Introduction to 2D materials

Nedjma Bendiab

Institut Néel, CNRS/ UGA, Grenoble, France

Me:

Nedjma BENDIAB
Professor at Grenoble Alpes University
working at Institut Néel, in Grenoble, with 2D materials since 2006,
nedjma.bendiab@univ-grenoble-alpes.fr

You:
How we will proceed

- Today:
20 min to agree on what/how we will learn and evaluate
Your expectations?
My expectations: learning the context (motivation, history), doing some physics,
remembering a few important concepts, working with textbooks and scientific articles

- 11 other lectures with me (from 2:15-4:15pm each Tuesday ):

starting with a 15 min test + 15 min correction (part of the “continuous exam” mark). 10
min break.

- Last session devoted to the analysis (by you) of (a) scientific article(s), with a 10 slides-
powerpoint expected as a deliverable within a week (part of the “continuous exam”
mark)

- 1h written final test (70% of the overall mark)

Overview on 2D materials

- What are we talking about in this lecture?

- What is different in 2D?
- A bit of history — a few important landmarks
- Big trends in academics and possible transfers to everyday’s life

4
 What changes with reducing dimentionality?
• Size effects

When the size decreases, the number of surface

atoms compared to the volume increases
Physical properties changes
ex: The melting temperature of a Cu nanowire is
350°C lower than the bulk
® The physics effects which became important
change
®Changes of chemical properties

• Quantum Phenomena

Confinement effects, enhanced many-electron interaction …

Tunable properties by gating and environmental screening

Source: C. Bréchignac, CNRS

What are we talking about?

6
 What are we talking about?

- Two-dimensional (2D) means that there is confinement in 1

direction, 2 degrees of freedom
- Strictly speaking, 2D material = single lamella, with no dangling
bonds at the top/bottom
- The lamella (also called layer) may be 1-atom- or few-atoms-thick
- By extension, 2, 3, etc, 10 layers are considered 2D
- A huge family of materials, each with a specific chemical
composition

7
 What is different in 2D?
Let’s take us the example of electrons:

The density of electronic states per unit volume and unit energy depends
strongly on dimensionality (degrees of freedom)

Remember:
in the derivation, the unit k-
space “volumes” change
whether there are 3, 2, 1, 0
degrees of freedom, and
knowledge on the k-E
relationship is needed.

8
 A bit of history
2D materials yesterday

Slide from Abhay Shukla,

9
IMPMC Paris
 A bit of history
2D materials yesterday

10
Slide from Abhay Shukla,
 A bit of history
The quest for truly 2D materials

Graphite, used in pencils MoS2, a well-know

because it’s lamellar lubricant in workshops,
(and it’s conductive!) because it’s lamellar

11
 A bit of history
The quest for truly 2D materials

12
 A bit of history
The quest for truly 2D materials
2004-2005: isolation by mechanical exfoliation yields high quality,
rather large, single layers!
→ the exploration of the physical properties could really start
then…

1 µm 1 µm

1 µm 1 µm

Geim, Novoselov & coworkers, Science

13
 A bit of history
The quest for truly 2D materials

14
 From Graphite to graphene

0.67 nm
 Our interest in Graphene
(from the point of view of an experimentalist phycisist)

2 exposed surfaces without any bulk

<<Naked & exposed >> 2D electron/hole gas
Mechanically stable, Atomically thin layer of macroscopic
lateral size
conductive layer with extremely high aspect ratio :
Thickness (0.5 nm) over width (0.1 m) > 109
– “Ultimate skin”
Can be manipulated, cleaned, etched, contacted using
(quasi)standard microelectronic processes.
 Carbon and Graphene
Carbon Graphene
Hexagonal lattice;
- 1 pz orbital at each site
- C
-
-
4 valence electrons

1 pz orbital

3 sp2 orbitals
 Carbon Atomic Orbitals
• Carbon is the 12th most abundant element
Abundance in atomic fraction in Earth's upper continental crust

• Average atomic weight 12.011 amu.

• Electronic configuration: 1s22s22p2

S. Thompson and J. Staley. Orbitals and Molecular Representation, Orbitals.pdf.

 Carbon: Hybridized Orbitals
• There are four valence electrons.
• The 2s and 2p can form hybridized orbitals.

S. Thompson and J. Staley. Orbitals and Molecular Representation, Orbitals.pdf.

 Organic Chemistry: p and σ bonds
• Two side-to-side 2pz orbitals form a p bond.
• Two co-axial 2p or sp orbitals form the σ bond.

McMurray and Fay. Chemistry 4th ed., Prentice-Hall, 2004.

Carbon: Hybridized Orbitals 2
Carbon: Hybridized Orbitals 2
Carbon: Hybridized Orbitals 2
 Hybridization sp 2

Crossover of sp2 gives strong σ bonds (mechanical stability) and p bonds (conductivity)

Electron cloud created by the overlaping p orbitals

Good electron mobility (aromaticity)
Limited reactivity (no dangling bonds)
Graphitic Forms:
Graphene, the mother of all sp2 carbon allotropes
2D

2004

Fullerenes C Nanotubes Graphite

«0D» « 1D » « 3D »

“The rise of graphene.” cond-mat/0702595

 Electronic states are governed by Quantum
confinement

Real space

k-space
Reciprocal space
2. Discovery of graphene
time line
seminal experiments
additional challenges
 Graphene stability
In the 1930s, Landau and Peierls (and Mermin, Mermin-Wagner theorem)
showed that thermodynamics prevented 2-d crystals in free state.

Thermodynamically stable? ???

In the 1930s, Landau and Peierls (and Mermin, later) showed
that thermodynamics prevented 2-d crystals in free state.
 Graphene stability
In the 1930s, Landau and Peierls (and Mermin, Mermin-Wagner theorem)
showed that thermodynamics prevented 2-d crystals in free state.

Landau: "The result obtained, strictly speaking,

means only that the fluctuational displacement
becomes infinite when the size (are) of the two-
dimensional system increases without limit (so that
the wave number may be arbitrarily small). But,
because of the slow (logarithmic) divergence of the
integral, the size of the film for which the
fluctuations are still small may be very great."
(section 137)
"Let us note first of all that, when T=0, a two-
dimensional lattice of any size could exist..."
(section 138).

Thermodynamically stable?
Ondulations and stress stabilize the structure
 A. Geim & K. Novoselov

Andre K. Geim and K.S. Novoselov

Nobel Prize of Physics 2010

U. Manchester (UK)
Chergonolovka (Russia)
 Mechanical Exfoliation of Graphite

Mechanical exfoliation of bulk Graphite / HOPG

« scotch tape technique » Optical microscopy AFM

STM

Defect free crystals randomly shaped and randomly positioned

Ishigami et al. Nanolett. 2007

Exfoliated Graphene flakes

zigzag edge

armchair edge
Epitaxial Graphene from silicon carbide
Graphitization of Silicon Carbide surface
by thermal annealing (vapor pressure of carbon is negligible compared to the one of
silicon)

Walt de Heer Group, Georgia Tech, Atlanta

No backgating, SiC is an expensive substrate

 CVD grown graphene on copper

DDintensity
Intensity G Intensity 2D Intensity
10μm

Image with standard CVD

Raman Intensity

4µm

A monolayer Single crystals

obtained with pulsed CVD: no
Z. Han, et al. Adv. Funct. Mater. 24, 964 (2014). multilayer patch
US Patent application, US 2013/887,424 , May 6, 2013
 CVD grown graphene on copper

rd d
da e
n Graphene ls Graphene
ta u
S P

50 µm 50 µm
SiO2 SiO2 Polycrystalline continuous film

Z. Han, et al. Adv. Funct. Mater. 24, 964 (2014).

US Patent application, US 2013/887,424 , May 6, 2013
 Why Multilayer bother us?

Pulsed CVD leads to high mobility purely

monolayered graphene

Z. Han, et al. Adv. Funct. Mater. 24, 964 (2014).

US Patent application, US 2013/887,424 , May 6, 2013
 Application of CVD graphene

Z. Han, et al. Adv. Funct. Mater. 24, 964 (2014).

US Patent application, US 2013/887,424 , May 6, 2013
 BATCH FABRICATION OF DEVICES
Plasma etching RIE O2, few seconds
Ti/Au
electrodes
Deep UV lithography 2 probes

Transport Measurements at 300K 𝜎 = 𝑒𝑛𝜇

Res

Mobility
2500 cm2/(V.s)
Res=

Ti/Au electrodes , 2 probes

Big trends in academics

44
 Mono-element 2D materials

• Silicene, Borophene
• Germanene, Phosphorene, Antimonene,
Stanene….
 Silicene (2D Si)

(change in z absciss)

G. LeLay Marseille U.
 Silicene (2D Si)

G. LeLay Marseille U.
Tao, Li, et al. "Silicene field-effect transistors operating
at room temperature." Nature nanotechnology 10.3
(2015): 227-231.

The carrier mobility was ∼100 cm2 V–1 s–1 for these initial devices. Conductivity 1 or 2 order
smaller than graphene.
Phosphorene (P@2D)
Black Phosphorus
 4. BEYOND
GRAPHENE
Boron nitride = « White graphene»
 hexagonal Boron Nitride (h-BN)
• Hexagonal lattice similar to Graphene
• Bernal stacking
• A,B sublattices respectively occupied
by B and N atoms
• 1.7 % lattice mismatch with respect to
Graphene
• 6 eV Gap, large breakdown voltage
• No dangling bonds,
• CHEMICALLY Inert
• high thermal conductivity.

Looks like the ideal substrate for Graphene !!!!

 On SiO2, the carrier mobility is limited by
scattering from charged surface states and
impurities , substrate surface roughness and
SiO2 surface optical phonons

NB: 300 K= 25 meV

Graphene physical Graphene@hBN
properties :
a substrate story

H. Arjmandi Tash et al, in preparation

C. Van Vo et al, APL 98, 181903 2011

Graphene@Iridium
AFM
 BN as a « buffer layer »
separating the graphene from the perturbating charges and
the roughness present at Silica surface

Dean, Cory R., et al. "Boron nitride substrates for high-quality graphene electronics." Nature
nanotechnology 5.10 (2010): 722-726.
Xue, Jiamin, et al. " Nature materials 10.4 (2011): 282-285.
 Flatter surface and no electron/hole puddles

Xue, Jiamin, et al. " Nature materials 10.4 (2011): 282-285.

Monolayers of Transition
metal dichalcogenides

Looks like h-BN view from the top

White balls
Green balls
Large Familly of materials
Various properties: insulator, semiconductor, semi-metal, metal, superconductor,
other quantum phase
Molybdenum Bisulfide 2H-MoS2
Thinning down TMDCs from Multi-Layers to
Monolayer: 2H-MoS2
Band Structure
10 ML 1 ML

From indiret band gap to direct band gap in

single layer: many more applications are
possible.

Li et al. J. Phys. Chem. C 2007, 111, 16192-16196

Thinning down TMDCs from Multi-Layers to
Monolayer: 2H-NbSe2

Decrease of the superconducting

transition while thinning down
Other electronic states in 2D
 Superconductivity in 2D: few-layers systems
2H-MoS2: Transition metal dichalcogenide and semi-conductor
The bulk indirect bandgap of 1.3 eV increases to a direct bandgap of 1.8 eV in single-layer
form. But by doping, superconductivity is induced.
Costanzo et al. Nature Nanotech. (2016)

Superconducting transition

Ye, J. T. et al. Science (2012).

Gate-induced superconductivity in atomically thin exfoliated crystals

Superconductivity in graphene with magic-angle
Cao et al., Nature Physics (2018): 2 papers

Twisted bi-layer graphene: equivalent of superlattices

In k-space: strong
effect on the
electronic bands.
Very flat bands at
magic angle

In real space: Moiré effect Strong concentration of electron density on AA stacking

zones: localisation effect (high effective mass)

Moiré Pattern -> Superlattice modulation (13nm)

Superconductivity in graphene with magic-angle
Cao et al., Nature Physics (2018): 2 papers

Twisted bi-layer graphene: superconductivity

Superconductivity in graphene with magic-angle
Cao et al., Nature Physics (2018): 2 papers

Twisted bi-layer graphene: Complex phase diagram

= Gating effect
Correlated insulating states at half-filling
Mott type Insulator (effect of Coulomb energy U and kinetic energy)
In situ electrical tunability of the charge carrier density : small change in carrier density -> rich
phase diagram.
Superconductivity in graphene with magic-angle
Cao et al., Nature Physics (2018): 2 papers

Twisted bi-layer graphene: Complex phase diagram

Phase diagram of cuprates

Similarity with bulk cuprates compounds: dome structure in phase diagram

Superconductivity appears near Mott insulating state (vs gate)

Magnetism in 2D
 Magnetism in 2D

ferromagnetism
Anti-
ferromagnetism

= magnetic field
Conclusion : Flatlands are new worlds to explore

• There is a lot to be done at 2D !

Possible transfer to everyday’s life

From ICFO’s website

81 — http://graphene.icfo.eu/2d-materials-applications/
 2D materials in Grenoble

Topics:
Synthesis, (nano)fabrication
Structural properties
Electronic properties
Optical properties
Magnetic properties

Tools:
Molecular beam epitaxy, chemical vapour deposition,
micro-transfers, lithography, diffraction, imaging,
spectroscopy, magnetometry, electronic transport, low
temperatures, high pressures, ab initio calculations,
model Hamiltonian calculations
Outline of the course

- Structure of 2D materials
- Phonons in 2D materials
- Electrons in 2D materials
- Growth of 2D materials