An Industry Moving Beyond Sight:

Thin Film Quantum Dot Solar Cells

JONATHAN CARDOSO
industry saw that 89.9% of these cells were
Keywords: Quantum dot, magnetron sputtering, made from mono- and multi-crystalline
colloidal, solar spectrum, solar cells, photovoltaics silicon wafers while only 7.4% from thin
films.2 High purity monocrystalline solar
I. Introduction
cells are constructed from cylindrical silicon
Academic research and industry production ingots for photovoltaic application.
surrounding solar cell technology has Monocrystalline silicon wafer solar cells
garnered fervent support in recent decades. have demonstrated solar cell conversion
First documented in 1941 as a light sensitive efficiency in excess of 24%.3 While
device, solar cells have undergone a series of efficiency has been on the rise for wafer
radical transformations.1 Fundamentally, a based solar cells, the end is in sight. Since
solar cell’s capability relies on the excitation 1961 it has been known that p-n junction
and subsequent injection of an electron from solar cells have a theoretical limit of 30%
the lower energy and tightly bound valence efficiency.4 This is, however, predicated on
band (VB) into the higher energy conduction very specific and potentially avoidable
band (CB). Crystalline semiconductors, conditions:
arranged into a lattice containing an immense
(1) One semiconductor material
number of atoms, allow for the production of
(2) One p-n junction
electron-hole pairs. The positively charged
(3) Non-concentrated sunlight
hole and negatively charged electron are
(4) Exciton energy in excess of bandgap
bound in a special quantum state localized in
undergoes thermal relaxation
a 3D region of space within the crystal. The
excited electron and simultaneously Further considerations have been explored
produced hole act across an energy potential, related to nanoscale structured solar cells,
allowing for the production of electricity hot carrier collection, and multi-junction
from incident photons. This bound pair, an allowing for theoretical energy conversion
exciton, along with the discovery of p-n efficiency in excess of 45%.5 This advance
junctions has escalated the energy conversion calls for radical changes to the basic
of light to viable levels of efficiency. structure of a solar cell. Thick wafer cells
reduce the ability for electron – hole
Historically silicon wafers have dominated recombination and impede progress in
the industrial solar cell landscape. These pushing efficiency, leaving the technology
simple p-n junction cells allow for electron unable to bridge the newly discovered gap in
excitation and transport, while maintaining efficiency limits. An industry vacuum
cheap production. In 2006 the photovoltaic slowly being filled by thin-film cells.6 This
paper reviews promising future solar cell a widening of the overall bandgap and new
technologies emphasizing long-term series of available transitions for the electron.
efficiency limits, industry wide scalability,
and novelty in order to extract maximum III. Quantum Dots: A Germanium Case
utility out of rising methodologies. It is Study
suggested that advancements in this field
should focus on versatile cells capable of In two dimensions the common quantum
maximum theoretical efficiency paired with mechanics analogy of a potential well locks a
total solar spectrum capture. particle into an inescapable local minimum of
potential energy. For semiconductor crystals
II. The Second-Generation Solar Cell there is an exciton effective Bohr radius,
equal to the distance between the electron and
Thin-film solar cells have drastically the hole. The Bohr radius generates a
reduced the sheer volume of production potential 3D sphere in which the exciton is
material, making it the cheaper alternative to bound. If the semiconductor material has a
wafers. The attenuation coefficient of a diameter less than or equal to the Bohr radius
material determines the penetration depth of then the crystal is known as a quantum dot
light prior to absorption. Attenuation (QD). Said QDs undergo quantum
coefficients are attainable by profiling a confinement effects that cause deviations
sample with UV-vis spectroscopy and from the optical and electrical properties of
thickness characterization. Through various the bulk material. Germanium’s remarkably
optical absorption characterizations it can be large exciton Bohr radius of 24nm makes it a
seen that thin films promote enhanced light highly marketable semiconductor once it is
absorption as a result of the longer optical imbued with quantum confinement effects.
path and efficient diffuse light scattering at Although silicon dominates the solar
the textured film surface.7 The first technology field its quantum effects stunted.
amorphous silicon (a-Si) solar cell was Silicon’s small exciton Bohr radius, paired
constructed in 1976 with a theoretical with its low density of direct bandgap
efficiency limit of 15%,8 while more recent transitions, makes advances in germanium
application in thin-film technology have QDs far more lucrative.11,12,13
demonstrated the versatility and high
potential for the material moving forward.9 The radiative transition of an electron
from the conduction band to the valence band
The bandgap and optical properties of in bulk indirect semiconductors requires
materials depend heavily on the thickness of phonon assistance, quantized lattice
the film, exemplified by germanium’s rapid vibrations carrying small amounts of energy,
bandgap expansion when thin films approach to avoid violating conservation of
10nm.10 The influence of quantum mechanics momentum. Electron-hole wave functions
contorts the bandgap edges introducing both 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 IV. Competing Synthesis Methodology
experiments found that Germanium’s energy
band structure is rich in several indirect and a. Colloidal
direct bandgap transitions between 0.6 and 6
eV, with strong curvature throughout the Manufacturing semiconductor quantum
entire Brillouin zone providing at least four dots can occur only through a limited
sets of transitions susceptible to size effects.11 number of processes, dominated by
colloidal synthesis. The process is heavily
Attempts to model size dependent dependent on thermal annealing to initiate
quantum confinement in 3D spherical Ge nanocrystal growth. Temperatures can often
particles began with Efros’ particle-in-a-box exceed 850C during producing, with rapid
approximation across a Lifshitz-Slezov annealing resulting in blueshift in the
lognormal radii distribution.14 Effective mass absorption spectrum.19 The purpose of
approximations (EMA) were extended to utilizing quantum dots in solar cells is to
contain Coulomb corrections15, while capture larger portions of the solar spectrum,
alternative empirical tight binding methods the set of all wavelengths and their
(ETBM)16 and sp3 tight binding models17 irradiance upon earth’s surface resulting
developed to compensate for EMA from our sun. Traditional wafer cells have a
deficiencies. Barbagiovanni’s18 simplified specific range of wavelengths they are
EMA for 3D Ge QD’s experiencing weak, capable of capturing. Reduction in the size
medium, and strong confinement, as well as of quantum dots results in a blue-shift with
a sp3 tight binding model were employed in respect to their absorption spectrum
Fig 1. The EMA generalization to the Kane consistent with an enlarged bandgap. These
Hamiltonian k p perturbation theory was not higher energy wavelengths can bridge the
included due to the commonly observed gap seen in Fig 1 while simultaneously
overestimation of bandgap shift. capturing a wider range of the solar
spectrum seen in Fig 2.

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
Figure 2: The average solar spectrum incident upon Earth
A series of colloidal methods have recently This gas aggregated method allows for a
undergone scalability vetting including hot- random dispersion of nanoparticles with
injection organometallic synthesis, customizable thickness. Recent work from
noninjection organometallic synthesis, Harvard has successful used dc magnetron
aqueous synthesis and biosynthesis sputtering to generate x-ray optics with
20
approaches. Currently a colloidal produced accurate micro-roughness and thickness to
cell holds the world record for quantum dot within 0.5 Angstroms.22 These industry grade
solar cell efficiency at 13.43%.21 While optics, while time consuming, are indicative
colloidal methods have seen attention as of of a rising future for the affordable scalability
late, the requirements of (1) wet synthesis of magnetron sputtered quantum dots. Gas
and (2) excessive thermal annealing are aggregated solar cells, as opposed to colloidal
troubling for future long-term advancements cells, are versatile in their thin film and
in the field of solar cell efficiency. Both quantum dot amalgamations.
processes limit options for semiconductor
and cathode components to avoid reaction to V. Future Industry: Third Generation
heat and liquid. Precise multilayering and
fine structures are also difficult to employ in a. Embedding Quantum Dots in Thin
a hot and wet environment. A low Films
temperature, dry alternative is often required.
Improving absorption of thin films or
b. Magnetron Sputtering quantum dots is dependent primarily on two
factors. (1) The scattering of light to ensure
The fabrication of mono disperse maximum time spent within the material and
quantum dots with controllable separation (2) quantum confinement with interfacial
distance is a prerequisite for successful surface-on-surface interactions. TiO2
application in a solar cell.12 Magnetron embedded in thin films have demonstrated
sputtering takes place under high vacuum the ability to utilize Mie scattering.23 When
conditions mediated by a noble gas plasma. the incident light is dispensed upon a material
Cluster size can be tuned by means of whose diameter is similar to the incident
aggregation length, carrier gas wavelength an elastic scattering occurs. This
concentration, etc. Bound between zero can be utilized to increase the overall
crystal diameter and no upper limit the absorption of a-Si thin films. Further research
nanoparticle size distribution can be found that embedding gold nanoparticles in
successfully modeled by a lognormal a-Si thin film of various thickness can cause
distribution centered about a strong mean. a tunable optical absorption.24 Magnetron
The non-reactive noble gas and low sputtering, in each of these cases, allows for
temperature vacuum setting allows for thin film and nanoparticle combinations.
minimized reaction with various potential Repeating the process can allow
construction methods. 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 Table 1: Current efficiently records for cross generational solar
current generated by the cell increased by cells
13%. In this case of thin film solar cells these
means more of the incident light is captured In reviewing competing approaches to
and not lost due to penetration through the solar cell design, materials, and
sample. Back reflectors have also recently methodology, it has become apparent that
been used to scatter light within flat thin- solely wafer and thin film designs must be
films, effectively improving the solar cell by abandoned entirely. There is great promise in
32%.26 the field of magnetron sputtered solar cells,
recently a fully gas aggregated germanium
VI. Conclusion quantum dot solar cell was created for the
first time.12 This cell paired quantum dots
This paper reviewed rising solar cell with Grätzel style construction utilizing
innovations stressing future theoretical electrolyte replenishment of electrons.
efficiency limits and large-scale feasibility as Magnetron sputtered cells are currently under
prime indicators of next stage cells. pursued relative to colloidal based designs
Upcoming pursuits in the field must but serve to be more material versatile and
emphasis maximum theoretical efficiency, could couple with multilayered thin films.
overall solar spectrum capture, and optimal While low in efficiency the cell is a proof of
material options. Advancements in third principle cell that could potentially be
generations quantum dot solar cells is combined with recent advances in Mie
ongoing. Bottlenecking material availability scattering, embedded in thin films, and
due to excusatory methodologies could outfitted with light traps to maximize
stagnate progress. 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.