Introduction to Nanotechnology

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(a) (LI (dl 10.1. SELF-ASSEMBLY 261 Figure 10.1. fransmission electron mrcroscqy images ol the successive growth of sslands of InAs on aGaAs (001) subslrale lor fradional monolayer coverages of (a) 0.1, (b) 0.3. (c) 0.6, and (d) 1 .O. The image sizes are 50nm x 50 nm loor (a) and 41) nm x 40 nm for (b) to (d). The insel for (a) IS an enlarged view of the GaAs substnale. [From J. €3. Belk. J. L. Sudijono, M. M. Holmes, C. F. McCanville, T. S. Jones. and R. A. Joyce, Surf. Sci 365, 735 (1996).] that is, the entity RS-Au is formed on a gold substrate, and the binding for the acid is RCO?-(MO),,, where MO denotes a metal oxide substmte ion, and the hydrogen atom H of the acid is rcclcawd at the formalion of the hiid. The alkancthiols RSH are The most widely used ligands because of their greater solubility, their compa- tibility with many organic functional groups, and their speed of reaction. They spontaneously adsorb QII thc surface; hence the term sefllnsrembk is applicable. In this section we consider thc sclf-assembly of the thiol ligtlnd X(CH1),, SH, where the terminal group X is methyl (CH3) and n typical value is 17 = 9 for decanethiol. corresponding to CI& for R. To preparc a gold substrate as an extended siae for the sclf-assembly, an electron beam or high-temperature healing elemcnt is used to maporate n polycrystalline layer of gold that is 5-300 nrn thick on to n polished support such as a glass slide, a r =-
262 SELF-ASSEMBLY AND CATALYSIS Figure 10.2. Hexagonal closepacked array of adsorbed Ralkanethiolale molecules (small solid circles) occupying one-sixth of the threefold Sites on the lattice 01 close-packed gold atoms (large circles). silicon wafer, or mica. The outermost gold layer, although polycrystalline, exposes local regions of a planar hexagonal close-packing atom arrangement, as indicated in Figs. 10.2 and 10.3. Various properties such as the conductivity, opacity, domain size, and surface roughness of the film depend on its thickness. The adsorption sites are in the hollow depressions behveen triplets of gold atoms on the surface. The number of dcpressions is the same as the number of gold atoms on the surface. Sometimes Cr or Ti is added to facilitate the adhesion. When molcciiles in the liquid (or vapor) phase come into contact with the substrate. they spontaneously adsorb on the clean gold surface in an ordered manner; that is, they self-assemble. The mechanism or process whereby the adsorption takes place involves each particular alkanethiol molecule CH,(CH,),zSH losing the hydrogen of its sulfhydryl group HS-, acquiring a negative charge, and adhering to thc surface as a thiolate compound by embedding its terminal S atom in a hollow between a triplet of Au Figure 10.3. Illustration of the self-assembly 01 a monolayer of rbalkanethioiates on gold. The terminal sulphur resides in the hollow between three closepacked gold atoms. as shown in Fig. 10.2. The terminal groups labeled by X represent methyl. [From J. L. Wilber and G. M. Whitesides, in Nanolechnobgy. G. Timp, ed.. Springer~Verlag, Berlin. 1999, Chapter 8, p. 336.1
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INTRODUCTION TO NANOTECHNOLOGY Char
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CONTENTS Preface xi 1 Introduction
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5.2 Carbon Molecules 103 5.2.1 Natu
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9.4 Excitons 244 9.5 Single-Electro
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PREFACE In recent years nanotechnol
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INTRODUCTION The prefix nano in the
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INTRODUCTION 3 he recognized the ex
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1000 (I) a 900 4 800 a 900 I 6 700
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INTRODUCTION 7 developed before the
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2.1. STRUCTURE 9 mechanics, the res
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X T 2.1. STRUCTURE 11 Figure 2.4. C
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2.1. STRUCTURE 13 Figure 2.6. Thirt
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Sodium Nanoparticle Na, Magic Numbe
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2.1. STRUCTURE 17 of the large anio
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2.1. STRUCTURE 19 other, and high-f
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2.2. ENERGY BANDS 21 Conduction Ban
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2.2. ENERGY BANDS 23 Figure 2.13. S
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2.2. ENERGYBANDS 25 band at point T
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A X ' Wavevector A Si c z 2.2. ENER
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2.2. ENERGY BANDS 29 bands of Figs.
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2.3. LOCALIZED PARTICLES 31 add ele
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1 meV 10 meV 100 meV FJ E W 1 eV 10
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3 METHODS OF MEASURING PROPERTIES 3
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3.2. STRUCTURE 37 Table 3.1. Crysta
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3.2. STRUCTURE 39 Figure 3.2. Two-d
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3.2. STRUCTURE 41 The widths of the
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44 METHODS OF MEASURING PROPERTIES
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3.3. MICROSCOPY 51 types of transit
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3.3. MICROSCOPY 53 Actual diverging
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Tunneling current Tunneling current
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3.3. MrCAOSCOPY 57 and the latter m
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3.4. SPECTROSCOPY 59 From Eq. (3.8)
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1 Average Panicle FWHM Size (nm) in
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CdSe colloidal NCs a = 1.2 nrn 3.4.
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El X-RAY TUBE 8000 - A 6000 - 4000
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2 N I w 3.0 2.5 2.0 1.5 1 .o 0.5 3.
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i 3.4. SPECTROSCOPY 69 NMR involves
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T=220K - 2G H FURTHER READING 71 Fi
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NUMBER OF ATOMS RADIUS (nm) 1 10 1
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I L 7 3 5 7 9 11 13 15 17 NUMBER OF
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JELLIUM MODEL OF CLUSTERS ATOMS CLU
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1.02 { 1.01 - 1 - 0.99 - 4.2. METAL
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4.2. METAL NANOCLUSTERS 81 Figure 4
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4.2. METAL NANOCLUSTERS 83 Figure 4
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-0 100 200 300 400 500 600 MASSICHA
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a 42. METAL NANOCLUSTERS 87 Figure
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. . . .. . - . D 111111111111111111
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3 4 2.5 0 cn g 2 0 z d 1.5 t a 9 1
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4.3. SEMICONDUCTING NANOPARTICLES 9
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4.4. RARE GAS AND MOLECULAR CLUSTER
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4.5. METHODS OF SYNTHESIS 97 d Figu
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4.5. METHODS OF SYNTHESIS 99 isopro
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PULSED LASER BEAM 1 1 1 1 1 I ROTAT
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5.1. INTRODUCTION CARBON NANOSTRUCT
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5.2. CARBON MOLECULES 105 methane d
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5.3. CARBON CLUSTERS 107 -0 20 40 6
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PHOTON ENERGY (electron volts) 5.3.
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Figure 5.6. Structure of the CEO fu
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1 30 0 14.1 14.2 14.3 14.4 14.5 LAT
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(c) 5.4. CARBON NANOTUBES 115 Figur
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5.4. CARBON NANOTUBES 1 17 The mech
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5.4. CARBON NANOTUBES 11 9 investig
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5.4. CARBON NANOTUBES 121 energy gr
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5.4. CARBON NANOTUBES 123 stretch c
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5.5. APPLICATIONS OF CARBON NANOTUB
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- v) 450 : 400 3 350 1 300 : 5 250
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BULK NANOSTRUCTURED MATERIALS In th
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h 8 0 6.1. SOLID DISORDERED NANOSTR
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6.1. SOLID DISORDERED NANOSTRUCTURE
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6.2. NANOSTRUCTURED CRYSTALS 153 qu
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6.2. NANOSTRUCTURED CRYSTALS 155 Fi
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158 BULK NANOSTRUCTURED MATERIALS 6
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160 BULK NANOSTRUCTURED MATERIALS w
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162 BULK NANOSTRUCTURED MATERIALS 0
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164 BULK NANOSTRUCTURED MATERIALS n
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166 NANOSTRUCTURED FERROMAGNETISM f
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168 NANOSTRUCTURED FERROMAGNETISM i
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170 NANOSTRUCTURED FERROMAGNETISM M
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172 NANOSTRUCTURED FERROMAGNETISM h
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174 NANOSTRUCTURED FERROMAGNETISM d
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176 NANOSTRUCTURED FERROMAGNETISM o
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4 h $ 3 7.5. NANOCARBON FERROMAGNET
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7.6. GIANT AND COLOSSAL MAGNETORESI
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1.4 N 1 1.2 z " 1 0 v 5 h 0.8 0 0.6
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7.6. GIANT AND COLOSSAL MAGNETORESI
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7.7. FERROFLUIDS 187 Figure 7.22. M
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7.7. FECIROFLUIDS 189 Figure 7.25.
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7.7. FERRQFLUlOS 191 FerroRuids can
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FURTHER READING FURTHER READING 193
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10- IR f IA -1 8.1. INTRODUCTION 19
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8.2. INFRARED FREQUENCY RANGE 197 1
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8.2. INFRARED FREQUENCY RANGE 199 d
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s C CTI e 8 9 4( 8.2. INFRARED FREQ
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8.2.3. Raman Spectroscopy 8.2. INFR
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8.2. INFRARED FREQUENCY RANGE 205 a
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- r I 520 51 8 v 6 516 a" 51 4 51 2
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8.2. INFRARED FREQUENCY RANGE 209 i
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Page 224 and 225: i E (cm-’ ) 20 c I 1 ID 0 4x107 8
Page 226 and 227: - ? m v .- - z In C a, c C - .. . .
Page 228 and 229: Excitatior I [eV]: 2.175 2.214 2.25
Page 230 and 231: 6 100 200 300 Time (ns) 8.3. LUMINE
Page 232 and 233: 400 nm Laser / Free excitons Trappe
Page 234 and 235: 8.4. NANOSTRUCTURES IN ZEOLITE CAGE
Page 236 and 237: FURTHER READING 225 P. Milani and C
Page 238 and 239: 9.2. PREPARATION OF QUANTUM NANOSTR
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Page 242 and 243: 9.3. SIZE AND DIMENSIONALITY EFFECT
Page 248 and 249: w n 3 2 1 9.3. SIZE AND DIMENSIONAL
Page 254 and 255: WE) Quantum Dot Number of Electrons
Page 256 and 257: 9.5. SINGLE-ELECTRON TUNNELING 245
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Page 264 and 265: 9.7. SUPERCONDUCTIVITY 253 horizont
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Page 292 and 293: I1 ORGANIC COMPOUNDS AND POLYMERS 1
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Page 302 and 303: 11.3. NANOCRYSTALS 291 R’ groups
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Page 318 and 319: BiodegradaWe surface 4 Functional g
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12.2. BIOLOGICAL BUILDING BLOCKS 31
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314 BIOLOGICAL MATERIALS which we w
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316 BIOLOGICAL MATERIALS Table 12.2
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318 BIOLOGICAL MATERtALS i J / Flgu
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320 BIOLOGICAL MATERIALS Pyrimidine
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322 BlOLMjlCAL MATERiALS (a) DNA do
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324 BIOLOGICAL MATERIALS so each wo
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326 BIOLOGICAL MATERIALS 12.4.2. Mi
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328 BIOLOGICAL MATERIALS tions they
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330 BIOLOGICAL MATERIALS hardened f
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13 NANOMACHINES AND NANODEVICES In
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334 NANOMACHINES AND NANODEVICES CA
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336 NANOMACHINES AND NANODEVICES Op
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338 NANOMACHINES AND NANODEVICES ti
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340 NANOMACHINES AN0 NANODEVICES PO
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342 NANOMACHINES AND NANODEVICES X
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344 NANOMACHINES AND NANODEVICES na
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346 NANOMACHINES AND NANODEVICES 31
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348 NANOMACHINES AND NANODEVICES -
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350 NANOMACHINES AND NANODEVICES re
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352 NANOMACHINES AND NANODEVICES 1
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354 NANOMACHINES AND NANODEVICES -1
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A.l. INTRODUCTION APPENDIX A FORMUL
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A.3. PARTIAL CONFINEMENT 359 limiti
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APPENDIX B TABULATIONS OF SEMICONDU
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TABULATIONS OF SEMICONDUCTING MATER
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Table B.8. Effective masses m+ rela
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372 INDEX amoeba, 3 16 amphiphilic,
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374 INDEX CdS, 9, 130, 213, 216, 36
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376 INDEX dispersion, 277 disulfide
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378 INDEX Ga (gallium) (continued)
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380 INDEX length (continued) critic
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382 INDEX multiple ionization, 93 r
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384 INDEX pi-conjugation, 282, 292
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silica, 269 silica-alumina, 269, 27
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388 INDEX wavefimction (continued)
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