Bloch

 theorem,  band  structure  and  graphene

Molecular and Materials Modelling (MMM)


HCI D4

Daniele Passerone
Empa, Swiss Federal Laboratories for Materials Science and Technology

Ueberlandstrasse 129, 8600 Dübendorf
daniele.passerone@empa.ch
 Outline

Bonding  in  solids  

Electrons  in  a  crystal  

Bloch  theorem  and  band  structure  

Tight  binding  

Carbon  allotropes  and  graphene  

Graphene  in  energy  applications  

Electronic  structure  of  graphene

Miller indexes
 Miller  indices

Atomic  Structure  and  Microstructure  of  Materials:  Lattice  Planes  and  Miller  Indices  

http://www.doitpoms.ac.uk/tlplib/miller_indices/lattice_index.php  

By  DoITPoMS,  Noel  Rutter,  Peter  Marchment,  released  under  CC  BY-­‐NC-­‐SA  2.0  license
 Credits

Kaxiras,  E.  Atomic  and  Electronic  Structure  of  Solids.  (Cambridge  University  Press:  Cambridge,  2003).

Reich,  S.,  Maultzsch,  J.,  Thomsen,  C.  &  Ordejón,  P.  Tight-­‐binding  description  of  
graphene.  Physical  Review  B  66,  035412  (2002).  

Bena,  C.  &  Montambaux,  G.  Remarks  on  the  tight-­‐binding  model  of  graphene.  
New  Journal  of  Physics  11,  095003  (2009).  

Liu,  J.,  Xue,  Y.,  Zhang,  M.  &  Dai,  L.  Graphene-­‐based  materials  for  energy  
applications.  MRS  Bulletin  37,  1265–1272  (2012).  

Wakabayashi,  K.,  Sasaki,  K.,  Nakanishi,  T.  &  Enoki,  T.  Electronic  states  of  
graphene  nanoribbons  and  analytical  solutions.  Science  And  Technology  Of  
Advanced  Materials  11,  54504  (2010).  

Novoselov,  K.  S.  et  al.  A  roadmap  for  graphene.  Nature  490,  192–200  (2012).

Roman  Fasel,  Pascal  RufOieux,  Oliver  Gröning,  Jinming  Cai  (Empa/nanotech@surfaces  Lab)  -­‐  Carlo  A.  Pignedoli,  Leopold  Talirz,  Stephan  Blankenburg  (Empa/  nanoteh@surfaces  Theory)
 From  free  atoms...  to  band  structure

From  isolated  carbon  atoms  to  diamond:  creation  of  energy  “bands”  from  energy  levels

Electrons  Oill  the  available  bands  from  the  bottom  

up  to  a  certain  level  called  Fermi  energy.  

in  a  metal  there  is  a  partially  eilled  band  and  there  

are  always  empty  states  available  for  conductivity  

a  semiconductor  or  insulator  can  conduct  only  if  

electrons  are  excited  from  the  valence  band  (eilled)  to  
the  conduction  band  (empty)  through  the  forbidden  
band  gap  (Eg)
Electrons  in  solids

AN  ELECTRON  “IS”  A  WAVE  

(Image:  J.  Trail  -­‐  Cambridge) 7
• A  FREE  ELECTRON  IS  A  PLANE  WAVE  WITH  PARABOLIC  
DISPERSION  

• AN  ELECTRON  IN  A  BOX  HAS  DISCRETE  LEVELS


(k  ~  wavenumber  ~  velocity  ~  momentum)  

• AN  ELECTRON  IN  THE  CRYSTAL  FEELS  THE  POTENTIAL  OF  

EMPTY
THE  ATOMS

FILLED
8
 Crystalline  solids  and  valence  electrons
8 1 Atomic structure of crystals 1.1 Building crystals from atoms 9

I-A II-A III--A IV--A V--A VI--A VII--A Noble

s1 s2 s2p 1 s2p 2 s2p 3 s2p 4 s2p 5 s2p 6
Li 3
Be 4 symbol Li 3 atomic number
B 5
C 6
N 7
O 8
F 9
Ne 10
Lithium Beryllium name Lithium
o
Boron Carbon Nitrogen Oxygen Fluorine Neon
BCC 1.23 HCP 0.90 crystal structure BCC 1.23 covalent radius (A) TET 0.82 GRA 0.77 HCP 0.70 CUB 0.66 MCL 0.64 FCC
39.08 134.4 melting point 39.08 (meV) 202.3 338.1 28.98 28.24 28.14 25.64
4.70 12.1 atomic concentration 4.70 (1022 cm-3 ) 13.0 17.6 4.36
9.4 3.3 resistivity 9.4 (µΩ cm) 4M 1.4 G
Na 11
Mg 12 Al 13
Si 14 15
P 16 17
S 18
Cl Ar
Sodium Magnesium Aluminum Silicon Phosphorus Sulfur Chlorine Argon
BCC 1.54 HCP 1.36 FCC 1.18 DIA 1.17 CUB 1.10 ORC 1.04 ORC 0.99 FCC
8.42 79.54 80.44 145.4 59.38 33.45 38.37 30.76
2.65 4.30 III-B IV-B V-B VI-B VII-B VIII VIII VIII I-B II-B 6.02 5.00 2.66
4.75 4.46 s2d 1 s2d 2 s2d 3 s2d 4 s2d 5 s2d 6 s2d 7 s2d 8 s2d 9 s d 2.67
2 10 230 G
K 19
Ca
20
Sc 21
Ti 22
V 23
Cr* 24
Mn 25
Fe 26
Co 27 Ni 28 Cu* 29 Zn 30 Ga31 Ge 32 33 As 34 35Se 36 Br Kr
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
BCC 2.03 FCC 1.74 HCP 1.44 HCP 1.32 BCC 1.22 BCC 1.18 CUB 1.17 BCC 1.17 HCP 1.16 FCC 1.15 FCC 1.17 HCP 1.25 ORC 1.26 DIA 1.22 RHL 1.21 HCP 1.17 ORC 1.14 FCC
28.98 96.09 156.3 167.3 188.1 187.9 130.9 156.1 152.4 148.9 116.9 59.68 26.09 104.3 93.93 42.23 46.45 33.57
1.40 2.30 4.27 5.66 7.22 8.33 8.18 8.50 8.97 9.14 8.45 6.55 5.10 4.42 4.65 3.67 2.36 2.17
21.6 3.7 51 47.8 24.8 12.9 139 9.71 6.34 6.84 1.67 5.92 47 M 12 M

Rb 37 Sr 38
Y 39 Zr 40 Nb* 41 Mo* 42 Tc 43 Ru* 44 Rh* 45 Pd** Ag*
46 47
Cd 48
In
49
Sn 50
Sb 51 52
Te 53
I
54
Xe
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
BCC 2.16 FCC 1.91 HCP 1.62 HCP 1.45 BCC 1.34 BCC 1.30 HCP 1.28 HCP 1.25 FCC 1.25 FCC 1.28 FCC 1.34 HCP 1.48 TET 1.44 TET 1.40 RHL 1.41 HCP 1.37 ORC 1.33 FCC
26.89 96.49 154.7 183.4 237.0 249.6 234.2 224.7 192.9 157.5 106.4 51.19 37.02 43.53 77.88 62.26 56.88 37.43
1.15 1.78 3.02 4.29 5.56 6.42 7.04 7.36 7.26 6.80 5.85 4.64 3.83 2.91 3.31 2.94 2.36 1.64
12.1 22.8 60 41.4 15.2 5.17 14 7.2 4.5 9.93 1.63 6.83 8.37 11 39 160 k

Cs 55 Ba 56 La 57 Ha 72 Ta 73 W 74 Re 75 Os 76 Ir 77 Pt** 78 Au* 79 Hg 80 Tl 81 Pb 82 Bi 83 Po 84 85At 86 Rn

Cesium Barium Lanthanum Hafnium Tantalum Wolframium Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Pollonium Astatine Radon

BCC 2.35 BCC 1.98 HCP 1.69 HCP 1.44 BCC 1.34 BCC 1.30 HCP 1.28 HCP 1.26 FCC 1.27 FCC 1.30 FCC 1.34 RHL 1.49 HCP 1.48 FCC 1.47 RHL 1.34
25.97 86.18 102.8 215.4 281.7 317.4 297.6 285.9 234.7 175.9 115.2 20.18 49.68 51.75 46.91
0.91 1.60 2.70 4.52 5.55 6.30 6.80 7.14 7.06 6.62 5.90 4.26 3.50 3.30 2.82
20 50 80 35.1 13.5 5.6 19.3 8.1 5.1 9.85 2.12 96 18 20.6 107

f 2d 0s2 f 3d 0s2 f 4d 0s2 f 5d 0s2 f 6d 0s2 f 7d 0s2 f 7d 1s2 f 8d 1s2 f 10d 0s2 f 11d 0s2 f 12d 0s2 f 13d 0s2 f 14d 0s2 f 14d 1s2
Ce 58 Pr 59
Nd 60 Pm 61 Sm 62 Eu 63 Gd 64 Tb 65 Dy 66 Ho 67 Er 68 Tm 69 Yb 70
Lu 71
Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium

FCC 1.65 HCP 1.65 HCP 1.64 RHL 1.62 BCC 1.85 HCP 1.61 HCP 1.59 HCP 1.59 HCP 1.58 HCP 1.57 HCP 1.56 FCC HCP 1.56
92.3 103.8 110.6 115.9 94.4 136.6 140.7 144.8 150.2 154.7 156.7 94.5 166.2
2.91 2.92 2.93 3.03 3.04 3.02 3.22 3.17 3.22 3.26 3.32 3.02 3.39
85.4 68.0 64.3 105.0 91.0 131.0 114.5 92.6 81.4 86.0 67.6 25.1 58.2

TheE.particular crystal
Kaxiras, Atomic and structure that noble-element
Electronic Structure atoms
of Solids (Cambridge assumePress,
University in solid is form weakly bonded solids in the FCC structure, in which the attractive interactions
form2003).
Cambridge,
called face-centered cubic (FCC). Each atom has 12 equidistant nearest neighbors are optimized by maximizing the number of nearest neighbors in a close packing
in this structure, which is shown in Fig. 1.2. arrangement. The only exception to this rule is He, in which the attractive interaction
Thus, in the simplest case, atoms that have no valence electrons at all behave like between atoms is so weak that it is overwhelmed by the zero-point motion of the
hard spheres which attract each other with weak forces, but are not deformed. They atoms. Unless we apply external pressure to enhance this attractive interaction,
 sp2  hybridization  and  covalent  bonding
The  possibility  of  combining  atomic  orbitals  to  form  covalent  bonds  in  a  crystal  is  well  illustrated  by  the  two-­‐dimensional  sp2  
example.
p p
A 1 A 2 A B 1 B 2 B
1 = p s + p px 1 = p s + p px
3 3 3 3
1 A 1 1 A B 1 B 1 1 B
A
2 = p s p pAx + p py 2 = p s p pBx + p py
3 6 2 3 6 2
1 1 1 B 1 B 1 1
A
3 = p s
A
p pAx p pAy 3 = p s p pBx p pB y
3 6 2 3 6 2
A A B B
4 = pz 4 = pz

• The  eirst  three  hybrid  orbitals  build  up  the  bonded  network,  the  last  pz  orbitals,  perpendicular  to  the  graphite  plane,  or  to  the  fullerene  surface,  can  form  bonding  or  
antibonding  combinations  with  neighboring  atoms.
Electrons  in  a  periodic  potential
 Electrons  in  crystal  potential

A  crystal  is  described  in  real  space  in  terms  of  the  primitive  lattice  vectors  a1,  
a2  and  a3  and  the  positions  of  atoms  inside  a  primitive  unit  cell  (PUC).  

R = n1 a1 + n2 a2 + n3 a3
The  lattice  vectors  connect  all  equivalent  points  in  space  (Bravais  lattice).  The  
PUC  is  deeined  as  the  volume  enclosed  by  the  three  primitive  lattice  vectors:

P UC = |a1 · a2 a3 |
We  only  need  to  know  all  relevant  real-­‐space  function  for  r  within  the  PUC  
since,  due  to  the  periodicity  of  the  crystal,  these  functions  have  the  same  
value  at  an  equivalent  point  of  any  other  unit  cell  related  to  the  PUC  by  a  
translation  R.    
Reciprocal  lattice  is  the  inverse  space  of  the  real  lattice.  The  reciprocal  
primitive  lattice  vectors  are  deeined  by:

2 (a2 a3 ) 2 (a3 a1 ) 2 (a1 a2 )

b1 = , b2 = , b3 =
a1 · (a2 a3 ) a1 · (a2 a3 ) a1 · (a2 a3 )
with  the  consequence  that

ai · bj = 2⇡
(2⇡)3
ij b1 · (b2 b3 ) =
P UC
 Electrons  in  crystal  potential  -­‐  2
We  can  construct  vectors  connecting  all  equivalent  points  in  reciprocal  space,  which  we  call  G  in  analogy  to  the  Bravais  lattice  
vectors:
G = m1 b1 + m2 b2 + m3 b3 , m1 , m2 , m3 : integers

Now,  this  gives  the  important  consequence  that  

R · G = 2 l, l = n1 m1 + n2 m2 + n3 m3 eiG·R = 1
for  all  G  and  R.  At  this  point,  we  can  write  any  function  with  the  periodicity  of  the  Bravais  lattice  as  
X
f (r) = eiG·r f (G)
G

We  are  ready  to  introduce  BLOCH’s  THEOREM:  

when  the  potential  in  the  single-­‐particle  hamiltonian  has  the  translational  periodicity  of  the  Bravais  lattice:

V sp (r + R) = V sp (r)

then  the  single-­‐particle  wavefunctions  have  the  same  symmetry,  up  to  a  phase  factor:

k (r + R) = eik·R k (r)

or,  equivalently:

k (r) = eik·r uk (r), uk (r + R) = uk (r)

 Born-­‐von  Karman  boundary  conditions
Inserting  the  wavefunction  in  the  Bloch  form  into  the  single-­‐particle  Schrödinger  equation  leads  to  an  equation  for  the  uk  
function:
" ✓ ◆2 #
1 ~rr
+ ~k + V sp (r) uk (r) = k uk (r)
2me i

We  now  consider  the  crystal  as  composed  by  Nj  unit  cells  in  each  direction,  with  the  number  macroscopically  large,  and  
assuming  periodic  boundary  conditions.  Then  the  number  of  distinct  values  that  k  may  take  is  N=N1N2N3

k (r) = k (r + N j aj )
nj
k = 1 b 1 + 2 b 2 + 3 b 3 ek·(Nj aj ) = 1 ) j = , nj any integer.
Nj
Nj Nj
nj = , . . . , 0, . . . , 1 (j = 1, 2, 3)
2 2

restrict  the  inequivalent  values  of  k  to  a  volume  in   1.  BZ

reciprocal  space:  THE  FIRST  BRILLOUIN  ZONE,  which  can  
be  shown  to  be  limited  by  planes  that  reelect  incident  
radiation  constructively.
Bragg  planes
 The  inequivalent  values  of  k  are  restricted  to  a  volume  in  reciprocal  space,  
known  as  the  eirst  Brillouin  Zone  (BZ).    

BRAGG  PLANES So  we  have  Nj  consecutive  values  of  the  index  nj.

Consider  now  a  plane  wave  of  incident  radiation  and  wave-­‐vector  q,  
scattered  by  the  planes  of  atoms  to  a  wave-­‐vector  q’.  

For  elastic  scattering,  |q|=|q’|.    

For  constructive  interference,  the  difference  between  the  incident  and  

reelected  bath  must  be  equal  to  lλ  (λ  wavelength).  So,  recalling  that  d=R  
(distance  between  equivalente  lattice  planes),  and  G∙R=2πl:

Squaring  both  sides,  and  recalling  that  it  is  elastic  scattering:

This  is  the  deeinition  of  the  Bragg  plane:  formed  by  the  tips  of  all  vectors  q  that  satisfy  the  above  equation  for  a  
given  G.  Varying  q,  we  can  identify  all  families  of  such  planes  (constructive  interference).  From  all  the  G  we  can  
then  eind  all  R,  and  thus  the  structure  of  the  crystal  (Bravais  lattice).
 BRAGG  PLANES  and  BRILLOUIN  ZONES

The  projection  of  q  on  G  is  equal  to  half  the  length  of  G  .    

This  allows  to  deOine  the  Oirst  BZ:  the  volume  enclosed  by  the  Oirst  set  of  Bragg  planes  around  the  origin  is  the  Oirst  BZ  

But  values  of  k  are  equivalent  if  one  adds  to  them  any  vector  G.  So  we  need  to  solve  the  DFT  equations  for  values  of  k  
within  the  Oirst  BZ  (or  any  single  BZ).  
 Band  structure

The  values  of  k  are  equivalent  if  one  adds  to  them  any  vector  G,  and  it  can  be  shown  that  the  eigenvalues  at  equivalent  k  points  
are  equal.  This  leads  to  two  possible  representation  for  a  band  structure.

FILLED BAND

Within  any  single  BZ  and  for  the  same  value  of  k  there  may  be  several  solutions  of  the  single-­‐particle  equation:  various  allowed  
states.  So  we  have  a  “band  index”  labelling  the  solution  at  growing  energies.  

In  the  free  electron  case,  and  with  2  electrons  per  primitive  unit  cell,  the  electrons  will  eill  all  the  eirst  band  (Fermi  level)    

In  a  weak  periodic  potential  (right),  the  electron  will  eill  until  the  Fermi  level),  and  there  is    eirst  gap  (2V2)  which  is  referred  as  
“band  gap”.
Density  of  states
Examples  of  density  of  states:
 The  tight  binding  method
Bloch’s  theorem  can  be  easily  exploited  through  an  approximation  that  starts  from  atom-­‐centered  wavefunctions  very  similar  
to  atomic  states.  The  potential  CLOSE  to  the  atoms  is  similar  as  in  the  gas  phase...


We  start  from  a  set  of  atomic  wavefunctions   l (r ti )



then  we  construct  states  that  obey  Bloch’s  theorem,  

1 X ik·R0
⇥kli (r) = p e l (r ti R)

 N R0



 kli (r + R) = eik·R kli (r)

 (n)
X (n)
and    we  seek  the  solution  of  the  band  problem  among  the  linear  combinations  of  such  states. ⇥k (r) = ckli kli (r)
l,i
Substitution  in  the  single-­‐particle  equation  delivers  a  “secular  equation”  which  can  be  solved  leading  to  energy  eigenvalues  and  
wavefunction  coefeicients.  At  each  k-­‐point,  we  expect  as  many  solution  as  the  product  of  the  number  of  atoms  in  the  PUC  by  the  
number  of  orbitals  associated  to  each  type  of  atom.

(n) (n) (n)

Xh (n)
i
(n)
sp sp
H ⇤k (r) = k ⇤k ⇥ ⇤⇥kmj |H | ⇥kli ⌅ k ⇤⇥kmj | ⇥kli ⌅ ckli = 0
l,i
The  following  integrals  need  to  be  determined:
X
⇥ kmj | kli ⇤ = eik·R ⇥ m (r tj ) | l (r ti R)⇤
R
X
⇥ kmj |Hsp | kli ⇤ = eik·R ⇥ m (r tj ) |Hsp | l (r ti R)⇤
R
 Tight  binding  (2)
Overlap  integrals  approximation:

⇥ m (r tj ) | l (r ti R)⇤ = lm ij (R)
⇥ m (r tj ) |Hsp | l (r ti R)⇤ = lm ij (R)✏l
⇥ m (r tj ) |Hsp | l (r ti R)⇤ = ((tj ti R) dnn )Vlm,ij

Example:  a  linear  chain  with  s-­‐orbitals

1
X
⇥kl (x) = eikna l (x na)
n= 1

The  eigure  shows  the  crystal  wavefunctions  (Bloch)  for  

different  values  of  k.  The  atomic  orbital  is  modulated  by  
a  phase  factor  calculated  at  the  atomic  site  x=na.  
 Linear  chain  with  s-­‐orbitals
Overlap  integrals  and  wavefunction:

Orthogonality ⇥⇥l (x)|⇥l (x na)⇤ = n0

Interaction  between  nearest  

neighbors
⇥⇤l (x)|Hsp |⇤l (x na)⇤ = ⇥l n0 + tl n±1

DIFFERENT  VALUES  OF  K  

CORRESPOND  TO  DIFFERENT  
⇥k (x) = ck kl (x) CRYSTAL  MOMENTUM  FOR  THE  
ELECTRON

The  secular  equation  is  one-­‐dimensional  and  easily  leads  to  the  dispersion  relation  

[⇤⇤kl (x)|Hsp |⇤kl (x)⌅ ⇥k ⇤⇤kl (x)|⇤kl (x)⌅]ck = 0

X X
ikna
⇥ e [⇥l n0 + tl n±1 ] = ⇥k eikna n0
n n

1D chain: k = l + 2tl cos(ka)

Z
⇤ sp
ts ⇥ s (x)H (x) s (x a)dx < 0
Graphene  and  its  applications

24
sp2-­‐like  hybridized  carbon  nanostructures

M.  Terrones  et  al.,  Nano  Today  (2010),  doi:10.1016/j.nantod.2010.06.010  

What  is  graphene?

• A  monolayer  of  carbon  atoms  packed  into  a  two-­‐

dimensional  (2D)  honeycomb  crystal  structure  
• Linear  dispersion,  as  described  by  Dirac  cone  
• Charge  carriers  behave  like  relativistic  particles  
described  by  the  Dirac  equation  for  spin  1/2  
particles

(massless  Dirac  fermions)  
• High  charge  carrier  velocity  of  106  m/s  
• Graphene  is  a  zero  band  gap  semiconductor
 Properties  of  graphene

• Electron  mobility  at  room  T:  15000  cm2V-­‐1s-­‐1  -­‐  at  low  T:  200000  
cm2V-­‐1s-­‐1

(Si:  1400  cm2V-­‐1s-­‐1)


• White  light  absorbance:  2.3%


• Thermal  conductivity:  (5.30±0.48)  ×  103  W·m−1·K−1


• Tensile  modulus  1TPa  (100  x  normal  steel  of  “same  thickness”)

27
 Graphene  in  solar  cells

Polymer  solar  cells  are  based  on  photon  absorption  by  

conjugated  polymers  at  room  temperature  creating  
bound  electron-­‐hole  pairs  called  excitons  

Charge  generation  requires  dissociation  of  the  excitons,  

a  process  favorable  at  the  interface  between  
semiconducting  materials  with  different  ionization  
potentials  and  electron  afOinities  (donors  and  
acceptors)  

Polymer  solar  cells  often  require  an  electron-­‐extraction  

layer  between  catode  and  active  layer  and  a  hole-­‐
extraction  layer  between  the  anode  and  the  active  layer  
Figure  from:  J.  Liu,  Y.  Xue,  M.  Zhang,  and  L.  Dai,  MRS  Bulletin  37,  
1265  (2012).   C60-­‐grafted  graphene  nanosheets  has  been  used  as  
electron  acceptor  and  can  improve  substantially  the  
[32]1.  Liu,  J.  et  al.  Advanced  materials  (DeerSield  Beach,  Fla.)  24,  
2228–33  (2012).   measured  density

[35]  D.  Yu,  K.  Park,  M.  Durstock,  and  L.  Dai,  The  Journal  of  Physical  


Chemistry  Letters  26,  1113  (2011). 

C60:  very  good  electron  acceptor

graphene:  very  good  charge  transport
Graphene  fabrication  and  applications
Novoselov,  K.  S.  et  al.  A  roadmap  for  graphene.  Nature  490,  192–200  (2012).

Figure from: R. S. Edwards and K. S. Coleman, Nanoscale 5, 38 (2013).

GRAPHENE                  GRAPHENE  OXIDE        REDUCED  GRAPHENE  OXIDE

Figure from: Erickson,  K.  et  al.  Determination  of  the  Local  Chemical  
Structure  of  Graphene  Oxide  and  Reduced  Graphene  Oxide.  
Advanced  Materials  22,  4467–4472  (2010).
 Energy  storage:  the  example  of  supercapacitors

Supercapacitors  are  electrochemical  devices  that  can  store  energy  and  release  it  with  high  power  capability    

Perfect  complement  for  batteries  or  fuel  cells  in  various  applications  

Electrostatic  charge  accumulation  on  the  electrode-­‐electrolyte  interface  (electric  double  layer  capacitance)  

The  electric  double-­‐layer  capacitance  is  proportional  to  the  effective  specieic  surface  area  of  an  electrode  material.  

GRAPHENE  HAS  A  THEORETICAL  SPECIFIC  SURFACE  AREA  OF  2.63  x  106  m2/kg  

Novoselov,  K.  S.  et  al.  A  roadmap  for  graphene.  

Nature  490,  192–200  (2012).

In a supercapacitor device two high-surface-area graphene-based electrodes (blue and purple hexagonal planes) are separated by a membrane (yellow).
 Best  reported  capacitance  performance  for  all  bulk  carbon  materials
Specieic  capacitance:  231  F/g  

Energy  density:  98Wh/kg  

Specieic  surface  area:  3523  m2/g  (according  to  3D  model)  

Synthesis Proposed  3D  structure

Zhang,  L.  et  al.  Porous  3D  graphene-­‐based  bulk  materials  with  exceptional  high  surface  area  and  excellent  conductivity  for  supercapacitors.  
ScientiSic  reports  3,  1408  (2013).
 The  case  of  graphene:  pz-­‐nearest  neighbor  tight  binding  on  a  A-­‐B  lattice

1 X ik·Rj
⇥kpz S (r) = p e pz (r tS Rj ) S = A, B
N j

The  solution  is  chosen  as  linear  combination  of  Bloch  functions:

⇥k (r) = cA (k) kpz A (r) + cB (k) kpz B (r)

The  Hamiltonian  is  written  by  only  assuming  hopping  between  eirst  neighbor,  and  setting  on-­‐site  energies  to  zero:
X
sp
H = t | A ⇤⇥ B | + h.c.
<i,j>

Two  atoms  in  the  unit  cell  correspond  to  two  secular  equations:

(k)cA (k) = t e ik·a1

+e ik·a2
+ 1 cB (k),
(k)cB (k) = t eik·a1 + eik·a2 + 1 cA (k).

The  diagonalization  of  the  corresponding  off-­‐diagonal  matrix  leads  to  the  expression  for  the  eigenvalues:

q
(k) = ±t 3 + 2 cos( 3kx a) + 4 cos( 3kx a/2) cos( 3ky a/2)
 Graphene  energy  bands
q
(k) = ±t 3 + 2 cos( 3kx a) + 4 cos( 3kx a/2) cos( 3ky a/2)

The  ab  initio  result  is  best  matched  with  t=2.7  eV.  This  leads  to  a  Fermi  velocity  at  K  
of  about  106  m/s.  

Graphene  is  a  zero-­‐gap  semiconductor  

Graphite  is  a  semimetal  (overlap  between  valence  and  conduction  band)

The  model  can  be  improved  by  

including  next  nearest  neighbor  
interactions  (here  shown  for  the  
case  of  a  (10,10)  nanotube)