An Industry Moving Beyond Sight:
Thin Film Quantum Dot Solar Cells
JONATHAN CARDOSO
Keywords: Quantum dot, magnetron sputtering,
colloidal, solar spectrum, solar cells, photovoltaics
I. Introduction
Academic research and industry production
surrounding solar cell technology has
garnered fervent support in recent decades.
First documented in 1941 as a light sensitive
device, solar cells have undergone a series of
radical transformations.1 Fundamentally, a
solar cell’s capability relies on the excitation
and subsequent injection of an electron from
the lower energy and tightly bound valence
band (VB) into the higher energy conduction
band (CB). Crystalline semiconductors,
arranged into a lattice containing an immense
number of atoms, allow for the production of
electron-hole pairs. The positively charged
hole and negatively charged electron are
bound in a special quantum state localized in
a 3D region of space within the crystal. The
excited electron and simultaneously
produced hole act across an energy potential,
allowing for the production of electricity
from incident photons. This bound pair, an
exciton, along with the discovery of p-n
junctions has escalated the energy conversion
of light to viable levels of efficiency.
Historically silicon wafers have dominated
the industrial solar cell landscape. These
simple p-n junction cells allow for electron
excitation and transport, while maintaining
cheap production. In 2006 the photovoltaic
industry saw that 89.9% of these cells were
made from mono- and multi-crystalline
silicon wafers while only 7.4% from thin
films.2 High purity monocrystalline solar
cells are constructed from cylindrical silicon
ingots for photovoltaic application.
Monocrystalline silicon wafer solar cells
have demonstrated solar cell conversion
efficiency in excess of 24%.3 While
efficiency has been on the rise for wafer
based solar cells, the end is in sight. Since
1961 it has been known that p-n junction
solar cells have a theoretical limit of 30%
efficiency.4 This is, however, predicated on
very specific and potentially avoidable
conditions:
(1) One semiconductor material
(2) One p-n junction
(3) Non-concentrated sunlight
(4) Exciton energy in excess of bandgap
undergoes thermal relaxation
Further considerations have been explored
related to nanoscale structured solar cells,
hot carrier collection, and multi-junction
allowing for theoretical energy conversion
efficiency in excess of 45%.5 This advance
calls for radical changes to the basic
structure of a solar cell. Thick wafer cells
reduce the ability for electron – hole
recombination and impede progress in
pushing efficiency, leaving the technology
unable to bridge the newly discovered gap in
efficiency limits. An industry vacuum
slowly being filled by thin-film cells.6 This
paper reviews promising future solar cell
technologies emphasizing long-term
efficiency limits, industry wide scalability,
and novelty in order to extract maximum
utility out of rising methodologies. It is
suggested that advancements in this field
should focus on versatile cells capable of
maximum theoretical efficiency paired with
total solar spectrum capture.
II. The Second-Generation Solar Cell
Thin-film solar cells have drastically
reduced the sheer volume of production
material, making it the cheaper alternative to
wafers. The attenuation coefficient of a
material determines the penetration depth of
light prior to absorption. Attenuation
coefficients are attainable by profiling a
sample with UV-vis spectroscopy and
thickness characterization. Through various
optical absorption characterizations it can be
seen that thin films promote enhanced light
absorption as a result of the longer optical
path and efficient diffuse light scattering at
the textured film surface.7 The first
amorphous silicon (a-Si) solar cell was
constructed in 1976 with a theoretical
efficiency limit of 15%,8 while more recent
application in thin-film technology have
demonstrated the versatility and high
potential for the material moving forward.9
The bandgap and optical properties of
materials depend heavily on the thickness of
the film, exemplified by germanium’s rapid
bandgap expansion when thin films approach
10nm.10 The influence of quantum mechanics
contorts the bandgap edges introducing both
a widening of the overall bandgap and new
series of available transitions for the electron.
III. Quantum Dots: A Germanium Case
Study
In two dimensions the common quantum
mechanics analogy of a potential well locks a
particle into an inescapable local minimum of
potential energy. For semiconductor crystals
there is an exciton effective Bohr radius,
equal to the distance between the electron and
the hole. The Bohr radius generates a
potential 3D sphere in which the exciton is
bound. If the semiconductor material has a
diameter less than or equal to the Bohr radius
then the crystal is known as a quantum dot
(QD). Said QDs undergo quantum
confinement effects that cause deviations
from the optical and electrical properties of
the bulk material. Germanium’s remarkably
large exciton Bohr radius of 24nm makes it a
highly marketable semiconductor once it is
imbued with quantum confinement effects.
Although silicon dominates the solar
technology field its quantum effects stunted.
Silicon’s small exciton Bohr radius, paired
with its low density of direct bandgap
transitions, makes advances in germanium
QDs far more lucrative.11,12,13
The radiative transition of an electron
from the conduction band to the valence band
in bulk indirect semiconductors requires
phonon assistance, quantized lattice
vibrations carrying small amounts of energy,
to avoid violating conservation of
momentum. Electron-hole wave functions
confined within nanoparticle dimensions,
smaller than the exciton effective Bohr
radius, can, however, yield comprehensive
conduction band shifts to reduce the
necessity of phonons. Previous quantum dot
experiments found that Germanium’s energy
band structure is rich in several indirect and
direct bandgap transitions between 0.6 and 6
eV, with strong curvature throughout the
entire Brillouin zone providing at least four
sets of transitions susceptible to size effects.11
Attempts to model size dependent
quantum confinement in 3D spherical Ge
particles began with Efros’ particle-in-a-box
approximation across a Lifshitz-Slezov
lognormal radii distribution.14 Effective mass
approximations (EMA) were extended to
contain Coulomb corrections15, while
alternative empirical tight binding methods
(ETBM)16 and sp3 tight binding models17
developed to compensate for EMA
deficiencies. Barbagiovanni’s18 simplified
EMA for 3D Ge QD’s experiencing weak,
medium, and strong confinement, as well as
a sp3 tight binding model were employed in
Fig 1. The EMA generalization to the Kane
Hamiltonian k p perturbation theory was not
included due to the commonly observed
overestimation of bandgap shift.
Figure 1: Theoretical quantum confinement modeling for Germanium
bandgap dependence on size. Max TEM bandgap widening from
0.67eV to 1.08eV is based on 6nm Ge particles.17,18,12
IV. Competing Synthesis Methodology
a. Colloidal
Manufacturing semiconductor quantum
dots can occur only through a limited
number of processes, dominated by
colloidal synthesis. The process is heavily
dependent on thermal annealing to initiate
nanocrystal growth. Temperatures can often
exceed 850C during producing, with rapid
annealing resulting in blueshift in the
absorption spectrum.19 The purpose of
utilizing quantum dots in solar cells is to
capture larger portions of the solar spectrum,
the set of all wavelengths and their
irradiance upon earth’s surface resulting
from our sun. Traditional wafer cells have a
specific range of wavelengths they are
capable of capturing. Reduction in the size
of quantum dots results in a blue-shift with
respect to their absorption spectrum
consistent with an enlarged bandgap. These
higher energy wavelengths can bridge the
gap seen in Fig 1 while simultaneously
capturing a wider range of the solar
spectrum seen in Fig 2.
Figure 2: The average solar spectrum incident upon Earth
A series of colloidal methods have recently
undergone scalability vetting including hot-
injection organometallic synthesis,
noninjection organometallic synthesis,
aqueous synthesis and biosynthesis
20
approaches. Currently a colloidal produced
cell holds the world record for quantum dot
solar cell efficiency at 13.43%.21 While
colloidal methods have seen attention as of
late, the requirements of (1) wet synthesis
and (2) excessive thermal annealing are
troubling for future long-term advancements
in the field of solar cell efficiency. Both
processes limit options for semiconductor
and cathode components to avoid reaction to
heat and liquid. Precise multilayering and
fine structures are also difficult to employ in
a hot and wet environment. A low
temperature, dry alternative is often required.
b. Magnetron Sputtering
The fabrication of mono disperse
quantum dots with controllable separation
distance is a prerequisite for successful
application in a solar cell.12 Magnetron
sputtering takes place under high vacuum
conditions mediated by a noble gas plasma.
Cluster size can be tuned by means of
aggregation length, carrier gas
concentration, etc. Bound between zero
crystal diameter and no upper limit the
nanoparticle size distribution can be
successfully modeled by a lognormal
distribution centered about a strong mean.
The non-reactive noble gas and low
temperature vacuum setting allows for
minimized reaction with various potential
construction methods.
This gas aggregated method allows for a
random dispersion of nanoparticles with
customizable thickness. Recent work from
Harvard has successful used dc magnetron
sputtering to generate x-ray optics with
accurate micro-roughness and thickness to
within 0.5 Angstroms.22 These industry grade
optics, while time consuming, are indicative
of a rising future for the affordable scalability
of magnetron sputtered quantum dots. Gas
aggregated solar cells, as opposed to colloidal
cells, are versatile in their thin film and
quantum dot amalgamations.
V. Future Industry: Third Generation
a. Embedding Quantum Dots in Thin
Films
Improving absorption of thin films or
quantum dots is dependent primarily on two
factors. (1) The scattering of light to ensure
maximum time spent within the material and
(2) quantum confinement with interfacial
surface-on-surface interactions. TiO2
embedded in thin films have demonstrated
the ability to utilize Mie scattering.23 When
the incident light is dispensed upon a material
whose diameter is similar to the incident
wavelength an elastic scattering occurs. This
can be utilized to increase the overall
absorption of a-Si thin films. Further research
found that embedding gold nanoparticles in
a-Si thin film of various thickness can cause
a tunable optical absorption.24 Magnetron
sputtering, in each of these cases, allows for
thin film and nanoparticle combinations.
Repeating the process can allow
nanoparticles to be mono-dispersed three
dimensionally through various subsequent
layering.
b. Light Traps
Large light traps have been used to direct
light toward thin films.25 These 3D external
traps keep the light inside the material for a
longer time, increasing the likelihood of
absorption. A silver hexagonal array of
parabolic concentrators was deemed the most
effective method. Overall, the short circuit
current generated by the cell increased by
13%. In this case of thin film solar cells these
means more of the incident light is captured
and not lost due to penetration through the
sample. Back reflectors have also recently
been used to scatter light within flat thin-
films, effectively improving the solar cell by
32%.26
VI. Conclusion
This paper reviewed rising solar cell
innovations stressing future theoretical
efficiency limits and large-scale feasibility as
prime indicators of next stage cells.
Upcoming pursuits in the field must
emphasis maximum theoretical efficiency,
overall solar spectrum capture, and optimal
material options. Advancements in third
generations quantum dot solar cells is
ongoing. Bottlenecking material availability
due to excusatory methodologies could
stagnate progress.
Table 1: Current efficiently records for cross generational solar
cells
In reviewing competing approaches to
solar cell design, materials, and
methodology, it has become apparent that
solely wafer and thin film designs must be
abandoned entirely. There is great promise in
the field of magnetron sputtered solar cells,
recently a fully gas aggregated germanium
quantum dot solar cell was created for the
first time.12 This cell paired quantum dots
with Grätzel style construction utilizing
electrolyte replenishment of electrons.
Magnetron sputtered cells are currently under
pursued relative to colloidal based designs
but serve to be more material versatile and
could couple with multilayered thin films.
While low in efficiency the cell is a proof of
principle cell that could potentially be
combined with recent advances in Mie
scattering, embedded in thin films, and
outfitted with light traps to maximize
efficiency. These recent advances open the
door for magnetron sputtering and
germanium semiconductors to take the reins
in the new era of quantum solar cells.
 References

1. Ohl RS. Light-sensitive electric device. 1946 Jun 25 [accessed 2018 Nov 28].
https://patents.google.com/patent/US2402662/en

2. Neuhaus D-H, Münzer A. Industrial Silicon Wafer Solar Cells. Advances in OptoElectronics. 2007
[accessed 2018 Nov 19]. https://www.hindawi.com/journals/aoe/2007/024521/abs/.
doi:10.1155/2007/24521

3. Zhao J, Wang A, Green MA, Ferrazza F. 19.8% efficient “honeycomb” textured multicrystalline and
24.4% monocrystalline silicon solar cells. Applied Physics Letters. 1998;73(14):1991–1993.
doi:10.1063/1.122345

4. Shockley W, Queisser HJ. Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells. Journal of
Applied Physics. 1961;32(3):510–519. doi:10.1063/1.1736034

5. Xu Y, Gong T, Munday JN. The generalized Shockley-Queisser limit for nanostructured solar cells.
Scientific Reports. 2015 [accessed 2018 Nov 19];5.
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4557037/. doi:10.1038/srep13536

6. Chopra KL, Paulson PD, Dutta V. Thin‐film solar cells: an overview. Progress in Photovoltaics:
Research and Applications. 2004;12(2‐3):69–92. doi:10.1002/pip.541

7. Poruba A, Fejfar A, Remeš Z, Špringer J, Vaněček M, Kočka J, Meier J, Torres P, Shah A. Optical
absorption and light scattering in microcrystalline silicon thin films and solar cells. Journal of Applied
Physics. 2000;88(1):148–160. doi:10.1063/1.373635

8. Carlson DE, Wronski CR. Amorphous silicon solar cell. Applied Physics Letters. 1976;28(11):671–
673. doi:10.1063/1.88617

9. Chen X, Jia B, Saha JK, Cai B, Stokes N, Qiao Q, Wang Y, Shi Z, Gu M. Broadband Enhancement in
Thin-Film Amorphous Silicon Solar Cells Enabled by Nucleated Silver Nanoparticles. Nano Letters.
2012;12(5):2187–2192. doi:10.1021/nl203463z

10. Goh ESM, Chen TP, Sun CQ, Liu YC. Thickness effect on the band gap and optical properties of
germanium thin films. Journal of Applied Physics. 2010;107(2):024305. doi:10.1063/1.3291103

11. Heath JR, Shiang JJ, Alivisatos AP. Germanium quantum dots: Optical properties and synthesis. The
Journal of Chemical Physics. 1994;101(2):1607–1615. doi:10.1063/1.467781

12. Cardoso J, Marom S, Mayer J, Modi R, Podestà A, Xie X, Huis MA van, Vece MD. Germanium
Quantum Dot Grätzel-Type Solar Cell. physica status solidi (a). 0(0):1800570.
doi:10.1002/pssa.201800570

13. Vece MD. Using Nanoparticles as a Bottom-up Approach to Increase Solar Cell Efficiency. KONA
Powder and Particle Journal. 2018 Mar 31:2019005. doi:10.14356/kona.2019005

14. Efros A. interband light absorption in semiconductor spheres. Soviet Physics Semiconductors.
1982;16:772–775.
15. Kayanuma Y. Quantum-size effects of interacting electrons and holes in semiconductor microcrystals
with spherical shape. Physical Review B. 1988;38(14):9797–9805. doi:10.1103/PhysRevB.38.9797

16. Wang Y, Herron N. Nanometer-sized semiconductor clusters: materials synthesis, quantum size
effects, and photophysical properties. The Journal of Physical Chemistry. 1991;95(2):525–532.
doi:10.1021/j100155a009

17. Niquet YM, Allan G, Delerue C, Lannoo M. Quantum confinement in germanium nanocrystals.
Applied Physics Letters. 2000;77(8):1182–1184. doi:10.1063/1.1289659

18. Barbagiovanni EG, Lockwood DJ, Simpson PJ, Goncharova LV. Quantum confinement in Si and Ge
nanostructures. Journal of Applied Physics. 2012;111(3):034307. doi:10.1063/1.3680884

19. Xu SJ, Wang XC, Chua SJ, Wang CH, Fan WJ, Jiang J, Xie XG. Effects of rapid thermal annealing
on structure and luminescence of self-assembled InAs/GaAs quantum dots. Applied Physics Letters.
1998;72(25):3335–3337. doi:10.1063/1.121595

20. Pu Y, Cai F, Wang D, Wang J-X, Chen J-F. Colloidal Synthesis of Semiconductor Quantum Dots
toward Large-Scale Production: A Review. Industrial & Engineering Chemistry Research.
2018;57(6):1790–1802. doi:10.1021/acs.iecr.7b04836

21. Sanehira EM, Marshall AR, Christians JA, Harvey SP, Ciesielski PN, Wheeler LM, Schulz P, Lin LY,
Beard MC, Luther JM. Enhanced mobility CsPbI3 quantum dot arrays for record-efficiency, high-voltage
photovoltaic cells. Science Advances. 2017;3(10):eaao4204. doi:10.1126/sciadv.aao4204

22. Hong J, Romaine S, The MiXO team. Miniature lightweight X-ray optics (MiXO) for surface
elemental composition mapping of asteroids and comets. Earth, Planets and Space. 2016;68(1):35.
doi:10.1186/s40623-016-0409-1

23. Giannakoudakis G, Vece MD. Improving optical absorption in a-Si thin films with TiO2 Mie
scatterers. The European Physical Journal D. 2017;71(4):101. doi:10.1140/epjd/e2017-70570-7

24. Faraone G, Modi R, Marom S, Podestà A, Di Vece M. Increasing the optical absorption in a-Si thin
films by embedding gold nanoparticles. Optical Materials. 2018;75:204–210.
doi:10.1016/j.optmat.2017.10.025

25. Dijk L van, Paetzold UW, Blab GA, Schropp REI, Vece M di. 3D-printed external light trap for solar
cells. Progress in Photovoltaics: Research and Applications. 2016;24(5):623–633. doi:10.1002/pip.2702

26. Plasmonic Scattering Back Reflector for Light Trapping in Flat Nano-Crystalline Silicon Solar Cells.
[accessed 2018 Nov 20]. https://pubs.acs.org/doi/pdf/10.1021/acsphotonics.6b00070

27. Nakamura K. Current status and technology trend of crystalline Si solar cell. In: 2017 24th
International Workshop on Active-Matrix Flatpanel Displays and Devices (AM-FPD). 2017. p. 94–97.