Defect energies, band alignments, and charge carrier recombination in polycrystalline Cu(In,Ga)

122 Pages·2004·3.7 MB·English

Defect energies, band alignments,
and charge carrier recombination
in polycrystalline Cu(In,Ga)(Se,S)2 alloys
DISSERTATION
zur Erlangung des akademischen Grades
Doctor rerum naturalium
(Dr. rer. nat.)
genehmigt von
der Fakultät Mathematik und Naturwissenschaften
der Technische Universität Dresden
von
Mircea Cassian Turcu
geboren am 29. September 1970 in Temesburg, Rumänien
Gutachter: Prof. Dr. K. Leo
Prof. Dr. W. Jaegermann
Dr. habil. U. Rau
Eingereicht am: 01.09.2003
Tag der Verteidigung: 15.03.2004

Acknowledgments
I would particularly like to express my gratitude to my supervisor Dr. U. Rau, leader
of the device analysis group at the Institute for Physical Electronics (ipe), University of
Stuttgart, for his continued guidance, patient advice, and valuable assistance throughout this
work.
I would like to thank Prof. Dr. K. Leo, head of the Institute of Applied Photophysics,
Technical University of Dresden, for initiating this work, for supplying the framework, and
for help in many situations.
I also like to thank Dr. H. W. Schock for many useful discussions and ideas regarding
my work, for constructive criticism, and for support within the compound semiconductors
group which he leads at the ipe.
I am very grateful to Prof. Dr. J. H. Werner, head of the ipe, for encouraging my work
and for the access to all facilities at the ipe.
I am very thankful to Prof. Dr. I. Muscutariu from West University of Timisoara,
Romania, for help in different situations, for support and for encouragement.
I thank I. Kötschau (ipe) for supplying an important part of the samples used in this
work and O. Pakma (Faculty of Arts and Science, University of Mugla, Turkey) for together
performing some measurements. I also thank my colleagues at the ipe for fruitful
collaboration and for help during my work.
I am indebted to my family for continuous support, encouragement, and unconditioned
love without which this work would not have been possible.
Finally, I acknowledge the financial support of the German-Israeli foundation and of
the German Ministry for Education and Research.

Table of contents
Symbols and abbreviations v
Abstract ix
1. Introduction 1
2. Band offsets in semiconductor heterojunctions 4
2.1. Introduction 4
2.2. Band lineup measurement techniques 5
2.3. Anderson approach - the electron affinity rule 7
2.4. The Frensley - Kroemer approach 9
2.5. The Harrison model 10
2.6. Virtual gap states - Tersoff approach 11
2.7. The charge neutrality level 14
2.8. The dielectric midpoint energy 15
2.9. The dangling - bond approach 17
2.10. The deep level model 18
2.11. Linearity of band offsets 20
2.12. Closing remarks 22
3. Fundamentals of Cu(In,Ga)(Se,S)2 materials and devices 24
3.1. The Cu(In,Ga)(Se,S)2 chalcopyrite system 24
3.2. Thin film Cu(In,Ga)(Se,S)2 - based solar cells 28
4. Experimental methods 34
4.1. Absorber preparation 34
4.2. Absorber composition and morphology 35
iii
iv TABLE OF CONTENTS
4.3. Photoluminescence 35
4.4. External quantum efficiency 36
4.5. Electrical characterization 36
5. Photoluminescence spectroscopy 38
5.1. Basics 38
5.2. Results 41
5.3. Discussion 44
5.4. Conclusion 46
6. Admittance spectroscopy 47
6.1. Basics 47
6.2. Composition dependence of defect activation energies 50
6.3. Band gap evolution diagrams 55
6.4. Numerical values 58
6.5. Full width at half maximum 59
6.6. Concluding discussion 61
7. Electrical transport analysis 64
7.1. Basics 64
7.2. Results 68
7.3. Discussion 75
7.4. Conclusion 78
8. Summary and outlook 80
Appendices 84
A. Defects and device performance 84
B. Determination of band gap energies of Cu-chalcopyrite alloys 87
C. Determination of absorber composition 88
D. Determination of inflexion frequencies in the capacitance spectra 89
E. Determination of activation energy of recombination 91
References 94
Symbols and abbreviations
ac alternating current
AS admittance spectroscopy
bV, bC, bg, bowing coefficient of valence/conduction band edge, of bandgap energy
C heterojunction capacitance
CNL charge neutrality level
CV capacitance-voltage
D(E) energetic distribution of defects in the band gap
De diffusion constant for electrons
DAP donor-acceptor pair
DLTS deep level transient spectroscopy
DME dielectric midpoint energy
EA, Ea thermal activation energy of defects, of recombination
EBP branch point energy
Edg dielectric gap energy
EF Fermi level energy position
Eg band gap energy
En Ep
pin, pin n-type and p-type doping pinning levels
EQE external quantum efficiency
eT emission rate of traps
ET bulk defect level of electronic transition N2
EV, EC valence and conduction band edges
E00 tunneling energy
f frequency of the electrical signal
fi inflexion frequency of the capacitance spectra
FF fill factor
FWHM full width at half maximum
-34 π
h Planck constant, 6.62617×10 J·s (ħ = h/2 )
ħω emitted photon energy (photoluminescence)
I emitted photoluminescence intensity
v
vi SYMBOLS AND ABBREVIATIONS
jr, jSC recombination current density, short circuit current density
j0 reverse saturation current or reverse saturation current density
JV current-voltage
k wavevector
-23
kB Boltzmann constant, 1.38066×10 J/K
Le diffusion length for electrons
me, mh, m0 electron and hole effective mass, electron rest mass
*
m effective tunneling mass
NA doping density
Nv, Nc effective density of states in the valence and conduction band
nid ideality factor
N1, N2 electronic transition detected by AS in chalcopyrites
NT concentration of the bulk acceptor N2
PL photoluminescence
P excitation power (photoluminescence)
-19
q elementary charge, 1.60218×10 C
3
s, p, sp atomic orbitals and hybrids
Sif interface recombination velocity for holes
T absolute temperature
V applied voltage
Vbi built-in voltage
VOC open circuit voltage
vth thermal velocity of charge carriers
w space charge width
x Ga/(Ga+In) ratio of Cu(In,Ga)(Se,S)2 alloys
y S/(S+Se) ratio of Cu(In,Ga)(Se,S)2 alloys
χ electron affinity
∆Eif E −E
F energy distance C F at the CdS/absorber interface
∆E ∆E
V , C valence and conduction band offset between bulk chalcopyrite alloys
∆Eif ∆Eif
V , C valence and conduction band offset at the CdS/absorber interface
∆T shift of PL peak energy under increasing temperature
∆P shift of PL peak energy under increasing excitation power
∈d dangling bond energy
SYMBOLS AND ABBREVIATIONS vii
∈s, ∈p p-state, s-state atomic orbital energy
εs static dielectric constant
-14
ε0 vacuum dielectric constant, 8.85418×10 F/cm
ξ0 temperature-independent pre-exponential factor of inflexion frequency
p
φb hole barrier at the CdS/absorber interface
φn, φp Schottky barrier height at metal/n-type or metal/p-type semiconductor
φm metal work function
ϕ0 energy position of the charge neutrality level

η solar cell efficiency
λ wavelength
σp thermal capture cross section of defects

ω angular frequency