P-N Junction Thin Film Solar Cells
P-N Junction Thin Film Solar Cells
• Solar radiation
9 Electromagnetic wave
9 Solar spectrum
MAE 493R/593V- Renewable Energy Devices 9 Solar global radiation
[Link]
What are Photovoltaics (Solar Cells)? What are Photovoltaics (Solar Cells)?
Photovoltaics is the direct conversion of light into electricity at Photovoltaic Cell Type:
the atomic level
Heterojunction thin-film solar cell
• Silicon Si) and other thin-film silicon)
• Cadmium Telluride (CdTe)
• Copper indium gallium selenide (CIS or CIGS)
Valence band 5s
4d
1s 3d
2s Core level
p-n Junction Thin 3p
3s
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Energy band structure of solids Fermi level & energy band structure of solids
Organic molecules: "Fermi level" is the term used to describe the
top of the collection of electron energy levels at
• The HOMO level is to organic absolute zero temperature.
semiconductors and quantum
dots what the valence band is to
inorganic semiconductors. The Fermi level is the surface of that sea at
absolute zero where no electrons will have
• The same analogy exists enough energy to rise above the surface.
between the LUMO level and the
conduction band.
[Link]
hv → h + + e −
Eg
photon hole electron
Under light irradiation, the electrons jump from the valence band to the
conduction band
The photo-generated electrons in the conduction band are delocalized, able
to transport for a long distance, forming electric current
Positive-charge holes are generated in the valence band when the electrons
leave
The photo-generated holes in the valence band are delocalized, able to
[Link] transport for long distance, forming electric current
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Energy band structure of solids Energy band structure of solids
Photo-current in solid materials: (Ephoton = hc/λ)
ZnO nanowire
light 3.2 eV
Au electrode
Photo-excitation of semiconductor
Transmittance
• Doping silicon lattice with group V elements can creates extra electrons
• Silicon is group IV element – with 4 electrons in their valence shell. in the conduction band — negative charge carriers (n-type), As- donor.
• When silicon atoms are brought together, each atom forms covalent • In n-type semiconductors, the electrons are considered to be the majority
bond with 4 silicon atoms in a tetrahedron geometry. charge carrier
• Doping concentration /cm3 (1016/cm3 ~ 1/million).
By courtesy of Xiangfeng Duan By courtesy of Xiangfeng Duan
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Energy band structure of solids p-n Junction Thin Film Solar Cells
Principles - How p-n thin film solar cells work
p-n diode I-V characteristics
⎡ ⎛ eV ⎞ ⎤
I = I 0 ⎢exp⎜⎜ ⎟⎟ − 1⎥ ¾ Consider p-n junction with
⎣ ⎝ nk BT ⎠ ⎦ very narrow n-region.
p-n Junction Thin Film Solar Cells p-n Junction Thin Film Solar Cells
Principles - How p-n thin film solar cells work Principles - How p-n thin film solar cells work
n-type junction p-type n-type junction p-type
Stage 3: charge separation upon light
Stage 1: before light illumination illumination
¾ The bands are aligned ¾ Electrons flow to the lower energy
conduction band
level
¾ Holes flow to the opposite direction
Eg ¾ Electron-hole pairs continue to be
generated
Valence band Valence band
[Link] [Link]
p-n Junction Thin Film Solar Cells p-n Junction Thin Film Solar Cells
Principles - How p-n thin film solar cells work Principles - How p-n thin film solar cells work
n-type junction p-type
Stage 5: current output
¾ current lows through the external
circuit a p-n junction solar cell is
connected to an external circuit
• No material is consumed.
• The process has no any moving components, which enables high reliability
and silent operation.
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p-n Junction Thin Film Solar Cells p-n Junction Thin Film Solar Cells
• Therefore the existence of built-in field E0 is important to create • Only those EHPs photogenerated within Le to the SCR can contribute to
accumulated electrons in the n-side and holes in the p-side. the photovoltaic effect.
• For long wavelength photons Æ absorbed in the neutral p-side Æ no E • Those photogenerated EHPs further away from SCR than Le are lost by
field Æ diffusion. recombination.
EHPs EHPs
Minority carrier diffusion Thus, it is important to have
exp(−αx) exp(−αx)
length Le. the minority carrier
x diffusion length Le as long x
Le = 2 Deτ e
as possible. Æ By
choosing Si p-n junction
τe- recombination lifetime of to be p-type which makes
electron. electrons to be minority
De- diffusion coefficient on Lh carriers; the electron Lh
W Le W Le
the p-side. diffuse length in Si is
greater the hole diffusion
EHP: electron-hole pair Iph length. Iph
Source: University of South Alabama Source: University of South Alabama
p-n Junction Thin Film Solar Cells p-n Junction Thin Film Solar Cells
• For long wavelengths, 1–1.2 μm, α is small Æ absorption depth 1/α • For EHPs photogenerated by short-wavelength photons absorbed in the
is typically greater than 100 μm. Æ Need a thick p-side and long n-side, within diffusion length Lh, can reach SCL and swept across to
the p-side.
minority carrier diffusion length Le.
• The photogenerated of EHPs that contribute to the photovoltaic effect
occurs in a region of
EHPs EHPs
absorption
coefficient
Lh + W + Le absorption
exp(−αx)
Thus, p-side is 200-500 If the terminals are shorted exp(−αx) coefficient
μm and Le is shorter than x then the excess electrons on x
that. the n-side can flow through
the external circuit to
Photons are absorbed and neutralize the excess holes in
recombined near the the p-side Æ this current is
crystal surface Æ losses. Lh W Le called photocurrent. Lh W Le
Iph Iph
Source: University of South Alabama Source: University of South Alabama
p-n Junction Thin Film Solar Cells p-n Junction Thin Film Solar Cells
Photovoltaic I-V Characteristics: Photovoltaic I-V Characteristics:
• Consider an ideal p-n junction photovoltaic device connected to a • If I is the light intensity, then the short circuit current is
resistive load R.
I sc = − I ph = − KI K is constant that depends on particular device
• I and V define the convention for the direction of positive current and
positive voltage.
• The photocurrent does not depend on the voltage across the p-n junction,
because it always some internal field to drift the photogenerated EHP.
Light
I Isc = –Iph
• If R is not short circuit Æ the positive voltage V appears across the p-n
junction as a result of the current passing through.
V Iph V=0
R
• If the load is short circuit Æ the only current in the circuit is due to
photogenerated (photocurrent),Iph.
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p-n Junction Thin Film Solar Cells p-n Junction Thin Film Solar Cells
Photovoltaic I-V Characteristics: Photovoltaic I-V Characteristics:
• The voltage across the load R (with opposite polarity) reduces the • The total current (solar cell current), I = Id − Iph
built in potential V0 of the p-n junction and hence leads to ⎡ ⎛ eV ⎞ ⎤
minority carrier injection and diffusion. I = − I ph + I 0 ⎢exp⎜⎜ ⎟⎟ − 1⎥ Id
• When a solar cell drives a load R, R has the same voltage as the solar • Or they can be found easily from load line construction.
cell but the current through it is in the opposite direction to the • The load line cuts the solar cell characteristics at P. Point P
convention that current flows from high to low potential. satisfies both equations Æ represent the operating point of the
• The current I’ and voltage V’ can be found by solving two previous circuit.
equations simultaneously Æ not trivial analytical procedure. I (mA)
Voc
I (mA) V′
Voc 0 V
V′ 0.2 0.4 0.6
Light 0 V
I 0.2 0.4 0.6
I-V for a solar cell under an
I-V for a solar cell under an illumination of 600 Wm-2.
V illumination of 600 Wm-2. –10 Slope = – 1/R
–10 Slope = – 1/R Operating Point
Operating Point
I′
R I′ Isc= –Iph The Load Line for R = 30 ž
I Isc= –Iph The Load Line for R = 30 ž P
P (I-V for the load) (I-V for the load)
–20 Source: University of South Alabama
–20 Source: University of South Alabama
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p-n Junction Thin Film Solar Cells p-n Junction Thin Film Solar Cells
Band gap effect on energy efficiency: Band gap effect on energy efficiency:
Si has Eg = 1.1 eV Æ correspond to a threshold wavelength of
1.1 μm Æ The incident energy with wavelength > 1.1 μm is • Efficiency:
then wasted (~ 25%). η = (VocIscFF)/Pin
2.5 Voc ∝Eg,
Black body radiation at 6000 K Isc ∝ number of
Spectral 2.0 AM0
absorbed photons
Intensity 1.5
dW cm-2 (μm)-1 AM1.5
• Decrease Eg, absorb
or 1.0 more of the spectrum hv > Eg
kW m-2 (μm)-1
0.5
• But not without
0 sacrificing output
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
voltage
Wavelength (μm)
Source: University of South Alabama By courtesy of Xiangfeng Duan
p-n Junction Thin Film Solar Cells p-n Junction Thin Film Solar Cells
Energy efficiency - Single crystalline versus polycrystalline :
Effects of electron-hole recombination on energy efficiency:
p-n Junction Thin Film Solar Cells p-n Junction Thin Film Solar Cells
Energy Efficiency: 100% Incident radiation First Generation– Single Junction Silicon Cells:
• For a given solar spectrum, 89.6% of 2007 Production
× 0.74 Insufficient photon energy
conversion efficiency depends on hυ < Eg
45.2% Single Crystal Si
the semiconductor material 42.2% Multi-crystal SI
properties and the device structure. • Limit efficiency 31%
Excessive photon energy
Near surface EHP recombination • Single crystal silicon - 16-19%
• Considering all losses, the × 0.59 hυ > Eg efficiency
maximum electrical output power is • Multi-crystal silicon - 14-15%
~21 % for a high efficiency Si solar efficiency
cell. × 0.95 Collection efficiency of photons
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p-n Junction Thin Film Solar Cells p-n Junction Thin Film Solar Cells
Second Generation –Thin Film Cells: Third Generation – Multi-junction Cells
CdTe 4.7% & copper indium gallium selenide (CIGS) 0.5% of 2007 Production
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Dye-Sensitized Solar Cell (DSSC) Dye-Sensitized Solar Cell (DSSC)
Operating principle of DSSC: The operating cycle of redox reaction Operating principle of DSSC:
light
light
• Transparent
• Electrically conductive
• Connections to load
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Dye-Sensitized Solar Cell (DSSC) Dye-Sensitized Solar Cell (DSSC)
Components of DSSC: Components of DSSC:
Dye: (also called molecular sensitizers), organic semiconductor, usually Dye: organic semiconductor
Ruthenium complex molecules
• Band gap is small enough to adsorb visible light or infrared light
(Ephoton = hc/λ).
• Good match in band structure between dye and metal oxide
• Stable during light irradiation
• Must have carboxylate or phosphonategroups, Ligands are
chemisorbed to metal oxide semiconductor surface
3.2 eV
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Dye-Sensitized Solar Cell (DSSC) Dye-Sensitized Solar Cell (DSSC)
The electron diffusion length in photoanode: Components of DSSC:
Electrolyte: redox couple to reduce dye
• Usually iodide/tri-iodide couple
• Reduces dye after electron injection to TiO2
• Oxidized by contact with second electrode
I 3− + 2e ⇔ 3I −
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Organic Solar Cells
by courtesy of Qing-Hua Xu
Operating principle:
Four processes:
Light absorption
Exciton Diffusion
Charge Transfer/separation
Charge Collection
Active layer
Donor (p-type)
Acceptor (n-type)
cathode
anode [Link]
earch/projects/teratransport/
Carbon Trust
Charge
collection
Optical absorption length ~ 100nm
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Organic Solar Cells Organic Solar Cells
Overall energy efficiency of organic solar cells:
Overall energy efficiency:
Tobin Mark’s group: PNAS 2008; 105:2873‐2787
Thomas Kietzke, Advances in OptoElectronics. doi:10.1155/2007/40285 Thomas Kietzke, Advances in OptoElectronics. doi:10.1155/2007/40285
acceptor
3,4,9,10-perylenetetracarboxylicbis-benzimidazole
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Organic Solar Cells Organic Solar Cells
Thin film manufacturing techniques: Spin-coating techniques:
(2) Wet processing: Suitable for polymers Solution is dropped on the rotating
substrate
Spin coating
Screen printing By centrifugal force, solution spreads on
Inkjet printing the substrate
Doctor blading
Thin film properties depend on rotation
speed curve, solution, temperature, vapor
pressure of material…
Lawrence Kazmerski, National Renewable Energy Laboratory (NREL) By courtesy of Jim Dunlop, NJATC Curriculum Specialist
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Photovoltaic System to Utility Grid Photovoltaic System to Utility Grid
By courtesy of Jim Dunlop, NJATC Curriculum Specialist By courtesy of Jim Dunlop, NJATC Curriculum Specialist
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Photovoltaics Market Photovoltaics Market
SAN FRANCISCO, CALIFORNIA, March 17, 2010
Worldwide solar photovoltaic (PV) installations reached 6.43 GW in 2009
The PV industry generated $38 billion in global revenues in 2009, while
successfully raising more than $13.5 billion in equity and debt, up 8% on the
prior year Worldwide PV Markets are Booming!
When it comes to non-silicon-based costs, however, the top company in China can
produce a module at a cost of USD 0.90 per watt, compared with around USD
1.50 per watt for European companies.
Source: Becky Stuart, PV Magzine, 12/272010
Source: Kyocera Solar, Inc 2007 Source: Kyocera Solar, Inc 2007
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History of Photovoltaic Cells
1839 The photovoltaic effect was first recognized in by French physicist A.
E. Becquerel.
1883 The first solar cell was built, by Charles Fritts, who coated the
semiconductor selenium with an extremely thin layer of gold to form
the junctions. The device was only around 1% efficient.
1888 Russian physicist Aleksandr Stoletov built the first photoelectric cell
1905 Albert Einstein explained the photoelectric effect.
1946 Russell Ohl patented the modern junction semiconductor solar cell in
which was discovered while working on the series of advances that
would lead to the transistor.
1954 The silicon p-n junction photovoltaic cell was developed by The highly
efficient solar cell was first developed by Daryl Chapin, Calvin
Souther Fuller and Gerald Pearson at Bell Laboratories
1980 First polymer based solar cells.
1986 First organic solar cell with donor and acceptor was invented by
Tang.
1991 A dye-sensitized solar cell (DSSC) was invented by Michael Grätzel
and Brian O'Regan at the École Polytechnique Fédérale de
Lausanne.
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In p-n junction solar cells, electron transport primarily occurs across a junction due to the built-in electric field that separates electrons and holes, allowing for unidirectional current flow through an external circuit . In contrast, DSSCs rely on a photo-sensitized anode where electron transport involves the injection of electrons from the dye into the conduction band of TiO2, followed by transport through the porous structure to reach a transparent conducting electrode . DSSCs operate with the help of an electrolyte that regenerates the dye by transferring electrons, which is a process distinct from the solid-state junction operation observed in traditional p-n junction solar cells .
DSSCs provide several advantages over traditional silicon-based solar cells, including lower production costs due to the use of less expensive materials and simpler manufacturing processes . They can be manufactured on flexible substrates, allowing for more versatile applications and lighter weight panels . Additionally, DSSCs perform better under various light conditions, including high-angle incidence, low intensity, and partial shading, due to their broad spectral response and lower dependence on specific light conditions for efficient operation .
Doping silicon with group V elements introduces additional electrons into the conduction band, making silicon an n-type semiconductor. This process creates extra electrons, which are considered negative charge carriers. The energy band structure is altered as the concentration of electrons in the conduction band increases, modifying electrical conductivity and the majority carrier type in the semiconductor .
Thin-film solar cells typically exhibit efficiencies in the range of 8-11%, with some advanced designs reaching up to 18% under optimal conditions . In contrast, multi-junction solar cells, which stack different types of layers to capture various wavelengths of light, have significantly higher efficiencies, achieving around 30% in typical configurations and over 40% in laboratory settings . This increased efficiency is due to the ability of multi-junction cells to utilize different bandgaps in their layers to capture a broader spectrum of solar radiation .
The minority carrier diffusion length is crucial as it determines how far carriers generated by absorbed photons can move before recombining. In p-n junction solar cells, only electron-hole pairs generated within a diffusion length of the space-charge region (SCR) contribute to the photovoltaic effect. Longer diffusion lengths allow for more efficient capture and separation of photogenerated carriers, which is essential for achieving higher conversion efficiencies . If the diffusion length is short, a significant portion of carriers will recombine before reaching the junction, leading to lower efficiency .
Dye molecules in DSSCs are designed to have a bandgap small enough to absorb visible light, facilitating the excitation of electrons to higher energy levels upon light absorption. These molecules are typically structured to match the conduction band of the metal oxide semiconductor (e.g., TiO2), ensuring efficient electron injection into the semiconductor upon photoexcitation. This molecular alignment is critical for maximizing the overlap of energy states, which enhances the charge generation and transfer efficiency to the semiconductor .
Charge separation in DSSCs begins with the absorption of light by a dye on the photoanode, which excites electrons. These electrons are injected into the conduction band of the TiO2 semiconductor. The dye molecules, having lost electrons, are then regenerated by electrons supplied from the electrolyte, usually an iodide/triiodide redox couple. Meanwhile, the conduction band electrons travel through the TiO2 to reach a transparent conducting oxide layer and eventually flow through an external circuit, while the oxidized dye extracts electrons from the electrolyte .
Organic solar cells face several challenges, including relatively low efficiency, typically around 2-6%, compared to other cell types . They have limited charge-carrier mobility and a large optical band-gap, which restricts their absorption to shorter wavelengths unless new materials are developed to absorb in the red and near-infrared regions . Additionally, organic materials used have poor stability under UV exposure and generally have a short exciton diffusion length, necessitating precise nanoscale structuring to ensure effective charge separation and collection . Despite these issues, their low production cost and potential for flexible applications offer notable advantages if these challenges can be addressed. .
In DSSCs, the electrolyte facilitates the regeneration of the dye by providing electrons that replace those injected into the TiO2. The most commonly used electrolyte system is the iodide/triiodide redox couple. Despite its function, the liquid electrolyte poses several limitations, notably its corrosive nature, instability over long periods, and challenges in sealing the cell to prevent leakage, which can impact device durability and performance . The need for an electrolyte also limits the possibility of integrating solid-state designs, which could otherwise improve cell durability and commercial viability .
A p-n junction in thin-film solar cells consists of a p-type and an n-type semiconductor placed in close contact, forming a junction where an electric field is established. Upon light illumination, electron-hole pairs are generated, and the built-in electric field at the junction facilitates the separation of these charge carriers. Electrons are driven towards the n-type side, while holes move towards the p-type side, allowing for the generation of an electric current through an external circuit when connected, thus producing electricity .