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E SC 482

Victor Acero
Graphene Use in Nanoscale Photonics and Optics
Abstract
Human progress through the eons has been categorized by the materials that defined that
specific era; it can be seen by our categorization of human progress as the Stone, Bronze, Iron,
and now Silicon Age. However, many, including myself, would argue that the next age is that of
nanomaterials, within that realm 2D materials will lead. The exploitation of the unbelievably
small and bizarre quantum world will herald new success and advances for humanity, and in light
of that this review paper will chose to focus in on Graphene, being the first 2D material to be
made. In order to make this review a concise one only its potential in the field of Nanoscale
Photonics and Optics will be discussed in depth, along with a brief but fulfilling background on
graphene itself. The technologies of interest for which graphene can be used to improve them are
Quantum Dots, LEDs, Solar Cells, Wave Guides, and even Biosensors(1-13).

Birth of Venus: Graphene is discovered


2D crystal materials were though of theoretically and hypothesized about, however they were
ultimately deemed impossible for a variety of reasons. First it was thought to be
thermodynamically impossible, due to the fact that nanosized particles of a material (such as
gold) have a much lower melting temperature than bulk piece of material. So with the insanely
high surface-to-volume ratio it was theorized that a 2D plane of atoms would simply not be
thermodynamically favorable or stable at room
temperature(1). It was also predicted that at the very
least the structure would lose all long range order
due to the density of phonons in the material and the
lack of bonds in the z direction to help dampen any
thermal disturbances to the lattice. Despite these
believes, a researcher at the University of
Manchester, Dr. Geim, theorized that if you can
make a 1000 atom thick sheet of graphite why cant
you simple peel away at it. It was a simple approach
but using tape he was able to refine his bulk
graphite down to 10 sheets of graphene. With Figure 1: (from left to right, top to bottom)
further work and refinement of the technique they Graphene (2D), Graphite (3D),
Carbonnanotube (1D), and Buckeyballs
were able to make samples that were truly a single (0D)
sheet of graphene(1). Later on as characterization experiments were performed it was discovered
that graphene had thermal and mechanical properties that rivaled that of carbon nanotubes (high
thermal conductivity, for example), as well as very low absorption with only 2.3% of red light.
More famously, however, it was superconducting at room temperature and its charge carriers
were more realistically described by a modified Dirac equation than a Schrodinger equation(1).
The E v k graph for single layer graphene is not the quadratic cone that other semiconductor
materials have, but instead its a linear cone with a sharp end, and since the second derivative of
this graph is 0 it can be deduced mathematically that the charge carrier is indeed massless.
These basic discoveries about the properties and the potential for graphene ignited a race for
discovering the best methods for making cheap, high quality, monolayer, large area graphene(as
opposed to few-layer-graphene). A few of the techniques that were developed in the years that
followed Dr. Geims discovery were carbon nanotube unzipping, chemical vapor deposition
(CVD), epitaxial growth on silicon carbide, ultrasonic mechanical exfoliation, and even layer-by-
layer self-assembly(2). These methods all offer a unique
advantage over the next, however the most favored
method for high quality graphene tends to be CVD,
where graphene is CVDd onto a Cu or Al film, where
its growth is self-terminating, and then the metal is
etched away. This is fantastic for high quality graphene,
but is a very expensive process and large surface areas
are not quick or easy. On the other end of the spectrum
LBL self-assembly is a good process for making crude
Figure 2: Graphene grains on a copper
film few-layer-graphene cheaply, but fails at making high
quality monolayer graphene(1-2).
Graphene, especially with all of the new fabrication methods, has been the focus of study in
physics and engineering for just over a decade. For physicists, due to its ability to be super
conductive at room temperature and exhibit unique quantum properties, it offers an opportunity
to explore understanding of the half-integer quantum Hall effect and the predictions of such
phenomena as Klein tunneling, zitterbewegung, the Schwinger production, supercritical atomic
collapse, and Casimir-like interactions between adsorbates on graphene(1)(7). For engineers it
offers to opportunity to exploit of all the unique characteristics of graphene in unique
engineering applications, ranging from the development of better transistors to the development
of biosensors with the detection limit of a single molecule(2).
Quantum Dots
LEDs cant, at least with current technologies, produce white light efficiently because most
LEDs are capable of making a lot of blue and yellow, but not very much red or green. This meant
that a lot of energy had to expended in order to produce enough red and green for a bright display
while also making enough for broad primary colors. This inefficiency is something that has
started to attract more people to the technology of Quantum
Dots (QD)(6). Quantum dots are essentially nanosized
semiconductor crystals that confine carriers/light in the x, y,
and z direction, which allows them to be very fine tuned to a
specific wave length of fluorescence. Depending of the size
of the QD an exciton, hole/electron pair, will recombine to
Figure 3: Example of the different emit light; it will emit red light if it is a larger dot and blue
colors that QDs can give off as size light if it is a smaller dot(5).
varies.

However the toxicity of standard fluorescence probes using AIIBVI semiconductors or


rare earth fluorides makes this technology slightly less palatable, which is where graphene comes
in. Graphene QDs were made using the cage opening of buckey balls (C60) by subjecting them
to a mixture of concentrated sulfuric acid, sodium nitrate, and potassium permanganate. This was
an improvement upon previous techniques were the graphene was simply mechanically or
chemically cut down to size, because the size of the constant size of C60 buckey balls was able
to generate constant size graphene flakes of 2-3 nm. While the Graphene QD (GQD) was more
environmentally friendly than traditional ones, it still did not allow for a range of QDs to be
made and was not capable to compete with industry demand(2). However at rice university
scientists were able to oxidize coal at varying temperatures to produce a wide range of graphene
sheets, which through ultrasonication were able to be separated by size. GQDs were synthasized
from biutminous coal, coke, and
anthracite by sonicating the coal in
sulphuric acid and nitric acid,
followed by heat treatment at 100-120
degrees Celsius, with the temperature
being able to directly control the
oxidation process and thus affect the
final size of the GQD(10). The type of
coal used also affected the size of the
GQD that would be generated. The
Figure 4: The opening of a bcukey ball into a small graphene GQDs made in this experiment were
flake is shown (a). The optical properties of the chemically
treated (strong acid and oxidizers) graphene are shown (b). able to range from 5 to 120 nm in size,
thus being able to generate a wide
range of colors (as opposed to the buckeyball GQDs). This experiment was also able to make the
GQDs much cheaper than GQDs have every been made, because they used coal which comes in
at $60 a ton, much cheaper than batches of graphene/carbonnano tubes/buckeyballs(5)(10).

More Applications of QDs

QDs are far more fluorescent than LEDs and open the door, due to their small size, to flexible
electronics. However their uses can also be biomedical, because they are also far more
fluorescent than typical fluorophores so they would be drastically better for tagging proteins or
other biological molecules(5).

Solar Cells
In the quest for renewable and sustainable energy solar cell technology has been research
extensively. However, even though solar panels have been able to achieve efficiencies of 10-15%
it is impossible to achieve a 100% efficiency solar cell, disregarding thermodynamic
impossibilities, because of the need to optimize between
having a semiconducting material with a small bandgap
capable easily being jumped by electrons but a weak voltage
or a large band gap and a strong voltage(8). Optimization
between these and many more factors has landed solar cells
in this range of efficiency. Furthermore, there is a quest to
make them not only more efficient but light and durable as
well, for added convenience to regular consumer use.
Currently perovskites, a structure of calcium titanium oxide,
are a huge hit with the research community and efficiencies
of ~50 percent have been reached by perovskite/silver
nanowire solar cells(11). However, these perovskite based
solar cells use an electron collection layer that requires
sintering at 500 C, which greatly hinders low cost
production, application on plastic substrates, and application
with multijunction devices. Thin film devices such as
perovskite based meso-superstructure solar cells (MSSCs)
Figure 5: An SEM of the structure typically use titanium oxide or zinc oxide as the electron
of this device is shown (a). A collection layer, because they can avoid shunting and leakage
computer generated schematic of
the device is shown (b). current under an applied reverse bias. However they need to
achieve high crystallinity first, so as to achieve high charge
mobility, but this requires the high temperature sintering. This is were graphene nanoflakes can
be incorporated and greatly reduce the sintering temperature needed for the electron collection
layer to be made(6-8).
The University of Oxfords Dr. Nicholas was able to show superior performance of an electron
sensitive material made from both graphene nanoflakes (GNF) and titanium oxide(TO). The
graphene flakes were made from liquid phase sonication (LPS), which is a more complex
method of mechanical exfoliation that can yield higher quality sheets (in terms of impurities) of
on average 5 layers. The titanium oxide and GNF were mixed and sintered at 150 degrees
Celsius, which is drastically lower than the temperatures usually used to sinter the TO. The
reason hypothesized for this is that TO attaches to the GNF and the individual GNF then are in
contact with each other which allows for the high electron mobility of graphene to be exploited,
while also using the ability of TO generate electrons(11). The heightened charge mobility due to
graphenes properties allows composite to not require a high temperature to create a good crystal
structure of pure TO, which is what would normally allow for a good charge mobility to be
achieved. The research even showed that the GNF and TO mixture was able to generate higher
voltages and currents than most high temperature sintered TO layers used in other solar cells
(Though of course there are some newer cells that performed much better, this simply signifies
the superiority over common perovskite based solar cells)(8). The GNF and TO interaction also
aids mobility, because it lowers the recombination resistance present in the layer. The
recombination resistance is lowered because the TO undergo an efficient electron transfer to
graphene, at which point the majority electron density will reside in the graphene and the TO will
be left depleted(12). This matters because this layer is directly in contact with the a perovskite
layer, but with TO coating on the GNF, the GNF arent actually contacting the perovskite only
the depleted TO are contacting the perovskite(1).

Wave Guides and Modulators


Integrated Optical Modulators with high-
speed modulation and large optical bandwidths
are relied on to be tools for on-chip optical
interconnects. However, despite vast amounts of
research in the last few years on semiconductor
modulators and waveguides, silicon/germanium
semiconductors are still on the order of
millimeters, thus being completely impractical
for use in nano/micro electronics.Even with
enhancement with modulators, the bandwidth of
Figure 6: This is a Current Density vs Voltage
the silicon waveguides is still intrinsically small
graph. It shows the electronic properties of due to inherent material properties. However
different type of TiO2 and GO configurations. graphene is a material that is capable of having
a tuned fermi level, depending on the tuned chemical, size, and electrical properties of
graphene(4).
Researchers at the University of California Berkley have tuned Graphene's fermi level to
modulate guided light at more than 1GHz. As said previously, there are many ways to tune the
fermi level, however in this case the fermi level was manipulated by changing the drive
voltage(4). This voltage affected modulation capabilities by changing the transmission properties
by shifting the fermi level away from the Dirac point. When the Fermi energy is lower than the
half photon energy (-hv/2) there are no electrons available for interband transitions. The
transverse of this also holds true, where Fermi energy is increased to hv so that all electron
states in resonance with light are occupied. These both work to increase transmission, which then
directly dictates the electroabsorption modulation. Operation at higher photon energy (h) always
requires a larger change in the Fermi level (EF)Furthermore, due to the fact that they have a
broad operation spectrum, especially compared to traditional semiconductors, of 1.35 to 1.6
micrometers(2). This ultra fast and broadband properties are due to two things. Firstly, the high
speed operation is due to the fast carrier mobility and the fact that speed limiting processes of
photo carrier generation and relaxation occur on an order of picoseconds, which actually means
theoretically (with control of density and layers) the operation modulation frequency could very
well be 500 GHz. The unique optical properties and its broadband operation would be due to the
high frequency dynamic conductivity for Dirac fermions being constant, which allows for
graphene's optical absorption to be independent of wavelength. it is capable of integration onto
nanoelectronics and enable novel on-chip optical communication(6-7). This low voltage, ultra-
fast graphene modulator/waveguide
(Figure) was actually the smallest to
date.
Applications for waveguides
As far as applications for
graphene waveguides or modulators, they could be used in quantum computing. One idea for
quantum computers involves two photons, perhaps generating by the exciton in a GQD,
Figure 7: Representation (3D Model) of the Au to Pt to travelling down their own determined
Graphene waveguide and Si Waveguide setup. Also path, at which point they come close and
shown is a photograph of the graphene waveguide,
which then is aided by turning Si waveguide. either continue on their path, recombine
on one of two sides, or completely
destructively interfere. This availability of 4 states is what would allow for them to be used in
computing, however this would recquire, especially as the tech advances, the use of small, quick,
and broad band waveguides to carry the light on their own respective paths.
Biosensors
Surface Plasmon Resonance (SPR) biosensors are governed by some very complex physics, but
have a fantastic sensitivity, sometimes being able to detect a single molecule or antigen. SPR
uses coherent oscillations of Surface plasmons (SPs) are coherent oscillations of metal
conduction electrons on a metal surface, where it meets with a dielectric. These oscillations are
usually caused by electromagnetic radiation on the surface of a piece of metal(3). The promising
and appealing potential of SPR sensors lies in the very high environmental sensitivity of the
surface plasmons (at an excited state at the interface) to change the refractive index of the
dielectric. This change in the dielectric then changes the propagation constant of the surface
plasmons, and finally the cascade of events ends with the resonance of the surface plasmons and
the interacting optical wave. This means that by measuring the interaction of light with the
surface we can understand angular, wavelength, intensity, or phase modulation caused by the
surface plasmons. These surface plasmons are very sensitive to environmental factors, as
discussed, which means that they are also very appealing to label free detection schemes. The
principle behind it is that a charge on a biomarker, such as alpha-fetoprotein which is used to as a
marker for liver cancer, could affect the propagation constant of the surface plasmons and thus
affect incident light in a detectable and quantifiable manner(3)(13). This is something that could
potentially help phase out more difficult to use tests, and more unreliable as well, such as ELISA.
ELISA is a chemical assay used for the detection of a variety of molecules and biomarkers, such
as alpha-fetoprotein or glucose.
Graphene has been used to improve SPR biosensors, A*STAR Singapore University was
able to fabricate a biosensor that was well improved by the addition of a graphene (s). There
were two purposes to incorporating graphene into the biosensor. First, if an SPR biosensor is
being used to detect a molecule such as DNA what should happen is that the DNA should be
attached near the gold so that the change in surface plasmon propagation is noticeable(9).
However, carbon molecules poorly adhere to gold which is the SPR material of choice, thus the
sensitivity of the SPR sensor is greatly reduced. However graphene is capable of attaching to
such molecules and if used as a coating was added to the gold, it would be able to improve
performance(3). Furthermore, as was learned in the
waveguide section of this review, graphenes unique
optical properties allow it to strengthen the sensitivity of
the SPR sensor to changes in the dielectric layer, more
so than without it. However, this is yet another
application were perfectly pure monolayer graphene is
not needed and might actually lessen instrument
sensitivity. Work with non-pristine graphene in
biosensors has also been used in the University of
Minnisotta in developing glucose and alpha-fetoprotein
biosensors, which used LBL self-assembly to make a Figure 8: Basic functioning
very rough graphene flake surface. However it was good principle of an SPR biosensor with
enough to adhere well to biomarkers and its properties were an added graphene layer.
kept intact. Alas, this paper digresses, it has been found that with varying layers of graphene onto
SPR biosensors, it is possible to increase sensitivity even further. It does this by allowing for
larger shifts in the dielectric properties and thus a greater shift in the angle of the incident light
reflecting off the gold surface, however the mechanism for this is not yet understood (9)(13).

Conclusion
Hopefully this review is capable of summarizing the discovery of graphene, the advancements in
the fabrication of graphene, the physics of graphene, and lastly the wide array of research areas
and potential applications of graphene in the field of nanophotonics and nanooptics.This paper
was mostly to focus on scope in order to give an idea of potential of the material, not so much on
a singular technology and the details of the underlying physics at play. This broad overview
hopefully yields a more creative understanding of the material and inspiration for potential
research applications for graphene.
As much as I have praised the abilities of
graphene it is worth noting that there is
currently vast amounts of research in finding
other 2D materials. This is being done in
order to discover if there is an easier to
fabricate 2D material or perhaps even a
material with a more tunable bandgap than
that of graphene. However, graphene still
holds as the most versatile and preferred 2D
material, especially in terms of applicability
to industry.

Figure 9: Graphic displaying the wide array of 2D materials. Discussing these in depth was simply far
out of the scope of the review.

References
1. Geim, A. K. (2009). Graphene: status and prospects. Science (New York, N.Y.),
324(5934), 15304. http://doi.org/10.1126/science.1158877

2. Geim, A. K., & Novoselov, K. S. (2007). The rise of graphene. Nature Mater., 6(3), 183
191. http://doi.org/10.1038/nmat1849

3. Homola, J., Yee, S. S., & Gauglitz, G. (1999). Surface plasmon resonance sensors:
review. Sensors and Actuators B: Chemical, 54(1-2), 315. http://doi.org/10.1016/S0925-
4005(98)00321-9

4. Liu, M., Yin, X., Ulin-Avila, E., Geng, B., Zentgraf, T., Ju, L., Zhang, X. (2011). A
graphene-based broadband optical modulator. Nature, 474(7349), 6467.
http://doi.org/10.1038/nature10067

5. Bacon, M., Bradley, S. J., & Nann, T. (2014). Graphene Quantum Dots. Particle &
Particle Systems Characterization, 31, 415428. http://doi.org/10.1002/ppsc.201300252

6. Lui, C. H., Liu, L., Mak, K. F., Flynn, G. W., & Heinz, T. F. (2009). Ultraflat graphene.
Nature, 462(7271), 339341. http://doi.org/10.1038/nature08569

7. Nair, R. R., Blake, P., Grigorenko, A. N., Novoselov, K. S., Booth, T. J., Stauber, T.,
Geim, A. K. (2008). Universal Dynamic Conductivity and Quantized Visible Opacity of
Suspended Graphene. Science (New York, N.Y.), 320, 1308.
http://doi.org/10.1126/science.1156965
8. Wang, J. T. W., Ball, J. M., Barea, E. M., Abate, A., Alexander-Webber, J. a., Huang, J.,
Nicholas, R. J. (2014). Low-temperature processed electron collection layers of
graphene/TiO 2 nanocomposites in thin film perovskite solar cells. Nano Letters, 14(2),
724730. http://doi.org/10.1021/nl403997a

9. Wu, L., Chu, H. S., Koh, W. S., & Li, E. P. (2010). Highly sensitive graphene biosensors
based on surface plasmon resonance. Opt. Express, 18(14), 1439514400.
http://doi.org/10.1364/OE.18.014395

10. Ye, R., Xiang, C., Lin, J., Peng, Z., Huang, K., Yan, Z., Tour, J. M. (2013). Coal as an
abundant source of graphene quantum dots. Nature Communications, 4, 2943.
http://doi.org/10.1038/ncomms3943

11. You, P., Liu, Z., Tai, Q., Liu, S., & Yan, F. (2015). Efficient Semitransparent Perovskite
Solar Cells with Graphene Electrodes. Advanced Materials, n/an/a.
http://doi.org/10.1002/adma.201501145

12. Zang, J., Ryu, S., Pugno, N., Wang, Q., Tu, Q., Buehler, M. J., & Zhao, X. (2013).
Multifunctionality and control of the crumpling and unfolding of large-area graphene.
Nature Materials, 12(4), 3215. http://doi.org/10.1038/nmat3542

13. Zhang, J., Sun, Y., Xu, B., Zhang, H., Gao, Y., Zhang, H., & Song, D. (2013). A novel
surface plasmon resonance biosensor based on graphene oxide decorated with gold
nanorod-antibody conjugates for determination of transferrin. Biosensors &
Bioelectronics, 45, 2306. http://doi.org/10.1016/j.bios.2013.02.008

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