Materials for Solar Cells: Semiconductors

 In this lecture, we will explore the fascinating world of materials used in solar cells,
specifically focusing on semiconductors.
 These materials play a crucial role in converting sunlight into electricity, making them the
heart of solar technology.
 We will analyze their properties, types, manufacturing, and applications, providing a
comprehensive understanding of this essential component.

What are Semiconductors?

 Semiconductors are materials with electrical conductivity between conductors and

insulators.
 They have a partially filled valence band and an empty conduction band, separated by a
band gap.
 By absorbing light with energy equal to or greater than the band gap, electrons can be
excited from the valence band to the conduction band, creating a flow of electricity.

Semiconductors occupy a unique position in the electrical conductivity spectrum. Unlike

conductors, they don't readily allow current flow, but unlike insulators, they can be manipulated
to conduct electricity under specific conditions. This characteristic, combined with the presence of
a band gap, makes them ideal for solar cell applications.

Types of Semiconductors

 Crystalline silicon (c-Si): Most common, abundant, mature technology, high efficiency,
affordable.
 Cadmium telluride (CdTe): Thin-film, high efficiency, lower cost than c-Si, toxicity
concerns.
 Copper indium gallium selenide (CIGS): Thin-film, high efficiency, flexible, complex
manufacturing
Several types of semiconductors are used in solar cells, each with its own advantages and
disadvantages. Crystalline silicon remains the dominant choice due to its abundance, mature
technology, and affordability. However, thin-film options like CdTe and CIGS offer potential for
lower costs and flexibility, although they come with their own challenges.

Properties of Semiconductors for Solar Cells

 Band gap: Determines the range of light wavelengths that can be absorbed and converted
to electricity
 Crystal structure: Influences light absorption and charge carrier mobility.
 Doping: Introduction of impurities to create p-type (positive charge carriers) and n-type
(negative charge carriers) regions for efficient current flow
 Efficiency: Percentage of sunlight converted into electricity.

Several key properties determine the suitability of a semiconductor for solar cells. The band gap
must match the solar spectrum for efficient light absorption. Crystal structure affects how light
interacts with the material and how charge carriers move within it. Doping allows for the creation
of a p-n junction, the heart of the solar cell, where electricity is generated. Finally, the overall
efficiency of the material is crucial for maximizing energy production.

Emerging Semiconductors for Solar Cells

 Perovskites: Hybrid organic-inorganic materials, promising for high efficiency, low

cost, and flexibility.
 Organic semiconductors: Carbon-based materials, lightweight, potentially printable, but
lower efficiency.
 Quantum dots: Semiconductor nanoparticles, tunable band gap, potential for multi-
junction cells.

The search for new and improved materials for solar cells is ongoing. Perovskites offer exciting
potential due to their high efficiency and ease of fabrication. Organic semiconductors are
 lightweight and potentially printable, but their efficiency needs improvement. Quantum dots have
tunable properties, enabling the design of multi-junction cells for broader light absorption.

Manufacturing process for crystalline silicon (c-Si)

Raw Materials:

 Quartz: The main raw material for c-Si is quartz, a mineral form of silicon dioxide (SiO2). Quartz
is abundant in the Earth's crust and is typically mined from open-pit mines

 Chemicals: Various chemicals are used throughout the c-Si manufacturing process, including
hydrogen chloride (HCl), trichlorosilane (SiHCl3), and dopants such as boron and phosphorus.

Process Steps:

1. Silicon Production:

 The first step is to purify the quartz to obtain high-purity silicon metal. This is typically
done by reacting the quartz with carbon in an electric arc furnace at high temperatures
(around 3,000°C). The resulting silicon metal is still not pure enough for c-Si, so it
undergoes further purification steps.

2. Polysilicon Production:
  The purified silicon metal is then converted into polysilicon, which is a high-purity form
of silicon with a polycrystalline structure (i.e., it consists of many small crystals). This is
typically done by a process called the Siemens process, which involves the chemical
reaction of trichlorosilane (SiHCl3) with hydrogen (H2) to form high-purity silicon.

3. Ingot Formation:

 The polysilicon is then melted and grown into single crystals, or ingots. There are two main
methods for this:
o Czochralski (CZ) method: In this method, a seed crystal is dipped into molten
polysilicon and slowly withdrawn, allowing the silicon to crystallize onto the seed
in a layer-by-layer fashion. This method produces monocrystalline silicon ingots.

o Float-zone (FZ) method: In this method, a rod of polysilicon is melted by a focused

laser beam, and the molten zone is moved along the rod. This method also produces
monocrystalline silicon ingots, but with higher purity than the CZ method.
4. Wafer Slicing:

 The ingots are then sliced into thin wafers, typically using a diamond wire saw. The
thickness of the wafers depends on the intended application (e.g., solar cells
vs. microchips).

5. Doping:

 The wafers are then doped with impurities (e.g., boron or phosphorus) to create p-type and
n-type regions, which are necessary for the electrical conductivity of the devices. Doping
is typically done by diffusion and ion implantation.

6. Device Fabrication:
  The wafers are then processed to create the desired devices, such as solar cells or
microchips. This may involve additional steps such as etching, metallization, and
passivation.

Additional Notes:

 The c-Si manufacturing process is energy-intensive and can generate significant

greenhouse gas emissions. There is ongoing research to develop more sustainable methods
for c-Si production.
 There are two main types of c-Si: monocrystalline silicon (mono-Si) and multicrystalline
silicon (multi-Si). Mono-Si is more pure and efficient, but also more expensive than multi-
Si.
 c-Si is the most widely used material for solar cells and microchips. However, other
materials, such as thin-film silicon and gallium arsenide, are also becoming increasingly
important.

Manufacturing process for Cadmium telluride (CdTe)

Cadmium telluride (CdTe) is a material used in thin-film solar cells, offering advantages like high
absorption and low-cost manufacturing. However, it's essential to be aware of its potential safety
and environmental concerns. Here's a breakdown of CdTe manufacturing details:

Production process:

 Starting materials: Cadmium and tellurium are sourced and refined.

 Deposition: The CdTe layer is deposited onto a substrate (such as glass) using following
techniques.
o Close-spaced sublimation (CSS): Cadmium and tellurium are heated, sublimating
and reacting to form CdTe on the substrate.
o Vapor-transport deposition (VTD): A carrier gas like hydrogen transports
precursor materials, reacting to form CdTe on the substrate.
  Formation of p-n junction: Doping layers are added to create positive and negative regions
within the CdTe, allowing for electricity generation.
 Electrodes: Metal contacts are applied to collect electricity.
 Encapsulation: The cell is protected with glass and encapsulant layers.

Key points:

o High-throughput: Manufacturing is relatively fast and efficient compared to other solar

cell technologies.
o Safety concerns: Cadmium is toxic and requires strict handling procedures to protect
workers and the environment.
o Environmental considerations: Emissions and waste disposal need careful management to
minimize environmental impact.
o Recycling: Recycling infrastructure for CdTe modules is still developing.

Manufacturing process of Copper indium gallium selenide (CIGS)

Copper indium gallium selenide (CIGS) is a promising thin-film solar cell material offering high
efficiency and potential for flexible applications. Here's a breakdown of its manufacturing details:

Substrate:

 Typically, glass or plastic (flexible) substrates are used. Soda-lime glass is common
due to affordability.

CIGS Deposition:

This is the crucial step, often done in a vacuum using various techniques:

 Co-evaporation: Individual elements (Cu, In, Ga) are evaporated and react with
selenium vapor to form CIGS.
  Sputtering: Targets of each element are sputtered, and the ejected atoms combine with
selenium to form CIGS.
 Electrodeposition: Ions of the elements are dissolved in solution and deposited onto
the substrate to form CIGS.
 The exact process and composition (ratio of Cu, In, and Ga) influence the solar cell's
properties and efficiency.

Device Layers:

 After CIGS deposition, additional layers are added to form the complete solar cell
structure:

o Buffer layer: A thin layer, often cadmium sulfide (CdS), is deposited to create a p-
n junction with CIGS (absorber layer).

o Window layer: Usually zinc oxide (ZnO) layers are deposited for transparent
conductivity and carrier collection.

Challenges and Considerations:

 CIGS manufacturing involves several complex steps requiring precise control for optimal
performance.
 Indium scarcity and potential toxicity of elements including cadmium (in CdS) raise
concerns about sustainability and environmental impact.
 Achieving high efficiency and reproducibility across large-scale production remains a
challenge.
Point to ponder: Why FZ method is more efficient than CZ

Contamination Sources in CZ:

 Crucible: In the CZ method, the molten silicon sits in a quartz crucible. However, even
high-purity quartz can leach impurities like oxygen and carbon into the melt.
 Dopant Diffusion: CZ uses dopants to adjust electrical conductivity, but these dopants can
also diffuse into unwanted areas, impacting purity.

FZ Eliminates These Issues:

 No Crucible: The FZ method melts a polycrystalline rod using an induction

coil, eliminating the crucible and its associated contamination.
 Zone Refining: As the molten zone moves along the rod, it acts like a purification
zone. Impurities tend to segregate towards the melt ends, leaving the remaining crystal
purer.

Additional Advantages of FZ:

 Homogeneity: FZ provides more uniform dopant distribution compared to CZ, leading to

consistent electrical properties throughout the ingot.
 Lower Defect Density: The absence of a crucible and controlled melting process minimize
stress and defects in the crystal.

However, FZ also has limitations:

 Production Rate: Slower compared to CZ due to the zone-by-zone melting process.

 Ingot Size: FZ typically produces smaller diameter ingots compared to CZ.

Choosing the Right Method:

The choice between CZ and FZ depends on specific needs:

 CZ: Suitable for larger-scale production of moderately pure ingots for cost-sensitive
applications.
 FZ: Preferred for high-purity requirements, especially in sensitive applications like power
electronics and advanced detectors.