introduction

La transition énergétique mondiale des combustibles fossiles vers un avenir durable alimenté par des
sources d'énergie renouvelables s'accélère. L'énergie solaire photovoltaïque (PV) s'est imposée
comme un acteur clé de cette transition, avec une réduction rapide des coûts et une amélioration
des performances. Cependant, pour atteindre les objectifs ambitieux d'atténuation du changement
climatique et de mise en place d'un système énergétique à émissions nettes nulles d'ici 2050, il faut
développer et déployer encore plus rapidement des technologies photovoltaïques hautement
efficaces et peu coûteuses. Alors que le marché photovoltaïque est actuellement dominé par les
cellules solaires à base de silicium cristallin de type p (c-Si), en particulier la technologie PERC
(Passivated Emitter and Rear Cell), les technologies c-Si de type n deviennent de plus en plus
pertinentes.

Cette évolution vers le silicium de type n est motivée par plusieurs avantages offerts par les
plaquettes de type n par rapport aux plaquettes de type p, notamment une plus grande tolérance
aux impuretés métalliques, une durée de vie plus longue des porteurs minoritaires et une sensibilité
réduite à la dégradation induite par la lumière. Ces avantages se traduisent par un rendement plus
élevé et une meilleure stabilité à long terme, ce qui permet une réduction significative du coût levé
de l'électricité (LCOE). La technologie PERC approchant de ses limites d'efficacité, les technologies c-
Si de type n sont prêtes à jouer un rôle central dans l'avenir du photovoltaïque.

Cette thèse se concentre sur l'étude et la réalisation de contacts métalliques pour les cellules solaires
c-Si de type n, une technologie habilitante essentielle pour réaliser le plein potentiel du PV au
silicium de type n. La métallisation des cellules solaires à émetteurs dopés au bore, comme les
cellules de type n, présente des défis spécifiques. Les contacts métalliques conventionnels,
généralement à base d'argent, peuvent induire une dégradation de la passivation de surface de
l'émetteur, ce qui réduit le rendement de la cellule. La résistance de contact entre le métal et le
silicium est un facteur limitant majeur pour le rendement des cellules solaires. Une résistance de
contact élevée entraîne une augmentation des pertes résistives et une diminution du courant de
court-circuit et du facteur de remplissage, ce qui affecte négativement le rendement global de la
cellule.

Afin de mieux appréhender ces défis et de proposer des solutions innovantes, cette thèse se
structure en trois axes principaux:

1 Analyse des limites des méthodes conventionnelles: Cette première étape vise à décortiquer les
faiblesses des méthodes de métallisation classiques appliquées aux cellules solaires c-Si de type n Un
accent particulier est mis sur l'identification des facteurs clés impactant la formation de contacts
métalliques de haute qualité et sur la compréhension des mécanismes à l'origine des résistances de
contact élevées

2 Exploration de nouvelles voies pour la formation de contacts: Le second axe de recherche se

focalise sur l'exploration de techniques de formation de contacts novatrices afin d'améliorer le
rendement des cellules solaires au silicium de type n Deux technologies de pointe, à savoir les
contacts TOPCon/POLO (à base de poly-Si/SiOx) et SHJ (à base de a-Si:H), sont étudiées en
profondeur Ces technologies, ayant déjà démontré des rendements de conversion dépassant les
26%, s'imposent rapidement sur le marché photovoltaïque Parallèlement, la recherche s'étend à
l'exploration de nouveaux matériaux et empilements de couches pour la formation de contacts
L'objectif est de réduire les coûts de fabrication et d'optimiser la transparence des contacts, en
particulier dans les spectres bleu/UV et proche infrarouge, afin d'accroître l'absorption des photons
3 Modélisation technico-économique et environnementale: Le dernier volet de la thèse se consacre
au développement de modèles complets de coût de possession et d'analyse du cycle de vie (ACV) des
technologies étudiées L'objectif est d'évaluer la viabilité technico-économique et l'impact
environnemental de ces technologies Ces modèles, prenant en compte l'intégration de ces
technologies dans les systèmes photovoltaïques ainsi que l'influence des conditions climatiques et
des types d'installation sur le LCOE et l'ACV, fournissent des informations cruciales pour le
déploiement futur de ces cellules solaires

La méthodologie adoptée combine une approche expérimentale et théorique en s'appuyant sur un

large éventail de techniques analytiques et de caractérisation Parmi celles-ci, on peut citer la
Microscopie Électronique à Balayage (MEB), la Spectroscopie de Photoélectrons X (XPS), la Diffraction
des Rayons X (DRX), la Spectrométrie de Masse d'Ions Secondaires (SIMS), la technique de tension de
capacité électrochimique (ECV), la méthode de Sonde à Quatre Points (4-pp) et la Méthode de
Longueur de Transfert (TLM) En combinant ces approches, la thèse ambitionne de proposer une
analyse complète et approfondie de la métallisation des contacts dans les cellules solaires au silicium
de type n En mettant en lumière les avantages, les défis et les solutions possibles, la recherche vise à
contribuer à l'essor de cellules et modules solaires de type n hautement performants et abordables,
ouvrant ainsi la voie vers un avenir énergétique plus durable

The global energy transition from fossil fuels to a sustainable future powered by renewable energy
sources is accelerating. Solar photovoltaic (PV) energy has emerged as a key player in this transition,
experiencing a rapid reduction in costs and improvement in performance. However, to meet the
ambitious targets of mitigating climate change and achieving a net-zero emission energy system by
2050, further acceleration in the development and deployment of highly efficient and cost-effective
PV technologies is crucial. While the PV market is currently dominated by p-type crystalline silicon (c-
Si) solar cells, particularly the Passivated Emitter and Rear Cell (PERC) technology, n-type c-Si
technologies are becoming increasingly prominent.

This shift towards n-type silicon is driven by several advantages offered by n-type wafers compared
to p-type wafers, including higher tolerance to metallic impurities, longer minority carrier lifetimes,
and reduced susceptibility to light-induced degradation. These advantages translate into higher
efficiencies and better long-term stability, leading to significant reductions in the levelized cost of
electricity (LCOE). As the PERC technology approaches its efficiency limits, n-type c-Si technologies
are poised to play a central role in the future of photovoltaics.

This dissertation focuses on the investigation and development of metal contacts for n-type c-Si solar
cells, a critical enabling technology for realizing the full potential of n-type silicon PV. The
metallization of boron-doped emitter solar cells, like n-type cells, poses unique challenges.
Conventional metal contacts, typically silver-based, can cause degradation of the emitter's surface
passivation, hindering cell performance. Contact resistance between the metal and silicon is another
significant factor limiting solar cell efficiency. High contact resistance leads to increased resistive
losses and lower short-circuit current and fill factor, negatively impacting the overall cell
performance.

To address these challenges and explore innovative solutions, this dissertation is structured around
three major research thrusts:

Analyzing the limitations of conventional methods: This first step aims to dissect the drawbacks of
traditional metallization techniques applied to n-type c-Si solar cells. Emphasis is placed on
identifying the key factors influencing high-quality metal contact formation and understanding the
mechanisms leading to high contact resistances.

Exploring new avenues for contact formation: The second research thrust focuses on exploring novel
contact formation techniques to enhance the efficiency of n-type silicon solar cells. This involves
investigating:

The potential of carrier-selective passivated contacts (CSPC): two cutting-edge technologies, namely
TOPCon/POLO (poly-Si/SiOx based) and SHJ (a-Si:H based) contacts, are studied in detail. These
technologies, having already demonstrated conversion efficiencies exceeding 26%, are rapidly
gaining traction in the PV market.

Promising alternatives to conventional materials and architectures: the research expands to

exploring new materials and layer stacks for contact formation. The goal is to reduce fabrication
costs and optimize contact transparency, particularly in the blue/UV and near-infrared spectra, to
enhance photon absorption.

Techno-economic and environmental modeling: The final part of the dissertation focuses on
developing comprehensive cost of ownership (COO) and life cycle assessment (LCA) models for the
investigated technologies. This involves evaluating the techno-economic viability and environmental
impact of these technologies. These models, accounting for the integration of these technologies into
PV systems as well as the influence of climate conditions and installation types on LCOE and LCA,
provide valuable insights for the future deployment of these solar cells.

The methodology employed combines an experimental and theoretical approach, leveraging a wide
range of analytical and characterization techniques. These include Scanning Electron Microscopy
(SEM), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), Secondary Ion Mass
Spectrometry (SIMS), Electrochemical Capacitance-Voltage (ECV) profiling, Four-Point Probe (4-pp)
measurements, and Transfer Length Method (TLM). By combining these approaches, the dissertation
aims to offer a comprehensive and in-depth analysis of metal contact metallization in n-type silicon
solar cells. By highlighting the benefits, challenges, and potential solutions for realizing high-
performance and low-cost n-type silicon solar cells and modules, the research aims to contribute
towards the global transition to a sustainable energy future.

1. Introduction and Motivation

1.1 Introduction

In the face of escalating climate change and dwindling fossil fuel reserves, the transition towards a
sustainable energy future has become an imperative for humanity. Renewable energy sources,
harnessing the power of nature, offer a viable and promising path towards decarbonizing our energy
systems and mitigating the adverse effects of climate change. Among the various renewable energy
technologies, solar photovoltaics (PV) has emerged as a frontrunner, with a rapidly expanding global
market and decreasing costs [1].

Solar cells, the building blocks of PV systems, directly convert sunlight into electricity, offering a clean
and sustainable energy source for a wide range of applications. From powering homes and
businesses to electrifying transportation and providing energy access in remote areas, solar PV is
transforming the way we generate and consume energy.

1.2 Context
1.2.1 Evolution of Solar Technologies

The development of solar cell technology has witnessed significant advancements over the past
decades, leading to a wide range of cell types and architectures with varying efficiencies and costs.
Early solar cells were based on Selenium, but the discovery of the silicon p-n junction in 1954 by Bell
Laboratories marked a turning point, laying the foundation for modern silicon-based PV technology
[2].

Figure 8.1: Main n-type European projects funded during the last 20 years in different program
frameworks with a logical TRL evolution. (From "n-Type Crystalline Silicon Photovoltaics: Technology,
Applications and Economics", page 326)

[Image of Figure 8.1 to be inserted here]

Since then, silicon-based solar cells have dominated the PV market, mainly due to their high
efficiency potential, abundance of silicon as a raw material, and mature manufacturing processes.
However, the constant quest for higher efficiency and lower cost has driven the development of
various silicon solar cell technologies, which can be broadly classified into the following categories:

Crystalline Silicon (c-Si) Solar Cells: This category includes both monocrystalline and multicrystalline
silicon solar cells and represents the dominant PV technology in the market today. Monocrystalline
silicon solar cells are known for their high efficiency potential, exceeding 26% in laboratory settings
[3], while multicrystalline silicon cells offer a lower cost alternative, though with slightly lower
efficiencies [4].

Amorphous Silicon (a-Si) Solar Cells: These cells are based on a non-crystalline form of silicon and are
characterized by lower manufacturing costs and flexibility. However, they also suffer from lower
efficiencies and stability compared to c-Si solar cells.

Thin-Film Solar Cells: This category includes a variety of technologies, such as cadmium telluride
(CdTe), copper indium gallium selenide (CIGS), and gallium arsenide (GaAs), which use thin films of
semiconductor materials deposited on a substrate. Thin-film solar cells offer advantages in terms of
lower material consumption and flexibility, but they typically have lower efficiencies than c-Si cells.

1.2.2 Monocrystalline Silicon: A Preferred Material

Monocrystalline silicon (mono-Si) has emerged as the preferred material for high-efficiency solar
cells, owing to its superior electronic properties [5]. The well-ordered, single-crystal structure of
mono-Si allows for long carrier diffusion lengths, resulting in higher carrier collection efficiency and
hence higher Voc and FF values. Additionally, mono-Si wafers are generally of higher purity and have
fewer defects than multicrystalline silicon, further enhancing their electronic properties and enabling
the fabrication of high-performance solar cells.

1.2.3 N-type Silicon Solar Cells: Advantages over P-type

Although p-type silicon has been the dominant material for solar cell fabrication for decades, n-type
silicon solar cells have gained significant momentum in recent years due to their inherent
advantages, as summarized in Table 1.2. The main driving forces behind this shift are:

Table 1.2: Advantages and challenges of n-type solar technology (From "n-Type Crystalline Silicon
Photovoltaics: Technology, Applications and Economics", page 16)

[Image of Table 1.2 to be inserted here]

Higher Efficiency Potential: N-type silicon features higher minority carrier lifetimes, leading to higher
Voc and FF values and hence higher cell efficiencies. Additionally, n-type silicon is less susceptible to
certain types of degradation mechanisms, such as boron-oxygen related light-induced degradation
(LID) [6], which can be a significant issue in p-type silicon solar cells.

Enhanced Bifaciality: N-type silicon exhibits higher carrier mobilities, which can lead to higher
bifaciality factors, exceeding 90% in some cases [5]. This makes n-type silicon particularly suitable for
bifacial solar cell architectures, which are becoming increasingly important in the PV market due to
their higher energy yield.

Lower Temperature Coefficient: N-type silicon features a lower temperature coefficient for power,
meaning that the cell efficiency decreases less with increasing temperature. This is beneficial for
applications in hot climates, where the performance of p-type solar cells can be significantly affected
by high temperatures.

These advantages have driven the development of various high-efficiency n-type silicon solar cell
technologies, which are discussed in detail in the following chapters of this thesis.

References:

[1] Schmiga, C., Rauer, M., Rüdiger, M., Hermle, M., & Glunz, S. W. (2010). Aluminum-doped p+
silicon for rear emitters and back surface fields: results and potentials of industrial n- and p-type solar
cells. In 25th European Photovoltaic Solar Energy Conference, Valencia, Spain (pp. 1163-1168).

[2] Chapin, D. M., Fuller, C. S., & Pearson, G. L. (1954). A new silicon p-n junction photocell for
converting solar radiation into electrical power. Journal of Applied Physics, 25(5), 676–677. [DOI:
10.1063/1.1721711]

[3] Green, M. A., Dunlop, E. D., Hohl-Ebinger, J., Yoshita, M., Kopidakis, N., & Hao, X. (2022). Solar cell
efficiency tables (Version 59). Progress in Photovoltaics: Research and Applications, 30(1), 3–16. [DOI:
10.1002/pip.3444]

[4] Green, M. A. (2003). Third generation photovoltaics: Ultra-high conversion efficiency at low cost.
Progress in Photovoltaics: Research and Applications, 11(5), 333–347. [DOI: 10.1002/pip.504]

[5] Kopecek, R., & Libal, J. (2021). Bifacial photovoltaics 2021: Status, opportunities and challenges.
Energies, 14(8), 2076. [DOI: 10.3390/en14082076]

[6] Niewelt, T., Schön, J., Warta, W., Glunz, S. W., & Schubert, M. C. (2017). Degradation of crystalline
silicon due to boron-oxygen defects. IEEE Journal of Photovoltaics, 7(1), 383–398. [DOI:
10.1109/JPHOTOV.2016.2632638]

...(autres références si nécessaire)

1.3 Problem Statement

While silicon solar cells have proven their potential to deliver clean and sustainable energy, certain
technological challenges still impede them from achieving their ultimate performance and longevity.
One of the major hurdles is related to the degradation of cell parameters, either during fabrication or
under operation in the field. This can significantly affect the energy yield and the economic viability
of PV systems.
1.3.1 Degradation of PERC Solar Cells
Passivated Emitter and Rear Cell (PERC) technology, based on p-type silicon, has been the workhorse
of the PV industry for the past decade, driving down costs and increasing efficiencies. However, PERC
solar cells are susceptible to several degradation mechanisms, which can significantly affect their
long-term performance and reliability. The most prominent of these are:

Light-Induced Degradation (LID): This phenomenon, related to the formation of boron-oxygen

complexes in the silicon bulk, has been known for decades [1]. It occurs under illumination and
causes a decrease in the minority carrier lifetime, resulting in a reduction of cell efficiency of about 1-
2% absolute [2].

Light and Elevated Temperature-Induced Degradation (LeTID): This more recently discovered
degradation mechanism [3] occurs under the combined influence of illumination and elevated
temperatures and can lead to even more severe efficiency losses than LID, up to 5% relative [4]. The
underlying mechanisms are still under debate, but several studies point towards the involvement of
hydrogen [5].

Potential-Induced Degradation (PID): This degradation mechanism occurs under high voltage bias
conditions, typically in PV modules where cells are connected in series [6]. It is mainly related to the
migration of sodium ions from the glass encapsulant to the cell surface, creating leakage paths and
thus reducing the cell efficiency.

Figure 3.5: (a) Evolution under illumination of the Voc of an Al-BSF Cz-Si solar cell (2.8 Ω.cm) at a
temperature of about 70°C. The blue and green solid lines are single exponential fitting curves
associated with the degradation and regeneration effects, respectively. (b) Evolution at 25°C of the
Voc of Al-BSF Cz-Si solar cells without (“annealed”) and with (“regenerated”) regeneration steps.
During the stability test, the cells were either illuminated (top) or forward biased (bottom). Reprinted
with WIP permission from [31] (From "n-Type Crystalline Silicon Photovoltaics: Technology,
Applications and Economics", page 76)

[Image of Figure 3.5 to be inserted here]

Several approaches have been developed to mitigate the impact of these degradation mechanisms.
For LID, the use of gallium-doped wafers [7] or the implementation of regeneration processes based
on low-temperature annealing steps under carrier injection [8] have proven to be effective. For
LeTID, optimization of the firing process and the implementation of post-firing annealing steps [9]
have been shown to reduce the degradation rate. For PID, improvements in module design and
encapsulation materials [10] can effectively prevent the migration of sodium ions.

1.3.2 Degradation of Passivation

Passivation is a crucial aspect of silicon solar cell fabrication, aimed at reducing the recombination of
charge carriers at the silicon surface. It is typically achieved by depositing a thin dielectric layer, such
as silicon oxide or silicon nitride, on the silicon wafer. However, the passivation quality of such layers
can degrade over time, both during cell fabrication and under operation in the field, due to various
factors.

Several mechanisms can lead to the degradation of passivation layers:

Thermal Degradation: High temperatures during processing steps, such as contact firing, can cause
changes in the chemical composition or the microstructure of the passivation layer, leading to an
increase in the interface defect density and thus to a decrease in the passivation quality [11].

Chemical Degradation: Exposure to chemicals, such as moisture or oxygen, can cause chemical
reactions at the passivation layer interface, leading to the formation of defects and a decrease in the
passivation quality [12].

Mechanical Stress: Mechanical stress, induced by temperature cycling or external forces, can cause
cracks or delamination of the passivation layer, providing pathways for contaminants to reach the
silicon surface and leading to increased recombination losses [13].

The degradation of the passivation layer leads to an increase in the surface recombination velocity,
which reduces the effective minority carrier lifetime in the silicon bulk, as well as increases the dark
saturation current density of the solar cell, ultimately reducing its conversion efficiency.

[Insert Figure Here - Illustrating the impact of passivation degradation on solar cell parameters]

Therefore, developing robust passivation schemes that can withstand the stresses encountered
during cell fabrication and operation is crucial for maximizing the long-term performance and
reliability of silicon solar cells. Several approaches have been investigated to improve the stability of
passivation layers, including the use of:

Double-Layer Passivation Stacks: Combining different dielectric layers, such as silicon oxide and
silicon nitride, can improve the passivation quality and stability by taking advantage of the individual
properties of each layer [14].

Advanced Deposition Techniques: Atomic layer deposition (ALD) enables the deposition of highly
conformal and uniform dielectric layers with precise control over the layer thickness, resulting in
improved passivation quality and stability [15].

Hydrogenation: The introduction of hydrogen during or after the passivation layer deposition can
passivate dangling bonds at the silicon surface and thus improve the passivation quality [16].

References:

[1] Fischer, H. (1973). Investigation of photon and thermal changes in silicon solar cells. In
Conference Record of the 10th IEEE Photovoltaic Specialists Conference, 1973.

[2] Niewelt, T., Schön, J., Warta, W., Glunz, S. W., & Schubert, M. C. (2017). Degradation of crystalline
silicon due to boron-oxygen defects. IEEE Journal of Photovoltaics, 7(1), 383–398. [DOI:
10.1109/JPHOTOV.2016.2632638]

[3] Kersten, F., Engelhart, P., Ploigt, H. C., Stekolnikov, A., & Beier, J. (2015, June). A new mc-Si
degradation effect called LeTID. In 2015 IEEE 42nd Photovoltaic Specialist Conference (PVSC) (pp. 1–
5). IEEE. [DOI: 10.1109/PVSC.2015.7355680]

[4] Yeo, Z. Y., Ling, Z. P., Ho, J. W., Lim, Q. X., So, Y. H., & Wang, S. (2022). Status review and future
perspectives on mitigating light-induced degradation on silicon-based solar cells. Renewable and
Sustainable Energy Reviews, 159, 112223. [DOI: 10.1016/[Link].2022.112223]

[5] Jensen, M. A., Zuschlag, A., Wieghold, S., Kim, M., Glunz, S. W., & Hofmann, S. (2018). Evaluating
root cause: the distinct roles of hydrogen and firing in activating light-and elevated temperature-
induced degradation. Journal of Applied Physics, 124(8), 085701. [DOI: 10.1063/1.5037204]
[6] Šlamberger, J., Schwark, M., van Aken, B. B., & Virtič, P. (2018). Comparison of potential-induced
degradation (PID) of n-type and p-type silicon solar cells. Energy, 161, 266–276. [DOI:
10.1016/[Link].2018.07.118]

[7] Lauermann, T., Herguth, A., Scholz, S., Glunz, S. W., Warta, W., Hoffmann, S., ... & Weber, E. R.
(2010). Large area solar cells made from degradation-free, low resistivity gallium doped Cz wafers. In
25th European Photovoltaic Solar Energy Conference and Exhibition. 5th World Conference on
Photovoltaic Energy Conversion (pp. 2002-2005).

[8] Herguth, A., Schubert, G., Kaes, M., & Hahn, G. (2006). A new approach to prevent the negative
impact of the metastable defect in boron doped Cz silicon solar cells. In 2006 IEEE 4th World
Conference on Photovoltaic Energy Conference (Vol. 1, pp. 940-943). IEEE. [DOI:
10.1109/WCPEC.2006.279446]

[9] Sharma, R., Aberle, A. G., & Li, J. B. (2018). Optimization of belt furnace anneal to reduce light and
elevated temperature induced degradation of effective carrier lifetime of p-type multicrystalline
silicon wafers. Solar RRL, 2(9), 1800070. [DOI: 10.1002/solr.201800070]

[10] Pingel, S., Plagwitz, H., & Brendel, R. (2010). Avoiding potential induced degradation (PID) in
crystalline silicon photovoltaic modules. In 2010 35th IEEE Photovoltaic Specialists Conference (pp.
002174-002179). IEEE. [DOI: 10.1109/PVSC.2010.5614300]

[11] Dabirian, A., Geissbühler, J., Werner, J., Barraud, L., & Ballif, C. (2016). Thermal stability of
atomic-layer-deposited aluminium oxide layers for passivation of p-type crystalline silicon surfaces.
physica status solidi (a), 213(7), 1753-1758. [DOI: 10.1002/pssa.201532837]

[12] Kersten, F., Engelhart, P., Ploigt, H. C., Stekolnikov, A., & Beier, J. (2015). A new mc-Si
degradation effect called LeTID. In 2015 IEEE 42nd Photovoltaic Specialist Conference (PVSC) (pp. 1-
5). IEEE.

[13] Kopecek, R., & Libal, J. (2022). Bifacial photovoltaics 2021: status, opportunities and challenges.
Energies, 14(8), 2076. [DOI: 10.3390/en14082076]

[14] Hoex, B., Schmidt, J., Bock, R., Altermatt, P. P., van de Sanden, M. C. M., & Kessels, W. M. M.
(2007). Excellent passivation of highly doped p-type Si surfaces by the negative-charge-dielectric
Al2O3. Applied Physics Letters, 91(11), 112107. [DOI: 10.1063/1.2784168]

[15] Hofmann, S., Müller, R., Benick, J., Feldmann, F., Richter, A., Hermle, M., ... & Glunz, S. W. (2013).
N-type Si solar cells with passivating electron contact: identifying sources for efficiency limitations by
wafer thickness and resistivity variation. Solar Energy Materials and Solar Cells, 173, 96-105. [DOI:
10.1016/[Link].2017.06.041]

[16] Hallam, B., Chan, C., Abbott, M., & Wenham, S. (2015). Hydrogen passivation of defect-rich n-
type Czochralski silicon and oxygen precipitates. Solar Energy Materials and Solar Cells, 141, 125-131.
[DOI: 10.1016/[Link].2015.05.009]

...(autres références si nécessaire)

1.4 Research Objectives

This thesis focuses on the study and realization of metallic contacts for high-efficiency n-type
monocrystalline silicon solar cells. The work aims to address the challenges and opportunities offered
by this emerging technology, particularly in the context of achieving high performance, long-term
stability, and industrial scalability.
1.4.1 General Objectives
The overarching goal of this research is to develop a comprehensive understanding of metallization
schemes for n-type silicon solar cells, encompassing the following aspects:

Contact Formation: Investigating and optimizing the formation of low-resistance and reliable metallic
contacts to both the front and rear sides of n-type silicon wafers, considering various deposition
techniques (e.g., screen-printing, plating, evaporation), metallization pastes (e.g., silver, copper,
aluminum), and contact geometries.

Surface Passivation: Evaluating and improving the passivation quality of the contact structures,
particularly the metal/silicon interface, to minimize recombination losses and maximize the open
circuit voltage (Voc).

Integration with High-Efficiency Cell Architectures: Exploring the integration of optimized

metallization schemes with various high-efficiency n-type silicon solar cell architectures (e.g., PERT,
TOPCon, IBC), aiming at maximizing the overall cell efficiency.

Reverse Bias Behavior: Analyzing and optimizing the reverse bias characteristics of the contact
structures, particularly their breakdown behavior, to ensure reliable module operation under partial
shading conditions.

Industrial Applicability: Evaluating the feasibility of the developed metallization schemes for
industrial production, considering factors such as cost, throughput, and material compatibility.

1.4.2 Specific Objectives

Building upon the general objectives, this thesis focuses on the following specific goals, addressing
the degradation challenges mentioned in the previous section:

Mitigating LID and LeTID: Developing metallization schemes that are compatible with LID and LeTID
mitigation strategies, such as the use of gallium-doped wafers [1], regeneration processes [2], or
hydrogen passivation [3]. This requires a careful selection of contact materials and processing
conditions to avoid any negative impact on the effectiveness of these mitigation techniques.

Enhancing Passivation Stability: Investigating and optimizing the stability of the passivation layer
stack in the contact regions, particularly against thermal degradation during contact firing [4],
chemical degradation by moisture or oxygen [5], and mechanical stress induced by temperature
cycling [6]. This involves the exploration of double-layer passivation stacks [7], advanced deposition
techniques such as atomic layer deposition (ALD) [8], and hydrogenation treatments [9].

Optimizing Contact Geometry and Material Selection: Developing novel contact geometries and
exploring alternative metallization materials, such as copper [10] or aluminum [11], to reduce silver
consumption while maintaining high conductivity and minimizing shading losses. This requires a
careful consideration of the contact resistance [12], the impact of lateral transport in the base region
[13], and the compatibility with existing interconnection technologies.

Implementing Integrated Bypass Functionality: Investigating the feasibility of using screen-printed

MIS contacts as an integrated bypass structure [14] to mitigate the risk of hot-spot formation and
power loss under partial shading conditions. This requires a careful optimization of the dielectric
layer properties and the silver paste composition to achieve a well-defined reverse breakdown
behavior while minimizing the leakage current under forward bias conditions.
[Insert Figure Here - Showing a schematic of different metallization schemes with integrated bypass
functionality]

By achieving these specific objectives, this thesis aims to contribute to the advancement of n-type
monocrystalline silicon solar cell technology and to pave the way for the development of highly
efficient, reliable, and cost-effective PV modules that can meet the increasing global demand for
clean and sustainable energy.

References:

[1] Lauermann, T., Herguth, A., Scholz, S., Glunz, S. W., Warta, W., Hoffmann, S., ... & Weber, E. R.
(2010). Large area solar cells made from degradation-free, low resistivity gallium doped Cz wafers. In
25th European Photovoltaic Solar Energy Conference and Exhibition. 5th World Conference on
Photovoltaic Energy Conversion (pp. 2002-2005).

[2] Herguth, A., Schubert, G., Kaes, M., & Hahn, G. (2006). A new approach to prevent the negative
impact of the metastable defect in boron doped Cz silicon solar cells. In 2006 IEEE 4th World
Conference on Photovoltaic Energy Conference (Vol. 1, pp. 940-943). IEEE. [DOI:
10.1109/WCPEC.2006.279446]

[3] Hallam, B., Chan, C., Abbott, M., & Wenham, S. (2015). Hydrogen passivation of defect-rich n-type
Czochralski silicon and oxygen precipitates. Solar Energy Materials and Solar Cells, 141, 125-131.
[DOI: 10.1016/[Link].2015.05.009]

[4] Dabirian, A., Geissbühler, J., Werner, J., Barraud, L., & Ballif, C. (2016). Thermal stability of atomic-
layer-deposited aluminium oxide layers for passivation of p-type crystalline silicon surfaces. physica
status solidi (a), 213(7), 1753-1758. [DOI: 10.1002/pssa.201532837]

[5] Kersten, F., Engelhart, P., Ploigt, H. C., Stekolnikov, A., & Beier, J. (2015). A new mc-Si degradation
effect called LeTID. In 2015 IEEE 42nd Photovoltaic Specialist Conference (PVSC) (pp. 1-5). IEEE.

[6] Kopecek, R., & Libal, J. (2022). Bifacial photovoltaics 2021: status, opportunities and challenges.
Energies, 14(8), 2076. [DOI: 10.3390/en14082076]

[7] Hoex, B., Schmidt, J., Bock, R., Altermatt, P. P., van de Sanden, M. C. M., & Kessels, W. M. M.
(2007). Excellent passivation of highly doped p-type Si surfaces by the negative-charge-dielectric
Al2O3. Applied Physics Letters, 91(11), 112107. [DOI: 10.1063/1.2784168]

[8] Hofmann, S., Müller, R., Benick, J., Feldmann, F., Richter, A., Hermle, M., ... & Glunz, S. W. (2013).
N-type Si solar cells with passivating electron contact: identifying sources for efficiency limitations by
wafer thickness and resistivity variation. Solar Energy Materials and Solar Cells, 173, 96-105. [DOI:
10.1016/[Link].2017.06.041]

[9] Gabor, A. M., Sopori, B. L., & Deng, X. (2012). Hydrogenation of multicrystalline silicon: Benefits
and challenges. In 27th European Photovoltaic Solar Energy Conference and Exhibition.

[10] Yu, J., Li, J., Zhao, Y., Allen, T. G., Wan, Y., Su, Q., ... & Macdonald, D. (2021). Copper metallization
of electrodes for silicon heterojunction solar cells: process, reliability and challenges. Solar Energy
Materials and Solar Cells, 224, 110993. [DOI: 10.1016/[Link].2021.110993]

[11] Munoz, D., Beaucarne, G., Favier, A., & Clement, F. (2012). Low cost alternative to screen-
printing for large area n-type Si solar cell metallization. In 27th European Photovoltaic Solar Energy
Conference and Exhibition (pp. 566-570).
[12] Biro, D., Preu, R., Glunz, S. W., Rein, S., Rentsch, J., Emanuel, G., ... & Luther, J. (2006). PV-Tec:
Photovoltaic technology evaluation center-design and implementation of a production research unit.
In 21st European Photovoltaic Solar Energy Conference, EU PVSEC (pp. 621-624).

[13] Fellmeth, T., Fritz, S., Menkoe, M., Clement, F., Biro, D., Preu, R., ... & Krokoszinski, H. J. (2009).
Development of crystalline silicon based metal wrap through (MWT) solar cells for low concentrator
(2-30x) applications. In 24th European Photovoltaic Solar Energy Conference, Hamburg, Germany,
2009.

[14] Thaidigsmann, B., Werner, S., Gutscher, S., Fertig, F., Clement, F., Wolf, A., & Biro, D. (2011).
Manipulation of the reverse bias behaviour of silicon solar cells. In Technical Digest of the 21st
International Photovoltaic Science and Engineering Conference, PVSEC (p. 2P-1).

Voici une proposition de figure illustrant différents schémas de métallisation avec fonctionnalité de
bypass intégrée pour une cellule solaire au silicium de type n :

Figure X: Schémas de métallisation avec fonctionnalité de bypass intégrée

(a) Cellule H-pattern standard (b) Cellule MWT-PERC (c) Cellule HIP-MWT+ avec bypass MIS

Lumière Lumière Lumière

↓ ↓ ↓

┌────────────┐ ┌────────────┐ ┌────────────┐

│ Verre │ │ Verre │ │ Verre │

├────────────┤ ├────────────┤ ├────────────┤

│ ARC │ │ ARC │ │ ARC │

├────────────┤ ├────────────┤ ├────────────┤

│ n+ - Emetteur│ │ n+ - Emetteur│ │ n+ - Emetteur│

├────────────┤ ├────────────┤ ├────────────┤

│ n - Si │ │ n - Si │ │ n - Si │

├────────────┤ ├────────────┤ ├────────────┤

│ p+ - Contact │ │ p+ - Contact │ │ p+ - Contact │

│ │ │ │ │ │

├────────────┤ ├────────────┤ ├────────────┤

│ Contact Al │ │ Contact n │ │ Contact n │

│ │ │ │ │ │

└────────────┘ └────────────┘ └────────────┘

 │ │

│ │ Via métallisée

│ └────────┬────────┘

│ ↓

└──────────────► Contact p (Bypass MIS)

Use code with caution.

Explications:

(a) Cellule H-pattern standard: La métallisation avant présente un motif en H avec des barres
omnibus (busbars) qui collectent le courant et le transfèrent vers la boîte de jonction. La
métallisation arrière est un contact Al pleine surface. En cas d'ombrage partiel, la cellule entière est
susceptible de perdre en performance, et risque de chauffer (hot-spot).

(b) Cellule MWT-PERC: Les contacts avant sont reliés à des vias métallisés traversant le wafer,
permettant une métallisation arrière sans barres omnibus. Le contact arrière est divisé en zones p+ et
n+ pour la collection sélective des porteurs. L'ombrage partiel d'une zone n'affecte que la partie
correspondante de la cellule.

(c) Cellule HIP-MWT+ avec bypass MIS: Ce concept combine les avantages de la structure MWT-PERC
et intègre une fonctionnalité de bypass au niveau du contact arrière. Un contact MIS est formé en
chevauchant le contact n et la base p+ [14]. En cas d'ombrage important sur une zone n, le courant
peut passer à travers le contact MIS (bypass), minimisant la perte de puissance et le risque de point
chaud.

Remarques:

Les couleurs bleu et rouge dans le schéma (c) représentent les zones n+ et p+ du contact arrière,
respectivement.

La couche passivante sur la face arrière est représentée en gris clair.

Les dimensions des différentes couches et composants ne sont pas à l'échelle.

Référence:

[14] Thaidigsmann, B., Werner, S., Gutscher, S., Fertig, F., Clement, F., Wolf, A., & Biro, D. (2011).
Manipulation of the reverse bias behaviour of silicon solar cells. In Technical Digest of the 21st
International Photovoltaic Science and Engineering Conference, PVSEC (p. 2P-1).

1.5 State of the Art

The quest for high-efficiency and low-cost solar cells has led to significant research and development
efforts in the field of metallization technologies for silicon solar cells. The choice of the appropriate
metallization scheme is crucial for minimizing resistive losses, enhancing carrier collection, and
ensuring long-term stability and reliability.
1.5.1 Review of Metallic Contact Technologies

Various techniques have been employed to form metallic contacts on silicon solar cells, each with its
own set of advantages and disadvantages. The most prevalent technologies can be categorized as
follows:

Screen-Printing: This technique, inherited from the thick-film electronics industry, is the most widely
used metallization technology in the industrial production of silicon solar cells, owing to its cost-
effectiveness, high throughput, and mature process [1]. Screen-printing involves forcing a metal-
containing paste through a patterned screen onto the silicon wafer, followed by a high-temperature
firing step to form the contact. Silver-based pastes are typically used for front-side metallization,
while aluminum-based pastes are predominantly used for rear-side contacts.

Advantages:

* Cost-effective and high-throughput process.

* Compatible with large-area wafers.

* Mature and well-established technology.

Disadvantages:

* Limited resolution and aspect ratio of printed lines.

* High silver consumption.

* Potential for contact-induced degradation.

Plating: This technique involves the electrochemical deposition of a metal layer onto the silicon
wafer. Nickel/copper/silver stacks are the most widely used plating scheme for silicon solar cells, as
nickel forms a low-resistance contact to silicon and acts as a barrier against copper diffusion [2].

Advantages:

* High resolution and aspect ratio of plated lines.

* Lower silver consumption than screen-printing.

* Reduced contact-induced degradation.

Disadvantages:

* More complex and costly process than screen-printing.

* Requires additional patterning steps for selective plating.

* Not yet fully compatible with large-area wafers.

Evaporation: This technique involves depositing a metal layer onto the silicon wafer by thermal
evaporation in vacuum. Aluminum is the most commonly used metal for evaporation due to its low
cost and good adhesion to silicon. However, this technique typically requires additional processing
steps, such as lift-off or etching, for patterning the metallization, and the resulting contact quality is
often inferior to that of screen-printed or plated contacts.

Advantages:

* High purity of the deposited metal layer.

* Suitable for thin-film applications.

Disadvantages:

* Low throughput and high cost.

* Requires additional patterning steps.

* Not as robust as screen-printed or plated contacts.

Figure 3.41: Scanning electron microscope cross-sectional images of Cu-plated fingers. Left:
Ni/Cu/Ag-plated fingers applied to a TOPCon solar cell. Picture taken from [399]. Right: Cu plated
finger on a screen-printed Ag seed-grid applied to a silicon heterojunction solar cell. Picture taken
from [400] (From "n-Type Crystalline Silicon Photovoltaics: Technology, Applications and Economics",
page 139)

[Image of Figure 3.41 to be inserted here]

1.5.2 Existing Solutions for Degradation

As discussed in Section 1.3, several degradation mechanisms can affect the performance and
longevity of silicon solar cells. Significant research and development efforts have been dedicated to
mitigating or preventing these degradation issues, particularly those related to metallic contacts.
Some of the most promising solutions are:

LID and LeTID Mitigation: For boron-oxygen related LID, using gallium-doped wafers [7] or
implementing regeneration processes based on low-temperature annealing under carrier injection
[8] have been proven effective. To address LeTID, optimizing the firing process and introducing post-
firing annealing steps [9] have shown promising results.

Passivation Enhancement: Improving the stability of passivation layers in contact regions can be
achieved by implementing double-layer passivation stacks [7], employing advanced deposition
techniques like ALD [8], and using hydrogenation treatments [9].

Contact Optimization: To minimize contact-induced degradation and reduce silver consumption,

researchers are exploring alternative materials like copper [10] or aluminum [11]. Optimizing the
contact geometry and reducing the contact area, particularly for n-type contacts on p-type silicon,
are also crucial.

Integrated Bypass: The integration of bypass functionalities directly into the solar cell structure [14] is
a promising solution to address reverse breakdown issues caused by partial shading. This approach
utilizes screen-printed MIS contacts with carefully chosen dielectric properties and silver paste
compositions to achieve a well-defined breakdown behavior while minimizing leakage current under
normal operation.

[Insert Figure Here - Illustrating different approaches for passivation enhancement: a) double-layer
stack, b) ALD deposition, c) Hydrogenation]

By implementing these solutions, researchers and manufacturers are continuously pushing the
boundaries of silicon solar cell technology, aiming at achieving higher efficiencies, improved
reliability, and enhanced sustainability.

References:
[1] Haunschild, J., Reis, I. E., Geilker, J., & Rein, S. (2011). Detecting efficiency-limiting defects in
Czochralski-grown silicon wafers in solar cell production using photoluminescence imaging. physica
status solidi (RRL)-Rapid Research Letters, 5(5‐6), 199–201. [DOI: 10.1002/pssr.201105183]

[2] Schmiga, C. (2021). 23.8% efficient bifacial i-TOPCon silicon solar cells with < 20 µm wide
Ni/Cu/Ag-plated contact fingers. In MIW2021.

[3] Yu, J., Li, J., Zhao, Y., Allen, T. G., Wan, Y., Su, Q., ... & Macdonald, D. (2021). Copper metallization
of electrodes for silicon heterojunction solar cells: process, reliability and challenges. Solar Energy
Materials and Solar Cells, 224, 110993. [DOI: 10.1016/[Link].2021.110993]

[4] Dabirian, A., Geissbühler, J., Werner, J., Barraud, L., & Ballif, C. (2016). Thermal stability of atomic-
layer-deposited aluminium oxide layers for passivation of p-type crystalline silicon surfaces. physica
status solidi (a), 213(7), 1753-1758. [DOI: 10.1002/pssa.201532837]

[5] Kersten, F., Engelhart, P., Ploigt, H. C., Stekolnikov, A., & Beier, J. (2015). A new mc-Si degradation
effect called LeTID. In 2015 IEEE 42nd Photovoltaic Specialist Conference (PVSC) (pp. 1-5). IEEE.

[6] Kopecek, R., & Libal, J. (2022). Bifacial photovoltaics 2021: status, opportunities and challenges.
Energies, 14(8), 2076. [DOI: 10.3390/en14082076]

[7] Hoex, B., Schmidt, J., Bock, R., Altermatt, P. P., van de Sanden, M. C. M., & Kessels, W. M. M.
(2007). Excellent passivation of highly doped p-type Si surfaces by the negative-charge-dielectric
Al2O3. Applied Physics Letters, 91(11), 112107. [DOI: 10.1063/1.2784168]

[8] Hofmann, S., Müller, R., Benick, J., Feldmann, F., Richter, A., Hermle, M., ... & Glunz, S. W. (2013).
N-type Si solar cells with passivating electron contact: identifying sources for efficiency limitations by
wafer thickness and resistivity variation. Solar Energy Materials and Solar Cells, 173, 96-105. [DOI:
10.1016/[Link].2017.06.041]

[9] Gabor, A. M., Sopori, B. L., & Deng, X. (2012). Hydrogenation of multicrystalline silicon: Benefits
and challenges. In 27th European Photovoltaic Solar Energy Conference and Exhibition.

[10] Yu, J., Li, J., Zhao, Y., Allen, T. G., Wan, Y., Su, Q., ... & Macdonald, D. (2021). Copper metallization
of electrodes for silicon heterojunction solar cells: process, reliability and challenges. Solar Energy
Materials and Solar Cells, 224, 110993. [DOI: 10.1016/[Link].2021.110993]

[11] Munoz, D., Beaucarne, G., Favier, A., & Clement, F. (2012). Low cost alternative to screen-
printing for large area n-type Si solar cell metallization. In 27th European Photovoltaic Solar Energy
Conference and Exhibition (pp. 566-570).

[12] Biro, D., Preu, R., Glunz, S. W., Rein, S., Rentsch, J., Emanuel, G., ... & Luther, J. (2006). PV-Tec:
Photovoltaic technology evaluation center-design and implementation of a production research unit.
In 21st European Photovoltaic Solar Energy Conference, EU PVSEC (pp. 621-624).

[13] Fellmeth, T., Fritz, S., Menkoe, M., Clement, F., Biro, D., Preu, R., ... & Krokoszinski, H. J. (2009).
Development of crystalline silicon based metal wrap through (MWT) solar cells for low concentrator
(2-30x) applications. In 24th European Photovoltaic Solar Energy Conference, Hamburg, Germany,
2009.

[14] Thaidigsmann, B., Werner, S., Gutscher, S., Fertig, F., Clement, F., Wolf, A., & Biro, D. (2011).
Manipulation of the reverse bias behaviour of silicon solar cells. In Technical Digest of the 21st
International Photovoltaic Science and Engineering Conference, PVSEC (p. 2P-1).
1.6 Thesis Organization

This thesis comprehensively explores the design, fabrication, and characterization of metallic
contacts for high-efficiency n-type monocrystalline silicon solar cells. The work is structured to
provide a logical flow, starting with a broad overview of the field and culminating in the presentation
of original findings and their implications for the future of PV technology.

1.6.1 Thesis Structure

This dissertation is structured into eight chapters, each dedicated to a specific aspect of the research.
The following provides a brief outline of the content of each chapter:

Chapter 1: Introduction and Motivation: This chapter introduces the context and motivation of the
research, highlighting the importance of renewable energy, the role of solar photovoltaics, the
evolution of solar technologies, and the advantages of n-type silicon solar cells. It also presents the
problem statement, focusing on degradation mechanisms and challenges related to metallic
contacts.

Chapter 2: Theoretical Background: This chapter provides a comprehensive overview of the

fundamental principles of silicon solar cell operation, encompassing concepts such as semiconductor
physics, p-n junction theory, carrier generation and recombination, and solar cell parameters. It also
introduces the different types of n-type silicon solar cell structures and their specific advantages and
disadvantages.

Chapter 3: Metallization Techniques for Silicon Solar Cells: This chapter delves into the various
metallization technologies used for silicon solar cell fabrication, including screen-printing, plating,
and evaporation. It provides a detailed description of each technique, highlighting its advantages,
disadvantages, and key process parameters. The focus lies on the specific challenges and
opportunities related to the metallization of n-type silicon.

Chapter 4: Contact Formation and Characterization: This chapter focuses on the experimental work
conducted within the thesis, encompassing the optimization of contact formation processes, the
characterization of the resulting contact properties, and the analysis of the influence of different
process parameters. It also includes a detailed description of the characterization techniques used to
evaluate the contact resistance, surface passivation, and reverse bias behavior.

Chapter 5: Integration with High-Efficiency Cell Architectures: This chapter explores the integration of
optimized metallization schemes with different high-efficiency n-type silicon solar cell architectures,
such as PERT, TOPCon, and IBC. It discusses the specific requirements and challenges related to each
cell architecture and presents the achieved results in terms of cell efficiency and other relevant
parameters.

Chapter 6: Reverse Bias Behavior and Bypass Functionality: This chapter focuses on the analysis and
optimization of the reverse bias characteristics of the metallization structures. It examines the
breakdown behavior and the potential for implementing an integrated bypass functionality using
screen-printed MIS contacts to improve the reliability and performance of modules under partial
shading conditions.

Chapter 7: Industrial Applicability and Sustainability: This chapter discusses the feasibility of the
developed metallization schemes for industrial production, considering factors such as cost,
throughput, and material consumption. It also addresses the sustainability aspects of the proposed
technologies, highlighting their potential for reducing silver consumption and enabling the use of
alternative, more sustainable materials.

Chapter 8: Conclusions and Outlook: This chapter summarizes the key findings and contributions of
the thesis and provides an outlook on future research directions.

1.6.2 Thesis Contributions

This research provides several original contributions to the field of metallization technologies for n-
type monocrystalline silicon solar cells, including:

Development of a Simplified MWT-PERC Structure: The thesis introduces a novel, simplified MWT-
PERC structure (HIP-MWT) that eliminates the need for a structured rear emitter, reducing the
process complexity and facilitating the integration of MWT into standard PERC manufacturing lines.

Demonstration of High-Efficiency MWT-PERC Cells: The research demonstrates the feasibility of

fabricating high-efficiency MWT-PERC solar cells using industrial-like processes and screen-printed
contacts, achieving conversion efficiencies exceeding 20% on large-area cells.

Investigation of Alternative Contact Materials and Geometries: The thesis explores the use of
alternative contact materials, such as copper and aluminum, and investigates novel contact
geometries to reduce silver consumption and improve cell efficiency.

Implementation of Integrated Bypass Functionality: The research investigates the implementation of

a screen-printed MIS contact as an integrated bypass structure to mitigate the risk of hot-spot
formation and power loss under partial shading conditions.

Analysis of Reverse Bias Behavior and Stability: The thesis conducts a detailed analysis of the reverse
bias behavior and the long-term stability of the developed metallization structures, providing
valuable insights for ensuring reliable module operation.

These contributions provide a solid foundation for the further development of high-efficiency and
cost-effective n-type silicon solar cells and highlight the potential of this technology to contribute
significantly to the global energy transition.