Table Of ContentNanotechnologies
Nanotechnologies
Concepts, Processing and Applications
Pierre Camille Lacaze
Series Editor
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Firstpublished2013inGreatBritainandtheUnitedStatesbyISTELtdandJohnWiley&Sons,Inc.
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Table of Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv
PART1.CONCEPTS,DISCOVERIESANDTHERAPID
DEVELOPMENTOFNANOTECHNOLOGIES. . . . . . . . . . . . . . . . . . 1
Chapter1.NanotechnologiesinContext:SocialandScientific
AwarenessoftheirImpact . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.Feynman,thevisionary . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.Nanotechnologiesandtheirdefinition . . . . . . . . . . . . . . . . 5
1.3.Theconsiderationofnanotechnologiesbyscientific
organizations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.4.Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Chapter2.TheRapidExpansionofNanotechnology:
NewWaysofObservingtheInfinitesimalandtheDiscovery
ofCarbonaceousNanomaterialswithUnusualProperties . . . . . . 13
2.1.Improvingtoolsforobservingtheinfinitesimal . . . . . . . . . . 15
2.1.1.Transmissionelectronmicroscopes . . . . . . . . . . . . . . . 15
2.1.2.Scanningelectronmicroscopes . . . . . . . . . . . . . . . . . . 18
2.1.3.Near-fieldmicroscopes . . . . . . . . . . . . . . . . . . . . . . . 21
2.1.3.1.Thetunnel-effectmicroscope(STMorscanning
tunnelingmicroscopy) . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.1.3.2.Atomicforcemicroscopy . . . . . . . . . . . . . . . . . . . 26
2.2.Thediscoveryofnewcarbonaceousnanomaterials. . . . . . . . 28
2.2.1.Somebasicconceptsrelativetotheelectronicstructure
ofcarbonandtothebondingrulesbetweencarbonatoms . . . . . 29
vi Nanotechnologies
2.2.1.1.Theenigmaofcarbonatoms . . . . . . . . . . . . . . . . . 29
2.2.1.2.Diamondortheperfectanduniquetetrahedral
chainofcarbonatoms. . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.2.1.3.Graphiteortheintrusionofπelectronsin
theassemblyofcarbonatoms. . . . . . . . . . . . . . . . . . . . . . 32
2.2.2.Thefullerenesorgraphitesheetsrolledintoaball . . . . . . 34
2.2.3.Carbonnanotubes:tubesofgraphitesheets . . . . . . . . . . 36
2.2.4.Grapheneorgraphite“sheets”. . . . . . . . . . . . . . . . . . . 39
2.2.4.1.Theidentificationofgraphene . . . . . . . . . . . . . . . . 39
2.2.4.2.Someremarkableelectricalproperties . . . . . . . . . . . 41
2.2.4.3.Remarkableprogress:solid,flexibleandeasily
manipulatedgraphenepaper. . . . . . . . . . . . . . . . . . . . . . . 43
2.2.5.Linkbetweenconjugatedcarbonaceousnanomaterials . . . 45
2.3.Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.4.Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Chapter3.NanomaterialsinAllTheirForms:NewProperties
DuetotheConfinementofMatter . . . . . . . . . . . . . . . . . . . . . . 49
3.1.Thedifferenttypesofnano-objects:mainmethods
ofpreparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.1.1.ColloidalsolutionsofgoldNPs. . . . . . . . . . . . . . . . . . 50
3.1.2.HybridandmagneticNPs(ferromagneticfluids). . . . . . . 52
3.1.3.SemiconductingNPs(quantumdots) . . . . . . . . . . . . . . 54
3.1.4.Phospholipidvesiclesandencapsulationbyliposomes . . . 58
3.1.5.Nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.2.Organizingnanoparticlesintoarrays . . . . . . . . . . . . . . . . . 63
3.2.1.Self-assembly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.2.1.1.Molecularself-assemblyandtheformationof
nanometricnetworks . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.2.1.2.Self-assemblyofNPsonsolidsurfaces . . . . . . . . . . 70
3.2.2.Assemblingbyultrathinaluminamembranes . . . . . . . . . 74
3.2.3.Assemblingbycolloidallithography. . . . . . . . . . . . . . . 75
3.3.Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.4.Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Chapter4.SomeAmazingPropertiesofNanomaterials
andofTheirAssemblyintoNetworks. . . . . . . . . . . . . . . . . . . . 81
4.1.Thefirsteffectoftheconfinementofmatter:
unusualcatalyticandphysicochemicalproperties. . . . . . . . . . . . 81
4.2.TheoptoelectronicpropertiesofNPsdueto
confinement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
TableofContents vii
4.2.1.Someconceptsofphysicsthatcanbeappliedto
solidmaterials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
4.2.2.Theplasmonresonanceeffectandthe
opticalpropertiesofgoldNPs. . . . . . . . . . . . . . . . . . . . . . . 85
4.2.3.SurfaceenhancedRamanscattering . . . . . . . . . . . . . . . 87
4.2.4.ThephotothermiceffectorhowtoheatupgoldNPs . . . . 89
4.2.5.TheoptoelectronicpropertiesofQuantumDots. . . . . . . . 89
4.3.TheamazingpropertiesofNPnetworksor
nanostructuredsurfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
4.3.1.Wettabilityofstructuredsurfaces. . . . . . . . . . . . . . . . . 91
4.3.2.Opticalproperties. . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4.3.2.1.Photoniccrystals. . . . . . . . . . . . . . . . . . . . . . . . . 97
4.3.2.2.Waveguides. . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
4.3.2.3.QdotLASERdiodes . . . . . . . . . . . . . . . . . . . . . . 100
4.3.2.4.Antireflectivesurfaces . . . . . . . . . . . . . . . . . . . . . 105
4.3.2.5.PlasmoniccrystalsandtheSERSeffect . . . . . . . . . . 106
4.3.3.Nanoelectronicsappliedtothedetectionof
traceelements:nanowiretransistors . . . . . . . . . . . . . . . . . . . 109
4.3.3.1.TheoperatingprincipleoftheFETsensor. . . . . . . . . 110
4.3.3.2.Anexampleofhowitcouldbeapplied:
detectingexplosives. . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
4.3.3.3.Electronicnoses . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.4.Conclusionsandperspectives. . . . . . . . . . . . . . . . . . . . . . 113
4.5.Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
PART2.APPLICATIONSANDSOCIETALIMPLICATIONSOF
NANOTECHNOLOGY. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
Chapter5.Nanoelectronicsofthe21stCentury . . . . . . . . . . . . . 119
5.1.Somehistory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
5.2.Molecularelectronics. . . . . . . . . . . . . . . . . . . . . . . . . . . 123
5.2.1.SingleElectronics.Dreamorreality? . . . . . . . . . . . . . . 124
5.2.1.1.Electronboxandelectrontransferbyquantum
tunneling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
5.2.1.2.Thesingle-electrontransistor(SET) . . . . . . . . . . . . 127
5.2.2.Theultimatestep:themolecule. . . . . . . . . . . . . . . . . . 130
5.2.2.1.Technicalissuesintheassemblyof
ametal/singlemolecule/metaljunction. . . . . . . . . . . . . . . . 130
5.2.2.2.Moleculardiodesmadefromself-assembled
organicmolecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
5.2.2.3.Electricalpropertiesofself-assembledorganic
layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
viii Nanotechnologies
5.2.2.4.Theorganicfield-effecttransistor . . . . . . . . . . . . . . 135
5.2.3.Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
5.3.Spintronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
5.3.1.Electronspinandferromagneticmaterials . . . . . . . . . . . 138
5.3.2.Magnetoresistance . . . . . . . . . . . . . . . . . . . . . . . . . . 139
5.3.3.Giantmagnetoresistance . . . . . . . . . . . . . . . . . . . . . . 140
5.4.Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
5.5.Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
Chapter6.EnergyandNanomaterials . . . . . . . . . . . . . . . . . . . 147
6.1.Electrochemicalstorageofelectricity . . . . . . . . . . . . . . . . 148
6.1.1.Electricalpropertiesofanaccumulator . . . . . . . . . . . . . 150
6.1.2.Lithiumbatteries . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
6.1.2.1.ThefunctionaloriginalityofaLi-ion
electrochemicalcell . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
6.1.2.2.Nanotechnologytotherescue:thegraphene
solution? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
6.1.3.Electrochemicalcapacitorsandsupercapacitors. . . . . . . . 157
6.1.3.1.Peculiaritiesoftheelectrochemicalcapacitor. . . . . . . 158
6.1.3.2.Thedevelopmentsandthestateoftheart. . . . . . . . . 161
6.1.4.Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
6.2.Theconversionofsolarenergyintoelectricalenergy . . . . . . 165
6.2.1.Theprincipleoftheconversion. . . . . . . . . . . . . . . . . . 166
6.2.1.1.Thephotoelectriceffectanditshistory. . . . . . . . . . . 166
6.2.1.2.Photoionizationofasemiconductorandcollection
ofthechargesattheelectrodes . . . . . . . . . . . . . . . . . . . . . 168
6.2.2.Theinorganicroutebasedonmineralsemiconductors . . . 170
6.2.3.Theorganicroute. . . . . . . . . . . . . . . . . . . . . . . . . . . 172
6.2.3.1.Organicphotovoltaiccells. . . . . . . . . . . . . . . . . . . 172
6.2.3.2.Grätzeldye-sensitizedsolarcells(DSSC). . . . . . . . . 176
6.3.Fuelcells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
6.3.1.FunctionalprinciplesofPEMFCs . . . . . . . . . . . . . . . . 181
6.3.2.Canthecostofdihydrogenfuelcellsbereduced? . . . . . . 183
6.4.Generalconclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
6.5.Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
Chapter7.NanobiologyandNanomedicine. . . . . . . . . . . . . . . . 193
7.1.Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
7.2.Bionanoelectronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
7.2.1.ThemultiplexeddetectionofPSAusing
“transistorized”nanowires . . . . . . . . . . . . . . . . . . . . . . . . . 195
7.2.1.1.Immunologicalassayofproteinsbylabeling. . . . . . . 195
TableofContents ix
7.2.1.2.Useofnanowirenetworks. . . . . . . . . . . . . . . . . . . 197
7.2.1.3.ThesimplifiedandultrasensitivedetectionofPSA . . . 197
7.2.1.4.Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
7.2.2.Connectingtheorganicandtheartificial . . . . . . . . . . . . 201
7.2.2.1.Theconstructionofananosensorand
itsfunction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
7.2.2.2.Protonexchangesandtheirinhibition
bycalciumions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
7.2.2.3.Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
7.3.Nanomedicine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
7.3.1.Biologicalbarriersandthealterationof
thecellulartissuesurroundingatumor . . . . . . . . . . . . . . . . . 206
7.3.1.1.Theextravasationofnanoparticles
towardcanceroustissue. . . . . . . . . . . . . . . . . . . . . . . . . . 208
7.3.2.Nanoprobesforinvivoreal-timeimaging . . . . . . . . . . . 210
7.3.2.1.Imageryresultingfromplasmonresonance
ofgoldNPsandfromtheirinteractionwithenzymes
characteristicofapathologicalprocess. . . . . . . . . . . . . . . . 210
7.3.2.2.Luminescenceimagingtriggeredbyenzymesor
reactiveoxygenspeciescharacteristicofapathology. . . . . . . 213
7.3.2.3.Magneticresonanceimagingcoupledwith
nanophototherapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
7.3.2.4.Aninnovativestrategyforanimproved
penetrationoftheNPsinthecancerouscelltissue. . . . . . . . . 218
7.3.3.Challengesofnanomedicineandsome
significantclinicalresults. . . . . . . . . . . . . . . . . . . . . . . . . . 221
7.3.3.1.Thefirstcommercialnanomedication . . . . . . . . . . . 221
7.3.3.2.Newpathsindevelopment . . . . . . . . . . . . . . . . . . 223
7.3.4.Problemsrelatedtothetoxicityofnanomaterials. . . . . . . 228
7.3.4.1.Afewgeneralconsiderations. . . . . . . . . . . . . . . . . 228
7.3.4.2.Themultiplecausesofnanomaterial-induced
toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
7.3.4.3.Recommendationsforabetterevaluation
ofNPtoxicity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
7.4.Conclusionsandperspectives. . . . . . . . . . . . . . . . . . . . . . 234
7.5.Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Chapter8.NanoroboticsandNanomachinesoftheFuture . . . . . 239
8.1.Naturalmolecularmachines . . . . . . . . . . . . . . . . . . . . . . 240
8.1.1.ATP-synthase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
8.1.2.Myosin:alinearproteinnanomotor . . . . . . . . . . . . . . . 242
8.2.Artificialmolecularmachines . . . . . . . . . . . . . . . . . . . . . 243
x Nanotechnologies
8.2.1.Artificialmolecularmachinesinsolution. . . . . . . . . . . . 244
8.2.1.1.Rotaxanes(translationalmolecularshuttles) . . . . . . . 245
8.2.1.2.Catenanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
8.2.1.3.Promisingapplicationsfordiagnosisandtherapy . . . . 251
8.2.2.Nanomachineswithmechanicalproperties. . . . . . . . . . . 253
8.2.2.1.Rotorsandgyroscopes . . . . . . . . . . . . . . . . . . . . . 254
8.2.2.2.“Motorized”molecularvehicles . . . . . . . . . . . . . . . 256
8.3.Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
8.4.Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
ConclusionsandOutlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
IndexofNames. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
Preface
Lately, nanotechnologies have become an important social issue. Every
so often they are the subject of major debates in the media, and their
illustrationissometimesclosetosciencefiction.
It is true that this domain constitutes a huge break with the daily
microscopic world to which we are accustomed, even if only by using
concepts of quantum mechanics, which are very different from those of
classical physics. This leads us to think about physical phenomena in a
completelydifferentway.
Effects owing to the minuteness of objects often result in unexpected
discoveries, which are increasing in number every day, to which innovative
applications are constantly being added. These should revolutionize our way
oflifeinthefuture.
Nanosciences and nanotechnologies have gradually been introduced, first
in a modest and anonymous fashion in the 1960s (though the word
“nanotechnology” was used for the first time in 1970), becoming a strategic
researchprinciplebytheturnofthecentury.Nanotechnologyisnowamajor
field in science that has been developed by industries and universities,
encouraged and subsidized by the most influential research organizations of
all the developed countries and also every so often used as a form of
advertising.
There is no doubt that nanotechnologies are interesting and we are all
aware that future developments must come from mastering them. This is a
booming industry, in terms of diversity as much as in the number of
applications; one day’s progress is very rapidly surpassed by discoveries
