs contribute to more affordable panel prices (0.40 $/W) [1]. The highest

efficiency achieved to-date for this material is 23.1% demonstrated by First Solar, which is still

lower than the theoretical limit [2]. In recent years, a CST (CdSe XTe1-X)/CdTe device

architecture has helped increase the short circuit current density (JSC) near the ideal JSC for CdTe

(31.7 mA/cm2). The fill factor (FF) has reached 80% [3]. JSC and FF are already close to their

theoretical limits. Therefore, only increasing the open-circuit voltage (VOC) can help to increase

efficiency further. The current level of VOC for polycrystalline p-type CST/CdTe solar cells is

approximately 900 mV. For monocrystalline CdTe solar cells, VOC higher than 1000 mV has

been achieved [4]. Achieving a similar VOC for polycrystalline cells is the biggest remaining

challenge. A net p-doping higher than 1016 cm-3 and minority carrier lifetimes of tens of

nanoseconds are required to reach this goal [5]. However, even with both conditions fulfilled, the

maximum VOC remains around 900 mV for the polycrystalline cells.

Copper (Cu) has been typically used for the formation of back contact. It plays an

important role in increasing the p-doping concentration [6]. A specific quantity of Cu is essential

to enhance cell performance, but exceeding this amount is detrimental to performance and also

affects the stability of the cell in the long term by shunting [7]. The annealing temperature of the

xi
back contact controls Cu diffusion into the absorber. Under optimal Cu conditions, p-type doping

is typically in the 1014 cm-3 range, which is insufficient for demonstrating VOC higher than 1000

mV.

p-type doping of CdTe is challenging [8]. Group V elements such as Phosphorous (P),

Antimony (Sb), and Arsenic (As) can act as p-type dopants by replacing the Te atom [9].

Incorporating CST as part of the absorber layer has recently proved beneficial because it

enhances the JSC, and Se has been shown to increase carrier lifetime. Therefore, doping CST

layer can also serve as an alternative way of increasing the overall doping density for the

absorber.

For single crystal n-type CdTe solar cells, VOC higher than 1000 mV is observed.

Therefore, an n-type CdTe architecture can be used to reach the goal of 1000 mV VOC because it

is easier to increase the n-doping concentration of CdTe (1016-1017 cm-3) while maintaining a

high minority carrier lifetime [10]. Group III elements, such as Indium (In) or group VII

elements, such as Chlorine (Cl) can be used as n-dopants.

CdTe thin films can be deposited either under Cd or Te-rich conditions. The as-deposited

films are essentially stoichiometric, a small deviation in the stoichiometric is difficult to measure

[11]. Cd-rich films can be intrinsically n-type, and Te-rich films p-type. Cd-rich films can have

Tellurium vacancies (VTe) or Cadmium interstitials (Cdi). VTe are shallow donors [12]. When Cdi

ionize, they will contribute electrons, resulting in n-type conductivity for non-extrinsically doped

films. Also, when CdTe films are grown under Cd-rich conditions, they exhibit fewer mid-gap

defects, resulting in a higher lifetime [13].

For designing high-efficiency n-type CdTe solar cells, a suitable transparent p-

heterojunction partner is important. The performance, especially the VOC and JSC depends

xii
significantly on a heterojunction partner. The required properties for a suitable transparent

heterojunction partner are high work function (small ∆EV) to match n-type CdTe, high bandgap

for lower light absorption, and good lattice matching for lower recombination. Only a limited

amount of research has been done on single crystal n-type CdTe films and no significant research

on suitable transparent p-type heterojunction partners exists. Single crystalline n-type CdTe cells

utilized a-Si heterojunction as a p-type partner/contact [14].

There are several potential candidates for the p-type transparent heterojunction partners

such as CuXZn1-XS, CuSCN, CuMO2, CdXMg1-XTe, CuI, and NiO. This work focused on CuI and

CuSCN as p-type transparent heterojunction partners. From their properties and simulations,

both CuI and CuSCN seemed suitable as transparent p-type heterojunction partners for n-type

CdTe. Moreover, they can also work as a transparent p-type back contact for the p-type

CST/CdTe solar cells to form bifacial solar cells and utilize light from both the front and back

side of the cells, thus, higher power density can be achieved.

In this work, the CST layer was studied by varying Se composition, CST thickness, As

doping, and CdCl2 treatment conditions. The device performance was optimized to find the best

condition for higher efficiency.

The effect of the CuI and CuSCN on the performance of the n-type and p-type CdTe solar

cells was investigated. The thickness, annealing time and temperature, and surface treatment on

the cell characteristics—VOC, JSC, and FF—were also studied.

xiii
 Chapter 1: Introduction

Global energy demand continues to rise due to the growing human population and

improved quality of life. The main sources required to meet this demand are typically fossil fuels

such as coal, natural gas, and oil. They provide 79% of the electricity demand in North America

and account for 90% of the world’s total energy consumption [15]. However, these resources are

finite, and their costs are rising dramatically. As more fossil fuels are harvested, finding new

sources becomes more difficult, and exploiting those poses more challenges and sometimes

dangers as well. Another concern about fossil fuels is that they cause global warming, and so

have a severe impact on the world’s climate change [16]. To meet the ongoing energy demand,

extensive research is being conducted to discover new and efficient energy sources. Renewable

energy is one of the most crucial energy sources in today’s world. Common sources of renewable

energy are solar, wind, tide, biomass, and geothermal, which cover 21% of total U.S. energy

consumption [17]. Various economic and environmental impacts make renewable energy vital

for the future of our society. It is clean energy and has a positive environmental impact. Utilizing

renewable energy can significantly reduce current greenhouse gas emissions. Solar energy is the

most crucial form of renewable energy because it is harnessed from the sun, an abundant energy

source. The International Energy Agency predicted that 42% of the world’s energy supply will

be renewable, and solar and wind will be sources accounting for 25% of these energy supplies

[18].

1
Table 1.1 Levelized cost of energy (LCOE) for all generation resources entering service by 2025
Source: U.S. Energy Information Administration, Energy Outlook of 2021

Table 1.1 shows the LCOE of different types of power plants. LCOE (Levelized Cost of

Energy) means the cost of energy generation over its lifetime. Solar technology has the minimum

LCOE compared to the other technologies which makes it an attractive source of energy.

1.1 PV Technologies

Solar energy is the most abundant natural energy source, originating from the sun, the

ultimate source of power. Solar cells convert this solar energy into electrical energy. Various

solar technologies are available in the market, classified into three major groups: wafer, thin

film, and emerging thin-film technologies.

1.1.1 Wafer Technology

Wafer technology covers both silicon (Si) and Gallium Arsenide (GaAs) solar cells.

Silicon (Si) dominates the global market, accounting for 90% [19]. It includes both crystalline Si

and multi-crystalline Si solar cells, known as first-generation solar cells. Developed in the 1950s,

Si remains the most widely used type of solar cell today [20]. It requires a 150-200 µm absorber

due to the low absorption coefficient of the material. Group III-V semiconductor GaAs is another

2
popular technology for space power applications. Because GaAs solar cells have a high

absorption coefficient, they can be manufactured with a thin profile. However, this technology is

expensive, which is why it is primarily popular for space applications [21].

1.1.2 Thin Film Technology

Thin film technology is referred to as second-generation solar cells. Its promise has been

its potential for lower manufacturing costs than the wafer technology. Thin film technology uses

direct bandgap semiconductors, resulting in a high absorption coefficient. That’s why only a few

µm thick absorber layer is required compared to hundreds of microns wafer-based technology.

Thus, the amount of materials required for thin film technology is lower. The widely known thin

film solar cells are cadmium telluride (CdTe), amorphous silicon (a-Si), and Copper Indium

Galium Diselenide (CIGS). A-Si uses no toxic substances, making it environmentally friendly

[22]. However, a-Si technology does not quite exist today - it is not competitive. The challenge

lies in its inherent instability, making it unsuitable for large-scale production [23]. This is why

CdTe and CIGS are more popular alternatives. CdTe is already available commercially with the

world leader in this technology First Solar projected to install approximately 25 GW of global

CdTe technology capacity by 2026 [24]. It is suitable for utility-scale applications and large-

volume manufacturing [25]. The cost of CIGS is higher than CdTe, and production volumes

remain low. However, it is suitable for flexible and lightweight module applications since it can

be deposited on flexible substrates.

1.1.3 Emerging Thin Film Technology

Emerging thin film technology is recognized as third-generation solar cells. It is still in

the early stage of research and development. Dye-sensitized, organic, perovskite and quantum

dot solar cells fall into this category. The dye-sensitized solar cells are low-cost and

3
environmentally friendly with competitive efficiency [26]. The issue with this type of solar cell

is the electrolyte's thermal sensitivity, but research is underway to address this problem. Organic

solar cells are the branch of solar energy that utilize conductive polymers to absorb light and

carrier transport for electricity production. The perovskite solar cell is an organic technology

representing the most promising advancement in solar energy. It utilizes elements with a

perovskite structure as an absorber layer. It is inexpensive and well-suited for mass production,

making it an excellent option for future photovoltaic applications [27]. In a decade, the efficiency

increased from 3.8% to 25.7% [28-29] for this solar cell. Quantum dot solar cells are another

emerging PV technology where quantum dots are incorporated in the absorber layer, featuring a

tunable bandgap that can be adjusted to absorb various ranges of optical energy. Although

currently, quantum dot solar cells exhibit low efficiency, they hold the potential for higher

efficiency levels in the future [30].

1.2 Advantages of CdTe

CdTe possesses a direct optical bandgap of 1.45 eV, enabling it to encompass the visible

solar spectrum. With a high absorption coefficient of nearly 105 cm-1, just 2 µm of this material

is sufficient to absorb 99% of incident radiation. Additionally, it can be doped both n-type and p-

type, allowing the fabrication of both n-type and p-type solar cells from this material. Simple

manufacturing techniques and minimal material requirements contribute to the cost-effectiveness

of this technology. Currently, most of the solar energy market is dominated by Si, with CdTe

accounting for only 5% of the global market [31]. However, CdTe has significant future potential

if challenges can be overcome, its efficiency can approach 25% from the current level (23.1%).

Figure 1 shows the best cell efficiency achieved in the laboratory condition for various

technologies (single and multijunction).

4
Figure 1 The reported best cell efficiency table of recent years by the National Renewable
Energy Laboratory (NREL)

5
 Chapter 2: Semiconductors and Solar Cells

2.1 Semiconductors

Semiconductors are those materials or substances that have electrical conductivity

between conductors and insulators. In the pure form, they have very low conductivity and are

called intrinsic semiconductors. When external impurities are added, their conductivity can be

increased significantly, and they are called extrinsic semiconductors. The impurities are known

as dopants. Based on the majority charge carriers (electron/hole), semiconductors can be n-type

or p-type. Majority carriers exist at greater concentrations and minority carriers at lesser

concentrations. n-type semiconductors have electrons as majority carriers and holes as minority

carriers, and p-type semiconductors have holes as majority carriers and electrons as minority

carriers. When an electron moves from the valence band to the conduction band in a

semiconductor, it leaves behind a void called “hole”. For example, Si is a group IV

semiconductor. When a group V (phosphorous) dopant is added, the extra electron will make it a

n-type semiconductor. Similarly, when a group III dopant (boron) is added to the Si, it will

become a p-type semiconductor due to holes. n-type dopants are called donors, and p-type

dopants are called acceptors. The bandgap of a semiconductor is the energy difference between

the valence band maximum and the conduction band minimum. Based on the bandgap, there are

two kinds of semiconductors: direct and indirect bandgap semiconductors. In direct bandgap

semiconductors, the maximum of the valence band lies directly below the minimum of the

conduction band (same momentum). In indirect bandgap semiconductors, the valence band

maximum does not lie directly below the conduction band minimum (not the same momentum).

6
Direct bandgap semiconductors have a high absorption coefficient. Semiconductors comprise

two or more elements are called compound semiconductors. For example: CdTe, ZnTe, CuI,

CuSCN. Compound semiconductors are widely used in various industries (opto and power

electronics, high-speed electronics, etc) [32].

2.2 pn Junction

When a p and n-type semiconductors are combined to form a junction, this is referred to

as a pn junction. When contact is made between them, electrons from the n-type semiconductor

will diffuse into the p-side and vice versa. This will create a region without any electrons or

holes, which is called a depletion region and the voltage across the pn junction at equilibrium

condition (no external voltage) is called built-in potential (Vbi). The mathematical expression of

Vbi is:

(1.1)

where KT/q is the thermal voltage, NA, ND and ni are the acceptor, donor, and intrinsic carrier

concentration, respectively.

Under the forward bias condition, the barrier decreases and increases in the reverse bias

condition (shown in Figure 2).

Figure 2 pn junction under no (left), reverse (middle), and forward bias (right)

7
 Figure 2 shows the pn junction under different biasing conditions (no bias, forward and

reverse bias), where EV, EC, Vbi, VF, and VR represent the valance band maximum, conduction

band minimum, built-in potential, forward and reverse bias voltage, respectively. The energy

difference between EC and EV is called bandgap (Eg=EC-EV). pn junction can be of two types:

homojunction and heterojunction. If the junction is formed between the same semiconductor, it is

known as a homojunction. Conversely, if the junction is made using two different semiconductor

materials, it is called a heterojunction.

2.2.1 pn Heterojunction

When a p-type semiconductor makes a junction with a different n-type semiconductor,

then it is called a pn heterojunction. For example, the CdS/CdTe junction is a heterojunction.

Due to varying bandgap and electron affinity of two semiconductors, a pn heterojunction exhibits

offsets in the valence and conduction bands. This results in the creation of barriers that affect the

collection of electrons and holes (Figure 3).

2.3 Solar Cell Operation

A solar cell is a pn junction that generates electricity from sunlight. This effect is called

the photovoltaic effect (PV). The PV effect was discovered by Edmond Becquerel in 1839. The

first practical solar cell was created by Bell Laboratories in 1954. The PV effect works in 3 steps.

• Absorption of light

• Generation of charge carriers

• Collection of charge carriers

When light incident on the solar cell, photons with an energy higher than the bandgap

energy will be absorbed and create electron-hole pairs. These carriers are known as light-

generated carriers. Carriers generated in or close to the depletion region come under the

8
influence of the electric field and are separated. The separated charge carriers are collected at the

metal contacts on the two sides of the junction.

2.3.1 p-type CdTe Solar Cell Operation

A heterojunction consisting of a wide bandgap CdS (n-type) and a narrow bandgap CdTe

(p-type) is shown in Figure 3. Here, CdS is the window layer and CdTe is the absorber layer.

Photons with energy less than the bandgap of CdS pass through this layer and get absorbed in the

CdTe absorber layer. Since CdS has a wider bandgap, it enables greater photon absorption in the

CdTe absorber, resulting in increased generation of photogenerated carriers. Photons absorbed

in the CdTe layer will create electron-hole pairs. The carriers generated in the depletion region

and within the diffusion length of the CdS/CdTe junction will be collected. The band alignment

between CdS/CdTe is important especially the conduction band offset (∆EC). A small conduction

band (+∆EC) spike will reduce the interface recombination and enhance the VOC [33]. However,

a large +∆EC can create a barrier to carrier collection, thereby diminishing cell performance. A

small cliff (-∆EC) will increase interface recombination.

Figure 3 Band diagram of n-type CdS/p-type CdTe

9
2.3.2 n-type CdTe Solar Cell Operation

Figure 4 shows a heterojunction between n-type CdTe and p-type transparent

heterojunction partner, where n-type CdTe is the absorber layer and p-type heterojunction

partner is the window layer. The light shines through the p-type heterojunction partner to the n-

type CdTe absorber. That is why the p-type heterojunction partner should be transparent so that

most of the light can get absorbed in the n-type CdTe and generate electron-hole pairs. Charge

carriers generated in the depletion region and within a diffusion length will be collected in the n

and p-side of the junction. A small spike in the valence band (+∆EV) will reduce the interface

recombination and improve the VOC. However, a large spike will act as a barrier for carrier

collection, thus reducing the cell performance. A small cliff (-∆EV) will increase the interface

recombination.

Figure 4 Band diagram of n-type CdTe/p-type heterojunction partner

2.4 Solar Cell Terminologies

To understand the solar cell’s performance, an equivalent circuit can be used to model it.

The most commonly used model is a single-diode equivalent circuit as shown in figure 5. The

10
key components for this model are a current source in parallel with a forward-biased diode,

series (RS), and shunt (RSH) resistor. The current source accounts for the photocurrent generated

by the solar cell due to the absorption of photons from the sunlight and creates electron-hole

pairs. The diode represents the pn junction characteristic with the direction of current flows. The

series resistor (RS) accounts for the resistive loss due to the current flowing through the solar cell

material. The shunt resistor (RSH) represents the leakage that does not go through the load due to

cell imperfections. The output current of a single-diode equivalent model can be represented as

follows [34]:

(1.2)

where IL is the photo-generated current, I0 is the dark saturation current, V is the output voltage

across the terminal, RS is the series resistance, RSH is the shunt resistance, q is the electron

charge, n is the ideality factor (between 1-2), K is the Boltzmann Constant, and T is the

temperature of the solar cell in Kelvin.

Figure 5 Solar cell equivalent circuit

11
2.5 Photo Conversion Efficiency

The ratio of maximum electrical output power (POUT) to the input power (PIN) is called

efficiency (η). The mathematical expression of efficiency (η) is:

(1.3)

where Pin is the input power, VOC is the open circuit voltage, JSC is the short circuit current

density, and FF is the fill factor.

VOC is the maximum output voltage achieved from the solar cell operating without load (open-

circuited). VOC is a function of bandgap, carrier concentration, and lifetime. It can be expressed

as:

(1.4)

where KT/q is the thermal voltage, NA is the acceptor concentration, ∆n is the excess carrier

concentration, and ni is the intrinsic carrier concentration.

The above equation clearly shows that VOC can be increased by doping and excess carrier

concentration. That is why in-situ (during deposition) and ex-situ (after deposition) doping is

used to achieve higher VOC.

The short-circuit current (ISC) is the current when the output is short-circuited (zero load

resistance). The short circuit current (ISC) is usually represented as current density (JSC).

(1.5)

where A is the solar cell's effective area.

FF represents the squareness of the solar cell's JV curve (see Figure 6). It is calculated

from the solar cell's maximum power (PM= VM *IM). In the I-V curve, there is a point where the

12
product of current and voltage (V×I) is maximized. This point is known as Maximum Power

Point (MPP).

(1.6)

Figure 6 Dark and light I-V of a solar cell

2.6 Solar Spectrum and Quantum Efficiency

The solar spectrum is the range of light radiation from the sun. It extends from ultraviolet

to the infrared region. The visible solar spectrum is from 400-700 nm. Air Mass is the ratio of the

path length for sunlight to the vertical path length (zenith). The international standard for

characterizing terrestrial solar is Air Mass 1.5 Global (AM 1.5G). AM 1.5 is defined as a zenith

angle of 48.2°.

Quantum efficiency (QE) is a crucial parameter for solar cells, and it measures the

effectiveness of a solar cell in converting photons into charge carriers. QE is the ratio of the

number of carriers collected to the number of incident photons at a given energy. It is a function

of wavelength and is usually expressed as a percentage. QE can be described as external

quantum efficiency (EQE) or internal quantum efficiency (IQE). EQE considers all losses, while

13
IQE measures the efficiency only by accounting for the photons that have been absorbed by the

cell. The mathematical expression of EQE is:

(1.7)

where Iph(λ) is the photocurrent generated at wavelength λ, Pin(λ) is the photon flux, and E(λ) is

the photon energy at wavelength λ.

Figure 7 “AM 1.5 Global” spectra for solar cell characterization

14
 Chapter 3: Evolution of the CdTe Solar Cells

3.1 CdTe Solar Cells Development History

Frerichs first produced CdTe in crystalline form in 1947 [35]. The reaction occurred

between Cd and Te vapors at hydrogen ambient. In 1954, Jenny and Bube reported the p and n-

type CdTe for the first time using extrinsic dopants/impurities [36]. Later, Kruger and de Nobel

proved that the conductivity of the CdTe can be changed by altering the Cd and Te stoichiometry

[37].

Rappaport fabricated single-crystal CdTe homojunction solar cells of 2% efficiency in

1959 [38]. They were deposited by diffusing Indium (In) into the p-type CdTe to form a n-type

CdTe. Cusano demonstrated the first thin film CdTe solar cells in 1963 [39]. In 1968, Andirovich

proposed the typical CdTe device structure, n-CdS/p-CdTe [40]. At that time, the efficiency was

only 1%. Kodak achieved 10% efficiency in 1981 and AMETEK 12% in 1990. After 1990, CdTe

research was led by USF and Photon Energy. C. Ferekides and J. Britt achieved an efficiency of

15.8% in 1992 [41]. In the late 1990s, NREL progressed the CdTe research by pushing the

efficiency beyond 16% [42].

Since the beginning of the 2000s, First Solar has held record CdTe devices. To date, the

highest record efficiency for First Solar is 23.1% [43]. CdTe is also the leading thin film solar

technology with a module efficiency of 19.0% [44].

15
3.2 CdTe Solar Cells Present and Future

Due to the redesign of the structure, the efficiency of the CdTe thin-film solar cells has

improved significantly over the last couple of years. The front contact of the CdTe solar cells is a

highly conductive transparent oxide (TCO). There are a wide variety of TCOs used for CdTe

solar cells. The widely used options are FTO (Flourine Tin Oxide), ITO (Indium Tin Oxide),

AZO (aluminum Zinc Oxide), and CTO (Cd2SnO4) [45]. Among them, FTO is widely used due

to its high-temperature stability. The low-bandgap CdS window layer causes parasitic absorption

in the lower wavelength region. That is why CdS is replaced or partially replaced by a high

resistivity transparent layer (HRT). The most commonly used HRTs are i-SnO2, i-ZnO, and

MZO [46]. Some groups use MZO to create a spike in the conduction band to achieve higher

VOC. Others use i-SnO2 with a very thin layer of CdS to have negligible parasitic absorption. The

introduction of Se to form an alloy with CdTe has resulted in a new device architecture due to

the enhancement of both JSC by the bandgap reduction, and minority carrier lifetime

imrovements in the CST films. That is why JSC and FF are approaching the Shockley-Queisser

limit. However, the VOC remains below 900 mV for polycrystalline CdTe devices; only a few

groups report a VOC of 900 mV [47-49]. Only single crystal CdTe devices reported a VOC above

1000 mV [50-51]. The Shockley-Queisser limit for the VOC is 1113 mV, which means we are

still missing 226 mV for the polycrystalline cells and the VOC enhancement is the only way to

achieve the next milestone of 25% efficiency. Table 3.1 shows the efficiency trend for the CdTe

solar cells and the requirement to achieve 25% efficiency in the future.

16
Table 3.1 CdTe solar cell efficiency trend from the literature

Record Cell Efficiency JSC VOC FF Comments Ref.

(%)
(mA/cm2) (mV) (%)

USF 1993 15.8 25.1 843 74.5 CdS/CdTe 52

Matsushita 16.0 26.1 840 73.1 CdTe absorber 53

1997

NREL 2001 16.7 25.9 845 75.5 CdTe absorber 54

GE 2012 18.3 27.0 857 79.0 CdTe absorber 55

FSLR 2012 18.7 28.6 853 76.7 CdTe absorber 56

FSLR 2014 22.1 31.7 887 78.5 CdSeTe absorber 57

ASU 2016 17.0 22.3 1036 73.6 Single crystal CdTe 58

FSLR 2023 22.3 31.5 898 78.9 CdSeTe absorber 43

FSLR 2024 23.1 CdSeTe absorber

Target 25.0 32.0 975 80.0 CdSeTe absorber 59

3.3 CST (CdSeXTe1-X) Layer Optimization and Doping

CST/CdTe bilayer structure helps increase both JSC and minority carrier lifetime. Since

CST is an alloy, the composition of this layer can be varied. The bandgap of this layer can vary

from 1.45 to 1.74 eV. It initially decreases until 40% Se due to the bowing effect and then

17
increases [60]. From the literature, people found higher-efficiency CST/CdTe solar cells by

forming graded absorbers between CST and CdTe [61]. The graded CST/CdTe absorber can be

achieved in three different ways. (1) Se can be alloyed with CdTe during deposition; Swanson et

al. demonstrated this technique in 2017 [62]. (2) depositing the CdSe/CdTe film stacks on top of

the MZO or SnO2 layer followed by an “aggressive” CdCl2 heat treatment for the intermixing of

CdSe and CdTe to form a graded absorber. (3) the pre-alloyed CST source can be used to deposit

the CST layer and, subsequently, the CdTe layer, and then CdCl2 heat treatment can be done to

achieve the graded CST/CdTe absorber. Munchi et al. achieved an efficiency of 19.1% by using

this technique [63]. The third method is the most effective one to obtain CST/CdTe graded

absorber using the CSS process. For this method, the thickness and Se composition of the CST

layer can play a crucial role to form better graded CST/CdTe absorbers.

To achieve a VOC >1000 mV, it is necessary to have doping >1016 cm-3 with a 100 nS

lifetime. Since the CST layer is also a part of the absorber layer, doping this layer can be an

alternative way to increase the overall doping concentration of the CST/CdTe absorber to obtain

higher VOC. Over many years, Cu is the most popular element to dope CdTe. However, doping

concentration is limited in the mid 1014 cm-3 with Cu due to the self-compensating donor, such as

interstitial (Cui) [64]. Moreover, Cu can create stability issues and performance degradation due

to the high diffusivity of the Cu ions. Group V dopants (As, P, Sb) can be used to dope CdTe p-

type. In 2016, Single crystal CdTe showed a VOC greater than 1000 mV with higher doping

stability and a 100-fold lifetime with group V dopant (P) [50]. Excellent stability is caused by the

slower diffusion of group V dopants compared to Cu. Table 3.2 shows the doping level and

minority carrier lifetime achieved for the CdTe with As and P doping.

18
Table 3.2 CdTe doping level achieved for single and polycrystalline cells

Type Dopant VOC Doping Lifetime Ref.

(mV) (cm-3) (ns)

Single Crystal P 1017 1.50E+17 400 65

As 860 6.00E+16 - 66

As 830 2.16E+16 40-45 67

P 860 9.34E+15 40-47 67

Polycrystalline As 917 2.00E+16 5.7 68

As - 3.00E+16 1.6 69

P - 5.50E+15 1.6 69

As 763 3.00E+16 1 70

P 850 1.00E+16 1 71

Some groups reported higher performance (> 20%) for the polycrystalline CdTe cells

with As doping. Metzger et al. have reported an efficiency of 20.8% with As doping for the

CST/CdTe cell with a carrier density of 1016 cm-3 [72]. Moreover, First Solar’s 2023 world

record device of 22.3% efficiency uses As to dope CST and CdTe [68]. Arsenic has a higher

dopant activation level and can lead to higher stability than other dopants.

19
 A passivated back contact can further improve the VOC. This helps to reduce the interface

recombination and increase the VOC. The significant challenge for making ohmic contact with

CdTe is its high work function (typically 5.7 eV). No metal has such a high work function.

Higher VOC can be achieved if a transparent and stable passivated back contact can be utilized in

the CdTe solar cells. Moreover, this will create a bifacial configuration, which will help to

increase the JSC by utilizing light from both the front and back of the devices. According to First

Solar, this will be the future device structure towards 25% efficiency (shown in Figure 8).

Figure 8 Past, present, and future device structure for the CdTe solar cells (from First Solar)

20
3.4 n-type CdTe Solar Cells and Challenges

The major challenge of the CdTe solar cell is the open circuit voltage (VOC). The VOC has

been limited to approximately 900 mV for polycrystalline solar cells. For p-type single-crystal

solar cells, VOC of more than 1000 mV has been reported [50]. The main hurdle for improving

VOC for the polycrystalline p-type solar cell is achieving high doping without affecting the

lifetime. However, with high doping (> 1016 cm-3) and lifetime (100 ns) in the p-type CdTe solar

cell, it is still not possible to achieve VOC higher than 900 mV. On the other hand, n-type CdTe

cell is highly dopable (>1016 cm-3), which makes it more promising for fabricating cells with VOC

above 1000 mV. Single crystal n-type CdTe solar cells have already demonstrated a VOC higher

than 1000 mV [4]. For n-type CdTe solar cells, it is critical to develop a p-type highly

transparent heterojunction partner. An effective transparent p-type heterojunction partner should

have the following properties: a large bandgap, a good lattice match with CdTe to reduce the

interface recombination, high doping (> 1016 cm-3), and an effective band alignment (small

valence band offset) with n-type CdTe for efficient carrier collection (electrons, holes).

Moreover, the transparent contact can be used in the p-type CST/CdTe devices to achieve higher

current density by absorbing light from both the front and back of the solar cells. Table 3.3

shows the properties of some potential p-type heterojunction partners for n-type CdTe solar cells.

Their effectiveness as a p-type heterojunction partner with n-type CdTe solar cells is discussed

based on their properties (bandgap, electron affinity, band offset, dopability, and lattice constant)

found in the literature.

21
Table 3.3 Bandgap, electron affinity, ΔEC, ΔEV, doping, and lattice constant of various p-type
heterojunction partners

Material Band-gap Electron ΔEC ΔEV Doping Lattice Ref.

(eV) Affinity (eV) (cm-3) Constant

(eV)
(eV) (Å)

ZnTe 2.26 3.53 0.75 -0.06 1.00E+21 6.10 73-77

ZnSeXTe1-X 2.26-2.82 3.53-4.09 0.2-0.8 -1.18--0.06 1.00E+19 5.67-6.10 78-81

CdXZn1-X Te 1.45-2.26 3.53-4.28 0-0.75 -0.06-0 3.00E+18 6.10-6.48 82-88

CdxMg1-xTe 1.45-3.45 3.25-4.28 0-1.03 -0.97-0 4.00E+17 6.42-6.48 82-88

CuXZn1-XS 2.10-3.45 1.90-3.90 0.4-2.4 -1.62-1.73 1.00E+21 3.96-5.41 93-97

CuSCN 3.40 2.10 2.18 0.23 1.00E+18 3.85 98-100

Cu2O 2.17 3.20 1.08 0.36 2.30E+21 4.27 101-102

CuAlO2 3.46 2.50 1.78 -0.23 3.60E+18 2.86 103-106

CuGaO2 3.60 1.80 2.48 0.33 3.49E+16 2.98 107-109

SrCu2O2 3.30 2.20 2.08 0.23 6.10E+17 5.47 110-111

CuI 3.10 2.10 2.18 0.53 1.00E+20 6.05 112, 113

NiO 3.70 1.46 2.82 0.57 1.00E+19 4.26 114-118

CuInSe2 1.00 4.50 0.23 0.23 2.00E+17 5.81 119-122

22
Figure 9 Simulated I-V of n-type CdTe solar cells at bandgap 1.10 (top left), 2.10 (top right),
2.70 (bottom left), and 3.00 eV (bottom right) of p-type heterojunction partners at different ΔEV

Figure 9 shows the simulated I-V results of the n-type CdTe solar cells at different ΔEV

of the p-type heterojunction partners. From the simulation results, it is clear that ΔE V=+0.30 eV

performs best despite the bandgap of the p-type heterojunction partner. Higher ΔEV can cause a

kink in the I-V, which will result in a dramatic reduction in performance. That is why it is also

essential to find a p partner that will make a ΔEV close to 0.30 eV with n-type CdTe.

23
 Reviewing the materials listed in Table 3.3, Sb2Te3 with bandgap (0.21 eV) and refractive

index (6.20) make it unfavorable as a p-type heterojunction partner. NiO has a ΔEV 0.57 eV,

therefore, it is also unsuitable. CuInSe2 has a bandgap of only 1.04 eV which will cause more

light absorption, and ΔEV higher than 0.30 eV. That is why Sb2Te3, NiO, and CuInSe2 can not be

superior p-type heterojunction partners. CuSCN and CuI are selected as p-type transparent

heterojunction partners of the n-type CdTe solar cells due to their properties mentioned in the 3.5

and 3.6 paragraphs. They also can be used as a transparent back contact of the p-type CST/CdTe

devices to achieve higher current density. Moreover, CuSCN and CuI are Cu compounds, so

annealing at higher temperatures can enhance the net doping concentration.

3.5 CuSCN Properties

Recent advances in the research have shown the tremendous potential of CuSCN as the p-

type heterojunction partner. The favorable properties are as of Table 3.3:

• a work function (5.50 eV) very close to CdTe (5.73 eV), which makes it suitable as a p-

type heterojunction partner

• the valence band offset (∆EV) is only 0.23 eV. It has been used as a hole transport layer

for p-CdTe solar cells since 2015 [137]

• a low refractive index (2.65) and high doping (1018 cm-3)

• It is a low-cost and solution-processible material. It also improves the device stability

compared to the metallic Cu device

CuSCN film can be prepared in two ways.

• Wet process: CuSCN powder needs to be dissolved in a suitable solvent. After that,

stirring at a certain or room temperature for a couple of hours for fully dissolution. The

solution can then be filtered using a PTFE filter to remove larger particles. Spin coating

24
 speeds and solution concentrations can vary the thickness of the CuSCN film. After the

spin coating of CuSCN, the film needs to be heated for solvent removal [137]

• Thermal Evaporation [139]

Figure 10 Modeling band diagram of CdTe solar cells with CuSCN [137]

From the band diagram above, it can be seen that the valence band offset between the p-

CdTe and CuSCN is favorable for hole extraction. Moreover, it repels electrons from the back

interface, reducing back interface recombination and enhancing carrier collection efficiency.

3.6 CuI Properties

CuI is a highly conductive wide bandgap (3.1 eV) p-type transparent semiconductor. It is

intrinsically p-type due to the Cu vacancies. It also has a high conductivity (600 S-cm-1) [140].

CuI can exist in three different phases. It has a stable zinc blend phase (γ-CuI) at below 350°C, a

typical p-type semiconductor. It has a wurtzite phase (β-CuI) at 350-380°C and a rock salt phase

(α-CuI) higher than 380°C [141]. Some favorable properties are:

• a work function of 5.20 eV that is in between the CdTe (5.73 eV) and ITO (4.7 eV)

which makes it suitable to work as a back contact for the CdTe solar cells

25
 • a valence band offset of only 0.53 eV or 0.13 eV with n-type CdTe [112]

• a low refractive index (2.10) and high intrinsic carrier concentration (1017 cm-3). Carrier

concentration can be enhanced significantly by adding extrinsic dopants [143]

• It is a low-cost and solution-processible material. Single-crystal CuI can also be

deposited using the solution-recessed spin coating [144]

CuI can be deposited by many techniques. For example, drop casting, pulsed laser

deposition, electrodeposition, vacuum evaporation, spin coating and sputtering. Among them,

solution-processed spin coating is very popular. Spin coating gives highly conductive and

transparent (> 90%) CuI film. CuI can be dissolved in various solvents such as acetonitrile,

dipropyl sulfide, 2-methoxyethanol, and even deionized water. Solvent selection is crucial for

depositing high-quality CuI films. Acetonitrile is the widely used solvent for dissolving CuI.

3.7 Interface Passivation Layer

To reach an efficiency higher than 25% for the CdTe solar cells, the requirements are

doping concentrations >1016 cm-3, minority carrier lifetime >100 ns, and interface recombination

velocity < 103 cms-1 [145]. Usually, the interface recombination velocity for CdTe solar cells is

high (105 cm-s-1). Doping concentrations > 1016 cm-3 are possible by doping group V elements

for p-type CdTe and group III elements for n-type CdTe. Lifetime has also improved

significantly due to the introduction of Se, CdC2 treatment, and high-quality film production.

However, due to the lattice mismatch between p and n-type layers and band bending resulting

from junction formation, interface recombination plays a vital role in the CdTe solar cell's

performance. It can be significantly reduced if a passivation layer of the high bandgap is added

and Al2O3 has shown promise as a passivation layer compared to other oxides [146]. The use of

Al2O3 can reduce surface electron concentration. It exhibits a negative fixed charge, which repels

26
electrons and also reduces defects in the interface (chemical passivation). Thus, it reduces

recombination in the interface [147]. The use of Al2O3 helps to achieve a great improvement in

the PL intensity and thus produces the best TRPL lifetime.

Figure 11 CdTe TRPL data with TiO2, Ta2O5, SiO2, and Al2O3 front interface passivation layers
[147]

TRPL data of different passivation layers show that TiO2 and Ta2O3 have reduced the

TRPL lifetime. SiO2 results in very small improvements while Al2O3 shows significant

improvements in TRPL. Kuciauskas, Darius, et al. reported an interface recombination velocity

of less than 100 cm-s-1 [149]. However, a thicker layer of Al2O3 will reduce conductivity and

27
work as a barrier layer that is responsible for poor performance. That’s why a very thin layer of

Al2O3 should be used.

3.8 Objective of This Study

The current state of the art for CdTe solar cells is a CST/CdTe graded absorber. The CST

layer needs to be optimized to achieve the highest efficiency. This can be done by choosing the

suitable Se composition, CST thickness, As-doping of the CST layer, and CdCl2 heat treatment.

First, the suitable Se composition must be found to obtain the highest current possible without

significantly affecting VOC and FF. The CST thickness can be varied to find the optimum

thickness with CdCl2 heat treatment. Se composition and CST thickness are essential to achieve

a CST/CdTe graded absorber. Finally, As-doping of the CST layer can be done using the CSS

process to achieve a higher VOC by increasing the net doping concentration.

Since the passivated transparent back contact can help achieve efficiency > 25%, CuSCN

and CuI were developed and applied as the transparent passivated contact to form a bifacial

structure to obtain higher JSC and VOC. Since both of these are Cu compounds, annealing the

CST/CdTe structure after CuSCN or CuI deposition at higher temperatures was done to achieve

higher VOC by doping with Cu.

Finally, since n-type CdTe solar cells have the potential to achieve higher VOC than p-

type, n-type CdTe solar cells were fabricated with CuSCN and CuI as transparent p-type

heterojunction partners. CuSCN and CuI were also used as interfacial layers to reduce the

interface recombination to obtain higher performance with the standard ZnTe:Cu p-type partner.

The major issue of the n-type CdTe solar cells was high interface recombination, which caused

poor performance. Finally, some surface treatments (Br-methanol solution, NP acid solution) and

Al2O3 passivation layer were utilized in the n-type CdTe solar cells to improve the interface.

28
 Chapter 4: Experimental Details

This chapter describes the details of our p-type and n-type CdTe solar cells fabrication

process. First, the architecture of different types CdTe solar cells is discussed. It also describes

the significance of each layer with its fabrication process and all process conditions. It describes

why a specific material was used and how some of the process parameters were varied to obtain

a specific goal.

4.1 Device Architecture of p-type CST/CdTe Solar Cells

The superstrate device structure of CST (CdSexTe1-x) /CdTe solar cells is shown in Figure

12. In the superstrate configuration, light is shone through the glass substrate. On the other hand,

in the substrate configuration, light comes from the other direction of the glass substrate. A

transparent conducting oxide (ITO) layer, followed by a buffer layer (MZO) was deposited on

the glass substrate via RF sputtering. Subsequently, the window (CdS) and absorber layers (CST

and CdTe) were deposited by close-spaced sublimation (CSS). After depositing CdTe, back

contact was applied.

Figure 12 p-type CST /CdTe solar cells structure

29
4.1.1 Substrate

The CdTe solar cell has a superstrate structure and was fabricated on a glass substrate.

The glass substrate that was used for this work is Corning EagleXG. It can withstand high

temperatures (above 600°C), so it is popular for research applications. For commercial

applications, TEC (Transparent Electro-Conductive) glasses are used [150].

4.1.2 Transparent Conducting Oxides (TCOs)

A transparent semiconductor was used as a front contact for CdTe thin-film solar cells.

Usually, an oxide is used as front contact, that is why it is called transparent conducting oxide

(TCO). TCO should have high conductivity and electron affinity (around 4.5 eV) to produce an

ohmic contact with CdS. The characteristics of the TCOs are:

• low resistivity (< 10-4 Ω-cm)

• highly transparent (wide bandgap) in the 400-1000 nm wavelength

• stable at a higher temperature

The TCO used for this work was indium tin oxide (ITO). It was deposited by RF

sputtering. ITO has low resistivity (1.75x10-4 Ω-cm), making it highly suitable for this

application [151].

4.1.3 Buffer Layer

The buffer or passivation layer was applied on top of the ITO to reduce interface

recombination, thereby increasing the minority carrier lifetime. The ternary compound

magnesium zinc oxide (MZO) was used as a buffer layer. MZO possesses high excitation

binding energy and a large, tunable bandgap (3.37- 7.60 eV), making it popular for applications

in thin-film solar technology [152]. By adjusting the bandgap, a small spike can be created in the

30
conduction band of the CdTe solar cells. This spike can reduce interface recombination, improve

the minority carrier lifetime, and consequently increase the VOC.

4.1.4 Window Layer

Several groups use MZO as a window layer. However, our MZO-based CdTe solar cells

are sensitive to the heat treatment process during fabrication. This can create high-concentration

trap states in the MZO/CdTe interface, which decreases the VOC [153]. Therefore, a very thin

(20-25 nm) layer of Cadmium Sulfide (CdS) was applied after depositing MZO. CdS can be

deposited by a few different techniques, such as close-spaced sublimation (CSS), chemical bath

deposition (CBD) and sputtering. In this study, it was employed the CSS technique for

depositing CdS because it allows the production of high-quality, large-grain films that are free of

pinholes.

4.1.5 CST (CdSeXTe1-X) Absorber Layer

The bandgap of CdTe is 1.45 eV. Incorporating CST (CdSeXTe1-X) as an additional

absorber layer with CdTe reduced the bandgap to as low as 1.36 eV. The bandgap of the CST

layer depends on the Se composition; it decreases with Se composition up to 40% and then

increases due to the bowing effect. The use of CST increases the JSC, reaching values as high as

30.5 mA/cm². The CST alloy can be prepared either by the interdiffusion between the CdSe and

CdTe, or by direct deposition from the CST source. For the CdSe and CdTe interdiffusion,

residual CdSe can reduce the JSC due to the bandgap of CdSe (1.74 eV) [154]. Therefore, CdSe

thickness needs to be optimized. For this work, CST was directly deposited from a CST source

by the CSS process, with the Se composition controlled by adjusting the source temperature.

31
4.1.6 CdTe Absorber Layer

CdTe can be deposited using various techniques, such as: atomic layer deposition (ALD)

[155], metal-organic chemical vapor deposition (MOCVD) [156], electrodeposition [157-158],

screen printing [159-160], close-spaced sublimation (CSS) [161-162], thermal evaporation [163-

164], DC- RF sputtering [165-167], and vapor transport deposition (VTD) [168-169]. For this

work, the CSS process was used, as its high-temperature nature results in larger grains with

fewer grain boundaries. Higher processing temperature also increases the junction quality and

reduces the resistivity of the CdTe films [170]. Other processes, for example, sputtering and

physical vapor deposition can cause smaller grains. The use of oxygen positively impacts the

CdS/CST interface [171]. However, oxygen slows the deposition rate, resulting in smaller grains

while producing a high-density film with fewer pinholes.

4.1.7 CdCl2 Heat Treatment

CdCl2 heat treatment is a crucial step in fabricating p-type CdTe solar cells. It was done

after thermally evaporating CdCl2. The most notable effects of this treatment include:

• recrystallizes the absorber layer, leading to increased grain sizes. Additionally, it

passivates the grain boundaries [172], thereby decreasing grain boundary recombination

and enhancing the minority carrier lifetime [173]

• enhances interdiffusion between the CdS/CdTe or CdS/CST interface. This interdiffusion

boosts the electronic properties of the junction [174]

• increases the carrier collection in the longer wavelength region [175]

4.1.8 Back Contact Formation

To efficiently collect carriers and minimize recombination at the back of the solar cells, a

robust back contact is essential. CdTe has a high electron affinity (4.28 eV) and a bandgap of

32
1.45 eV. Therefore, to establish an ohmic contact with CdTe, the metal should have a work

function of at least 5.73 eV. However, finding a material that satisfies this requirement is

challenging. Two methods can be used to meet this prerequisite because of the difficulty of p +

doping of CdTe. First, treating the surface can create a Te-rich layer, producing a p+ surface.

Next, a buffer layer can be deposited between the p+ surface and the metal contact. This surface

treatment not only generates a p+ surface but also eliminates any contaminants or oxides that

may have formed during the CdCl2 heat treatment process. The surface treatment can be

performed using either dry or wet etching methods. Wet etching is commonly used for treating

CdTe surfaces. Notably effective wet etching solutions include bromine/methanol mixtures (BM)

[178-179], nitric and phosphoric acid mixtures (NP) [180], and chromate etches

(k2Cr2O7/H2SO4) [181]. The BM solution was used for this work.

4.1.9 Experimental Process

The superstrate cell configuration of p-type CST/CdTe was:

ITO/MZO/CdS/CST/CdTe/Back Contact. The transparent glass substrate used was corning

EagleXG glass. First, the glass was rinsed and cleaned with hydrofluoric acid (HF). Then Indium

Tin Oxide (ITO) at a thickness of 6000Å and Magnesium Zinc Oxide (MZO) at a thickness of

1000Å were deposited by RF sputtering. CdS was deposited using the close-spaced sublimation

(CSS) process at source and substrate temperatures of 640 and 500°C respectively. Alloys of

undoped and As-doped CST with varying compositions of Se were fabricated by combining CdTe

(99.999%), CdSe (99.999%), and Cd3As2 powders in a hydrogen ambient. CST was deposited by

CSS with substrate and source temperatures of 580°C and 680°C respectively. A CdTe layer of 4

µm is deposited at the same condition as CST, followed by the CdCl2 heat treatment of the

structure at 410-440°C temperatures. Before applying the back contact, the samples were rendered

33
Te-rich by briefly etching them in a bromine methanol solution. For the standard device, Cu-

doped graphite paste was used to make back contact. For the transparent back contact cells, CuI or

CuSCN was used as back contact.

4.1.10 CST (CdSeXTe1-X) Source with Different Se Compositions

The carrier generation (short circuit current) is influenced by the absorber's bandgap.

Therefore, reducing the bandgap of CST is crucial for enhancing carrier generation. This

reduction in bandgap can be achieved by adjusting the CST's Se composition, which is dependent

on the source temperature of the CSS deposition. Figure 13 shows the CSS chamber of CST

deposition. The source block holds the CST source, and the substrate block holds the substrate,

which was kept at a lower temperature [182]. A quart lamp controlled the temperature of the CST

source and substrate. A higher source temperature resulted in a higher Se composition.

Figure 13 CSS deposition chamber

Figure 14 below illustrates how the Se composition varies with different source

temperatures. 10% Se composition was found for 715, 30% for 745, and 40% for 775°C source

temperatures.

34
Figure 14 Se composition at different source temperatures

4.1.11 Spin Coating Process

Solution-processed spin coating is a quick and simple process. Additionally, spin coating

equipment is inexpensive and requires minimal electrical power, making the overall process

cost-effective. This technique can produce thin, uniform films of various thicknesses. Several

parameters, such as solution concentration, speed, and multiple coatings, can be adjusted to

control the film thickness. Moreover, high-speed processing which facilitates rapid drying, can

further expedite film formation.

The solution was prepared and then stirred for 4-5 hours for complete dissolution (of

CuSCN and CuI). After that, it was filtered out using a PTFE filter to eliminate large particles.

The solution was subsequently applied to a spinning substrate. Once the spin coating was

complete, the sample was annealed to evaporate the solvent. A high solubility limit solvent was

selected as it minimizes solvent-related defects.

Figure 15 shows the spin coater that was used for this work. The speed can be varied

from 0-8000 RPM. An uniform film was observed for a speed of 3000 RPM or higher.

35
Figure 15 Spin coater

4.1.12 CuSCN Spin Coating

Solvent selection for the spin coating is an important process step. A few important

points should be considered when choosing the right solvent. (1) the material should be highly

soluble in the solvent. (2) the solvent should be non-toxic. A highly toxic solvent will be

hazardous to people and the environment. (3) The boiling point of a solvent is also important.

The desired material should not dissociate at the boiling point of the solvent.

From the literature, few solvents are found for the CuSCN spin coating. Table 4.1 shows

the CuSCN solvents with their boiling point [183].

Among all these solvents, DPS, DMF, and NMP have low solubility limits for the

CuSCN and DES is very toxic, so NH4OH and DMSO were used in this work to prepare the

CuSCN solution.

36
Table 4.1 CuSCN solvents with their boiling point [183]
Solvent Name Boiling Point

(°C)

Dimethyl Sulfide (DMS) 37

Ammonium Hydroxide (NH4OH) 38

Diethyl Sulfide (DES) 92

Dipropyl Sulfide (DPS) 142

Dimethyl Formamide (DMF) 153

Dimethyl Sulfoxide (DMSO) 189

N-methyl-2-pyrrolidone (NMP) 202

Figure 16 CuSCN in NH4OH (left) and DMSO (right) solvent

Figure 16 shows the color of CuSCN solution in NH4OH and DMSO solvents. The

solution concentration was 10 mg/mL (0.08 M). CuSCN made a dark blue color in NH4OH and a

dark gray color in DMSO solvent. This color came from the partial formation of [(Cu(NH3)2]2+

complex. Other literature reported a similar color for the CuSCN solution [183]. Each spin-
37
coating cycle resulted in a very thin film, which was difficult to measure with a thickness

profilometer. To determine the thickness per spin-coating cycle, a glass substrate spinning at

3000 RPM was spin-coated 10x times, and thickness was measured and found to be 155 nm.

Subsequently, the thickness was calculated assuming 15.5-16 nm CuSCN film per spin cycle.

4.1.13 CuI Spin Coating

CuI can be dissolved in a few different solvents, such as acetonitrile, dipropyl sulfide, 2-

methoxy ethanol, and deionized water. Among them, acetonitrile is the most popular. CuI is

nicely soluble in this solvent and can even form a single-crystal CuI film.

Figure 17 CuI in Acetonitrile solvent

Figure 17 shows the CuI in acetonitrile solvent. It formed a light green color. The

solution concentration was 10 mg/mL (0.10 M). For thickness calibration, 10 spin coatings were

done, and 270 nm thickness was found. A thickness of 27 nm per spin coating cycle was

subsequently used. Multiple spin coatings were done to achieve the desired thickness.

Films produced of CuSCN and CuI were very transparent. Figure 18 shows the

transparency of both CuSCN and CuI film.

38
Figure 18 Plain glass (left), glass with CuSCN film (middle) and CuI film (right)

4.2 Device Architecture of n-type CdTe Solar Cells

The device structure of n-type CdTe is shown in Fig. 19. Transparent conducting oxide

(ITO) was deposited on an HF (Hydrofluoric Acid) cleaned glass substrate. Then the CdS layer

was fabricated by CSS followed by the n-type CdTe absorber layer deposition by the EVT

(Elemental Vapor Transport) process. After that, the p-type transparent heterojunction partner

and back transparent conducting oxide (ITO) were deposited.

Figure 19 n-type CdTe solar cells structure

4.2.1 Experimental Process

The device configuration of our n-type CdTe solar cells was: ITO/CdS/n-type CdTe/p-

type transparent heterojunction partner/ITO. The Corning EagleXG glass was cleaned, and a
39
4000Å layer of ITO was deposited at a substrate temperature of 250°C using RF sputtering.

Following this, a thin layer of CdS was deposited through the CSS process at source and substrate

temperatures of 640°C and 500°C respectively. The n-type CdTe layer, measuring 4-6 µm, was

then fabricated using the EVT process. By adjusting the temperature or flow rate, either Cd-rich

or Te-rich films were deposited. Subsequently, the p-type heterojunction partner was deposited on

top of the n-type CdTe via sputtering or spin coating. Finally, a 3000Å layer of ITO was deposited

as the back contact layer.

4.2.2 EVT Process

EVT stands for Elemental Vapor Transport deposition. The EVT system comprises

distinct zones for facilitating different materials, including the Cadmium (Cd) zone, Tellurium

(Te) zone, dopant (D) zone, and the mixing zone (Figure 20). Each zone can be independently

heated to the desired temperature and supplied with an inert gas using quartz lamps and mass flow

controllers (MFC). Vapor from each zone converged in the mixing zone, where they mixed and

deposited onto the substrate. The Cd/Te vapor ratio can be adjusted by controlling the vapor

pressure by varying the zone temperatures and flow rates. This allowed for the growth of either

Cd or Te-rich films, aiding in defect level control, which subsequently influenced doping levels

(n-type or p-type).

Figure 20 Schematic diagram of the EVT deposition system

40
 Chapter 5: Experimental Measurements

5.1 Current Voltage (I-V) Measurement

Light current-voltage (I-V) measurement is used for measuring solar cell efficiency.

From this measurement, open circuit voltage (VOC), and fill factor (FF) can be extracted under a

certain illumination (AM 1.5G). From these values, the efficiency of the solar cell can be

calculated. A calibrated Solar simulator was used to simulate the solar spectrum at an air mass of

1.5G. A Keithley 2410 source meter was used to apply bias, and current output was measured as

the DC bias voltage was swept; the measurement used 4 probes to eliminate parasitic contact

resistances. Dark I-V can also be measured to determine the diode quality by extracting some

parameters such as the diode factor and shunt resistances.

5.2 Spectral Response (SR) Measurement

A solar cell's short circuit current density (JSC) can be extracted by measuring its spectral

response (SR). SR shows how well a solar cell can convert the light of a certain wavelength to

electricity. By analyzing this wavelength-based response, we can reduce the loss of the solar cell.

Moreover, it can be used to determine material properties such as bandgap. SR can also be used

to design multijunction solar cells to generate a broader spectra response. This measurement

utilized an Oriel monochromator (model no. 74100) with a Quartz Line lamp (model 43707)

serving as the light source. The light output was calibrated using a Si photodiode that was

calibrated at the National Renewable Energy Laboratory (NREL). The JSC of the solar cells was

then calculated using SR data and the AM1.5G standard tables.

41
5.3 Capacitance-Voltage (C-V) Measurement

The Capacitance-voltage (C-V) measurement is a common technique for the calculation

of the depletion width capacitance of a semiconductor junction. This measurement gives the

method to estimate the net doping profile of the semiconductor devices. The measurements were

performed using an HP 4194A impedance/gain-phase analyzer at 3 kHz or 30 kHz with -2 V to

+0.5 V bias voltage.

5.4 X-ray Diffraction (XRD)

X-ray diffraction (XRD) is the widely used characterization technique for phase

identification of a crystalline material and can provide information about the unit cell parameters.

It can also determine whether the material is amorphous or polycrystalline. Additionally, the

composition of ternary compounds (such as CST and MZO) can be calculated using the

relationship between the lattice constant and composition. A Panalytical X’Pert MRT was

employed to obtain the diffraction peak. The scan was conducted over a 2θ range of 20-90°.

From this measurement, the interplanar spacing/distance (d) was determined, which was then

used to calculate lattice constant (a) from the Miller indices.

(1.8)

Here, h, k, and l are the Miller indices. Using Vegard's Law, the Se composition of the CST layer

was attained from the lattice constant.

A(x)= x ACdSe+ (1-x) ACdTe (1.9)

where A(x), ACdSe, and ACdTe are the lattice constants of the CST, CdTe and CdTe, respectively.

5.5 Scanning Electron Microscope (SEM)

Scanning electron microscope (SEM) creates images of a sample by scanning the surface

with a focused electron beam of energy around 0-30 keV. The electrons interact with atoms of

42
the sample, providing signals that give information about the surface topography. For this study,

Hitachi SU800 and SU70 are used to generate the images at different magnifications to

understand the effect of substrate temperature, CdCl2 annealing temperature, and Cd/Te ratios on

the grain sizes. Moreover, the system has an energy dispersive spectroscopy (EDS) detector,

which can provide compositional analysis of a semiconductor or metal compound. The Se

composition of the CST layer measured using EDS was within 5% values of XRD data.

43
 Chapter 6: Optimization of p-type CST/CdTe Solar Cells

This chapter discusses the performance optimization of the CST/CdTe solar cells. Since

the CST layer helps to reduce the absorber bandgap and subsequently increases the JSC, the Se

composition of the CST layer needs to be optimized to maximize JSC. The Se composition of the

CST layer was varied from 0-40%. After finding the suitable Se composition, the thickness of

the CST layer and CdCl2 heat treatment were varied to determine the thickness that produced the

better-graded CST/CdTe absorber. The CdCl2 heat treatment does not only control the

interdiffusion between the CST and CdTe layers but also passivates the grain boundaries to

increase the minority carrier lifetime. Finally, since CdTe is difficult to dope, the CST layer was

also doped with As (Arsenic) to achieve higher doping, which could lead to a higher VOC.

6.1 Effect of CdS Thickness

The thickness of the CdS layer plays an essential role in the performance of the

CST/CdTe solar cells. It has a bandgap of 2.42 eV, so the thick layer can absorb light at lower

wavelengths. So, the optimum thickness is necessary for higher carrier collection and FF (fill

factor).

CdS deposition was done three different times (25, 45, and 90 seconds) to achieve 15, 25,

and 50 nm thickness, as shown in Figure 21. At 410°C CdCl2 annealing temperature, for 15 nm

CdS thickness, no current loss was found in the lower wavelength. For 25 nm, some loss was

seen. However, for the 50 nm, a significant current loss was observed at wavelengths below 650

nm. This loss cannot be attributed just to CdS (which absorbs below 510 nm) but rather due to

the formation of another interfacial compound between CST and CdS.

44
Figure 21 CdS thickness effect in the spectral response

Table 6.1 VOC, FF, and JSC of CdTe solar cells at different CdS thicknesses
CdCl2 CdS thickness VOC FF JSC Efficiency
treatment (nm) (mV) (%) (mA/cm2) (%)
410°C 15 800 59.50 27.82 13.24
25 780 54.40 26.39 11.20
50 780 60.90 23.66 11.24
430°C 15 800 57.40 27.17 12.48
25 800 61.80 27.62 13.65
50 780 53.90 27.31 11.48

From Table 6.1, for 410°C CdCl2 heat treatment, 15 nm thickness resulted in the highest

current because no current loss was found with a JSC of 27.82 mA/cm2, which also led to a higher

efficiency (13.24%). For 25 and 50 nm of CdS, there was residual CdS as well as another

interfacial compound formed between CST and CdS, which was responsible for the current loss

in the short wavelength region. However, for 430°C CdCl2 heat treatment, 25 nm CdS showed

better overall performance (13.65%). This was because, at this temperature, there were no

residual CdS, so no current loss was found.

45
6.2 Effect of CdCl2 Annealing Temperatures

As-deposited (no CdCl2 heat treatment) CdTe cells exhibit poor performance. A CdCl2

heat treatment is required as it helps to increase the grain size (in small grain films) and

passivates grain boundaries. Table 6.2 shows the cell performance for 0.5 µm CST at different

CdCl2 annealing temperatures. In these cells, the CST layer was doped with As (Arsenic).

Table 6.2 VOC, FF, and JSC of CdTe solar cells at different CdCl2 annealing temperatures
CdCl2 treatment VOC FF JSC Efficiency
2
(°C) (mV) (%) (mA/cm ) (%)
410 800 63.90 27.73 14.17
420 800 63.50 27.73 14.09
430 810 65.60 28.11 14.93
440 730 42.50 26.94 8.36

With the increasing CdCl2 annealing temperature, the VOC, JSC, and FF increased untill

430°C because of the increase in minority carrier lifetime. However, at 440°C, the performance

degraded significantly most likely due to a high amount of chlorine reaching the front interface

and the bulk of the material, which can lead to higher recombination. For this work the optimum

CdCl2 annealing temperature was found to be 430°C.

Figure 22 Monochromatic I-V measurement at 410 (left) and 430°C (right) CdCl2 annealing
temperature
46
 Monochromatic I-V (Figure 22) was measured at several wavelengths (460, 540, 700,

800, and 850 nm) using filters of 20 nm bandwidth. At 410°C, with the increase in wavelength,

the FF decreased, and at 430°C, with the increase in wavelength, the fill factor stayed the same,

which indicated a higher minority carrier lifetime at 430°C.

6.3 Effect of Selenium (Se) Composition of the CST (CdSeXTe1-X) Layer

The Selenium (Se) composition of the CST layer determines the absorber's bandgap.

Higher Se composition has a lower bandgap due to the bandgap bowing effect. The lowest

bandgap was found at 40% Se. After that, it increased with the Se composition. Also, the

addition of Se to CdTe results in a higher minority carrier lifetime and, thereafter, higher VOC.

The Se composition of the CST layer was confirmed from XRD and EDS measurements and was

compared to values found in the literature. The XRD data of CdTe, CdSe, and CST (at different

Se compositions) films are shown in Figure 23. From the XRD peaks, it is clear that CdTe,

CdSe, and all CST films were polycrystalline. CdTe had a cubic structure, CdSe had a hexagonal

structure, and all CST films (Se composition at 10-40%) had a cubic structure with preferential

orientation along the (111) direction. Similar behavior had been reported elsewhere.

Figure 23 XRD data of CdTe, CdSe, and CST films at various Se compositions

47
Figure 24 (111) peak of CdTe, CST, and CdSe films

Figure 24 depicts the (111) peak of CdTe, CdSe, and CST (Se composition- 10 to 40%)

films. It was found that with the increase of Se composition, this peak shifted to the right. Similar

Se composition was also measured from the EDS (Energy Dispersive Spectroscopy) (shown in

chapter 5).

Figure 25 VOC and bandgap as different Se compositions

48
 Figure 25 shows the VOC and bandgap change with the Se composition. With the increase

of the Se composition, VOC decreased. This was due to the reduction of the bandgap of the CST

layer. The lowest VOC was found at 40% Se. The reduction of the VOC at 40% Se was higher

possibly due to a higher conduction band offset at this composition. VOC was lower at 430°C

CdCl2 annealing temperature; this could be the formation of a thicker CST film at the higher

CdCl2 annealing temperature.

Figure 26 JSC and FF as different Se compositions

From Figure 26, it is clear that JSC and FF both increased with the increase of the Se

composition till 27%. This was because of the lower bandgap, higher minority carrier lifetime,

and graded absorber structure. The highest JSC and fill factor were observed at 27% Se. Both fill

factor and JSC decreased drastically at 40% Se. This was most likely due to a higher conduction

band offset (ΔEC). A higher band offset worked as a barrier for the carrier collection. This was

also confirmed using device simulation shown in Figure 27.

49
Figure 27 Experimental (left) Vs. simulated (right) J-V at 27 and 40% Se

The simulation was done (Figure 27) for 27 and 40% Se composition of the CST layer

while considering similar CST and CdTe doping and lifetime. Only the ∆EC was used for the

corresponding Se composition. From the simulation, a kink was observed for 40% of Se

composition, similar to the experiment due to the higher ∆EC.

6.4 Effect of As (Arsenic) Doped CST (CdSeXTe1-X) on the Cell Performance

Figure 28 VOC vs. Se composition for undoped (left) and As-doped (right) CST/CdTe cells

50
 Fig. 28 shows the VOC for both undoped and As-doped CST/CdTe cells. It was observed

that the highest VOC for undoped and As-doped cells was 840 and 800 mV respectively. The As

doped cells showed 30-40 mV lower VOC consistently than undoped devices presumably due to a

lower minority carrier lifetime.

Fig. 29 demonstrates the effect of different Se compositions on JSC. No significant

difference was seen for both types of cells. The JSC found at 430°C CdCl2 annealing temperature

is higher than 410°C because of the lower bandgap at higher annealing temperature which

changed the intermixing between CST and CdTe.

Figure 29 Jsc vs. Se composition for undoped (left) and As-doped (right) CST/CdTe cells

Figure 30 shows the bandgap at different Se compositions for both undoped and As-

doped cells. With the increase of Se composition, the bandgap decreased because of the bowing

effect, that’s why VOC was lower and JSC higher at higher Se composition. Moreover, the 430°C

CdCl2 annealing temperature showed a lower bandgap than 410°C, because it affected the

intermixing between the CST and CdTe, therefore changing the final composition and thickness

of the CST layer.

51
Figure 30 Bandgap vs. Se composition for undoped (left) and As-doped (right) CST/CdTe cells

Figure 31 Net p-doping vs. Se composition for undoped (left) and As-doped (right) CST/CdTe
cells

Fig. 31 shows the net p-doping at different Se compositions. At higher Se composition,

higher net p-doping was found. This means that a higher Se composition may help to enhance

the dopability of the CST layer. The maximum p-doping of 3.20E+14 cm-3 was found for

undoped cells at 22% Se composition, and 1.87E+15 cm-3 for As-doped cells at 27% Se

composition.

52
6.5 Effect of CST (CdSeXTe1-X) Layer Thickness on the Performance

The thickness of the CST layer can be controlled by varying the deposition time. The

thickness was varied from 0.25-1.00 µm.

Table 6.3 VOC, FF, and JSC of 0.25-1.00 µm CST thickness at 410 and 430°C heat treatment
for 27% Se composition
Condition VOC FF JSC Efficiency
(mV) (%) (mA/cm2) (%)
CST-0.25 µm, CdCl2-410°C 790 57.70 26.20 11.94
CST-0.25 µm, CdCl2-430°C 810 62.70 26.75 13.59
CST-0.50 µm, CdCl2-410°C 790 63.00 27.73 13.80
CST-0.50 µm, CdCl2-430°C 820 68.30 28.11 15.75
CST-1.00 µm, CdCl2-410°C 780 63.30 27.86 13.75
CST-1.00 µm, CdCl2-430°C 790 65.90 28.50 14.84

Table 6.3 shows the CST thickness effect on the VOC, FF, and JSC at 27% Se. A CST

thickness of 0.50 µm produced higher VOC because of the higher bandgap. At 1.00 µm thickness,

the interdiffusion between the CST and CdTe was higher which caused the bandgap to decrease

more than the 0.50 µm thickness. For the same reason, JSC was slightly higher for the 1.00 µm

cell. However, 0.50 µm exhibited a higher FF. This may be because of producing a better-graded

absorber layer at 0.50 µm thickness. Though 0.25 µm CST thickness gave the same VOC as 0.50

µm thickness, it produced much lower JSC and FF because of the very thin layer of CST. Overall,

a 0.50 µm CST thickness produced a higher efficiency.

Figure 32 summarizes the performance of all CST/CdTe solar cells and shows a clear

trend in all the cell parameters (VOC, JSC, FF, and bandgap). With the increase of Se composition,

the bandgap decreased due to the bowing effect. That is why JSC increased, and VOC was

supposed to decrease. However, VOC decreased only slightly, possibly due to the higher lifetime

caused by higher Se composition. A clear rising trend was also observed in the FF with the Se

composition. The highest cell parameters were observed around 30% Se composition.

53
Figure 32 Summary of all CST/CdTe cells with 0.50 µm CST thickness

Based on all the experiments, the optimum condition found for the CST/CdTe solar cells

was: 0.50 µm CST with 30% Se composition heat treated at 430°C.

6.6 Summary of Chapter 6

The current state of the art for CdTe solar cells is CST/CdTe absorber. The use of a CST

layer increased the JSC by reducing the absorber bandgap, which depends on the Se composition

of the CST layer. Higher Se composition did not only increase the JSC but also the lifetime of the

minority carrier due to the passivation effect caused by the Se. That is why cell performance

54
increased with Se composition. Around 30% Se composition the CST/CdTe cell produced the

highest JSC (and FF). Compositions above 30% resulted in a significant reduction in FF due to

higher ∆EC. The CST layer thickness at different CdCl2 heat treatments was varied to form a

graded CST/CdTe absorber. A thickness of 0.25 µm for CST showed the lowest JSC and 1.00 µm

showed low VOC due to lower bandgap and low FF for the non-optimized graded absorber.

Optimum parameters were found to be 0.50 um CST layer with 30% Se composition, and CdCl2

heat treatment of 430°C.

55
 Chapter 7: p-type CST/CdTe Solar Cells with Transparent Back Contact

The back contact for the standard cell is Cu-doped graphite for the p-type CST

(CdSeXTe1-X)/CdTe solar cells. However, Cu-doped graphite contact is not transparent, so the

solar cells can not utilize light from the backside. That is why a highly conductive transparent

semiconductor was applied as back contact to allow light to shine through the back of the solar

cells to collect more carriers (bifacial solar cells). The standard cell structure was

(glass/ITO/MZO/CdS/CST/CdTe/Cu-doped graphite) and for bifacial cell

(glass/ITO/MZO/CdS/CST/CdTe/Transparent BC/ITO).

Figure 33 Standard (left) and bifacial (right) p-type CST/CdTe solar cells

56
7.1 p-type CdTe Solar Cells with CuI Transparent Back Contact

Figure 34 shows the XRD data of the CuI fine powder used for this work. The data

clearly shows that CuI was polycrystalline with a cubic structure. The major peaks were (111),

(220), and (311).

Figure 34 XRD data of CuI powder

Figure 35 Tauc plot of CuI film

57
 The reported bandgap for the CuI is 3.10 eV. Using transmission measurement data of the

CuI film prepared using the spin coating process, the Tauc plot shown in Fig. 35 was used to

extrapolate a bandgap of 2.90 eV. The sheet resistance of CuI spin-coated film was also

measured using the four-probe measurement technique. The lowest sheet resistance found was

6.55x103 Ω/□, corresponding to a conductivity of 12 S-cm-1.

CdTe solar cells were fabricated using CuI p-type transparent contact and performance

was compared for different back contact (CuI, Cu-doped graphite, ZnTe) cells.

Table 7.1 VOC, FF, and JSC of p-type CdTe solar cells with different back contacts
Condition VOC FF JSC Efficiency
2
(mV) (%) (mA/cm ) (%)
No CuI 600 66.00 23.72 9.39
With CuI 730 73.90 23.61 12.74
Standard Cell 820 64.60 24.16 12.80
ZnTe:Cu 740 51.50 25.04 9.54

Figure 36 Light J-V and SR of p-type CdTe solar cells with different back contacts

Figure 36 depicts the effect of different back contacts on the CdTe solar cell’s

performance. From Table 7.1, if no CuI back contact was used, the VOC found was 600 mV.

58
Once a back contact was applied, a VOC of 730 mV was achieved for CuI and 740 mV for ZnTe:

Cu cells. ZnTe:Cu back contact cells had a higher series resistance as shown in J-V, which is

why the FF was lower. Moreover, it showed a little sign of kink formation. Compared to ZnTe:

Cu back contact solar cells, the CuI solar cells showed excellent FF. It is speculated that CuI

helped to passivate the interface and improve back band alignment to reduce interface

recombination, resulting in 74% FF. CuI back contact cells showed a similar performance to Cu-

doped graphite back contact cells. However, Cu-doped graphite contact cells showed a higher

VOC (820 mV) than CuI back contact cells due to higher doping.

The effect of CuI thickness was also investigated. Each spin coating cycle produced a

thickness of 25 nm. Multiple spin cycles achieved 50, 75, and 125 nm thickness by keeping the

solution concentration and speed constant. Table 7.2 shows the cell performance with different

CuI thicknesses.

Table 7.2 VOC, FF, and JSC of p-type CdTe solar cells at different CuI thicknesses
Thickness (nm) VOC FF JSC Efficiency
(mV) (%) (mA/cm2) (%)
50 730 73.30 23.58 12.62
75 730 73.90 23.61 12.74
125 740 72.10 23.91 12.76

Figure 37 shows the light J-V and spectral response of the p-type CdTe solar cells with

different CuI thicknesses. Solar cell characteristics such as VOC, JSC, and FF were identical for all

CuI thicknesses. Therefore, the CuI thickness appeared to have little or no influence on the

performance. Once a minimum thickness of CuI was applied, the performance remained

essentially unchanged.

59
Figure 37 Light JV and SR of p-type CdTe solar cells at different CuI thicknesses

Solar cells with the CuI back contact had relatively low VOC (740 mV). Annealing was

done at higher temperatures to study the effect of potential Cu diffusion into the absorber, and its

impact on p-type doping and VOC.

Table 7.3 VOC, FF, and JSC of p-type CdTe solar cells at different annealing temperatures
Condition VOC FF JSC Efficiency
2
(mV) (%) (mA/cm ) (%)
No CuI 600 66.00 23.72 9.39
CuI Anneal-100 730 73.90 23.61 12.74
CuI Anneal-240 810 67.00 24.82 13.47
CuI Anneal-250 810 65.90 23.28 12.43

From Table 7.3, it is seen that VOC increased to 730 mV with the addition of the CuI layer

due to back interface passivation. When the CuI cells were annealed at 240 and 250°C annealing

temperature, the VOC increased to 810 mV potentially due to Cu diffusion into the absorber.

From the C-V measurement shown in Figure 39, the carrier concentration for the undiffused Cu

device was 6.0E+13 cm-3 and the 240°C annealed Cu diffused device was 2.0E+14 cm-3,

60
suggesting that CuI served as a source of Cu, which diffused in CdTe and increased its net p-

doping.

Figure 38 Light J-V and SR of p-type CdTe solar cells at different CuI annealing temperatures.

From the J-V characteristic in Figure 38, no rollover was seen at low annealing

temperature. However, the cells at the high annealing temperature showed some rollover. From

the spectral response, the 250°C annealing temperature showed low carrier collection in the

higher wavelength region, possibly due to excessive Cu diffusion into the CdTe at this

temperature and degradation of the minority carrier lifetime.

Figure 39 C-V measurements at different CuI annealing temperatures

61
7.2 p-type CST/CdTe Solar Cells with CuI Transparent Back Contact

The standard CdTe solar cells (i.e. without CST) have lower JSC (24 mA/cm2) due to the

1.45 eV bandgap of CdTe. Using a CST/CdTe absorber can enhance JSC due to the smaller

bandgap of CST. For the cells described here, the Se composition and thickness of the CST layer

were 30% Se and 0.50 µm, respectively. Illumination was done from both front and back to

measure the bifacial performance. The front illumination was the standard AM1.5G illumination

and the back illumination varied from 20-40% of the standard light.

Table 7.4 VOC, FF, and JSC of p-type CST/CdTe solar cells with CuI
Condition VOC FF JSC Efficiency
(mV) (%) (mA/cm2) (%)
Front Illumination (100%) 780 69.30 27.93 15.10
Back Illumination (100%) 630 72.30 2.46 1.12
Front (100%)+Back (20%) 780 69.50 28.68 15.55
Front (100%)+Back (40%) 780 69.10 29.18 15.73

Table 7.4 depicts the CST/CdTe cell performance with front, back, and both side

illumination. From only front-side illumination, the highest VOC achieved was 780 mV with an

efficiency of 15.1%. The highest FF of 72.3% was obtained for the only backside illuminated

cell. When the light was illuminated from both sides of the solar cells, JSC increased as expected

due to the additional carrier generation at the back. Higher back light intensity further increased

the JSC. The bifacial structure (both side light illumination) enhanced the efficiency by 3-5%.

Figure 40 shows the light J-V under the variation illumination conditions listed in Table 7.4.

62
Figure 40 Different illuminated light J-V of p-type CST/CdTe solar cells with CuI

7.3 p-type CdTe Solar Cells with CuSCN Transparent Back Contact

CuSCN was applied as transparent back contact on the p-type CdTe solar cells. Figure 41

shows XRD data of CuSCN fine powder used for this work. The data clearly shows that CuSCN

was polycrystalline with major peaks (020), (211), and (112).

Figure 41 XRD data of CuSCN powder

63
 CdTe solar cells were fabricated using CuSCN dissolved on various solvents as the back

contact and were compared with the Cu-doped graphite back contact solar cells (standard cells).

The solvents used for the CuSCN solution were DMSO and NH4OH).

Table 7.5 VOC, FF, and JSC of p-type CdTe solar cells with different back contacts
Condition VOC FF JSC Efficiency
2
(mV) (%) (mA/cm ) (%)
No CuSCN 600 66.00 23.72 9.39
CuSCN in NH4OH 690 69.30 23.72 11.34
CuSCN in DMSO 740 70.70 24.35 12.74
Standard Cell 820 64.60 24.16 12.80

From Table 7.5, if no CuSCN back contact was used, the VOC found was 600 mV. Once a

CuSCN back contact was applied, a VOC was increased to 690 mV for CuSCN in NH4OH

solvent and 740 mV for CuSCN in DMSO solvent. Moreover, The CuSCN back contact cells

showed an excellent FF (> 70%) compared to Cu-doped graphite back contact cells. CuSCN

helped to passivate the interface to reduce interface recombination, resulting in a higher VOC and

FF. Overall, CuSCN back contact solar cells performed similarly to Cu-doped graphite cells.

However, the VOC was lower for the CuSCN back contact cells than Cu-doped graphite cells due

to lower CdTe doping. Figure 42 shows the light J-V and SR of different back contact cells.

Figure 42 Light J-V and SR of p-type CdTe cells with different back contacts

64
Table 7.6 VOC, FF, and JSC of p-type CdTe solar cells with CuSCN at different annealing
temperatures
Condition VOC FF JSC Efficiency
2
(mV) (%) (mA/cm ) (%)
No CuSCN 600 66.00 23.72 9.39
CuSCN Anneal-100 740 70.70 24.35 12.74
CuSCN Anneal-240 810 71.90 24.48 14.26
Standard Cell 820 64.60 24.16 12.80

Figure 43 Light J-V and SR of p-type CdTe solar cells with CuSCN

Table 7.6 shows the CdTe cell performance at different CuSCN annealing temperatures.

At 100°C CuSCN annealing, the VOC was 740 mV. When the CuSCN cells were annealed at

240°C temperature, the VOC increased to 810 mV most likely due to Cu diffusion into the

absorber from CuSCN, which increased the net CdTe p-doping. Figure 44 shows the C-V

measurements at different CuSCN annealing temperatures. The net doping found at 100°C

annealing temperature was 7.08E+13 cm-3 and for 240°C, 3.11E+14 cm-3 due to the Cu diffusion

into the CdTe absorber. Moreover, the CuSCN back contact cells showed high FF (71.9%)

compared to standard cells because CuSCN created a better passivated back contact with less

interface recombination. That is why CuSCN back contact cells outperformed the standard (Cu-

doped graphite back contact) solar cells.

65
Figure 44 C-V measurements at different CuSCN annealing temperatures

7.4 p-type CST/CdTe Solar Cells with CuSCN Transparent Back Contact

CuSCN was finally applied as the back contact in the p-type CST/CdTe solar cells to

enhance JSC. The CST layer had a 30% Se composition and a 0.50 µm thickness. Light

illumination was done from both the front and back sides to measure the bifacial performance.

The back illumination was varied from 20-40% of the standard light condition.

Table 7.7 VOC, FF, and JSC of p-type CST/CdTe solar cells with CuSCN
Condition VOC FF JSC Efficiency
(mV) (%) (mA/cm2) (%)
Front Illumination (100%) 780 67.50 28.30 14.90
Back Illumination (100%) 620 63.40 2.46 1.12
Front (100%)+Back (20%) 780 67.80 29.05 15.36
Front (100%)+Back (40%) 780 67.10 29.55 15.46

Table 7.7 illustrates the CST/CdTe cell performance with front, back, and both side

illumination. With only front-side illumination, the highest VOC achieved was 780 mV with an

efficiency of 14.9%. A FF of 63.4% was obtained for only backside illumination. When the cell

was illuminated from both sides, JSC increased due to increased carrier generation from the back

illumination. Increasing the backside intensity increased the JSC even more as expected. The

66
bifacial structure (both side light illumination) enhanced the efficiency by 3-5%. Figure 45

shows the light J-V at various front and back illumination conditions.

Figure 45 Different illuminated light J-V of p-type CST/CdTe solar cells with CuSCN

7.5 Summary of Chapter 7

p-type CST (CdSeXTe1-X)/CdTe solar cells were successfully fabricated with CuI or

CuSCN as a transparent back contact. First, they were applied as back contact to the CdTe solar

cells. The VOC for the cells contacted with ITO was 600 mV. Once CuI or CuSCN was applied,

the VOC was increased to 730 mV for the CuI and 740 mV for the CuSCN (both annealed at

100°C). The thickness of the CuI and CuSCN layers had very little influence on the performance.

Moreover, due to the excellent conductivity, the CuI back contact helped to attain a high FF.

However, the VOC achieved was low at 100°C annealing temperature. 240°C annealing

temperature helped attain a VOC of 810 mV for CuI and CuSCN back-contacted solar cells due to

the Cu-diffusion into the CdTe absorber. For the CST/CdTe solar cells, a maximum VOC of 780

67
mV was achieved with CuI and CuSCN back contact with 28 mA/cm2 JSC. Since CuI and

CuSCN were transparent, light could also be shone through the backside. The maximum

efficiency for the CuI back contact solar cells was 15.10% for the front illumination and 1.12%

for the back illumination. The maximum efficiency for the CuSCN back contact solar cells was

14.90% for the front illumination and 1.12% for the back illumination. Bifacial illumination

increased efficiency by 3-5%.

68
 Chapter 8: n-type CdTe Solar Cells with Transparent p-type Heterojunction Partner

The p-type heterojunction partner plays a crucial role in the performance of n-type CdTe

solar cells. Both CuSCN and CuI can function as an effective p-type transparent heterojunction

partner for our n-type CdTe solar cells. They have a bandgap higher than 3 eV (3.10 for CuI,

3.40 eV for CuSCN) and a small ∆EV with n-type CdTe (0.53 eV for CuI, and 0.23 eV for

CuSCN). This chapter discusses the performance of n-type CdTe solar cells with CuI and

CuSCN heterojunction partners. To understand their effect on the performance (VOC, JSC, and

FF), as a function of material properties and processing such as annealing temperatures,

annealing time, film thickness, and CdTe n-doping. Their performance was comapared with our

standard ZnTe:Cu devices. ZnTe has a bandgap of 2.26 eV, so it can cause parasitic absorption

in the short wavelength range. Since CuI and CuSCN have larger bandgap (> 3 eV), higher JSC

can be achieved. The n-type CdTe was doped with Indium (In) to make it n-type and higher In

vapor concentration (ppm) gave higher net n-doping.

N-type CdTe films deposited by EVT (Elemental Vapor Transport) and doped with In

were used for these experiments. The device structure was glass/ITO/CdS/n-

CdTe/(CuI/CuSCN)/ITO. More information can be found in the previously published work

[184]. CdTe can be grown at different Cd/Te ratios. A lower than 1 Cd/Te ratio is suitable for p-

doping, and a higher than 1 is suitable for n-doping. The zone temperature and flow rate

controlled the ratio. An n-type CdTe solar cell was grown at different ratios, and it was found

that a higher ratio gave higher net n-doping.

69
Figure 46 SEM images of CdTe at different Cd/Te (0.5-top left, 0.7- top right, 1- bottom left, 2-
bottom right) ratios

Figure 46 shows the SEM images of the EVT CdTe at different Cd/Te ratios. uniform

grain size was observed at a lower Cd/Te ratio (<1). At a higher Cd/Te ratio (>1), grain sizes

were not uniform with some bigger grains.

Figure 47 CdTe normalized XRD at different Cd/Te ratios

70
 The diffraction spectra here correspond to the zinc blend structure of CdTe. The Cd/Te

ratio 0.3 showed the highest preferential orientation in the (1 1 1) direction. As the Cd/Te ratio

was increased, more peaks showed up with higher intensity.

8.1 CuI as p-type Heterojunction Partner

n-type CdTe with In doping was deposited using the EVT (Elemental Vapor Transport)

process. In doping concentration was varied to 1K and 10K ppm In. n-type CdTe was used as-

deposited, which means no CdCl2 treatment was performed. CuI was applied as a p-type

heterojunction partner. CuI-contacted cells were annealed at 100°C after CuI deposition to

remove the residual solvent.

Table 8.1 VOC, FF, and JSC of n-type CdTe with CuI and ZnTe:Cu heterojunction partner
p-type Contact VOC FF JSC Efficiency
(mV) (%) (mA/cm2) (%)
ZnTe:Cu, 1K In 480 57.70 10.00 2.77
CuI, 1K In 530 36.50 12.02 2.33
ZnTe:Cu, 10K In 500 51.80 11.92 3.09
CuI, 10K In 550 36.00 13.42 2.66

Figure 48 n-type CdTe with CuI and ZnTe:Cu as p-type heterojunction partner

71
 Table 8.1 shows the n-type CdTe cell's performance with CuI and ZnTe:Cu

heterojunction partner. For both partners, VOC and JSC increased with the CdTe doping from 1K

to 10K In, suggesting that increased doping can enhance VOC as expected. For the CuI cells, the

VOC was 50 mV and JSC 2 mA/cm2 higher than ZnTe:Cu cells; however, the FF with CuI was

lower compared to ZnTe:Cu most likely due to the higher valence band offset (∆EV) of 0.73 eV.

The light J-V and SR of the n-type CdTe with CuI and ZnTe:Cu are shown in Figure 48.

From the J-V, it is clear that cells with CuI heterojunction partners have a kink which was the

reason for the lower FF compared to the ZnTe:Cu cells. From the spectral response, it is seen

that cells with CuI have higher carrier collection in the longer wavelength. This means cells with

CuI had lower interface recombination than ZnTe:Cu cells.

8.1.1 Effect of CuI Annealing Temperature

After depositing the CuI, the n-type CdTe cells were annealed to remove the solvent and

increase the crystallinity. CuI cells were annealed at different temperatures from 100 to 250°C.

Annealing at 200 and 250°C was done in the inert ambient (He) to avoid the formation of CuO.

Figure 49 n-type CdTe with CuI at different annealing temperatures

72
 Figure 49 shows the VOC and JSC of the n-type CdTe solar cells with CuI annealed at 100-

250°C. The VOC was similar until 200°C and increased at 250°C. JSC decreased with increasing

annealing temperature. At 250°C, cells had very little carrier collection from the back

illumination. This was due to the change in the conductivity of the n-type CdTe, which was

confirmed from the SR measurement from front and back illumination.

Figure 50 shows the front and back-illuminated SR of the n-type CdTe solar cells at

250°C. Back illumination means light was shone through the CuI side, and front illumination

means through the glass side. At 250°C, high SR was obtained from front illumination, which

means the junction was on the front side, which means the n-type CdTe became p-type. This was

due to the excessive Cu diffusion into the n-type CdTe absorber from the CuI film.

Figure 50 Spectral response of n-type CdTe with CuI at different annealing temperatures

8.2 CuI as an Interfacial Layer

n-type CdTe solar cells with ZnTe:Cu p-type partner showed low FF and VOC. If a

passivated interfacial layer is applied, it should help enhance both VOC and FF. CuI was applied

as an interfacial layer between n-type CdTe and ZnTe:Cu.

73
Table 8.2 VOC, FF, and JSC of n-type CdTe with CuI as an interfacial layer
Structure VOC FF JSC Efficiency
(mV) (%) (mA/cm2) (%)
n-CdTe/ZnTe:Cu/ITO 580 43.20 9.16 2.30
n-CdTe/CuI/ZnTe:Cu/ITO 600 63.70 9.52 3.64
n-CdTe/ZnTe:Cu/CuIITO 470 54.70 8.32 2.14

From Table 8.2, n-type CdTe solar cells with ZnTe:Cu had a VOC of 580 mV. Adding

CuI as an interfacial layer increased the VOC to 600 mV. A significant increase was also observed

in the FF. This indicates a significant improvement in interface quality and a reduction in

interface recombination as a result of using CuI as an interfacial layer between CdTe and ZnTe.

Figure 51 Spectral response of n-type CdTe with CuI as an interfacial layer

Figure 51 shows the light J-V and SR of the n-type cells with a CuI interfacial layer. The

CuI interfacial layer helped to make a sharp J-V curve, which means that CuI increased the pn

junction quality. Moreover, SR showed improved carrier collection at the higher wavelength,

suggesting improved minority carrier lifetime (most likely due to a reduction in the interface

recombination).

74
8.3 CuSCN as p-type Heterojunction Partner

CuSCN is another suitable p-type heterojunction partner of the n-type CdTe solar cells

due to its properties (3.4 eV bandgap, 0.23 eV ∆EV). The bandgap of CuSCN allows light to pass

through it to the CdTe absorber, so more photons can be utilized to generate electricity. It was

deposited using solution-processed spin coating using DMSO and NH4OH solvent. Film

thickness for one-spin coating was found to be 15-16 nm. Multiple spin coatings were done to

achieve a thickness higher than 15 nm. n-type CdTe was doped with 1K ppm In. n-type CdTe

was as deposited means without any CdCl2 treatment.

Table 8.3 VOC, FF, and JSC of n-type CdTe with CuSCN as p-type heterojunction partner
Condition VOC FF JSC Efficiency
(mV) (%) (mA/cm2) (%)
CuSCN with DMSO 670 35.30 13.03 3.08
CuSCN with NH4OH 660 38.60 12.58 3.21

Figure 52 Light J-V and SR of n-type CdTe with CuSCN p-type partner

Table 8.3 shows the performance of n-type CdTe solar cells (VOC, JSC, and FF) with a

CuSCN p-type heterojunction partner. Figure 52 shows the light J-V and spectral response of the

75
n-type CdTe/p-CuSCN solar cells with DMSO and NH4OH solvent. The highest VOC achieved

was 670 mV for both solvents, with JSC being only around 13 mA/cm2, and the FF being limited

due to a kink in the J-V. The kink was possibly due to the poor interface between CuSCN and

CdTe. Moreover, the carrier collection was also low in the short wavelength region. Based on

these results, it appeared that the solvents used to date yield very similar device performance.

8.3.1 Effect of CuSCN Thickness

The thickness of CuSCN was varied by varying spin coating speed, solution

concentration, and multiple spin coating. For this work, speed and solution concentration were

kept constant, and only the number of spin coating cycles was varied to control the thickness. For

device fabrication, 2, 3, and 4 times spin coating was carried out leading to a film thickness of

approx. 35, 50, and 70 nm respectively. It was then annealed at 100°C for residual solvent

removal. Table 8.4 shows the cell performance with different CuSCN thicknesses.

Table 8.4 VOC, FF, and JSC of n-type CdTe with CuSCN as p-type heterojunction partner
Thickness VOC FF JSC Efficiency
(nm) (mV) (%) (mA/cm2) (%)
35 660 38.6 12.6 3.2
50 660 41.5 13.0 3.6
70 670 37.6 13.0 3.3

The effect of CuSCN thickness is shown in Figure 53. It can be seen that VOC and JSC

were essentially identical for all thicknesses. Only the FF was higher (41.5%) for the 50 nm

CuSCN film. Therefore, it can be concluded that the thickness has very little effect on cell

performance.

76
Figure 53 Light J-V and SR of n-type CdTe with CuSCN as p-type heterojunction partner

8.3.2 Effect of CuSCN Annealing Temperature

After depositing the CuSCN, the n-type CdTe structures were annealed to remove

residual solvent and increase crystallinity. CdTe cells are annealed at different temperatures

(100-200°C).

Figure 54 n-type CdTe with CuSCN at 100-200°C annealing temperatures

Figure 54 shows the VOC, JSC, and FF of the n-type CdTe solar cells with CuSCN

annealed at 100-200°C. The highest VOC, JSC, and FF were found at 100°C annealing

77
temperature. All cell parameters (VOC, JSC, and FF) decreased with increasing in the annealing

temperature. The SR decreased with increasing annealing time due to Cu diffusion.

8.3.3 Effect of CuSCN Annealing Time

After CuSCN film deposition, the n-type CdTe cell structure was annealed in ambient air

to remove residual solvent and increase crystallinity. Typically, the annealing was done for 10

mins at 100°C. For this experiment, the annealing time was varied from 10 to 30 mins to

determine whether annealing time impacts the performance.

Table 8.5 VOC, FF, and JSC of n-type CdTe with CuSCN as p-type heterojunction partner
Condition VOC FF JSC Efficiency
2
(mV) (%) (mA/cm ) (%)
Air Anneal-10mins 660 41.50 13.91 3.81
Air Anneal-20mins 690 44.70 14.10 4.35
Air Anneal-30mins 680 44.00 14.07 4.21

Table 8.5 shows the annealing time effect in the n-type CdTe/p-CuSCN cell performance

at 10-30 mins annealing time. The VOC increased by 20-30 mV with the increase in the annealing

time. A higher annealing time may enhance the film crystallinity. Moreover, since the annealing

was done in the ambient air, the oxygen might play a crucial role in the CuSCN film. CuSCN

film annealed in the oxygen ambient showed higher VOC than the inert ambient. Therefore,

oxygen might cause defect passivation and increase the film's conductivity, giving a higher

performance at a higher annealing time.

The light J-V and SR of the n-type CdTe with CuSCN at different annealing times are

shown in Figure 55.

78
Figure 55 n-type CdTe with CuSCN at different annealing times

8.3.4 Effect of CuSCN Doping

CuSCN doping can play an important role in the efficiency of n-type CdTe solar cells by

increasing the VOC. CuSCN doping can increase the depletion region in the n-type CdTe side,

thus giving higher VOC. Since CuSCN was deposited using solution-processed spin coating, thus

adding some dopants in the solution could work as a dopant to increase the doping of CuSCN.

Dopants must be soluble in the same solvent as CuSCN. From the literature, some groups used

CuI as a dopant source (I2 as the dopant) for the CuSCN solution [185]. Both CuSCN and CuI

are soluble in the NH4OH solvent used for this work. The weight percentages were varied as a

means to vary the dopant concentration, i.e. low doping vs high doping corresponded to 10%,

and 50%- of CuI material was added (by weight). The performance (VOC, JSC, and FF) of the n-

type CdTe solar cells at different doping levels is shown in Figure 56. The CdTe doping was also

varied here from 1K and 10K ppm In.

The VOC, JSC, and FF are similar for low and undoped CuSCN doping are similar to the

undoped CuSCN cells. However, the high-doping CuSCN exhibited lower cell parameters (VOC,

JSC, and FF).

79
Figure 56 n-type CdTe with different CuSCN doping levels

8.4 Effect of n-type CdTe Doping

The CdTe doping was then varied to study the effect of absorber doping. The CdTe

doping was varied by varying the Indium (In) vapor concentration. Figure 57 shows the n-type

CdTe net doping at different In vapor concentrations. The In vapor concentration was varied

from 0-20K ppm. With the increase of In vapor concentration the net CdTe doping increased; the

highest doping was found to be 2.4E+16 cm-3, corresponding to 20K ppm In vapor

concentration.

Figure 57 Net n-type CdTe doping vs. In vapor concentration

80
Table 8.6 VOC, FF, and JSC of n-type CdTe at different CdTe doping levels
In Vapor VOC FF JSC Efficiency
Concentration (ppm) (mV) (%) (mA/cm2) (%)
0K 620 45.8 13.4 3.8
1K 660 42.5 13.9 3.9
10K 650 47.6 15.5 4.8
20K 590 46.3 10.9 3.0

Table 8.6 shows the VOC, FF, and JSC at different n-type CdTe doping levels. The highest

cell performance was achieved for 10K In vapor concentration with a doping level of 9.7E+15

cm-3. 20K In vapor concentration showed the lowest cell performance, possibly due to the lowest

minority carrier lifetime at such high doping levels, which appears to be confirmed by lower

carrier collection in the longer wavelength for 20K In n-type CdTe absorber (Figure 58).

Figure 58 Light J-V and SR of n-CdTe/p-CuSCN at different CdTe doping

8.5 CuSCN as an Interfacial Layer

n-type CdTe solar cells with the standard p-type heterojunction partner ZnTe:Cu show

relatively low FF and VOC. If a passivated interfacial layer is applied, it could help to enhance

both VOC and FF. CuSCN has a work function between the ZnTe and CdTe, and therefore should

be a suitable option as an interfacial layer.

81
Table 8.7 VOC, FF, and JSC of n-type CdTe with CuSCN as an interfacial layer
Structure VOC FF JSC Efficiency
(mV) (%) (mA/cm2) (%)
n-CdTe/ZnTe:Cu/ITO 580 43.20 9.16 2.30
n-CdTe/CuSCN/ITO 660 41.50 13.02 3.57
n-CdTe/CuSCN/ZnTe:Cu 680 57.40 10.00 3.90

From Table 8.7, it is seen that n-type CdTe solar cells with ZnTe:Cu p-type

heterojunction partner had the lowest VOC, FF, and JSC (580 mV, 43.20%, and 9.16 mA/cm2).

With CuSCN p-type partner, cells had higher VOC (660 mV), and JSC (13.02 mA/cm2) compared

to ZnTe:Cu cells. However, the FF was low which is why the overall efficiency was low. When

CuSCN was applied as an interfacial between n-type CdTe and p-type ZnTe:Cu, VOC increased

to 680 mV and FF to 57.40% due to the work function, which gives the overall highest

efficiency.

Figure 59 shows the light J-V and SR of the n-type cells with a CuSCN interfacial layer.

The CuSCN interfacial layer helped to achieve a sharp J-V curve, which means that CuSCN

improved the pn junction quality.

Figure 59 Light J-V and SR of n-type CdTe with CuSCN as an interfacial layer

82
8.6 Surface Treatment

The spectral response of the n-type CdTe/p-CuSCN showed overall low carrier

collection. The main reason for the low carrier collection was potentially due to a non-optimum

interface. Because of the poor interface, the interface recombination velocity could be very high

(107 cm-S-1 or higher), which could cause significant interface recombination (from the

simulation results of the n-type CdTe solar cells shown in Figure 60). This led to the lower JSC.

Figure 60 Effect of the interface recombination velocity on the JSC

To study the impact of the interface, surface treatments or interfacial layers can be used

which can lower interface recombination and improve carrier collection. Bromine (Br) etching is

known to create a p-type surface in CdTe films; in this instance if a p-type surface forms, it can

result in a very shallow homojunction moving the junction away from the n-type CdTe/CuSCN

interface. CuSCN thickness was 50 nm and annealed at 100°C.

Table 8.8 Effect of Br etching on the n-type CdTe solar cell performance
Condition VOC FF JSC Efficiency
(mV) (%) (mA/cm2) (%)
No Br etch 660 41.50 13.91 3.81
Br etch 620 53.60 15.05 5.00

83
 Table 8.8 shows the n-type CdTe cell performance with Br etching. Br etching improved

both FF and JSC. The higher carrier collection could be a result of an improved interface.

Figure 61 Effect of the Br etching on the light J-V and SR

The effect of Br etching on the n-tye CdTe/CuSCN solar cells is shown in Figure 61. The

light J-V shows that Br etching helped reduce the kink which increased the FF. The spectral

response shows some increase in the carrier collection. These results seemed to suggest that the

n-type CdTe/CuSCN interface was improved, and further studies need to be carried out to

investigate this effect better.

8.7 Al2O3 as an Interface Passivation Layer

Al2O3 was also applied as an interfacial passivation layer using ALD (Atomic Layer

deposition) after n-type CdTe deposition. 1 cycle of ALD deposition was done to deposit 0.10

nm (1 Å) thickness. Larger Al2O3 thickness created a barrier that reduced the carrier collection

significantly. After depositing Al2O3, annealing was done at 300-500°C.

84
Figure 62 Effect of Al2O3 annealing temperature on the VOC and JSC

Figure 62 shows the effect of Al2O3 on the VOC and JSC of n-type CdTe solar cells. The

Al2O3 layer helped improve both VOC and JSC. This was due to the interface passivation caused

by Al2O3 [147]. With the increase of the annealing temperature, both VOC and JSC increased. The

highest JSC found was 18 mA/cm2 at 400°C annealing temperature. At annealing temperatures

higher than 400°C, both VOC and JSC decreased significantly.

8.8 Summary of Chapter 8

CuI and CuSCN were applied as transparent p-type heterojunction partners and

interfacial layers. For the CuI p-type transparent heterojunction partner, the VOC, and JSC

achieved were higher than ZnTe:Cu partner. However, the FF was significantly lower. The low

FF with CuI was due to the higher ∆EV with the n-type CdTe. With the increase of the CuI

annealing temperature, all the cell parameters (VOC, JSC, and FF) decreased due to the Cu

diffusion into the n-type CdTe absorber. CuI can also work as an interfacial layer, which helps to

reduce interface recombination. A VOC of 600 mV with a FF of 64% was attained with the CuI

interfacial layer. CuSCN worked better as a p-type heterojunction partner with the n-type CdTe

presumably due to the better band alignment. The highest VOC achieved with the CuSCN was

85
690 mV. Higher annealing time gave 20-30 mV higher VOC. Higher annealing temperature

negatively impacted the cell performance by diffusing the Cu into the CdTe absorber. CdTe

doping also has a significant impact on cell performance. The CdTe doping was varied from 0-

20K ppm In. 10K CdTe doping gave higher FF and JSC. This was possibly due to the good CdTe

film quality and better band alignment between n-type CdTe and CuSCN. Finally, CuSCN was

also applied as the interfacial layer in the n-type CdTe solar cells. VOC and FF improved

significantly with the CuSCN interfacial layer due to the passivation effect caused by CuSCN.

The VOC and FF achieved with the CuSCN interfacial layer are 680 mV and 58%, respectively. It

was clear that the interface plays a crucial role in the performance of our n-type CdTe solar cells.

Br (Bromine) etching improved the interface and increased both JSC and FF by reducing interface

recombination and increasing carrier collection. Using Al2O3 as a passivation layer also helped

improve both VOC and JSC. With the increasing Al2O3 annealing temperature, JSC increased, and

the highest JSC of 18 mA/cm2 was found at 400°C.

86
 Chapter 9: Conclusions and Future Opportunities

9.1 Conclusions

The CST layer Se composition and thickness with As (Arsenic) doping at various CdCl 2

heat treatments were studied to determine the optimum condition for the graded CST/CdTe solar

cells for maximum efficiency. The Se composition was varied from 0-40%, and CST thickness

from 0.25-1.00 µm with a CdCl2 heat treatment of 410-440°C. With the increase of Se

composition, VOC decreased, and JSC increased due to the bandgap reduction. FF (fill factor) also

increased with the Se composition till 30% due to higher passivation and graded absorber.

Overall, 0.50 µm CST thickness with a Se composition ̴ 30% and 430°C CdCl2 heat treatment

showed optimum performance. This was due to the optimum interdiffusion between the 30% Se

CST and the CdTe layer, which helped to form a better-graded absorber structure. Higher than

30% Se composition reduced FF significantly because of the higher ∆EC (conduction band

offset). As doping of the CST layer helpd to increase the net p-type doping concentration, but at

the same time, it reduced the VOC by 30-40 mV, presumably due to lowering the minority carrier

lifetime. The maximum net p-doping achieved was 1.87E+15 cm-3. Because of the hurdle of p-

type CdTe doping, the n-type CdTe absorber was another way to get a doping concentration

higher than 1016 cm-3, which could make it possible to get VOC over 1000 mV with efficiency to

the next level (25%).

For making the high-efficiency n-type CdTe solar cells, a highly doped, high work

function, and good lattice-matched p-type heterojunction partner is important. Based on our

literature review and simulation results, CuSCN and CuI had the potential to be an efficient p-

87
type transparent heterojunction partner. First, CuSCN and CuI were applied in the p-type

CST/CdTe solar cells as transparent back contact to fabricate a bifacial (transparent front and

back) structure so that light could be utilized both from the front and back sides of the solar cells.

CuSCN and CuI back contacts produced the passivation effect to reduce the interface

recombination and increase the VOC to 740 mV from 600 mV. Annealing them at 240°C

temperature helped to achieve a VOC of 810 mV with an efficiency of 15%. Moreover, utilizing

the CST/CdTe bifacial structure increased the efficiency by 3-5%.

Finally, CuI and CuSCN were applied as p-type heterojunction partners with our n-type

CdTe solar cells. For the n-type CdTe, doping was around 1E+16 cm-3 with In (Indium). CuI

heterojunction partner outperformed the standard p-type partner ZnTe:Cu in terms of VOC (50

mV) and JSC (2 mA/cm2). However, n-type CdTe with CuI showed low FF due to the kink

caused by higher ∆EV (0.73 eV) between n-type CdTe and CuI. CuI can also work as an

excellent interfacial layer, producing a VOC of 600 mV and an FF of 64%. n-type CdTe with

CuSCN p-type heterojunction partner attained a maximum VOC of 690 mV. However, the FF was

low with CuSCN possibly due to the poor interface and higher ∆EV. It was observed that the cell

performance decreased with the annealing temperature and increased with the annealing time. n-

type CdTe doping also affected the cell performance. 10K CdTe doping showed the highest

performance. It was also found that interface plays a crucial role in the n-type CdTe solar cells

performance. Br etching improves the interface, which helped to improve the JSC and FF to 54%.

The Al2O3 interface passivation layer helped to increase the JSC by reducing interface

recombination. JSC increased with the increase of Al2O3 annealing temperature, and the

maximum JSC of 18 mA/cm2 was found at 400°C.

88
9.2 Future Opportunities

For the p-type CST/CdTe solar cells, few changes can be made during the fabrication of

solar cells. First, since ITO (Indium Tin Oxide) is not a stable TCO at high temperatures, like

many other groups, FTO-coated TEC glasses can be used instead of ITO. Moreover, for this

work, CST and CdTe absorbers were doped with the Cu from the CuSCN or CuI layer by

annealing at higher temperatures (240°C). Instead, CST and CdTe layers can be separately doped

with As (Arsenic) to achieve higher doping, and then the CuSCN or CuI layer can be used as a

transparent back contact, which may help to improve performance. For the n-type CdTe solar

cells, different p-type heterojunction partners were tried. Still, the performance did not reach the

expected level. This proves that the quality of n-type CdTe film is not as expected. A detailed

study on the n-type CdTe defect and interface must be done. Similar to the CdCl2 treatment,

some treatment should be applied in the n-type CdTe solar cells to improve absorber quality. The

device structure can also be modified by applying some passivation layer to reduce interface

recombination.

89
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 Appendix A: Copyright Permissions

A.1 Permission for Figure 10

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A.2 Permission for Figure 11

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A.3 Permission for Figures 28, 29, 30, 31

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A.4 Permission for Figures 22, 23, 24, 25, 26, 27

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