Graphene

Fundamentals and

Emergent Applications

Jamie H. Warner
Department of Materials

University

of Oxford

Oxford,

UK

Franziska Schaffel
Department of Materials
University of Oxford
Oxford, UK

Alicja Bachmatiuk
IFW Dresden
Helmholtzstrafte 20

Dresden, Germany

Mark H. Rummeli
IFW Dresden
Helmholtzstrafte 20

Dresden, Germany

AMSTERDAM

ELSEVIER

WALTHAM

NEW YORK

SAN FRANCISCO

HEIDELBERG

OXFORD

PARIS

SYDNEY

LONDON

SAN DIEGO

TOKYO

Contents

1.

Introduction

1.1.

About the book

References

2.

The Atomic Structure of

Graphene and

Its

Few-layer
5

Counterparts
2.1.
2.2.
2.3.

2.4.

Graphene
BHayer, Trilayer

Carbon Nanotubes

16

Introduction

2.4.2.

Boron Nitride Nanosheets

17

2.4.3.

Transition Metal

20

2.4.4.

Transition Metal Oxides

2.4.5.

Silicene

2.4.6.

Graphene Oxide and Reduced Graphene

Graphane and Fluorographene

Nanostructured

16

Dichalcogenides

23
25

2.5.2.

Lithography
Patterning Graphene
Sonochemical Cutting of Graphene

2.5.6.

28
32
33

Introduction

2.5.5.

Oxide

Graphene

2.5.1.

2.5.4.

33
via

34
40

Crystallographically Selective Structuring of Graphene

Through Anisotropic Etching
Graphene Nanoribbon Formation by 'Unzipping'

41

Carbon Nanotubes

45

Bottom-up

Fabrication of

Graphene

References

Nanostructures

47

49

Properties of Graphene
3.1.

12

2.4.1.

2.5.3.

3.

10

Few-layer Graphene

Relationship of Graphene to
Other Layered 2D Crystals

2.4.7.
2.5.

5
and

Electronic

61

Properties

3.1.1.

Introduction

3.1.2.

The Band Structure of

61

61

Graphene

62

vi

Contents

3.1.3.

in

Transport Experiments

Graphene

References
3.2.

Chemical Properties of Graphene

73

3.2.1.

Introduction

73

3.2.2.

Covalent Functionalisation of

3.2.3.

Noncovalent Functionalisation

Graphene

of
3.2.4.

Graphene
Summary

83
84

Electron Spin Properties of

Graphene

3.3.1.

Introduction

3.3.2.

Spin and Magnetism

Magnetism and Spin
Summary

3.3.3.
3.3.4.

in

Graphite

87

in

Graphene

88
95

97

The Mechanical

99

3.4.1.

99

3.4.2.

Properties of Graphene
Elastic Properties and Intrinsic Strength
Adhesion, Tearing and Cracking of Graphene

3.4.3.

The Role of Defects and Structural Modification

the Mechanical Properties

Graphene Derivatives
Graphene-based Composites
on

3.4.4.
3.4.5.

3.5.

104
110
111
114

3.5.1.

114

Properties of Graphene
Thermal Conductivity

125

129

Mechanical Exfoliation

129

4.1.1.

Introduction to Mechanical Exfoliation

129

4.1.2.

Micromechanical Exfoliation

130

4.1.3.

Mechanical

Cleavage

134

4.1.4.

Mechanical

Milling

4.1.5.

Summary

of

of

Graphite
Graphite

135

135

References
4.2.

103

The Thermal

Methods for Obtaining Graphene

4.1.

102

References

References

4.

86
86

References
3.4.

74

80

References
3.3.

64
71

136

Chemical Exfoliation

137

4.2.1.

Introduction

4.2.2.

Review of Chemical Exfoliation

138

4.2.3.

Different Types of

147

4.2.4.

Different Types of Solvents

148

4.2.5.

Different Types of Sonication

150

4.2.6.

How

to

to

Chemical Exfoliation

Characterise

Graphene
4.2.7.

Other 2D

4.2.8.

Summary

References

Graphite

137

Chemically Exfoliated
151

Crystals

153
153
154

GD

Contents

4.3.

Reduced Graphene Oxide

4.3.1.
Graphene Oxide

155
155

4.3.2.

Chemical Reduction of

4.3.3.

Heat Treatment of

4.3.4.

Electrochemical Reduction of

4.3.5.

Summary

Graphene

Graphene

Oxide

156

Oxide

159

Graphene

Oxide

160

References
4.4.

162
of

Bottom-up Synthesis

Graphene from Molecular

Precursors

163

4.4.1.

Introduction

163

4.4.2.

Solution-based approaches
Sol utilisation Strategies

163

4.4.3.
4.4.4.

Solvothermal

166

4.4.5.

Chemothermal-based Approaches

167

4.4.6.

Self-assembly

170

Synthesis
of

164

and sonication

Graphene

Oxide Nanosheets

References
4.5.

Chemical

171

Vapour Deposition Using Catalytic

Metals

introduction

173

4.5.2.

CVD Basics

173

4.5.3.

Substrate Selection

174

4.5.4.

Substrate Pretreatment

175

4.5.5.

Graphene

176

4.5.6.

Early

4.5.7.

The Role of

Over Ni and Cu

Growth

177

4.5.8.

Hydrogen in The CVD

Graphene-other Metals and Alloys

4.5.9.

Segregation

CVD

Reaction

routes

183
184
186

187

Synthesis of Graphene

Over Nonmetals

189

4.6.1.

Introduction

189

4.6.2.

Aspects

Consider with Nonmetal Catalysts

Non-metals as Catalysts for CVD-grown

190

Graphene

191

4.6.3.

to

4.6.4.

Metal-assisted Routes

4.6.5.

Non-metals

as

195
for Carbon Nanowall

Catalysts
graphene)

Fabrication (vertical
4.6.6.
4.6.7.

Nanowall

4.6.8.

Substrate-free PECVD
Sheets

4.6.9.

Graphene
on

or

196

Nanosheet

Synthesis
Synthesis of Graphene

197
198

Formation from Solid-carbon Sources

Surfaces

198

References

Epitaxial

195

The Basics of Plasma-Enhanced Chemical

Vapour Deposition

4.7.

173

4.5.1.

References
4.6.

159

201

Growth of

Graphene

on

SiC

204

4.7.1.

Introduction

204

4.7.2.

Reaction Protocol

205

4.7.3.

Nucleation and Growth

206

C viii")

Contents

4.7.4.

Epitaxial Graphene

4.7.5.

Face-to-Face Growth

4.7.6.

Laser-induced Growth of

4.7.7.

Epitaxial Graphene

4.7.8.

Graphene Growth by

the SiC (0001) Face

on

208

Epitaxial Graphene

the SiC (OOOT) Face

on

Molecular Beam

of SiC
4.7.9.

Epitaxy
212

ofSiOx

213

SiC/Metal

Hybrid

Systems for

Graphene

Formation

References
Transfer to

Introduction

4.8.2.

Transfer of

216
216

Mechanically Exfoliated Graphene

Arbitrary Substrates

4.8.3.

Transfer of CVD-grown Graphene

to Arbitrary Substrates

4.8.4.

Transfer of

Graphene

4.8.5.

Towards

Universal Transfer Route for

Grown

on

Grown

on

on

219

SiC

223

Graphene

Arbitrary Substrates

225

Summary

226

227

Characterisation Techniques

5.2.

229

Optical Microscopy

229

References

237

Raman
5.2.1.

Spectroscopy

238

Introduction

238

References
5.3.

Scanning

246

Electron

Microscopy

248

References
5.4.

253

Transmission Electron

Microscopy

5.4.1.

Introduction

5.4.2.

Atomic Resolution
Atomic Scale

254
254

Imaging (TEM/STEM) and

Spectroscopy (EELS)

5.4.3.

Surface Contamination

5.4.4.

Determining

256
259

the Number of

Layers Through
(Scanning) Transmission Electron Microscopy
Characterisation of Defects in Graphene

261

5.4.6.

Characterisation of

272

5.4.7.

In-situ

5.4.5.

Graphene Edges
Manipulation of Graphene in

TEM

References
5.5.

216

Metals

References

5.1.

213
214

Substrates

Arbitrary

4.8.1.

to

5.

210

212

4.7.11.

4.8.6.

209

Graphene Synthesis on Cubic SiC/Si Wafers

Graphene From the Carbothermal Reduction

4.7.10.

4.8.

207

265
276
277

Electron Diffraction

280

5.5.1.

Introduction

280

5.5.2.

Determining the
Diffraction

Number of

Layers Using Electron

281

GD

Contents

Determining the Graphene Topography

Determination of Stacking Order and Identification

5.5.3.

5.5.4.

of Rotational
5.5.5.

Low-energy

Stacking Faults

287

Electron Diffraction

292

References
5.6.

294

Scanning Tunnelling Microscopy

Introduction to Scanning Tunnelling Microscopy
5.6.1.
5.6.2.
STM Studies of Graphite
5.6.3.
STM of Graphene on Metals
5.6.4.

STM of

5.6.5.

Summary

Graphene

on

Insulators

AFM

as a

Graphene

Introduction

5.7.2.

Graphene

5.7.3.

AFM Studies

5.7.4.

AFM

as a

on

309
309

Different Surfaces
on

310

GO

Tool to

313

Investigate and Engineer Physical

Properties

313
319

Mobility

and Field-effect

Mobility

5.8.1.

Introduction to the Hall Effect

5.8.2.

Measurement of the Hall

321
321

Mobility

on

Graphene

Samples
5.8.3.

322

Measurement of the Field-effect

Graphene
Maximising Mobility
Summary

Mobility

in
5.8.4.
5.8.5.

325

326
331

References

6.

331

Applications of Graphene
6.1.

299

307

Tool for

5.7.1.

Hall

298

306

References
5.8.

296
296

304

References
5.7.

284

333

Electronic Devices

333

6.1.1.

Introduction

6.1.2.

Metal-Oxide-Semiconductor Field Effect Transistors

(MOSFETs)

333

6.1.3.

The

336

333

6.1.4.

Graphene MOSFET
Opening a Band Gap

6.1.5.

Strain

6.1.6.

Field Induced Band

Engineering

338

Band Gap
in

338
338

6.1.10.

Gap
Bilayer Graphene
Graphene Nanoribbons
Further Techniques
The Optimisation of Mobility
Deposition of a High-K Gate Dielectric and
Low-Resistance Metal Contacts

341

6.1.11.

The

6.1.7.
6.1.8.
6.1.9.

6.1.12.
6.1.13.

of

Viability
Graphene
Radio-Frequency (RF) Electronics
Novel Field Effect Transistor Designs
in CMOS

339
340
340

342

343
344

Contents

Gas Sensors

6.1.14.

Metrology

6.1.15.

6.2.

345

and the Definition of the Ohm

346

Spintronics

352

6.2.1.

Introduction

352

6.2.2.

352

6.2.3.

Magnetoresistance using Carbon Nanotubes

Magnetoresistance using Graphene

6.2.4.

Summary

365

References
6.3.

Transparent Conducting

366
380

Nanoelectromechanical

384

6.4.1.

384

6.4.2.

6.5.

Systems (NEMS) using Graphene

Actuation, Detection and Quality Factor of NEMS
Graphene Electromechanical Resonators

396

Freestanding Graphene Membrances

6.5.1.
Free-Standing Graphene as the Ultimate Microscope

397

Slide

Graphene

397

Template
by Electrons
Free-Standing Graphene
as a

for

Catalyst-Free Graphene

Fabrication
6.5.3.
6.5.4.

402
as a

Subnanometer

Trans-Electrode Membrane

405

Permeability of Free-Standing Graphene

406

References

407

6.6.2.
6.6.3.
6.6.4.
6.6.5.
6.6.6.

Graphene-Based
Graphene

Materials in Supercapacitors

in Electrochemical

Superstrong Graphene Composites

6.7.1.
Graphene-Based Composites
6.7.2.
Ex Situ Polymerisation
6.7.3.
In Situ Polymerization
References

409

Double-Layer

Capacitors (EDLCs)
Graphene-Based Pseudo Capacitors
Graphene-Based Materials in Lithium Ion
Graphene-Based Materials in Fuel Cells
Graphene-Based Materials in Solar Cells

References

Index

409

Graphene-Based Energy Application

6.6.1.

6.7.

386

References

6.5.2.

6.6.

357

365

Electrodes

References
6.4.

346

References

411
414

Batteries

416
418
419

421
425
425
427

434
435

439