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ÌâÄ¿£ºScience  and  technology  roadmap  for  graphene,  related  two-dimensional  crystals,  and hybrid systems

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In  this  document  we  provide  an  overview  of  the  key  aspects  of  graphene  and  related materials (GRMs), ranging from fundamental research challenges to a variety of applications in a large number of sectors, highlithing the steps necessary to take GRMs from a state of raw potential to a point where they might revolutionize multiple industries.

Contents
Science and technology roadmap for graphene, related two-dimensional
crystals, and hybrid systems ........................................................................... 1
Abstract ............................................................................................................. 2
1.  Introduction ...............................................................................16
1.1 Graphene-based disruptive technologies: overview ............................. 18
1.1.1  Opportunities ..................................................................................................... 20
1.2 Scientific Output ...................................................................................... 25
1.2.1 Intellectual property landscape analysis ................................................................ 26
1.2.2 Graphene IP Landscape analysis ........................................................................... 27
2. Fundamental research ..................................................................31
2.1 Electronic transport ................................................................................................... 33
2.2 Spectroscopic characterization .................................................................................. 35
2.3 Magnetism and spin transport................................................................................... 37
2.4 Polycrystalline graphene ........................................................................................... 38
2.5 Thermal and mechanical properties of graphene .................................................... 39
2.6 Artificial graphene structures in condensed-matter systems ................................... 40
2.6.1 Honeycomb lattices in semiconductors .................................................................. 41
2.6.2 Honeycomb lattices with cold atoms ...................................................................... 43
2.7  Atomic scale technology in graphene and patterned graphene ....... 45
2.7.1 Graphene nanoribbons ........................................................................................... 46
2.7.2 Graphene quantum dots ......................................................................................... 49
2.7.3 Patterning- and proximity-induced properties in graphene.................................. 49
2.8  2d crystals beyond graphene ............................................................... 50
2.8.1 Characterisation of new 2d crystals ....................................................................... 51
2.8.2 Modelling of physical properties of new 2d crystals .............................................. 53
2.9   Hybrids of graphene and other 2d crystals........................................ 53
2.9.1 Electronic transport in lateral and vertical hybrid superstructures ..................... 54
2.9.1.1 Tunnelling and resonant tunnelling devices ...................................................... 54
2.9.1.2 Light emission and photovoltaics ........................................................................ 56
2.9.1.3 In situ characterization methods ......................................................................... 57
2.9.1.4 Hybrid structures for active plasmonics ............................................................. 58
2.10 Multiscale modelling of graphene-based structures and new 2d
crystals ............................................................................................................ 58
2.10.1 Ab-initio computations ......................................................................................... 59
2.10.2 Mesoscale modelling ............................................................................................. 62
2.10.3 High Performance Computing ............................................................................. 63
2.10.4 Further development of field-theory and kinetic theory methods ...................... 64
2.10.5 Correlations in multiple graphene layers ............................................................ 64
2.11 Graphene for high-end instrumentation ............................................. 65
2.11.1 Graphene for high energy physics instrumentation, Tokamaks and Stellarators
.......................................................................................................................................... 65
2.11.2 Graphene for Metrology ....................................................................................... 65
2.12 Perspectives ............................................................................................ 66
3. Health and environment ...............................................................68
3.1 In vitro impact .......................................................................................... 69
3.2 Cytotoxicity effects on graphene-coated surfaces ................................. 70
3.3 In vivo impact, biodistribution and pharmacokinetics ........................ 71
3.4 Bacterial toxicity ...................................................................................... 73
3.5 Biodegradation ......................................................................................... 74
3.6 Environmental impact ............................................................................. 74
3.7 2d crystals and hybrids ........................................................................... 75
3.8 Perspective ................................................................................................ 75
4. Production ......................................................................................78
4.1 Graphene production .............................................................................. 80
4.1.1 Dry exfoliation ........................................................................................................ 80
4.1.2 Liquid Phase exfoliation......................................................................................... 82
4.2 Growth on SiC .......................................................................................... 91
4.3 Growth on metals by precipitation ........................................................ 94
4.4 Chemical Vapour Deposition .................................................................. 96
4.4.1 Thermal CVD on metals ......................................................................................... 96
4.4.2 CVD on semiconductors and insulators .............................................................. 100
4.4.3 Plasma enhanced CVD ......................................................................................... 101
4.5 Molecular Beam Epitaxy growth of graphene on insulating surfaces
........................................................................................................................ 102
4.6 Atomic Layer Epitaxy ........................................................................... 103
4.7 Heat-driven conversion of amorphous carbon and other carbon
sources ........................................................................................................... 103
4.8 Chemical synthesis ................................................................................. 104
4.9 Nano-ribbons and quantum dots .......................................................... 105
4.10 Transfer and placement ...................................................................... 107
4.10.1 Transfer, placement and shaping....................................................................... 107
4.10.2 Graphene membranes ......................................................................................... 107
4.10.3 Transfer of individual layers .............................................................................. 108
4.10.4 Wet transfer of exfoliated flakes ........................................................................ 108
4.10.5 Dry transfer of exfoliated flakes ......................................................................... 110
4.10.6 Transfer of graphene grown on metals.............................................................. 111
4.10.7 Di-electrophoresis ............................................................................................... 111
4.10.8 Applications and processing of graphene inks .................................................. 112
4.11 Contamination and cleaning ............................................................... 113
4.11.1 Cleaning of graphene produced by MC ............................................................. 113
4.11.2 Cleaning after transfer ....................................................................................... 114
4.11.3 Removal of solvents/surfactants in LPE graphene ........................................... 114
4.12 Inorganic layered compounds ............................................................ 115
4.12.1. Mechanical cleavage ......................................................................................... 115
4.12.2 Laser ablation ..................................................................................................... 115
4.12.3 Liquid phase exfoliation ..................................................................................... 115
4.12.4 Synthesis by thin film techniques ....................................................................... 116
4.13 Graphene and other 2d crystal hybrids ............................................. 117
4.13.1 CVD growth of heterostructures ........................................................................ 118
4.13.2 Mechanical transfer............................................................................................ 118
4.13.3 Heterostructures from dispersions and inks ...................................................... 119
4.13.4 Bonding using polymers ..................................................................................... 119
4.14  Silicene, germanene, phosphorene, MXene and other graphenelike
systems .......................................................................................................... 120
4.14.1 Chemical modification of 2d crystals ................................................................. 121
4.15 Outlook and future challenges ............................................................ 122
5. Electronic devices ....................................................................... 124
5.1 Opening a band-gap in graphene ......................................................... 124
5.2 Graphene-based microelectronics and nanoelectronics ..................... 126
5.2.1 Transistor count in graphene circuits .................................................................. 130
5.3.1 Digital Logic Gates ............................................................................................... 131
5.2.2 Digital Non-volatile Memories ............................................................................. 133
5.2.3 Interconnects in Integrated Circuits .................................................................... 135
5.3 High frequency electronics .................................................................... 135
5.3.1 Analogue Voltage Amplifiers ............................................................................... 137
5.3.2 Graphene ring oscillators ..................................................................................... 139
5.4 Layered materials-based devices .......................................................... 141
5.5 Novel vertical and planar transistors and devices .............................. 143
5.5.1 Vertical tunnelling transistors and vertical hot electron transistors .................. 143
5.5.2 In-plane transport in 2d heterostructures ............................................................ 145
5.6 Electron emission ................................................................................... 147
6. Spintronics ................................................................................... 149
6.1 Graphene spintronics ............................................................................ 149
6.2 Spin injection in Graphene ................................................................... 150
6.3 Graphene spintronic devices for sensing ............................................. 152
6.4 Graphene spin gating............................................................................. 152
6.5 Graphene qubits ..................................................................................... 153
6.6 Spintronics using other 2d crystals and heterostructures ................. 154
6.7 Theory and Quantum Simulation ........................................................ 154
6.8 Outlook .................................................................................................... 155
7. Photonics and Optoelectronics .................................................. 156
7.1   Graphene saturable absorbers and related devices ........................ 161
7.1.1 2d crystals-based saturable absorbers .................................................................. 163
7.1.2 Output power/pulse energy ................................................................................... 164
7.1.3 Spectral coverage .................................................................................................. 165
7.1.4 Pulse width ............................................................................................................ 165
7.1.5 Repetition rate ....................................................................................................... 165
7.1.6 Other considerations ............................................................................................. 166
7.2 Photodetectors ........................................................................................ 166
7.2.1 Figures of merit .................................................................................................... 167
7.2.2 Physical mechanisms enabling photodetection ................................................... 168
7.2.3 Photoelectrical response in different devices ....................................................... 172
7.3 Graphene plasmonics ............................................................................ 183
7.3.1 Hybrid graphene-plasmon systems ...................................................................... 183
7.3.2 Intrinsic graphene plasmons ................................................................................ 185
7.4 Graphene-based antennas ..................................................................... 187
7.5 Hybrid graphene-nanocrystal for light emitting devices ................... 188
7.6 Graphene-based nanoscale optical routing and switching networks 189
8.   Sensors ..................................................................................... 191
8.1 Contact sensors ...................................................................................... 192
8.1.1 Nanoelectromechanical sensors ........................................................................... 193
8.1.2 Chemical sensors .................................................................................................. 196
8.2  Non-contact sensors .............................................................................. 199
8.2.1 Microwave detectors ............................................................................................. 199
8.2.2 Fast charge detectors ............................................................................................ 199
8.2.3 Strain sensors ........................................................................................................ 200
8.2.4 Magnetic sensors .................................................................................................. 200
8.2.5 Signal processing in ballistic graphene-based devices ........................................ 201
8.3 2d crystals and hybrids ......................................................................... 201
8.3.1 Chemical sensors .................................................................................................. 202
8.4 Future goals ............................................................................................ 203
9. Flexible electronics ..................................................................... 204
9.1 Key technology enablers ........................................................................ 205
9.2 Innovative flexible devices and user interfaces for consumer
electronics ..................................................................................................... 207
DOI: 10.1039/C4NR01600A9.2.1 Transparent conductive films ............................................................................... 207
9.2.2 Production of graphene transparent conductive films ........................................ 208
9.2.3 Mechanical performance of transparent films for flexible electronics .............. 210
9.2.4 Applications of graphene transparent conductive films...................................... 211
9.2.5 2d crystals and hybrids for flexible electronics ................................................... 214
9.3 Outlook .................................................................................................... 216
10. Energy storage and generation ............................................... 219
10.1 Batteries ................................................................................................ 219
10.2 Supercapacitors .................................................................................... 223
10.3 Fuel cells and hydrogen storage ......................................................... 226
10.4 Graphene solar cells............................................................................. 231
10.5 Thermoelectric devices ........................................................................ 234
10.6  Nanogenerators ................................................................................... 235
11. Composites ................................................................................ 238
11.1 Polymer-based composites .................................................................. 239
11.2  Ceramic-based composites ............................................................. 242
11.3 2d organic and inorganic nanocomposites based on chemically
modified graphene ....................................................................................... 243
11.4 Photonic polymer composites ............................................................. 245
12. Biomedical applications ........................................................... 248
12.1 Imaging and diagnosis ......................................................................... 249
12.2 Hyperthermia: photothermal ablation of tumours .......................... 249
12.3 Targeted drug delivery ........................................................................ 250
12.4 Gene transfection ................................................................................. 251
12.5 Bioelectronics and biosensors ............................................................. 251
12.6 Thin films, joint prostheses ................................................................. 254
12.7 Single-molecule genomic screening devices ....................................... 255
12.8 Plasmonic biosensors ........................................................................... 257
12.8.1 Utilizing graphene¡¯s intrinsic plasmons ............................................................ 258
12.8.2 Graphene as a functionalization-passivation gate-tuneable coating................ 259
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