Advancements in Silicon Solar Cells

Dennis L Waldron
Rajendra Bhatt
Shane T Seaman
Craig Ungaro
Outline
 Introduction
 Silicon based thin-film solar cells
 a-Si
 poly-Si
 Emerging Ways to Enhance Efficiency
 Manufacturing
 Conclusions
 Silicon solar cells
 Silicon technologies make up ~84% of the
world solar cell market
 There is a huge diversity in the different
types of silicon based solar cells on the
market
 Silicon has shown a strong learning curve in
the past, with a cost reduction of around
20% for each doubling of manufacturing
capacity in recent years
 Silicon solar cell variety

Amorphous silicon solar cell

http://www.tjlituo.com/ Polycrystalline silicon solar cell
http://earthandindustry.com/

Monocrystalline silicon solar cells

http://www.solarnavagator.net
 Solar cell market breakdown 2008, 2009

Juanits Kurtin, et. Al. "Photovoltaic manufacturing: Present status, future prospects, and research needs," J. Vac. Sci. Technol, vol. 3, no. 29, pp. 1-
16, May/Jun 2011.
 Why silicon?
 Silicon is the oldest PV technology, which partially
accounts for its market share
 Silicon is also a very well understood material due
to research in the integrated circuit (IC) industry
 Manufactured silicon is available in large
quantities from the IC industry
 There are second and third generation silicon cell
designs, as well as room for first generation cells
to be made cheaper and more efficient
 Due to their learning curve, silicon solar cells are
good candidates for the near future of the
photovoltaics industry
Outline
 Introduction
 Silicon based thin-film solar cells
 a-Si
 poly-Si
 Emerging Ways to Enhance Efficiency
 Manufacturing
 Conclusions
Silicon-based thin-film solar cells
 The single most important factor in
determining the cost of production is the
cost of the 250–300 μm-thick Si used in the
wafer-based technology of Si-solar cells
 Silicon based thin-film solar cells have a
very substantial cost reduction potential
 Two types of Si for thin-films
 Amorphous Silicon (a-Si)
 Polycrystalline Silicon (poly-Si)
a-Si compared to other Si cells
 Lower weight and fabrication costs, less
material used
 100-200°C deposition (PECVD) allows for
plastic substrates
 Much higher absorption coefficient- need
only about 1μm for visible light
 Drawback: minority carrier diffusion length
only ~300nm
Improving a-Si
 Improvements focus on absorbing more
light with less material
 Improvements can be classified broadly as:
 Front surface modification: generally to couple
more light into the cell
 Rear surface modification: generally to more
efficiently absorb coupled light
 Novel architectures
Front Surface Modification
 Does not generally alter the absorbance of the
Si itself, nor alter optical path length much
 Industry standard: λ/4 ARC- uses interference
effects to reduce front-surface reflections
 Newer methods: uses nano-textured surfaces
with features on the order of the wavelength
to create a gradient index change
 One example is a study done with nanorods
and nanocones
Front Surface Modification (cont)
 At normal incidence, the nanocone surface
absorbs 98.4% of 488nm light, compared to
85% and 75% for nanowire and no texture
 At angles up to 60° 90% absorption is
maintained, compared to 85% and 45%
Rear Surface: Texturing
 a-Si is unique in that it can use textured
substrates without suffering from cracks
and defects resulting from crystal structures
 Using a ZnO reflective backing with RMS
roughness of 70nm (360nm lateral
dimension), a relative efficiency increase of
20-25% has been observed
 Optical path length increased by at about double
 Resulted in higher ISC: more photons absorbed
Rear Surface: Texturing (cont)
 Another group has taken advantage of
plasmonic effects as well
 Hexagonal nanocylinders etched into glass,
coated with 10nm of titanium then 120nm of
silver (65nm deep, diameter 500nm)
 Results in localized surface plasmon polaritons
having a resonance in the green to red
 Improved absorption near Si-Ag interface
 Improved ISC; result: 27% higher relative eff.
Rear Surface: Photonic Crystals (cont)
 Both 1D and 2D structures have been
investigated
 Goal: create multiple plasmonic Bloch mode
resonances to increase absorbance
 With 1D structures, there is a strong
dependence on polarization: absorption is
higher for lower wavelengths Ex polarized,
and higher wavelengths of Ey polarization
Rear Surface: Photonic Crystals (cont)
 Polarization effects can largely be avoided
with 2D structures
 One group achieved a 50% increase in
absorption between 380 and 750nm with a
1D structure, resulting in 44% of the AM1.5
spectrum being absorbed, compared to 29%
with no texture
Rear Surface: Photonic Crystals (cont)
 Lines of a-Si are etched away to bare
substrate with laser holography and
reactive ion etching

 Period: 335nm, a-Si width: 194nm,

thickness 100nm
Architecture: NC Hybrids
 Use a layer of semiconducting nanocrystals
to tailor absorption spectrum, create
tandem structures, and potentially harvest
multiple electrons from UV photons
Architecture: NC Hybrids (cont)
 Only preliminary work done in this field so
far
 Charge transport across NCs tends to be
poor, so a very thin layer must be used
 Size of the NCs, as well as surface coatings
also effects charge transport, sometimes by
orders of magnitude
 A cell of this type has been constructed with
a 0.9% power conversion efficiency
Architecture: Coaxial Nanotube
 Cell construction:
 I: growth of MWNT (multiwall nanotube) on
tungsten (yellow) coated Si wafer
 II: deposition of a-Si
 III: deposition of ITO contact layer
 IV: alternate cut-away view
Architecture: Coaxial Nanotube (cont)
 MWNT’s resistance are independent of their
length and width (quantum resistors), thus
many electrical losses are avoided
 Device functions are many free-standing
photovoltaic NWs connected in parallel
 Results in a 25% relative eff. increase
compared to a planar cell as a result of
about a 25% increase in ISC and a slight gain
of VOC
Outline
 Introduction
 Silicon based thin-film solar cells
 a-Si
 poly-Si
 Emerging Ways to Enhance Efficiency
 Manufacturing
 Conclusions
 Poly-Si thin-film solar cells
 Advantage over a-Si:H- no light induced
degradation, higher efficiencies
 Compared to bulk-Si solar cells- very high cost
reduction potential
 Choice of substrate
 Basic criteria: readily available and
inexpensive
 Matching of thermal expansion coefficients
between the active film and the substrate
 Glass is a particularly promising supporting
material as it is cheap, transparent (enabling
superstrate), long-term stable, and readily Mismatch in thermal expansion
available in large quantities. coefficient can result in cracks
 Challenges:
Ref: Wenjing Wang, Ying Xu, and Hui Shen,
 doesn't permit lengthy high temperature Polycrystalline silicon thin-film solar cells on
steps various substrates, phys. stat. sol. (a) 203,
No. 4, 721–731 (2006) / DOI
 generation of a poly-Si film of large grain 10.1002/pssa.200564504
size at the low temperatures (T<650 °C)
 Crystallization of a-Si film to obtain poly-Si
 CSG Solar
 CSG company has reported crystalline silicon on CSG solar schematic
glass (CSG) solar cells with conversion efficiencies
of 10.4 %
 Borosilicate glass textured on both surfaces with
an antireflection coating of silicon nitride
deposited onto one side
 PECVD deposition of a-Si (1.5 μm) having an n+pp+
structure.
 Coated glass sheets are heated to 600oC in a batch
oven process to achieve solid-phase crystallization.
 Crystallographic defects are annealed by heating
the silicon very briefly to over 900oC.
 Remaining defects are passivated by exposure to
atomic hydrogen.
 Silicon is patterned by forming ‘grooves’
 ‘Crater’ contacts to n+ layer whereas Dimple
contacts to p+ layer
 Aluminum deposition over the rear device surface
and patterned into thin strips interconnecting the
n+ region of one cell to the p+ region of its Ref: M.A. Green et al., Crystalline silicon on glass
adjacent cell (CSG) thin-film solar cell modules, Solar Energy 77
(2004) 857–863
 Aluminium-induced crystallization (AIC)

 Shorter process time compared to

SPC
 Initial glass/Al/oxide/a-Si layer stack
is transformed into a glass/poly-
Si/oxide/Al(+Si) layer stack by a
simple annealing step below the
eutectic temperature of the Al/Si
system (577 °C)
 Si atoms diffuse through the Al
grain from amorphous to crystalline
phases
 Resulting poly-Si layer is continuous
and features large grains (over 10
µm)
 Absorber layers for solar cells can
then be made by epitaxial
thickening of these AIC layers.
 Conversion efficiencies up to 8%
have been reported
Ref: I. Gordon et al., Fabrication and characterization of highly efficient thin-film polycrystalline-silicon solar cells based on aluminum-
induced crystallization, Thin Solid Films 516 (2008) 6984–6988
 Fiber Laser Crystallization: An alternative approach for
preparing poly-Si thin films at low temperatures
 Uses a fiber laser of λ = 1064 nm to
crystallize a-Si film at room temperature
 The a-Si was deposited via PECVD system
(RF of 300 W, temperature of 450 °C,
using a 20% SiH4:80% NH3 mixture)
 A capping layer of a-SiOx with quarter
wavelength optical thickness was
employed on the a-Si surface to absorb
the infrared laser light
 Peak at 517 cm-1 for laser power = 25 W 40 W
indicates the beginning of crystallization
 The Raman peak intensity decreases
beyond 30 W due to the surface damage 30 W
caused by high energy laser beam.
25 M
 Pros: crystallization at room temperature,
high quality (crystallinity up to 90%) 10W
 Cons: higher laser density adversely affect
the surface and uniformity of grain size,
limited to film thickness < 500 nm
V.A. Dao et al., Fabrication of polycrystalline silicon thin films on glass substrates using fiber laser crystallization, Thin Solid Films 517 (2009)
3971–3974
 Light trapping mechanisms

 c-Si is a poor absorber of near-infrared light. To maintain a high

current in thin cells, an excellent light trapping scheme is required
 Most common techniques: Anti-Reflection Coating (ARC), Surface
Texturing, and Back Reflector
 Novel technique: Rear localized surface plasmons
 Rear surface plasmons

Ref: Zi Ouyang, Supriya Pillai, Fiona Beck, Oliver Kunz, Sergey Varlamov, Kylie R. Catchpole, Patrick Campbell, and Martin A. Green,
Effective light trapping in polycrystalline silicon thin-film solar cells by means of rear localized surface plasmons, Applied Physics Letters
96, 261109 (2010)
Outline
 Introduction
 Silicon based thin-film solar cells
 a-Si
 poly-Si
 Emerging Ways to Enhance Efficiency
 Manufacturing
 Conclusions
Emerging Ways to Enhance Efficiency
 Hot Carriers
 Spectral Conversion
 Quantum confinement
 Dots- MEG, bandgap tuning
 Wires- light trapping
 Wells-bandgap tuning, strain-balanced epitaxial
layer growth
Quantum Well
• QW is a potential barrier that confines particles
from three dimensions of freedom down to two
• Quantum confinement occurs when the thickness of
the well (potential barrier) is on the order of the de
Broglie wavelength of the carriers involved
• The concept of a quantum well can be applied to
solar cells to confine electrons and holes, and
reduce their likelihood of recombination
Quantum Well Solar Cell Construction
 Placing a thin layer of material with a given
bandgap energy between two layers of material
with a higher bandgap energy
 Layers of higher bandgap material sequester the
charge carriers to stay within the middle layer,
thus confining them to two dimensions.
 Makes the path that the charge carriers take to
the electrodes more efficient, increasing their
chances for collection.
 Other benefits:
 lower dark current
 increased radiation tolerance
 less efficiency decline with temperature
increase
 ability for bandgap tuning
 Quantum Well Solar Cells
 QWSCs are multi-bandgap devices
 Exhibit properties between that of heterojunction cells and
tandem solar cells
 Heterojunction cell
 total current is the sum of the currents
 voltage is limited by lowest bandgap material
 analogous to parallel circuitry
 Tandem solar cell
 total voltage is sum of the individual layers’ voltages
 current is limited by the lowest of the sub-cells
 analogous to series circuitry
 Quantum well solar cell (QWSC)
 voltage falls somewhere between that of the bulk and barrier
materials
 does not necessarily sum or reduce to the value of the lowest
one (due to quasi-Fermi levels)
 Quantum Well
 At least three layers are required for quantum well effect to
be observed
 Cannot be accomplished with a typical p-n junction
 Space charge region in a p-n junction is very narrow
 By adding an i-layer, the thickness of this space charge
region can be increased and a p-i-n junction is formed
 QW structure is grown in this intrinsic layer

Quantum Wells (SiGe)

Quantum Well Structure
 P-type region of “material-A” is grown on the substrate
 Undoped layer of “material-B” with a lower bandgap energy is deposited
on top of that called the well material
 An n-type layer of material-A is then added onto that
 P and N –type layers act as potential barriers
 Single Quantum Well (SQW) shown in figure below

Higher Bandgap Energy

Multiple Quantum Well (MQW) Structure
 The layer of well material (B) is followed by a barrier layer. This barrier
can be either:
 an intrinsic layer of material-A
 or a third material, “material-C,” with wider bandgap than material-B
 Then another layer of material-B is added
 B/A/B or B/C/B (is repeated for the desired number of QW layers)
 Completed with deposition of n-type material-A on top

i-layer with 6 QWs

 Quantum Well Bandgap Tuning
 As layer thickness of the QW approaches the size of the crystal lattice
constant, a quantum-mechanical effect occurs that gives the
semiconductor a different energy band structure than the bulk
material from which they are grown
 QWSCs offer the possibility of bandgap tuning in systems utilizing
layers with multiple elements (such as SiGe)
 Changing the ratio of the Si to Ge results in a changed bandgap.
 This provides another means of bandgap tuning
Bandgap Structure of MQWSC and
Thermally Assisted Quantum Tunneling

Bandgap diagram for a 5-well MQWSC.

 Lattice Matching
 The materials in the different layers typically have different atom
spacing, and therefore different lattice constants
 Lattice mismatch causes cracks and undesired properties at the
interface of the two materials if the layer thickness exceeds a critical
thickness, tc
 tc depends on the magnitude by which the lattice constants differ
Lattice Matching
 If the lattice constants of the materials are equivalent
very high quality films without dislocations can be grown
 Certain pairs of materials also match, such as GaAs/AlAs
and Ge/GaAs

 If lattices do not match defects can form:

 Strain Balancing
 If the lattice mismatch is only a few percent, and the layer is very thin
(~100Ǻ), layers can be grown with little to no defects
 The resulting layer will be either compressed or strained along the
surface plain in an effort to adapt its lattice constant to that of the
seed crystal
 Magnitude of strain increases linearly with layer thickness
 Strain Balancing
 If these layers are grown beyond the critical thickness (tc), it is
energetically favorable for the system to relieve the strain by forming
dislocations
 Islanding can occur as an additional means of reducing the elastic
strain energy of the film
 Either of these defects can lead to rough surfaces that are unsuitable
for device applications
 Strain Balancing with Silicon
 Highly useful for lattice mismatched materials that would otherwise work well
together in a semiconductor device, such as silicon and germanium.
 Ge is an indirect bandgap semiconductor with many properties that are very
desirable in solar cells
 Ge has a ~2.8 times increase in the bulk electron mobility, and a ~4 times increase
in bulk hole mobility compared to silicon
 However, Ge is not able to survive a fabrication process on its own due to the brittle
nature of Ge wafers and their inability to form stable oxides (water soluble).
 In addition, the limited use of Ge wafers makes them very expensive and they are
typically of lower quality than Si wafers
 Therefore, Ge must be heteroexpitaxially integrated with Si for use in solar cells
 Strain Balancing with Silicon
 A Ge lattice is ~4.2% larger than silicon’s
 Ge has to compress almost 4.2% to match the lattice of the
Si substrate.
 Because the difference in the Si/Ge lattice constants is so
large, the layers need to be very thin (40-100Ǻ) to achieve
epitaxial growth without defects.
 Strain Balancing in Si-based QWSCs
 Since QWSCs are based on the deposition of very thin layers, it is
possible to strain balance the SiGe in a QW structure
 Used to create a solar cell that covers the solar spectrum more
completely than Si
 Si has a bandgap energy of 1.1eV, and can absorb wavelengths of
~1100nm and lower.
 Ge has a bandgap energy of ~0.66eV so it can absorb wavelengths
up to ~1850nm.
 Different combinations of SixGe1-x can be made that have a
bandgap energy between 1.1eV and 0.66eV.
 These will generate photocurrent more efficiently for light with
energies that fall between that of Si and Ge.
 Back-Surface Reflectors and
Photon Recycling
 Thin nature of QWs causes their absorption to be less than that of
thick bulk layers.
 A back-reflector will allow a “second pass” of photons to be absorbed
in the QW
 This essentially doubles the photons’ path lengths, increasing the
short-circuit current
 Since radiative recombination that occurs in the wells produces low
energy photons, these photons would also have improved chance of
absorption in the QW region, thus increasing the cell’s open-circuit
voltage (photon recycling)
 Reflectors such as this would have large benefit in QWSCs, and
experiments have shown that they reduce dark current and increase
the absolute efficiency of SB-QWSCs by ~1%
Efficiency
 Experimental results show ~2% increase in
absolute efficiency of QWSCs compared to
tandem and multi-junction p-n cells made with
comparable material quality.
 This technology has not been matured as
QWSCs are third generation photovoltaic
devices.
 Much work is still needed to fully understand
how to optimize them, and fully utilize the
advantages that they potentially bring to the
photovoltaic industry.
Outline
 Introduction
 Silicon based thin-film solar cells
 a-Si
 poly-Si
 Emerging Ways to Enhance Efficiency
 Manufacturing
 Conclusions
Solar cell manufacturing
 The standard process for manufacturing
crystalline Si solar cells has not changed
much in the last 10 years
 Over 75% of all manufactured crystalline Si
solar cells use the same basic screen
printing process with minor variations.
 Manufactured cell efficiencies have been
improving, but have not yet reached the
levels seen in laboratory cells.
 Laboratory cell vs. manufactured module
efficiency

Juanits Kurtin, et. Al. "Photovoltaic manufacturing: Present status, future prospects, and research needs," J. Vac. Sci. Technol, vol. 3, no. 29, pp. 1-
16, May/Jun 2011.
 Feedstock cost
 Feedstock costs currently make up about
11% of the cost of a crystalline-Si solar cell
 A 40% reduction in feedstock cost is
equivalent to a 10% increase in relative
efficiency
 This makes feedstock cost reduction the
most efficient way to increase solar cell cost
efficiency
 PV grade silicon
 Typical crystalline Si cells are currently made with
integrated circuit (IC) grade silicon
 This is a very high purity silicon that is readily available
due to its use in the IC industry
 It may be possible to use a lower purity (PV grade)
silicon wafer without harming the efficiency of a solar
cell, especially with advanced passivation techniques
 PV grade silicon can be made from upgraded
metallurgical grade silicon, which can reduce the energy
cost of feedstock production for Si solar cells by 5
times.
 It is unclear if this will reduce cell efficiency too much
to be useful.
Kerfless wafers
 Up to 50% of the raw silicon used to make
wafers for crystalline Si PV cells can be lost
due to the sawing of wafers
 This loss is called kerf
 Technologies to reduce or eliminate kerf
losses can therefore reduce the raw
material cost of a crystalline Si PV cell by
50%
Silicon wafer cutting
Kerfless wafer manufacturing techniques
 Two kerfless wafer manufacturing techniques
are edge-defined film growth (EFG) and string
ribbon silicon.
 In EFG, Si wafers are pulled from a melt via a
graphite dye using capillary action
 Ribbon silicon is produced by pulling high
temperature strings through a crucible of
molten silicon
 These techniques can create multi-crystalline
silicon wafers up to 300um thick and .1m wide
with no kerf loss
Ultrathin silicon
 A third way to reduce feedstock use is to use
ultrathin silicon wafers
 These wafers are on the order of 40um thick,
as opposed to more typical thickness values of
over 150um for p-Si PV cells
 Advanced surface passivation and light
trapping techniques must be used to reduce
losses due to the thinner cells
 A 16.7% efficiency cell has been produced on
only 45um of silicon in a laboratory setting
 Ultrathin silicon manufacturing
techniques
 Ultrathin silicon wafers can be
produced via kerfless processes
 First, a thin Si layer is grown on
a substrate via heteroepitaxal
growth or by thermal
recrystallization of amorphous
Si.
 The layer is then lifted off of the
substrate or the substrate is
dissolved away
Ultrathin silicon problems
 Problems with these techniques is the loss
of efficiency due to increased surface
recombination losses and a decrease in light
trapping, and also that ultrathin wafers are
fragile
 Due to their fragility, steps must be taken to
ensure ultrathin Si wafers do not break
during post processing, and these steps add
an additional cost to manufacturing
processes
 Module vs. cell cost
 The manufacturing cost
of the solar cell only
accounts for about 50%
of the installed cost
 This means that as cells
get more efficient, the
overall cost per watt of
a solar system drops
dramatically
Cell efficiency
 The result of this is that a small drop in
efficiency can cause a large increase in the
$/watt cost of an installed system
 This has stymied new technologies, such as the
ones mentioned above, due to the small losses
in efficiency they can create
 Advanced techniques to reduce efficiency
losses from cheaper manufacturing techniques
are needed to enable their use in solar cell
manufacturing
Outline
 Introduction
 Silicon based thin-film solar cells
 a-Si
 poly-Si
 Emerging Ways to Enhance Efficiency
 Manufacturing
 Conclusions
Conclusions
 Si-based PV cells continue to advance and
improve in efficiency, quality, and affordability
 Commercially available technologies are
primarily advancing from a manufacturing
standpoint to drive down cost
 By merging Si with some of the various
technologies presented, new Si-based solar
cells are developing that could potentially
produce affordable photovoltaics with
efficiencies closer to the Shockley-Queisser
limit, and even beyond