2D Materials and Electromagnetic

Applications

November 10th, 2016

Tel Aviv University Antenna Symposium

George Hanson
Dept. of Electrical Engineering and Computer Science
University of Wisconsin-Milwaukee
 Introduction
Two-Dimensional Materials and Electromagnetic
Applications
2D materials: summary of current materials and their properties
(graphene, black phosphorus, hexagonal boron nitride, transition
metal di-chalcogenides (TMDCs) such as molybdenum disulfide, etc.)
EM modeling of 2D materials
Local and nonlocal infinitesimal sheet models, 3D model,
anisotropic models
Electronic and electromagnetic applications
 Introduction
Prerequisite concept of a bandgap

Conductors, semiconductors, and insulators can all be

explained by these types of band diagrams.

wikipedia.org
Introduction

Nature Photonics 8, 899907 (2014)

 Two-dimensional Materials and the
Four Minute Mile

For many years it was thought that the human body was incapable of
running a mile in under four minutes. In 1954 that barrier was
broken by Roger Bannister at Oxford University. Two months later
Australia's John Landy did it, and now it is commonplace.

For many years it was thought, based on thermodynamics, that it was

impossible for a single atomic layer to exist independently. articles.orlandosentinel.com

In 2004 Andrei Geim and his PhD student Konstantin Novoselov, at the
University of Manchester, obtained single-layer graphene using scotch tape
exfoliation. This works for a wide range of van der Waals solids.

Science, 2004
Geim and Novoselov submitted a three-page paper to Nature, where it was
rejected twice one reviewer said that isolating a stable, two-dimensional
material was impossible, and another said that it was not a sufficient
scientific advance.

In October 2004, the paper, Electric Field Effect in Atomically Thin Carbon
Films, was published in Science.

In 2010, Geim and Novoselov were awarded the Nobel Prize in Physics.

At the University of Manchester, the British government invested sixty

million dollars to help create the National Graphene Institute.

In 2013 the EU awarded a 1bn ($1.35bn) grant to the Graphene Flagship

Consortium based at Chalmers University (Sweden).

- Ten-year project involving 126 academic and industrial research groups.

Goal is to commercialize graphene and spur economic growth.

2D Materials are Hot!

Now, there are a
number of
companies
producing
graphene
commercially.
Current families of 2D materials

Blue: Monolayers stable under ambient conditions (room temperature in air)

Green: Probably stable in air
Pink: unstable in air but may be stable in inert atmosphere
Grey: 3D compounds that have been successfully exfoliated down to monolayers,
but for which there is little further information.

A. K. Geim and I. V. Grigorieva, van der Waals heterostructures, Nature 499, 419, July, 2013
 Universal Attribute of 2D Materials: Tunability, flexability
(bendability), transparency
2D materials cover the usual classes of electronic materials: insulators (e.g., hex
boron nitride), semiconductors (e.g., MoS2), and metals (e.g., graphene)

A 2D material is all surface, and so

the interface between the surface and a substrate, and the presence of adatoms
and defects can dramatically alter the materials properties.

2D materials can inherently be tuned using electrostatic or magnetostatic

fields little electronic screening takes place (there is no inside).

Lattice strain plays an important role in modifying the lattice constants,

leading to modifications of the energy bands. Strain engineering is an
emerging field.

Mechanically, their 2D nature is important as they are inherently flexible (weak

out-of-plane bonds), strong (strong in-plane bonds), and, of course, extremely thin.
The initial excitement over graphene: Dirac Cones

In graphene (and a few other 2D materials), the Ek

relation is linear (as occurs for photons) for low
energies near the six corners of the two-dimensional
hexagonal Brillouin zone.

The result is zero effective mass for electrons and

holes, and an energy-independent velocity.

Electron behave as Dirac fermions (they obey the relativistic Dirac equation,
and exhibit exotic effects such as Klein tunneling, half-integer quantum Hall
effect, ultrahigh carrier mobility). Dirac cones come in pairs with opposite
chirality.
Combining 2D Materials - van der Waals Heterostructures

A. K. Geim and I. V. Grigorieva, van der Waals heterostructures, Nature 499, 419, July, 2013.
General Electronic Applications
Digital Logic: electronic circuits are made mostly from metaloxidesemiconductor
field-effect transistors (MOSFETs).

There are three requirements for a good logic transistor:

high carrier mobility for fast operation,
high on/off ratio
low off-state conductance for low power consumption.

The 12 eV band gaps of Mo and W dichalcogenides can provide high on/off ratios
and with low power dissipation.

Recent MoS2 top-gated FETs showed excellent on/off current ratio up to 108, room
temperature mobility of >200 cm2 V-1 s-1.

Nat Nanotechnol 2011;6:14750

General EM Applications
Plasmonics and waveguiding/interconnects
Antennas
Optical devices, including modulators, detectors and emitters.

2D modulated waveguide

Plasmonic absorber
www.osapublishing.org iopscience.iop.org
Synthesis Methods for 2D Materials
Micromechanical exfoliation using scotch tape
Single and few atomic layer materials can be obtained by mechanical
exfoliation (first used by Grim for graphene). Material is peeled off
using scotch tape.
The monolayer yield is low; only suitable for laboratory scale, and
samples are typically tens of microns in size.
Resulting material has excellent structural integrity, high crystallinity,
and superior electrical properties.
Liquid exfoliation
Used to produce single and few layers 2D sheets at bulk scale.
Weak out-of-plane bonding in the layered materials and high surface
area results in the ability for molecules to be adsorbed between atomic
layers. This intercalation weakens interlayer adhesion and lowers the
energy barrier required for exfoliation.

A. Gupta, T. Sakthivel, and S. Seal, Recent development in 2D materials beyond graphene, Progress in Materials Science 73, 44-126, 2015.
 Synthesis methods for 2D materials
Sonication
Ultrasonic cleavage of weak out-of-plane bonding - bulk layered
material is dispersed in a solvent and sonicated for several hours.

Chemical vapor deposition (CVD)

The material to be coated is placed inside a vacuum chamber. The
coating material is heated until the material vaporizes. The vapor settles
on the material to be coated, forming a uniform coating. Adjusting the
temperature and duration of the process makes it possible to control the
thickness of the coating.
CVD has enabled the synthesis of large area and uniform thickness 2D
layers for large-scale fabrication.

A. Gupta, T. Sakthivel, and S. Seal, Recent development in 2D materials beyond graphene, Progress in Materials Science 73, 44-126, 2015. www.azonano.com
 Synthesis methods for 2D materials

Kitchen blender method to make graphene:

Take a high-power (400-watt) kitchen blender, water, detergent

(to act as surfactant), and 2050 grams of graphite powder
(pencil lead), run for 10-30 minutes.

The result was a large number of high-quality micrometre-

sized flakes of graphene, suspended in the water.

K. R. Patton et al., Scalable production of large quantities of defect-free few-layer

graphene by shear exfoliation in liquids, Nature Materials,13, 624, 2014.
Visualizing 2D materials
AFM of MoS2

An interference effect on
dielectric-coated SiO2/Si
substrates is commonly
used to visualize and
locate single and few
Optical micrograph of thin layers.
films of MoS2
AFM of graphene

optical micrograph of
graphene

Butler et al., Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene, ACS Nano, 2013, 7 (4), pp 28982926
 2D Materials Electromagnetic Modeling

Infinite contiguous 2D sheets are most accurately modeled as a two-sided

impedance surface having conductivity (S).

Conductivity may be anisotropic, non-local, non-linear, etc.

18
2D Materials Electromagnetic Modeling

In general, all (or most) 2D materials can be characterized by the tensor,

non-local Kubo conductivity.

This is a 2D conductivity (SI units Siemans (S), not S/m), accounting for both
intraband and interband contributions.

Electromagnetic boundary conditions are

Usually nonlocal aspects add considerable complication to the model.

However, for 2D nonlocal materials it is very easy! simply replace ()
with (,q).
2D Materials Electromagnetic Modeling of Graphene

For graphene in the local case, relatively simple formulas result:

where the Drude weight is

2D Materials Electromagnetic Modeling of Graphene

Pauli blocking

Optics Express, 20, pp. 23201-23214, 2012.

Graphene Optical Conductivity intraband and interband components

Onset of interband transitions

Drude conductivity
14
12
10
8 c=0
6
4 ' (mS)
2
0
-2
-4
'' (mS)
-6
-8
101 103 104 10 4 104
f (GHz)

14
12
10 ' (mS)
8 c=0
6
4
2
0 = intraband + interband
-2
-4
'' (mS)
-6
-8
101 2 3 4 5 67
102 2 3 4 5 67

f (GHz)
10 3 2 3 4 5 67
104 Intraband term is Drude-like
22
 2D Materials Electromagnetic Modeling of Graphene

An alternative model is to consider the material to have

some finite thickness, and to convert the 2D
conductivity to a 3D conductivity. Effective thickness d
is O(1 nm).

However, while convenient for some commercial simulators, one must be

careful in using this model. It can lead to a fine mesh and long run times, plus
inaccurate results.
2D Materials Electromagnetic Modeling of Graphene

The correct field behavior for a plasmon mode at the interface is

to have an odd normal electric field.

Gonalves and Peres , An Introduction to Graphene Plasmonics

World Scientific, 2016
2D Materials Electromagnetic Modeling
of Graphene

Even mode

Odd mode

However, a negative epsilon

slab waveguide supports both
and odd and an even mode.

Al and Engheta, JOSA B, 23,p. 571, 2006.

2D Materials Electromagnetic Modeling of Graphene
2D Materials Electromagnetic Modeling of Graphene
Error in finite-thickness model

E. Forati, G.W. Hanson, A.B. Yakovlev,and Andrea Al, A planar hyperlens based on a modulated graphene
monolayer, Phys. Rev. B (Rapid Communications) 89, 081410(R) 2014.
Primary Attributes of Several 2D Materials:

Graphene: a single layer of carbon atoms arranged in a regular

hexagonal pattern. Each atom participating in four bonds, one
strong in-plane bond with each of its three neighbors and one
weak out-of-plane -bond.

Graphene's hexagonal lattice can be regarded as two

interleaving triangular lattices.
Graphite consists of multiple graphene
layers.

Carbon nanotubes are rolled up graphene

sheets.

grapheneindustries.com, titianmedia.ca/wordpress 28
physicsforme.wordpress.com and photonics.com, nontrivialproblems.wordpress.com
Graphene

Graphene is the strongest material in the world

If a sheet of plastic cling wrap had the same

strength as pristine graphene, to puncture it with a
pencil would require applying a force on the order
of 20,000 N.

Graphene is a zero-bandgap semimetal. At finite temperatures it is essentially

a metal.

Graphene has the highest thermal conductivity of any material (2 x diamond).

Graphene has the one of the highest mobilities of any material (100 x Si).

Graphene can carry the highest current densities of any material (109 A/cm2 ;
1,000 x Cu).

One reason for these extraordinary properties is that graphene can be obtained
that is nearly defect-free (at least in small areas).
29
http://titianmedia.ca/wordpress/?p=1480
Graphene electronic properties

The Ek relation is linear (as occurs for

photons) for low energies near the six corners
of the two-dimensional hexagonal Brillouin
zone.

The result is zero effective mass for electrons and holes,

and an energy-independent velocity.

In this case the electron behave as Dirac fermions (They obey the
relativistic Dirac equation, and exhibit exotic effects such as Klein
tunneling.).

30
Graphene
General Potential Applications:

Transparent conducting electrodes, solar cells,

batteries, ultracapacitors, nanoelectronics, THz
plasmon oscillators, polarizers, filters, antennas,
surface plasmon modulators, interconnects.

Graphene transistor:

Many research teams (including IBM) have made

graphene transistors.
They can be extremely fast due to very high carrier
mobility, but they lack a band gap.
Typically, a bandgap of the order 1 eV at room
temperature is needed for a FET.
The best efforts to engineer a bandgap in graphene
have produced modest band gaps (a few hundred
meV). Thus, they dissipate lots of energy in the www.gajitz.com, www.sciencedirect.com, 31
and vorbeck.com
off state.
 Graphene

One somewhat electronic commercial example:

Vorbeck produces Vor-ink, a graphene-based

conductive ink for electronics.

There are some sports equipment (tennis racquets, bike

frames, etc.) that purport to use graphene.

It seems that there are no electronic/optical commercial

devices yet.

32
khelmart.wordpress.com, www.gajitz.com, www.sciencedirect.com
and vorbeck.com
 Graphene
In the optical range the low-temperature conductivity is dominated by the
interband term, and = 2 /2. The transmittance is |T|1-97.7%, where
= 2 0 /2 is the fine structure constant, which is in excellent agreement with
measurements.

Pauli
blocking

The intraband Drude conductivity has also been experimentally verified for graphene.

Science 6 June 2008 320: 1308.

 Graphene
Special Cluster on Graphene and Two-Dimensional Materials for Antenna Applications.
Antennas and Wireless Propagation Letters, Co-guest Editors: Hao Xin and George W. Hanson

Vor-Ink on cardboard.
 Graphene

Graphene ink G-102E (BGT Materials, U.K.) on paper.

 Graphene
Using graphene strips to form a hyperbolic metasurface
Transitional Metal Dichacolgenides

These are essentially semiconductors with parabolic bands.

They generally have the form MX2, where

M is one of the transition metals: partially filled d sub-shell; Molybdenum
(Mo), Wolfram (W), etc.) and
X a chalcogen atom: Sulfur (S), Selenium (Se), Tellurium (Te)
One layer of M atoms is sandwiched between two layers of X atoms, forming a
very thin structure (for MoS2, a monolayer has thickness 0.65 nm, not much
more then the thickness of graphene).

Crystal lattice

2D Mater. 2 ( 2015) 049501

 Transitional Metal Dichacolgenides

Mo and W dichalcogenides are semiconductors with band gaps around 12 eV.

The most common varieties are MoS2 and WS2.
TMD layers have a thickness of 0.60.7 nm, with strong covalent bonds in-plane
and weak van der Walls interactions out-of-plane.
Monolayer MoS2 has broken inversion symmetry, which leads to interesting
valley physics.
Applications as transistors and optical emitters
and detectors.

The band gaps of MoS2 and WS2 are indirect for

the bulk materials but direct for monolayers.

Primary applications seem to be electronic

(transistors), but also can be used for optical
applications in the range of energies of its
bandgap.
A. Gupta et. al, Recent development in 2D materials beyond graphene, Progress in Materials Science 73, 44-126, 2015.
Transitional Metal Dichacolgenides

EM Application Saturable Absorber

 Black Phosphorus (and phosphorene)

Black phosphorus (BP) is essentially a narrow-gap semiconductor.

BP forms a puckered surface due to sp3 hybridization.
It is one of the thermodynamically more stable phases of phosphorus, at ambient
temperature and pressure (white/yellow phosphorus is highly flammable and self-
igniting upon contact with air - it is stored under water).
BP is fairly reactive (hours to days), and must be passivated.

BP is highly anisotropic

Phys. Rev. B 89, 201408(R) (2014)

Black Phosphorus (and phosphorene)

BP has recently been exfoliated into its thin multilayers (5-30 nm) and single
layers (phosphorene), showing good electrical transport properties.
Optical absorption spectra of BP vary sensitively with thickness, doping, and
light polarization.
Potential for mid- to near-infrared spectrum applications: optoelectronics,
imaging, and detection.

BP band gap is direct for both

monolayers and finite-thickness
films, but the value of the band
gap is controllable, and depends
on the number of layers:
A large gap (~2 eV) for
monolayers decreasing
gradually to a narrow band
gap (about 0.3 eV) for bulk
black phosphorus.
Phys. Rev. B 89, 201408(R) (2014)
Black Phosphorus (and phosphorene)

The band gap spans a wide range of the electromagnetic spectrum, and bridges
the gap between graphene (zero band gap) and TMDs (wide band gap).

Possible applications:
Electronics (transistors).
Photovoltaic energy harvesting (optimized for
semiconductors with 1.2 eV1.6 eV band gap)
Fiber optic telecommunications (wavelengths in
the range of 1.2 m1.5 m, corresponding to
photon energies of 0.8 eV1 eV)
Thermal imaging (typically requires
semiconductors with gaps spanning from 0.1 to
1.0 eV).

J. Phys. Chem. Lett., 2015, 6 (21), pp 42804291

BP transistors

BP bridges the gap between graphene (very high mobility and poor current
on/off ratio) and transition metal dichalcogenides (low mobility and excellent
on/off ratio).

J. Phys. Chem. Lett., 2015, 6 (21), pp 42804291

Black Phosphorus Optical Conductivity

Conductivity
tensor

0

= 0

hyperbolic regime

10nm thick BP obtained at doping level 10x1013/cm2 (a,b)

and 5x1012/cm2 (c,d) normalized to 0 = 2 /4. Regions 1
and 3 show anisotropic inductive and capacitive responses,
respectively, and region 2 shows the hyperbolic regime.
Black Phosphorus (and phosphorene)
Some EM applications hyperbolic surface

Equifrequency surface for hyperbolic medium, < 0

2 + 2 2
+ = 02

Can also be implemented using

layered metal-dielectric
Hyperbolic Black Phosphorus

Equifrequency contour for 2D materials

Isotropic case black circle

Hyperbolic case ( < 0):
blue and green hyperbola

Slopes of hyperbola asymptotes

= /

Different slopes of hyperbolas

correspond to different levels of
doping.
Directional flow of energy in hyperbolic 2D materials

Energy flow in anisotropic material is

defined by direction of group velocity
= ()
i.e. orthogonal to equi-frequency
surface

Normals to hyperbolas point to the

same direction, causing propagation of
energy along narrow rays.

Different slopes correspond to different

values of doping, allowing for tunable
control of the propagation direction.

PRL 116, 066804 (2016)

Ray optics with hyperbolic surface plasmons
Hexagonal Boron Nitride (hBN)
hBN is essentially an insulator.
Boron Nitride (BN) arises from the reaction of boric oxide and potassium cyanide.
The microcrystalline powder form of BN has many uses as a lubricant or coating
(as is graphene) when chemical inertness at high temperature is required. It is a
white slippery solid.
BN can assume many crystalline phases; hexagonal (h-BN) including boron nitride
and cubic (c-BN) films are most common.
The spacing between successive layers is 0.334 nm, similar to graphene (0.333 nm).
The bond length between two successive B and the N atoms is 1.44 A.

A. Gupta, T. Sakthivel, and S. Seal, Recent development in 2D materials beyond graphene, Progress in Materials Science 73, 44-126, 2015.
Hexagonal Boron Nitride (hBN)
Electronic Applications: 2D hBN has been
considered a promising material 2D electronics,
including substrates, and gate dielectrics for 2D
transistors.
Electromagnetic Applications: hBN supports
phonon polaritons with extremely high confinement
and low loss (much smaller than graphene plasmons
polaritons)
hBN has natural hyperbolicity.
Both graphene plasmons and hBN phonons reside
in the mid-IR; promising as hetrostructures.
hBN is now being used as a substrate of choice for
graphene due to the preservation of high
(graphene) carrier mobility, as opposed to
conventional SiO2 substrates.
Phonon modes of hBN can couple to graphene
plasmons providing the possibility of interesting
effects, e.g., such as phonon-induced transparency. Nano Lett. 2015, 15, 31723180
 Silicene and Germanene

Bulk silicon (Si) cannot form a layered phase like graphite.

Experiments (first done in 20101) show that surface-assisted epitaxial
growth can produce 2D monolayers of silicon, termed silicene, showing a
honeycomb structure similar to those of graphene.
Free-standing silicene is expected to have a zero band gap (like graphene),
but a tiny gap can be opened in epitaxial silicene, due to the symmetry-
breaking induced by the interaction with the substrate.
Germanene is the germanium analogue of silicone, first produced in 20142.
As in silicene, it has zero bandgap.

EM applications?

1Applied Physics Letters 97 (22): 223109, 2010

2New Journal of Physics 16 (9): 095002, 2014
Summary

2D materials are of interest for many reasons

No screening - they are very tunable with applied static bias (or
optical pumping)

Some have Dirac cones

They tend to have very good mechanical and electrical properties

They come as metals, insulators, and semiconductors

They dont take up much space