Jonathan Cardoso

English AWD
Tom Akbari
Unit 3 Final Draft
29 October 2018

Out of Sight, Out of Mind: Quantum Solar Cells

Atomos – atom, the uncut, the indivisible, the smallest building block of reality. A word
birthed in 440 BC Greece sparking the dawn of the atomic theory, mankind’s strive to define the
fundamental infinitesimal unit. They were wrong of course, the atom isn’t the basic unit, but we
will use it to start this discussion. In that dreadful high school chemistry class students draw out
the nucleus of protons and neutrons. Around it are electrons, subatomic point particles with no
spatial extent carrying a negative charge and hurtling around the nucleus at fixed orbits. This vast
nested structure of orbiting electrons are enumerated by the chemical element: hydrogen has 1,
carbon has 6, and uranium driven nuclear bombs have 92. Electrons can be stimulated, with
enough energy, to move from a lower filled orbit (valence band) to one further away (conduction
band) in which they are ‘free’ to move. We’ve all experienced this.

When slaving away in the kitchen it is inevitable that you mistakenly grab a hot metal
handle and burn yourself. Once this has happened a few times at a young age it becomes
intuitive, a wood handle is safe to touch but keep away from metal. In thermodynamics these are
defined as insulator and conductors, impeding the transfer of heat energy and readily allowing
the transfer respectively. When introduced to similar concepts regarding electron transfer, the
intuition begins to fall short. It is outside our Newtonian realm of experience, our axiomatic
principles of being, our low-resolution depiction of the world. Just as with heat energy transfer,
when you stick a fork in the wall socket as compared to a piece of wood – only one of them will
end your day permanently via electric shock. Metals have overlapping valence and conduction
bands, allowing for constant free flow of electrons when introduced to a voltage difference.
Imagine a horizontal pipe filled with water. Introduce a pressure difference (voltage) and the
water flows (electricity). Insulators like wood have a large bandgap, the energy gap between the
valence and conduction bands, the energy you must introduce to the system to force an electron
movement, is immense. And then there exists semiconductors:
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Crystalline semiconductors, arranged into a lattice containing an immense number of atoms,

allow for the production of electron-hole pairs. Imagine an electron moving across the band gap
and filling a slot into the empty conduction band, it left behind a hole in the valence band that
acts a positive charge. This positively charged hole and negatively charged electron are bound,
they exist in a special quantum state that tends to keep them in a localized region of space within
the crystal. This pair is called an exciton, think of it as a new particle just like a proton, but
composed of the electron-hole pair occupying a certain small 3D space in the crystal.

Recall earlier that energy must be introduced to the system in order for an exciton to
form. Enter photons, electromagnetic radiation traveling at the ‘speed of light’ with no mass.
Despite having no mass, photons are capable of transferring momentum. Many college level
physics courses spanning the history of science from 1800 – 1950 could begin to illuminate the
phenomena of light, but for now think of light’s momentum transfer occurring in the same way a
heavy, fast moving train transfers momentum to a car mistakenly stuck on the tracks. Low
frequency and longer wavelength photons (red light) carry less energy than high frequency
photons (purple). This is the same reason why a red headlamp for reading at night is relaxing yet
a blue/purple light is damaging.

Supply the correct energy light to a piece of metal, the momentum fully transfers into the
atoms, forcing an electron to leave the valence band and slab entirely. Introducing higher energy
light simply causes the fleeing electron to travel at faster speeds, a result known as the
photoelectric effect. While it goes against intuition, increasing the light’s energy does not
produce more electrons. If the incident light frequency is too low the electron will not be raised
from the valence band - nothing will occur. For solar cells, however, the goal is not to bombard
the semiconductor with extremely high energy, but to capture the solar radiation spectrum. The
ideal solar cell has a semiconductor with a bandgap capable of responding to all wavelengths
shining down. The bandgap must be tuned to the wavelength, supply too much energy (x-rays)
and the light just passes right through the cell. As seen with the photoelectric effect, expose the
cells to low energy radio waves and electron cannot bridge the bandgap and form an exciton. The
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bandgap must match the incident light perfectly, elevating the electron exactly to the conduction
band and allowing for the flow of electrons (electricity) to generate across the semiconductor.

Just as the atom is not the basic building block of reality, bandgaps are more complex
than in Figure 1. The minimal energy state in the conduction band and the maximal energy state
in the valence band are each characterized by a certain crystal momentum. During a “direct”
transition the momentum of the electron and hole are the same in each band, so a photon of
sufficient energy can easily excite an electron into a higher band. “Indirect” bandgaps exist
where exposure to a photon is inadequate for electron excitation on its own. The electron most
also pass through an intermediate state and transfer momentum to the crystal lattice in order to
preserve conservation of momentum. This is less efficient and less likely to occur. Germanium, a
semiconductor, has an energy band structure rich in several indirect and direct bandgap
transitions between 0.6 and 6 eV, with strong curvature throughout the entire Brillouin zone.

To repeat, the name of the game for solar cells is solar spectrum capture. While
germanium has a number of transitions, potential avenues for excitons to form, they may be (1)
energies inefficiently related to the solar spectrum or (2) less accessible as a result of requiring
indirect bandgaps. The wavelength of light is directly proportional to the energy:
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Exposing germanium to 2067nm (infrared) light would correspond to 0.6 eV, one of the many
transitions available to germanium. This is, however, inconsequential compared to 500nm light
in the frame of reference of the solar spectrum. Materials science must find a way to create
semiconductors capable being ‘tuned’ to specific useful frequencies of light, and the answer lies
in quantum mechanics. This is a daunting subject, but can be simplified to one sentence:
Quantum mechanics is a means of describing the behavior of objects on the size scale of atoms,
where objects no longer behave like billiard balls on a pool table, but rather as waves and
complex probabilities.

Buckminsterfullerene, known as a buckyball, is

a cage-like structure of 60 carbon atoms. Human
perception exists at a certain level of magnification, all
the objects we recognize to be “real” from a grain of
sand to the open ocean exist on a size continuum.
Underneath this fabric of existence there are object we
have difficulty contextualizing within our known size
references. To think about a buckyball we will use a
comparison. We have all held an apple in our hand,
imagine it grows to the size of the earth, in this case a
buckyball, made of 20 carbon atoms, would now be the
size of the original apple. Simply put as a ratio
buckyball : apple = apple : earth. Central to quantum
mechanics is the principle of wave-particle duality, that all objects exist as both a wave and a
particle. This is the reason that light can travel as a wave, strike a piece of metal like a particle,
and send electrons flying away from the slab. This is the photoelectric effect described earlier.
This discussion on buckyballs is introduced simply to explore the concept of quantum behavior
from the periphery. Put a ship on the coast of the open ocean and suddenly the scene is more
digestible to the brain. We need to draw boundaries and paint the corners of quantum behavior to
get a decent grasp on how excitons play their role in quantum solar cells. A buckyball, in this
case, is the largest object to successful exhibit wave-particle duality in a lab setting visually. This
is to say, when subjected to the famous double slit experiment, the buckyball travelled through
two locations (two slits) at the same time. This particle behaved as a wave, just as a ocean wave
front can strike you and your friend at the same time in two different places on the beach.

This discussion on buckyballs is introduced simply to

explore the concept of quantum behavior, when a 3D object
occupies a certain small space it is no longer governed by
Newtonian mechanics as humans, cars, and pool balls are. For
semiconductor crystals there is an exciton effective Bohr radius,
equal to the distance between the electron and the hole. A cross
section of this is seen in the figure. In reality it forms a sphere
in the crystal lattice (black dots). Each semiconductor has a
unique Bohr radius, some large, some small. If the
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semiconductor crystal itself is sufficiently small, on the order of nanometers, the Bohr radius can
exceed the spatial dimensions of the lattice. Imagine erasing all the black dots outside the
circle. What remains is known as a 3D quantum dot (QD).
Quantum dots influence the optical properties of the crystal. The crystal behaves as both
a wave and a particle. Governed by the laws of quantum mechanics the curvature of the
bandgaps begin to shift and contort, introducing new transitions to the electron spanning a wide
range of energies. In general, the smaller the QD the wider the bandgap grows. This larger
bandgap means a higher energy photon is required, which relates to a high frequency / longer
wavelength. Furthermore, indirect bandgaps can be shifted to become direct, increasing the
likelihood of transitions at said energy gap. Germanium has a remarkably large exciton Bohr
radius of 24 nanometers, with strong curvature throughout the entire Brillouin zone providing at
least four sets of transitions susceptible to size effects.

1nm 24nm

This quantum confinement effect described above allows single ‘clusters’ of a

semiconductor like germanium to have shifted bandgaps. A cluster of 12nm, for example, might
be able to absorb light between 700 and 800 nm (red light). The surface of the solar cell can be
deposited with a wide range of cluster sizes, rather than using a bulk semiconductor with a well-
defined bandgap, quantum dots can be tuned to the solar spectrum. Capture can be maximized
between 250nm and 1250nm, consistent with the majority of the sun’s rays. A larger portion of
the QDs can be set to absorb near 500nm, where spectral irradiance is at a peak. Overall,
considerations can be taken to maximize capture of all the sun’s incident rays based on the solar
spectrum, location of the solar cell on the earth, and strength of the incident ray – all of which
can be guided by effective implementation of quantum dots.

References

1. Cardoso JC. 2018. Germanium Quantum Dot Grätzel‐Type Solar Cell. Physica Status
Solidi A: 1–8.