Introduction to Nanotechnology

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M Et3P OTf M=Pd M=Pt M=Pd, 41 % M=Pt. 79% 11.5. SUPRAMOLECULAR STRUCTURES 297 Figure 11.13. Molecular square formed by the self-assembly process of Fig. 11.1 1 from the subunits acyclic bisphosphane on the upper left and 2,9-diazabenzo[cd,/m]perylene on the upper right, where Et denotes an ethyl group -C2Hs, and M can be either a Pd or a Pt atom. The overall +8 charge of the structure is balanced by eight -OS02CF3 counterions, as indicated. [From Stang and Olenyuk, Nalwa (2000), p. 173.1 L'< L /" + X M = Pd, Pt X = -OTf, H20 L = Et,P, 1/2 dppp N 14+ Figure 11.14. Programmed self-assembly of two types of angular subunits to form a molecular square [From Stang and Olenyuk (2000), p. 180.1 4 x-
298 ORGANIC COMPOUNDS AND POLYMERS Figure 11.15. Molecular square formed by the self-assembly process of Fig. 11.14 showing bond angles, bond lengths, and interatomic distances expressed in angstrom (A) units (10A=1 nm), obtained from a single-crystal X-ray diffraction study. The symbol Et denotes an ethyl group -C2H5 and Ph, a phenyl group -C6H5. The overall charge of the structure +4 is balanced by four -OS02CF3 counterions. [From Stang and Olenyuk (2000), p. 181 .] called dendrimers or cascade molecules, which form by this type of cascade process. See Archut and Vogtle (2000) for more details. The first dendrimer preparation scheme, outlined in Fig. 1 1.17, started with three different diamine compounds: diamine itself (H2N-NH2), m-phenylenediamine, and 2,6-diaminopyridine. Initially the starting compound, H2N-X-NH2, was reacted with vinylcyanide (H2C=CH-CN) to replace the hydrogens of the amino groups @H2) with cyano groups CN, and form the double cyanide derivative (CN)2N-X-N(CN)2. This derivative compound was then reacted with sodium borohydride (NaBH4) using a Co2+ catalyst to form the second-generation compound (H2N)2N-X-N@H2)2 of the dendrimer iteration sequence. Figure 1 1.17 outlines the iteration sequence leading up to the formation of the third-generation compound [(H2N)2N]2N-X-N[N(”2)2]2 of the sequence (not shown in the figure). The notation is to call the compound obtained by two iterations the third-generation compound. The chemical structures for X in the m-phenylene and the 2,6-pyridine varieties of these diamine starting compounds H2N-X-NH2 are shown in the lower left of Fig. 1 1.17. Figure 1 1.18 provides another example of a polyaminoamine dendrimer (PAMAM). To estimate the size of a dendrimer such as this, we can use the crystallographic data of Wyckoff (1966) for the three normal (i.e., unbranched) aliphatic compounds CnH2n+2 with n = 8,18,36. The average transverse unit-cell
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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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v) - C 3 8 600 400 100 0 e e 10 20
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i E (cm-’ ) 20 c I 1 ID 0 4x107 8
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- ? m v .- - z In C a, c C - .. . .
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Excitatior I [eV]: 2.175 2.214 2.25
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6 100 200 300 Time (ns) 8.3. LUMINE
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400 nm Laser / Free excitons Trappe
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8.4. NANOSTRUCTURES IN ZEOLITE CAGE
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FURTHER READING 225 P. Milani and C
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9.2. PREPARATION OF QUANTUM NANOSTR
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i 9.2. PREPARATION OF QUANTUM NANOS
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9.3. SIZE AND DIMENSIONALITY EFFECT
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w n 3 2 1 9.3. SIZE AND DIMENSIONAL
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WE) Quantum Dot Number of Electrons
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9.5. SINGLE-ELECTRON TUNNELING 245
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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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