Nanomaterials Theory Problems and

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 ( CONTENTS)

c hapter 1: Introdu ction 1-17

1 Introduction ............................. ............................................................. l
2 Importont d iscoveries in na nom a terlals ................................................. 4
3 Basic physical principles a nd quantum effec ts ................................... ... .7
4 Synthesis ......................... .....................................................................8
s Characterization .......... ......................... .................................................8
6 Effect of size on various physica l properties ....................... ... .................9
7 Applications of the nanomaterials .. .... .......................... ............. ........... 12
8 About the book ............................ ......................................... ............... 14
Chapter 2 : Nanoscale Systems 18-102
1 Introduction .... ... ..... ... ................................. ..... ....... ............................ 18
2 Length scales in physics ... ................................... ......... ....................... 20
2.1 Plan ck 's scales in physics .... .. ................................ ..... ...................22
3 Nanostructures ..................... .. .. ...... ............................... ... .................. 23
3.1 Zero dimens ional nanostruc tures ... ......... ......................................25
3.2 One dimen s ional nanostructures .... ....... ........... ..... ........................26
3.3 Two dimension al nanostruct ures......... ............... ........................... 27
3.4 Three Dimen sional Nanostructure Materials ...... ............. ...............29
3.5 Nanodots............. .... .... .... ... ...................... ...... ...... ......... ................ 30
3.6 Thin Films.................... ........................................ ............. ..... .......3 1
3.6 .1 Applications of thin films .......................................... ............ 32
3.7 Nanowires ............................................................................ .. .... ... 33
3 . 7 . 1 Nanowire Size ............ ............... .............................. ........ ..... 3 4
3 .7.2 Quantum mechanical effects......... ............ ............................34
3. 7.3 Nanowire conductivity.............. ....... ..... .. .... .. .. ....................... 34
3.7.4 Applications of nanowire .............................. .. ... .................... 35
3 .8 Nanorod s ........................... . .............................................. ... ...... ... 37
4 Band Structure of m aterials at nanoscale ......... .... ................ ............ .. .42
4.1 Single crystal, polycrystal a n d amorphou s materials ......... ... ........ .43
4 .2 Band structu re of single crystal m aterials .. .................................. .44
4 .3 Band structure of a one dimensional ch ain of atoms .....................45
4 .4 Band gap of n anomaterials .. .......... ......... ............. ... .......................48
5 Density of States of materials at nanoscale ......................... .................49
 S. l Density of Stntt's in H :in uniform solid material.. .......................... 50
5.2 Dens ity of Stuks in a 20 uniform solid material ............................ 53
5.3 Dt'nsity of Stul<'N inn ll> uniform Holid materi<:il.. .......................... 54
6 Sizl' <>ff<'t'IN in 110110N.VMl<'mH .................................. •· .. · ... · · ... • · ... · ·•· ·•· ·•· ..• ss
b. l How m\m>p11rtid(•s rt•nct with other clcmcnts ................................. 55
<>.2 How m\m>parlid<'s l'lmngC' l·olor .................................................... 56
h.J lh)\\' mmopnrtidcs melt at lower tcmpernture11 ............................. 57
h.4 Size Eff<'C'I$ on the Optical Properties in Nanosystems ................... 57
7 Quuntun1 Confineinent ........................................................................61
7. l Application of Schrodinger's equation ............................................ 61)
7.2 Schrodinger's equation from wave packet ......................................67
7 .3 Solution of Schrodinger's equation in potential box with
rigid walls ..................................................................................... 68
7.4 Solution of Schrodinger's equation in potential step ...................... 71
7.5 Solution of Schrodinger's equation in rectangular potential
barrier: tunneling ..........................................................................77
8 Solved problems ..................................................................................82
9 Exercise .............................................................................................. 85
9.1 Short questions ............................................................................. 85
9.2 Long questions .............................................................................. 86
9.3 Multiple choice questions with answers .........................................87
9.4 Numerical problems ......................................................................87

Chapter 3: Synthesis of Nanomaterials 103-171

1 Introduction ...................................................................................... 103
1.1 What is synthesis? ...................................................................... 104
1.2 Different processes of synthesis of nanomaterials ........................ 104
1.3 Factors affecting the synthesis of nanomaterials .......................... 105
2 Synthesis of nan<>rnaterials ................................................................ 108
2.1 Top down approach ..................................................................... 108
2.2 Bottom up approach ................................................................... 110
2.3 Difference between top-down and bottom-up approach in
nanotechnology ........................................................................... 112
3 Photolithography ............................................................................... 112
3.1 Various steps in photolithography ............................................... 114
3.2 Some comments about photoresists ............................................ 116
3.3 Advantages of photolithography................................................... I 19
3.4 Disadvantages of photolithography .............................................. 120
 4 Ball milling ................................ ,....................................................... 121
4 .1 Description of ball milling machine .............................................. 122
4.2 Comments on the grinding media ................................................ 123
4 .3 Mathematics of ball mllling.......................................................... 125
4.4 Advantage of ball milling ............................................................. 126
4.5 Disad vantage of ball milling......................................................... 126
5 Oas phase condensation ............... ..................................................... 127
5.1 Basic principle of gas phase condensation ................................... 127
5.2 Advantage of gas phase condensation ................... .. .......... ........... 128
5.3 Disadvantage of gas phase condensation ..................................... 129
5 .4 Applications of gas phase condensation ..................................... 129
6 Vacuumdeposition .................... ...... ............ ..... .............................. .. . 130
6.1 Advantage of vacuum deposition ................................................. 131
7 Physical vapor deposition (PVD) ...... .... .'.............................................. 131
7 .1 Thermal evaporation ................... .............. .................................. 132
7 .2 Electron beam evaporation .......................................................... 133
7.3 Pulse laser deposition .................................................................. 137
8 Chemical vapor deposition (CVD) ........................ ,.............................. 142
8.1 Characteristics of CVD coatings .................................................. 144
8.2 Advantages of chemical vapor deposition technique ..................... 144
8 .3 Comparison between PVD and CVD............................................. 145
8.4 Difference between PVD techniques and CVD techniques .... ........ 145
8.5 Sol-gel process ............................................................................ 146
8.6 Electrodeposition ........................................................................ 149
8. 7 Spray Pyrolysis ................ .. .. .. ............................... ............... ........ 152
8.8 Hydrothermal synthesis .............................................................. 154
9 Colloidal methods ......... .................. ......................................... .......... 157
9. 1 Advantage of preparation through colloidal methods.................... 158
9.2 What are quantum dots? ............................................................. 158
10 Molecular Beam Epitaxy (MBE) Orowth of Quantum Dots ... ............... 159
10. 1 Molecular Beam Epitaxy (MBEJ ................................................. 160
10.2 Characteristics of MBE Growth .......... ...... ........................ .... ..... 161
10.3 Advantage of MBE Growth of Quantum Dots ............................. 162
10.4 Disadvantage of MBE Growth of Quantum Dots ........................ 163
11 Exercise ................ .. .... ....... .. .. .............. .. ........................................... 164
11 . l Short questions ............................................ ·· ........ ···· .... ·· ........ · 164
11 .2 Long questions ...... .................. ................. ................................. 167
11.3 Multiple choice questions with answers ..................................... 168
 172-259
Chapter 4 : Charaol orl•allon o f Nnno n'llllorlal1
l llllt'OthH'tlllll •• .................... ,, .................................................... ........ 172
!;} :\-1. ,. nlflicwtlon .............................................................................. 172
:2. 1 Ut•\8tt's Lnw fw X rny tllffrnc: tlo11 .................................................. l7S
:2.:2 Notes 0 11 U1omf11 low ................................... ................................ 176
:2.J Oe rivl\tlo11 of Schcri er formulu for c11tima llon or paiticle s ize ....... 177
:2.4 Williom11011-lloll plot or X-ray ......... .. ............................................ 178
2.5 \Vhot is X· rt\Y Diffraction Technique? .... .... .................................. 180
2.6 Whnt nre the objectives of X-ray Diffrac tion Technique? ............... 181
2.7 Different types or X-ray Diffraction Techniques .... ......... ... ............ 182
2 .8 Analysis or the characteristic XRD spectrum of a sample ............. 185
2. 9 Applications o f X-ray Diffraction ............................................ ...... 189
2.10 Solved Problems .................................................................. ...... 191
3 Optical microscopy ......................................... .... ............................... 193
3.1 Compound microscope ............................................................ .... 194
3.2 Different components of a light microscope .................................. 194
3.3 Resolution of a light microscope .................................................. 197
3.4 Advantages of an optical microscope ................. ... ............... ........ 198
3.5 Disadvantages of an optical microscope ................................... .... 198
4 Electron microscopy ....................................................................... ... 199
4.1 Louis de Broglie hypothesis: calculation of wavelength of an
electron .................................................................................... ... 199
5 Scanning electron microscopy (SEM) ................................................. 203
5. 1 Different types of SEM ................................................................. 204
5.2 Basic principles of scanning electron microscopy .................... .... .204
5 .3 Essential components of all SEMs include the following ........... .. .206
5.4 Sample-electron Interaction in SEM .......................................... .. 207
5.5 Applications of SEM .... , ............................................................... 207
5.6 Limitations of SEM ........................................ ......... ..................... 208
6 Scanning probe microscopy (SPM) ................................. .. .................. 210
6.1 Basic principle of scanning probe microscopy .............................. 211
6.2 Advantages or SPM.. .................................. ....... ..........: ................ 2 12
6.3 Disadvantages of SPM .... .. ............................. .. ............................ 2 12
1 Transmission electron microscopy (TEM) .......................................... .213
7 · I Bas1 ·c principle
· · of transmission electron microscopy .................... 214
7 .2 Different modes of operation ofTEM ................................... .. .. ..... 218
7 .3 High resoltt Lion transmission electron microscopy {HRTEM) ........ 21 Q
 7.4 Calculation of grain sizes from TEM Image .................................. 220
7.5 Particle size a na lysis o fTEM images tising lmageJ software ......... 220
7.6 Applications ofTEM and HRTEM ............... ..... ............................. 221
7.7 Relative comparison belween a light and a transmission
e lectron microscope ............................................................. ........ 222
7.8 Advantages ofTEM ................. ........... ... ........... .......... .................. 223
7.9 Disadvantages of TEM ........ ....... ............................ ...................... 223
8 Atomic force microscopy (AFM) ........ ... .......... ........... ............. ............. 224
8.1 Basic principle of operation of AFM ........ .............. ........ ........... .... 225
8 .2 Scanner in AFM .............................................. ...................... ...... 226
8.3 Probes in AFM ........................................................ .... ................ . 227
8.4 Properties of cantilever ....................... ......................................... 227
8.5 Different classes of AFM .............................................................. 227
8.6 Different modes of operation of an atomic force microscopy ......... 228
8.7 Traditional surface texture parameters in an AFM ....................... 229
8.8 Application of atomic force microscopy ................................. ....... 231
8.9 Advantages of atomic force microscopy ................ ........................ 231
8.10 Disadvantages of atomic force microscopy ................................. 231
9 Scanning tunneling microscopy (STM) ............................................... 232
9 .1 Basic principle of scanning tunneling microscopy ........................ 233
9.2 Application of scanning tunneling microscopy ............................. 236
9.3 Difference between a SEM and an AFM ....................................... 236
10 Solved theoretical and numerican problems ........................................ 237
11 Exercise ......... ... ................................................................................ 243
11.1 Short answer typt questions ..................................................... 243
11.2 Long answer type questions ...................................................... 245
11.3 Numerical problems .............. .................................................... 24 7
11.4 Multiple choice questions with answers ..................................... 249
Chapter 5 : Optical Properties of Nanomaterials 260-316
1 Introduction ................................................................. ..................... 260
2 Coulomb interaction in nanostructures ................................. ............ 261
3 Plasmonic nanomaterials ................................................................... 262
3.1 Surface plasmons ............ ............................................................ 262
4 Photonic crystals ......... .. ... ....... .. ...................................... ................. . 263
5 Quantum dots ... ....................... ......................................................... 265
6 Concept of dielectric constant for nanostructures ...................... ....... .,266
7 Charging energy of quantum dot ...................................................... .. 268
----- 8 Q\11llU I»ti Ill k• f\111
I r."' 1w11•
I U ll I h I<'• ""' q
11 hc' l \\ 1 I' ll II I I
.
.................
I uo11l-portac
les·········
······· .......... 270
............ 271
.. ...
. ............ ......... ............. 272
275
1
• r1ia11111 "'' ................. .... ..
Q (ll11lk) .........
8 2 'thlllll I h 1111 1 fllll' 11 11\lrl !Ith• Nill I fJVC'r o ther
"11T"Ct
9 l: """ uuh•i'i ~I
I .
Ill 1111 llf l
I 11111111 l'"I' rnnt ..• • ........
.......... .... 276
9 l lmpo1t1u1• • . , semiconductor .. 278
l\ttnl\lt11n ulkl 1111cllrN' bo nd gap 279
11
~ l tfl, "
m i llte•1 I 11111 .................. .
9 1111 11' ' '"' ' 111 <'< t 1111tl lml11<'c t bu nd gap........ . . .......... 281
lo h V'O\ll\111 "~ m, ···111 ' ...................
............. . 282
-• I "P ................. . .......... .
10 l h ,ill'C'\ t l>1111 t g .. .. ' ti temperature ....................... . 283
·o J \ an.l tl\)11 0 f band<
gop Wt 1 ....... ... .. . ............. .. . ..
.......... ..
• · I bond gap .........
lO 3 Opt1cnl ' s clcctnca I direct band semiconductor 285
l l ~ton m direct band and n ..................................................... .
anocrysta\s .... .. . .. .. .. .. .. . .. . .. .. . . .. .. . . ......................... 286
n · tion ..................................... · 289
J2 Dem·auon of Brus equa . Brus equation ............. ..
. d t ding o f the terms m 290
12.l Phy'S1ca1 un ers an . articles and excitons ........ .... . ......... .
13 Quan tit.at.we treatment of quas1-p ................................ 291
14 Radlati\.'c processes ........................... :................. and

H . l General formalization of absorption, emission .................... 292

luminescence .... · · ·· ·· · · .... · · · · .. · · .. · · · · ·· ·· · .. · · · · · · · · · · · · · · ·.... 294
14.2 Phosphor .................................................. . ............................... 295
14 _3 Absorption and transmission spectroscopy.... ............................
14
.4 Photoluminescence (PL).. ........................ .. ....................... .......... 295
15 Optical properties of nanostructures ........................ ......................... . 296
N
15. 1 anoparuc · Ies .............................. ....... ·.········· ············· .............. · 297
1s 2 Measurement of binding energy of exciton ................................. 297
16 Optica.J properties of heterostructures ..................................... .. ......... 298
16.J Quantum wells and quantum dots ..... .. .......... ................. .. ........ 299
16.2 Main characteristic features .... .... ..... ...... .. ............ .... ................. 301
17 Exercise ............................................................................................ 305
17. l Short answer type questions .. ......................... ........ ......... ......... 305
l 7.2 Long answer type questions .. ... .................. ..... ........... ............... 306
17.3 Numerical problems .. ........................................ ............ ... . .... .. .. 308
17.4 Multiple choice questions with a n swers .................. ............. : ..... 311
17.S Advanced Problems ... ... .. .......... .. .................... ................. ......... . 315
Chapter 6: Electron Tranaport in Nanomatertala 317-385

1 Introduction .. ......................................................... ......... .................. 317

2 Carrier transport in nanostructures........ ... . .. . . . .. . . .. .. 318
··························
 2.1 ~~~:;~,~:. ~~·t·~~~~.'~. ~~~~~'.~.~'.~.~. ·~·l· .~~,·~· .~~~~~~.~~'.~ ~~.~
.. ........••........ 320
3 Couloinb blO<'kndc <'ff<'c t ..................................................... ... · ...... · ... · 320
3. 1 Cond 1tio11s to oh <'tvc Co11lomh bin< kodc cff<'c.l. ........................... 322
3.~ E;\pc11m<'nllll rt'11111ls 1<'l111 nd to Cou lomb blcx kade effec t ............. 323
" Th<"nnion1c ('n1lsslu11 ............................................................. ............ · 325
4 l Rtl' hord. on's law ......................................................................... 326
4 .2 Child's lnw .................................................................................. 327
4.J Rel ared µhc no111c na ..................................................................... 329
s Localu:ied \-Crsus extended states ....................................................... 330
6 Tunneling Conduc tivity ....................................... ...... ....... ................. 332
6 .1 Conductivity due to uctuation induced tunneling ........................ 333
6.2 Conductivity due to multi-step tunneling through localized
states .... .................. ........... . .................................. ........... .. ......... 334
7 Hopping Conductivity ..... ............................................... .................... 336
7.1 Mott's law of variable range hopping conduction .......................... 336
7.2 Variable range hopping conduction under field ............................ 342
7 .3 Percolation theory ........................................................... .......... .. 343
7.4 Hopping conduction and percolation theory... ......... ..................... 345
8 Defects and lmpurities .................. ...................... ........ ....................... 348
8 .1 Impurity in solids ................... ...... .............. ...... : .......................... 349
8.2 Various types of defects ........ .... ................... ................................ 349
8.3 Topological defects ......................................... ... .... ...................... 358
8.4 Deep level defects and impurities .................. ..... ....... ............ ...... 359
8 .5 Surface defects ............. ......... ........... ........................................... 361
9 Exercise .......................... ....... .... ....................................................... 364
9.1 Short answer type questions ....................................................... 364
9.2 Long answer type questions ........................................................ 365
9.3 Numerical problems ...... ....................... ...... ...... ........................... 368
9.4 Multiple choice questions with answers ....................................... 369
9.5 Advanced problems for projects ............................. ..... .... ............. 379
Chapter 7 : Applicatlona of Nanomatedale 386-441
l Introduction .............................................................. ........... ... .......... 386
2 Application of nanoparticles ...................... .......... ....... ........................ 387
2 . 1 Applications of nanoparticles in medicine ...... .......... ........ .... ........ 388
2.2 Applications of nanoparticles in manufacturing and materials ..... 3 89
2.3 Applications of nanoparticles in environmental issues ................. 389
 2.4 Applications of nnnopntllclc a In ·norgy nnd e lectronics ...... .. .. ..... 389
3 Applications of q\lnntum dot& ..................................... ....................... 390
3.1 Applications of QDs In hlol11r1ngl11g ............................................... 392
3.l pph "Hons of QDR In photovoltulc dcvlccH ........... ...................... 393
3 r phcat \on~ of qut\ntum do tu ltt solar cclls.................................. 393
4 pp\\ a\tons of n onowil'ca ..................... ...... ....................................... 396
.\. 1 pphcations of 11a11owire lasers for ultrafast transmission ........... 398
4 .:2 Applications of semiconduc tor nanowires in sensing o f proteins
and chemicals .......................... ...................... ................... .......... 398
S Single electron transfer devices (no derivation) .. ...... ........................... 399
5 . 1 Structure of single electron transfer devices ............................... .400
5.2 Basic operations in single electron transfer devices .................... .400
5.3 Applications of single electron transfer devices ... ........................ .401
5.4 Ad\13.0tages of single e lectron transistors .. .. ........... ................. .... .40'.2
5.5 Disad,"a.Dtages of single e lectron transistors ............ .................. .. 403
5.6 Comparison between SET and metal oxide semiconductor FET ... .403
6 Carbon nanotube based trans istors ... .............. ................................. .404
6.1 Properties of carbon nano tu bes (CNT) ... .. .. .. ................ ................. 404
6 .2 Applications of CNT based transistors ........... ................. ............ .405
6 .3 Applications of carbon nanotube fie ld-effec t transistors
(CNTFETs) ...... .......... ........ ............. ... ... .......... .............................. 408
7 Heterostructure lasers ..... .. .. ........... .. ........................ ........... ..... ......... 409
8 Thin films for photonic devices (LED) and their applications in
solar cells ... .... ... .. ........ ............. .. .. ........................... ........................... 410
9 Magnetic quantum well ..................................................................... 412
10 Appllcations of magnetic dots in magnetic data stor age .. ........... ... .. .... 413
11 Micro electromechanical systems (MEMS) and their applications ....... 413
12 Nanoelectromechanical systems (NEMS) and their applications .......... 415
13 Importance of2D mate rials ....... .... ............ ............ ... .... ..................... 417
13. l Criteria for existence of Dirac cones ... ..... .......................... .. ...... 420
13.2 Graphene vs traditional 2d materials .......................................... 420
14 Magnetic nanoparticles ...................................... ......... ...... ....... ... ...... .421
15 Exercise ......... .... .............................. ..... .. .. .... .. ........ .. .... .. ... .... ..... ...... 426
15.1 Short answer type questions .................. .. ................. .. .. ... .. ....... 426
15.2 Long answer type questions ...................... .... ....... .. ..... ... .. .. .... ... 427
15.3 Multiple choice questions with answers
(Mixed from a ll chapters) ... .. ... ... .... .. .. .. ... ..... ... ..... ....... ..... ....... ... 427
 C hap te r 1 - Introduction

"To understand tlie t1ery lnrgc, we must understcmd the t1cry small" • Dcmocritt.111 {400 BC)

1 Introduction
'Nano' is a prefix used to describe 'one billionth' or 10-9 of something. It is really very small
compared to the objects observed in daily life. To have some idea of this nanoscale, we cit.e
here some examples in real life. The diameter of a hydrogen atom is,.,, lA(= 10- 10 m). If
-..-e place 10 hydrogen atoms side by side, it will measure a nanometer (lnm = io- 9 m); a
strand of DNA is 2.5 nm in diameter while a red blood cell is about 7,000 nm wide. A human
b&ir is between 50,000 and 100,000 nanometers thick, a single sheet of paper is around 75,000
nanometers thick, while a pinhead is around a million nanometers wide. If each person on
the earth was the size of a nanometer, everyone on the planet would fit into one HOT WHEELS
MATCHBOX CAR. Thus, nano is imper, super tiny.
The technology connected to this nanoscale science is termed as NANOTECHNOLOGY. The
concept of nanotechnology was introduced by NOBEL LAUREATE PHYSICST RICHARD p FEYN-
MAN in bis famous lcctw·e entitled " Ther e's plen ty of room at the bottom" in a meeting
of the American Physical Society in December, 1959. He predicted that it is possible to put
the entire 24 volumes of the Encyclopedia Britannica on the head of a pin. This idea was then
deemed to be impossible but now it is reality. Fifty years later, no one would question that the
twenty first c1intury is indeed a 'Nano Era'. Since then, there have been many revolutionary
developments in physics, chemistry and biology that have demonstrated Feynman's ideas of
manipulating matter at the atomic scale. The term NANOTECHNOLOGY was invented by NORIO
TANIGUCHI , a professor at the Tokyo University of Science in 1974 to describe extra-high pre-
ci1>iou am.I 11ltra-fi11t• Ji111c11sio11s. Profcs~or Tauigm:hi Jt•scribt•J the subjed "Na11otcclmology"
in the following way: Nano-technology mainly consists of the processing of separa-
tion, consolidation and deformation of materials by one atom or by one molecule"
He introduced the idea of 'top-down approach' for the fabrication of nanomaterials with a
Prediction of improvements and miniaturization in integraled circuits, optoelectronic devices,
mechanical devices and computer memory devices. Approximately ten years later, the 'bottom-
11P approach' was introduced by t< ERIC DREXLER during the discussion of creation of larger
objects from their atomic and molecular counterparts as the future of nanotechnology.
The field of nanotechnology is now a rapidly growing subJ~t and has direct enormous im-
plications in science and everyday life. Nanoscience is a cross disciplinary subject. Scientists
fr~m various subjects such as physics, chemistry, biology, medicine, computer science, materials
:.Cience and engineering are working on it for better understanding of the underlying facts re-
Nanomaterial:;: T hl'Ory Probloms nnd Soluc lo_n11_ _ _ _ _ _ _ _ _ _ __ _In_t_ro:...:d:.::u:.:::ct:,::io~n

latl'<i to nru\omnh'1·11tlH n11d 111\11oh•1·l111olo1tv S11d1 m llnho1 nt101111 from vari ous fields of science
an.> n·1m\rlmbll• m tl11s p1wt h111lt\1 1111hj1•1•1 n111l 1111 r1 rr1111lt, 11 huge tl'cl1nological advancement
hos tnkl•n pll\l'l' Tlw IMll ol 111111os1'11•1u·.. IH r1•ls\L1•d to I111• NL11d y of pliyHwnl phenomena and
manipu\11tim1 ,,f 11rntt· lials J\ I 11t 11111ic, 11mh•c·11lnr, 1111d 1111U'rnm oleocula r 1U'lllf'11, where propcrti~
<l1tf,·r~ntkant ly 11'\lm I hoM' nt n mocm111·0111c 11colt• Nnrwt1•d111ology 111 aasoc1ated with tJ1,.
<ll~(~n. l'h,\Tnrll'nznl 1011. produclion, nm! npplica.tion of strncturc'8, dt-vice11, and 8YBtelllll by
l"Qlttrolling :;hl\pc and sizl' at the mi croscopic scall' (nanOflcale) . Truly speaking, it JS th" col-
laborntiw outcome o f various subjl:'cts like p hysics, chemistry, biology, computer and material
~~ intrgratC'd with enginl-ering tech11 o logy at the nanoscale. In nanoteclJnoJogy, sc1encr
and rogineenug work together o n making t.he part icles, things and devices at the atomic and
mok-cular scales. So essentially one is studying nanomaterials and their properties and u~
othff is using those matel"ials and properties to create som ething new or different. :-<anotech-
oology and nanoscience got a n upsurge in the early 1980s with two major developments JD
scienoe: (i) the advances in computing power and (i i) material modeling coupled with sigru!-
ica.nt. ad\'anoes in characterization such as the scanning tunneling microscope (STM) and the
atomic fo~ microscope (AFM).
In this rapidly progressing field of nanoscience and nanotechnology, it is always instructivt> to
highligiu.. the most important and active areas to the scientific community. Nanomaterials cross
the boundary between nanoscience and nanotcchnologies and link these both areas together
Gtonerally, D.8Jlomaterials deal with sizes of 100 nanometers or smaller in at least one dimension
The mat.enal properties of nanostructures are different from the bulk due to the high surface
area over volume ratio and possible appearance of quantum effects at the nanoscale. Tht> study
of size and shape effeds o n the material properties has attracted enormous attl'ntion dtte 10
their scientific and industrial importance. Nanomaterials or the nanoparticles can be classically
illustrated in the following way: nanomateriul is an object that has at lea.it 01te d1meru-ion in
the nanometer 11cale approximately 1-100 nm. D ue to the reduction in the spatial dimension, or
oonJinement of particles or quasi particles in a particular crystallographic di~tiou within the
btructure, significant cha ngl1l in physical p.roporties of the system take place in that dirl'Ction
H.eoce cUM;sification of thi: nanotitrncturi:d nll\tt·l'ials 1md :;yst cms es:>entiruly depends on the
numher of dimensions which lie within thl' nl\nometer range.
The tkrm nano1naterial has a particu lar ml'aning . Nnnomaterirus a1v materials at the
n.anoscalt> whose propl'rtil'I! such as conductivi ty, colour and mechanical h11rdness change due
0

to th1:ir 1U1110S1.:Bh.• diml'ni;ions. Nanomatcriah; t'ncompl\S.-; 111! nanoscale moteri111s or m11teri11ls

that contain at le&!t on11 nanoscal<• strncllll't', uither o n t lwir s urfaces or internally. Thf.'Y can
be organic, inorg11J1ic o r biological. Nanonrnturin ls c:n11 bu or vnrious shap<':l a nd sizes sut:h
as nanoplat1111, nanoparti clc.'ti, nanowirl'11 nnd m111ot11bes and c1111 be enginet!red in laboratorie;;
wiLh sophibticat.cd computer-controlled l'q u ipnll'nts . NMomatt•rials are also available in nature.
Some exampll'll of suc:h naturn lly occurring nru1omalt'1 ia ls 11rc smoke, &·a spray and volciuiic
ash, as well as minerals, soils, salt pa1·ticlcs and biogonic particll'S. These materials have one

..
Nanomaterials: Theory Probloma o.nd Solutions
Introduction

or more dimensions in tht• nnno1111•tt-1· rn 1114t•.

Depending upon llw dmwnsio11nlily, 111111cm111turlole t•ar1 bt· clne11ifl1·d into the following cat-
<·gories:

L Systems conflnod 111 throe dimcnl;jlons (zoro dlm onslonnl structures): These sys-
tems huw all throe.• dimensions in I.he nanomclt•r range. No extc11Hion beyond nanometer
is allowt'tl in any dirnction. Examples of such ay11Lerns are: nanoparticles, nanogralns,
ua11oshells, nanocapsules, nanorin gs, fullerent's, colloidal particles, activated carbon, nan<>
porous silicon and quasi crystals.

2. Systems confined in two dimensions (one dimensional structures): These sys-

tems have one dimension in the nanometer range and other two dimensions have no re-
striction in length. Examples of such systems are: nanorods, nanofilaments, nanotubes,
quantum wires and nanowires.

3. Syste.m s confined in one dimension [two dimensional structures): These systems

have two dimensions in the nanometer range and t he third one has no restriction in length.
Examples of such systems are: discs, platelets, ultrathin films, super lattices and quantum
wells.

Nanomaterials possess unusual but interesting mechanical, electrical, optical and magnetic
properties and have created a high interest among the scientific community in recent years.
These interesting physical properties find a wide range of applications in technological fields.
Some of the materials along with their technological applications are mentioned below.

1. Nanophase ceramics are of particular interest because they are more ductile at elevated
temperatures as compared to the coarse-grained ceramics.

2. Nanostructured semiconductors are known to exhibit nonlinear opticn.I properties. Semi-

conductor quasi-particles also show quantum confinement eff~c.ts which ma~ lead to spe-
cial properties like the luminescence in silicon powders and s1hcon-germanmm qul\lltum
dots as ·infrared
' optoelectronic
· d ev1ces.
· Tl1ese se
• m'conductors
1 are used as window layers
in solar cells.

3. Nanosized metallic powders have been used for t he production of gas tight materials,
dense parts and< porous coatings.
•
These nnnopowd ers are ductile ind'nature and. have
• cold
tb
welding properties which make them su1'ta bl e for metal-metal bon mg espec11111Y m · e
electronic industry.
" . ., . . domains. One may expect that the grains
4. Single nanosized magnetic particles foim
. mono- d ' th d mains while boundaries
· t · J also correspon wi 0 '
m the magnetic nanophase ma ena s • . h special atomic structures with
1
correspond to disordered walls. Very small partic es nve

3
 Introduction
I I .
N tUlOJllf\~Ol' (\ tJ.
' l ' l1t101·v
< I'.
J'l'ohl1
-
nw t\ll cl ~ol11 t,lqn11
-

I I1·I1 lvo rluo t,o rtfH'c:lrd woportl ·H in a<lcHtion to the super-

' \ , imuooc>HIJ H>Hll,i·H htW" IJoru 111~cd for mechanical force
1111
dliwn•t(i t•lt•t·t.rn 11 h· · "t.l'H, wMi
0 1·n1t\l\S(tll't.l t1111 boh11v111111'. l\f(IW ,1c, . f . t'
IJ • (t' JI 11 ) f' 11• lil11h d11rn1lt Y l111'111·1r11\f,lo11 ut,m:i.tit,c ' r.md mf,1,gnct1c re n gcra ion.
trnrudl•r t'tT1> 11 t t1 , l , '·

. or pl111'inwtallic composition have a

5 Nt\nt~lriwt Hl'l'tl 1t1(•t11I d11Hl,t•rR 1t11d collnlc I11 <>J mouu~ · J · ,

· s pt'<' iC\ I illlpf\ L l 11 l'I\ t.1\ly t.h! nppl IrnLlo111J. 'l'Iwy wa y Herve 118 prccur~orH . 1or new type of
hl•ll' t'\1~1.ml'Oll1J ('/\IH ly8tH (CorLt•X-Ct\Ln.lys t;~ ) antl lf..LVO
J offcn:<l s ubs• tant1aJ advantages con- .
(.'\.'rning nrtivit.y, Hd t'cLlviLy flnd lif(.ltlmo in clwmlcal Lransformat1ons and electrocatalys1s
(fud ccUs) .
6. Nanostructurcd mctal -oxi<lo Lhin films aro roceiving a growing attention for the realizar
uon of gas st<naors (NOw , CO, C02, C H<t and aromatic hydrocarbons) with enhanced
sensitivity and selectivity. Nanostruct urecl metal-oxide (M n02) finds application for
rec.hargeabl(;' batteries for can; or consumer goods. Nanocrystalline silicon films are used
for highly transparent contacts in thin film solar cell. Similarly nanostructured tita.-
nfom oxide porous films are used for its high transmission and significant surface area
enhancement leading to strong absorption in dye sensitized solar cells.

7. Polymer based composites with a high content of inorganic particles have a high value of
dielectric constant and are suitable for photonic band gap structures.

The subject of the book "Nanomaterials: Theory, Problems and Solutions" are
classified into several sections and are presented with comprehensive discussion on each nnd
every topics. T he sections are mentioned below:

1. Important discoveries in nanomaterials

2. Basic physical principles and quantum effects

3. Synthesis and characterization of nanoma.terials

4. Optical and electrical properties of nanomaterinls

5. Effect of size on the properties of nanomaterials

6. Applications of nanomaterials

2 Important discoveries in nanomaterials

In this Rection, some of t.he important discoveries in nanotechnology are briefly mentioned
chronologically to grow interest among the readers in the subj ect NANOMATERI ALS.

4
 - :.~·· . . ~ . ..._ ··~ .....

Nanomaterials: Theory Problems and Solutions Introduction

In 1981 Alexei Ekimov, a Russian phyt-ilciRt, cllt~covorcd 11anocryRtalline, semiconducting

quantum dots in a glass matrix and conduct.e<l pioneering Rt11cl!ca of their electronic and optical
properties. T wo chemists Richard Sml\lloy and Ilulwrt Curl, o.t the Rice University in Texas
together with the astronomer Sir Harry I<roto at tht• University of Sussex discovered a new
form of carbon in 1985. T his new form of carbon was a stable cluster of 00 carbon atoms. Later
they constructed a model of the cluster as a molecule with 20 hexagons and 12 pentagons. It
was called carbon-60, a soccer-ball shaped molecule made of 60 carbon atoms joined together
as hexagons a.nd pentagons shown in Figure 1. They called the molecule buckminister fullerene
because the structure resembled the geodesic dome invented by Richard Buckmin.ister Fuller.
This new form of carbon could withstand very high pressure and heat. These three scientists
we.re awarded Nobel prize in Chemistry in 1996 for the discovery of this Buckyball of carbon
(C-60).
Ge.rd Binnig, Calvin Quate, and Christoph
Gerber invented atomic force microscope
(AF~I) in 1986. The AFM has the capa-
bility to view, me.asure, and manipulate ma- Covalent bond
terials down to fractions of a nanometer in
size. The discovery of this instrument pro- Pentagon
,;ded a tremendous upsurge in the field of
nanoscience and nanotechnology. It was pos-
Hexagon
sible to estimate various types of forces in-
trinsic to nanomaterials from the measure-
ments carried out with the help of AFM.
Figure 1: Buckyball (C-60)
In 1986 three chemists Paul Alivisatos,
Mounji Bawendi and Michael Steigerwald
showed that gold particles emit light in a different way at the atomic level. This experi-
mental observation was regarded as a major turning point in the field of nanotechnology. For
the first time the behaviour of atoms was seen to deviate from the prediction of classical theory.
This necessitated the need for quantum mechanics to explain why very small things behave in
a different way from thefr bigger counterparts.
Don Eigler and Erhard Schweizer at IBM's Almaden Research Center manipulated 35 in-
dividual xenon atoms to spell out the IBM logo in 1989. This is shown in Figure 2. This
demonstration provided a beautiful example of the precise manipulation of atoms and ushered
in practical applications of nanotechnology in diverse fields.
Sumio Jijima is an electron microscopist. In 1991, he discovered something str'.1°ge in a new
form of pure carbon with a few nanoscopic threads. He observed closed graphi~e structures
including nanoparticles in ele.ctron microscope and called them nanotubes. It is actually a
stretched out form of a buckyball, a sheet of carbon curved into a cylinder capped at .each
·1 bl b th · · gle and multiwall form. Such smgle
end. Nowadays carbon nanotubes are ava1 a e o m sm

5
 and colleagues at Mohil
ICM-48 in um. 1'hEst
Yw-ell as for drug delivery,

Flgllre 2: IB~f :ogo "1'.itten .nth xenon atoms.

l" 3!l\l ~._ t~··d th~ m \'NU~t 01· ~{Oil$ in

Th~ \.'ll~!Ni ~-.iroti$ .: m wit-
- .-s t-~ cbc:niC"N \.'\'\'ll~ which oc~\trtro in
.t:. nlli-c=.th af :\ ~ •ud. Hl' wa.:; awa.rded
~~ pri~ in cb~,mistry in 1999.
\\1th th~ di wry of :$'0phisti at€d in-
~ent: th~ ~,_,. lt.•\'l"l o.f u.nd~nmu1diug
the n t utt C1f liquids and ~l6..~ at the
&U1mic and m tt'ttlar l~Yds h • ~d"-anet.~ a
lot. Lquids Md - ht\\~ uo ~tnu:ture
and 11\n' c.allt"d amorphott$ How'-"' "r, m 2002,
a chc>mi~ M th~ North :volin ~t te ut-
' "ttlil t y J&me::i 0 . ~la.rt.in a.nd hi - tet\lll discov·-
~nd {\ CHE.\llCAL 1~nl. 'Clf'l.F' th t heJ~ $0-
t'Dtl:it - to Ueslgll tlw l"'Omp0::>1t ions and Slr\\t'-
Fi~'\lrt" 3 : inglt• wnll cnrbon nanotube (upper)
tures of sc.•wrnl ~l .· nd liqmd.$ h. is
tw<l U\\\ltiwiul t:•u-bon mwotnbc (lmVl'r)
worth mt:ut iouing lwre lb t th\' mo' Uh.·nt
of ~l~tron • \\'lt hin lUl t m bl\.:i ~n t -k~
in o ~iqm.> c..~paimt>nt ot th\.' ieun lnstil\lttl of 'D.>cllliol .gy in 2002. The shortest laser pulse,
ruovm.g fust~.r LhM ('\"l'I\ th~ Yibrst..ion of atoms ''-ns used fur this purpose. Laser cooling was

6
 Nanomaterials: Theory Probh•nui nnd Sol11 1.lo1iH
Introduction

i1~,·ented in 19 0. ~hi1:l opc11cd up n ll<'w chnpt.N 111 ulLrn... tow t.umpcrnturc phyalcs. Samples of
dilute atom •
doud~ II\ th<' mkro kt•)vlt1 l'l\ l tu'C
C"
WOl'Cl Cl'CllLcd n11d 11uccl fclr
.. "
· j on meMurement.
prccra
Nano k.-clvm tcmpcrnturc~ were needed to cxplon.i gl.Ulc1:1 llko t.he Boac-Ehmtein condeNat~.
The subject of ntu\otechuology hus received cm imme111:1e progress with the invention of
\"&ious intricate techniques of synthesis a.nd charncterizatioD.8. Such techniques are described
in a comprehensive ru1d systematic way in this book.

3 Basic physical principles and quantum effects

Newtonian mechanics deal with physics on the human scale in the macroscopic world. But
'"""' kllow from the kuowle<lge of mo<lcrn physics that the worl<l is <liffercnt than we are use<l
t-0 encountering using Newtonian mechanics. According to quantum mechanics, energy is not
continuous but instead comes in small "packets" known as quantum and the reality is really
probabilistic instead of deterministic. Such "weird" consequences of quantum mechanics are
averaged out on the macroscopic scales and therefore, are undetectable. However, at the
nanometer (10- 9 meters) scale, quantum· mechanics cannot be ignored and in fact , quant.um
mechanics begins to dominate. Nanotechnology literally opens up a world of possibility in that
it offers an oppo1tunjty to give a tangible explanation and use for quantum mechanics.
Matter is not discrete: instead, it is quantized. This means that it does not have a definite
siie or shape at the microscopic level because it is quantized. Energy is not continuous but
there are only certain incremental and allowable amounts of energy. Zero energy· state is not
an allowable energy state, so all particles must have some vibrational energy. In fact, matter
and energy are interchangeable and matter is dualistic, exhibiting characteristics of particles
and waves. Thls has been demonstrated by the double slit experiment for electrons. This
experiment shows that electrons exhibit interference wave properties that result in diffraction
and interference. nut under certain conditions, the wavefunctions associated with the electrons
disappear and the electrons act like particles.
We have a fundamental lack of understanding about the nature of matter: neither the
wave model nor the particle model can explain the essence of matter or radiation. ~1 the
macroscopic world, quantum mechanical and Newtonian mechanical p~·e~iction: of behav1~r ~f
the particles appear to agree. However, at the nanoscale their pred1ct1ons dwerge and it_ is
Ql.!antum mechanics that proves to be the most accurate. Consequently, quantum mechan'.cs
provides a more comprehensive understanding of how nature really is. Hence quantum physics
is the best model of reality. . . SchrOdinaer's
In this book wave-particle duality, basic formalism of quantum mechamcs,f b d tb t
' . 1 . d'ff .• t potential wells concept o oun s a es
equation qu·mtum confinement of partic es rn 1 eien · ' . d t d
• • • . . Tl · uld help -readers to un ers an
and quasi-particles and excitons are explored Ill detru 1· 11s wo .
the concepts used ~o explain the physical properties of nanomatenals.

L
 . lnt t'Od ur t 1011
Na.nomate1·it'1s: 'lhl'<n·y I l'Obk1m~ ~o~n~d~~l~)~u~ti~o~n~8----------------_.;.;.;..:,::;:._
I

4 S nth sis
., t su t 11t:~h~t1 f>l\l't icll'H of J\fll\0 11\0t r dim.,; nsio11s with
11
The mrun dmlll'\~'\' in nnnoh.'<'l\\\() IO~.Y I8
0
l~JU't'OW .1 '
sill' distribution tu\d I urlty. A t11Hubcr uf inl·l hotls ltnv b 't' n d v1.s :d ru\d nro
'
sm:c~ss.
- ·l • 1,,1.. .... ."toi·i· e~ to s,·ntht·size n1u,0$lructur ci mot •rinl~. Tn pnnclplc, nny method
&. JI,
1
ca~'blti of pt'Oducing wry
nl v' u::.'t.'-1 11\ ' vv .. ""
filw grnin sizl·d polyeryst-nlli n mnt.orinJ Ctu'I bu ut.1l~zud to produce
. ·' . .

\l~\Q('.l'\'Stn.lline nmte1·i:\ls. Gcnero.lly thrro nre two nppronchcs of th synth 'SlS or llf.\t\Omntc-
ri~s: Ci) reducing t hti size of t.he bulk nmtel'i~ls to the fine gnuns of nnnom ·tcr size, known
~ TOP oow1 APPROACH tu\d (ii) building up by self-B.S$ ·mbly of fewer ntoms or molecules,
known as BOTTOM UP APPROACH. In top down process hU"ge.r materials ru-e reduced to smnller
dimensions of the order of na.nomet.e.rs and in bottom-up approach the ma.te.rin.ls are build-up
to nanometer size. F\1rtl1er the commonly used methods of synthesis of nanomaterinls are cat.
egorized as physical and chemical methods. The physical methods include consolidation, gas
aggregation of monomer, inert gas evaporation, sputtering, ion berun method , bull milling nnd
lithography whereas t he chemicru methods include chemical precipitfl.tion and capping, sol-gel
method, micro-emulsion, condensed phase synthesis, reduction technique and electro-chemical
deposition.
Whatever be the method of synthesizing t he nanoparticles, it is essential to avoid the
coalesc~ce ~f particles into larger particles. T he objective of any method should be to achieve
~~::dispersity a.nd ~emical stability of the synthesized nanomnteriflls over n long period.
efor~ the synthesis routes which protect or passivate the p articles have b ecome nttrnctive
com~:e to :hhos~ which do not take care of long term stability or monodispersit y
ese syn es1s methods a.re used with differe t d .
phases in a variety of mater·al l l all n egree of success to produce nanocrystnlline
1 8 · su Y gas condens t · ch ·
precipitation technique ha b a ion, me a.meal alloying and chemicnl
ve een most commonly e 1 d
vapor deposition, sputtering and .. mp oye to produce nanocrystn.llites; while
layered nanocrystals. The ·sol- e1ectrodepos1t1on
. t ech ruques
· h ave b een u sed to synthesize the
f ge1 process is gene ll d
sa ion and mechanical alloyin ra Y use to produce clus t ers. Gas conden·
nanocrys t a11'ites. These methods
g are
of smost
th commonly
. e~p loyed to produce large quantities of
yn es1s are described in details in Chapter 3.

5 Characterization

In order to understand th .
essential to charact . e inter-relationship betwe
cnze nanoc. tall'
surcments related to such rys . inc materials on b
en structur
e~ and p l1YSical properties, it· ··is
~f nanoparticles and d characterizations invol h oth atonuc and nanometer scales. Mc11·
ng of the inter-particl . ·~rnunat1on of the shapes and size-:;
1mm · un erstandi ve t e det · · . ·
A ensc tn1port.ance both fr
nuniber f experimental t om
0 . sc·ient1·fi c and th e. interac tions. Tll ese .informations nrt. of
ch the
· e ruques have been eme industrial pomt · of view of applir1it11lll~
· ·
8 p 1oyed to "'eld
J •
. 1
struc tural in forrnntl<)tl •11
Na.nomatcrinls: Tll('ory Pro~llcmfl nncl Solut Inn Introduction

ntUlOC'r) htllilw nH\l<•rinlM. Tlw •' 1111 htclf' cllt1•1 t 1111! '°"' oplr t.N•lmlqur•'l au<"h M
1. ,\ tr1mi\' [,wtt' mH "''< 11pv (A Ff\ I}

In 'ftdd11 ion h' 1 l<'~l' dil"<'d microocoplc tuchniqueEJ, m a ny indirect techniques are also bf?ing
u: t.o \...N~n thl' dmrn.rtcristic infonm\tion of the nnnoma.terials. A few of such indirect
tt'\ ·1).q\lC'~ ~ ~~ follows:

1. A.~.::orption spect.ra

Di~chon of X-rays, electrons or neutrons

3 . Rutherford back scattering (RBS)

4.. Raman spectroscopy

5. Auger electron spectroscopy (AES)

6. Photoluminescence and Photoluminescence excitation

As for example, X-ray diffraction patterns for various sizes of nanocrystals show that the
peaks are broadened as the crystal size is reduced. T he absorption edge or peak is shifted
towards higher energy side by reducing the size of the system indicating the widening of the
forbidden energy gap of the material. These techniques are complementary to each other.
Depending on the system to be studied, one technique may be better than the other. These
direct and indirect techniques of characterization are discussed elaborately in Chapter 4.

6 Effect of size on various physical properties

All the materials - may be metals, semiconductors or ins ulators - have size dependent physico-
cb.emical properties below a certain critical size depending upon the details of the materials.
For most of the materialR, it is below 100nm. Thus geometrical structure, chemical bonds, ion-
ization potential, electronic properties, optical properties, mechnnical strength, melting point,
magnetic propertiea etc. nre all nffected by tha pn.rticle sizes. As for exnmple, a smrul sample
of gold has quite different propertien fro111 the ordi nary gold . A lump of gold is yellow in color.
If the lump i8 hroken into nanosized chunks, the gold would change color depending on the
size of the chunkH. At lOnm, it is no longer shiny and yellow but instead it absorbs green

9
light a.nd appears red . lts md ting t.<.•u1p<1n1.Lm1 d c 1·t•OHt'H d rfl8tic:td ly M Hli11 !1:1 dt•t:1•c•11t111d , Uol1l
1

also bchtwcs a cntolyst in thit.i n•l(i11ui of Hi1.11 but w1• k11ow llmt, 11, 111 d11J11il1·1~1ly J111•1t 1i.t tf 11•
micro/mt\cro scnlt" So, it is snll• t.o tll\Y tl111.L 11 lo11 w11t.Hw1 1 I< now n1·1· tolfJ.lly dlffc•1'f'l1t 1~t 111ui1m1:1ll1:,
ht•nc<.· th. birth of words i:;Hd1 rtH 11n11lH11t\L<.•rlnlH, 11 f\11ol,<•d111olo1~y nnd 111u1<mc;ll'JH;1•.
By breaking down n bHlk 1110.l<.•rial iut o 1111.11oahwd plu'Licl1•H, 1n11.11y of lt1t prorw1 t,l• ~H c1111 IJ1·
changt'<l ind<.'\.'ll. D 1 cont rortiug Lhe rna1111<.•r i11 wliicla 11araorm·tn·-Hc1t lc· mol1'<,1ilnr tttn 1<:t.1111·'f 1~11·
formc<l, it is p0$sibk to ·ontrol tho fumlamc.•11tal prop<.~rtiu1:1 of Lhl' mo.t<·ritllH. H11d1 pliyf1l1;1J.J r111t!
chemicru pi-opertil.:'s may include color, electrical conductivity, melting t<m1p1·rnt111·1·, 111.1.rdw·.,.,,
crack rt'Sist&1ce and strength. These properties change because of the largf• t'XV<~uff• of Uw
surface &"e8. of the nanomaterials.
\\lien particle sizes are reduced to the nanoscale, Lhe ratio of surface area to volum1~ ;,,.
creases dramatically. Very small particles are staggeringly reactive in many important drcmklll
reactions including those involving catalysts which occur at surfaces. This is one of tlw rnwm
that chemists a.re very excited about nanoscience. They try to increase surface area to get rnort
catalytic action. This speeds up almost all physical and manufacturing processes and incrca.3tl
the resource and energy efficiency of those prncesses and products.
Not only the chemical properties of nanomaterials are changed but also other physical
properties such as mechanical, thermal, optical, electrical are also greatly modified at the
nanolevel. Such modifications in the physical properties of nanomaterials are briefly mentioned
below.

1. Mechanical properties: It. has been observed that nanocrystallinc materials have r~
duced elastic modulus and density by 30% or less compared to their bulk countcrpartR.
This may be due to large free volume at. inter facial space and increased average intcr-
atomic dic;tance. Hardness or strength increases by 4-5 times than their bulk counterparts
with decreasing size. Diffusivity of nanon'laterials also increases up to double of the ini-
tial value of the bulk material. In nanomaterials, numerous interfaces provide paths for
difftLc;ion. As a result diffusivity increases which in turn, increases sinterability nt lower
temperatures.

2. Thermal properties: It is observed that. melting point is lowered with decreaRing

particle si7.e. It. may be reduced to half of the original melt ing point. The specific heat
and thermal expansion may increase up to 50% or more with reducing particle size.

3. Opt.ical properties: In small nanoclusters, the effect of reduced dimensionality on ele<r

~:~me ~tructure has the most profound effect on the energies of highest occupied molecu·
' orb~tal (HOMO) [valence bnnd] nnd the lowest unoccupied molecular orbital(LUMO)
[esse~t'.ally the conduction band]. The optical emission and adsorption occur wl.ien the
trnnl:)1t1on of electrons occur between these two states. Semiconductors and many other
metals show large changes in optical properties such as color as a function of particle size·

10
Nanomaterials: Theory Problems and Solutions Introduction

The color and transparency of materia ls change by chang ing the size of nanoparticles.
Hence these can be controlled by processing pa ra meters. Due to the increase in ef-
fective band gap of materials, absorptio11 spectra shift towa rds higher energy and for
small particle, it may show stepwise ~\bsorption by dccren.sing 1:1ize of nanocrystals. Col-
loidal suspenses of gold na noparticles have a deep red color which becomes progressively
more yellow as the particle size increases. Silver p articles of 40 nm exhibit blue color .
Silver particles of lOOnm exhibit yellow color. Prism shaped silver particles are red
in color. The properties like photo-catalysis, photo-conductivity, photo-emission and
electro-luminescence n.re a lso affected by reduced dimensionality. E nhanced lumines-
cence wit h fast response has been observed by decreasing size of nanocrystals. This
occurs because of changes in electronic structure. Fast response devices with the emis-
sion of desired color are being used in practical applications. Nanopa.rticles are also used
in lasers as t hese can be operated at lower threshold. Raman spectra has been affected by
t.he confinement of photons and phonoris in nanoparticles. Optical properties are found
to behave nonlinearly in semiconductor clusters in glass or polymer matrix .

4. Magnetic Properties: Experimental results show that the values of satw-ation mag-
netization of na.noparticles are smaller but coercive values are much larger than their
polycrystalline counter parts. This is because of their high surface to volume ratio and
increased effective anisotropy. Curie temperature of ferromagnetic materials decreases
with decreasing size of nanoparticles, a nd hence the substance remains paramagnetic
even below usual Curie temperature showing super paramagtetism. In nanocrystalline
phase, each particle is a single ferromagnetic domain. Giant magnetoresistance(GlVIR)
is also observed in nanoscale multilayers consisting of ~trong ferromagnet (Fe, Co, Ni)
· auc.l a Wl'akl'r lllag11<::tic or nou rnaguetic lrnffer(Cr, Cu). Thi:; GMR property is usually
employed in data storage and sensing.
Magnetic nanoparticles are used in a range of applications like imaging, bioprocessing,
refrigeration as well as high storage density magnetic memory media. The large smface
area to vol11mc ratio rcsult.s in a. substantial proportion of at.oms having ciiHcrent magnetic
coupling with neighboring atoms leading to differing magnetic propertit•s. Bulk gold
and platinum are nonmagnetic but at the nanosize they act as magnetic particles. Gold
nanoparticles become ferromagnetic when they are capped with the appropriate molecules
such as thiol. Ferroelectric materials (e.g. PbTi03) become non-ferroelectric at reduced
sizes (rv 20 nm) .
5. Electrical properties: The discovery of a number of intricate and sophisticated tech-
niques have opened up a huge possibility of synthesizing and manufacturing nanomate-
rials with de::;ired characteristics. It should be noted that for a particular material there
is always a critical size below which properties are size dependent. In these ma_terials
the length of reduced dimension has to be smaller than the phase coherent length or

11
 Introductioo

t 111 111••1111 1111• p11t h au rll.tt•1ll11( l11111~Lli for 1•l1•cLrm1H in th e rnatt'rials. In this domain it
llhl l\llll' t1•1 l1•11Klh .,.1•11lt·~. 1 l1•C'll'l1•11I prnp<•rU<·H rll'I' gn·o.ily affl'ctc<l by the size. Electrit;;ij
1

111 111 , Ivii v ht 14 ., ht1•i•d 11y d<•cn'nHlllg ti i t• t1l'l.l' ot' rinnocryHialH. Tha.nsition temp<:ratUre
l 1 t1

ul 1illlh ll1ltldm tlt1K 111nLt•l'ln lH {11 -1(. Y 1Jci'J,Cn:s01) iH n·<lucc<l a.n<l th~ materials J~
1tt>< 1tt1111l\\( thlty with lht1 rndudlou 111 Hi'l.l'H.

\\'h•" 1h1• lt't1Kt h i;mll' In n. i;yi;lcm h.1 retluced, the electroni c prope;ties change a11d '-
' I,,, t ml\l11ly l o th e incrc1u;i11g influence of the wav~like property of the electrons (quan.
tum mi f hrrn lclll err •cli;) mid t he scfl.rcity of scattering cent ers. As the size of the syi;~
1 1 :iom1 lOrnp11mblc with the de Broglie wavelength of the electrons, the discrete nat11r~
of t1w 1·nl•rgy 2'ln.tcs becomes npparent, although a fully discrete energy spectrum i.'3 orJJ
oh ,·rvttl In itystcms thnt nre confined in all three dimensions. In certain cases, conduct.
ing mntcrif\ls bc.'Come insulators below a critical length scale as the energy bands Cf:aSI!
t.o ovc..'f'lnp Owing to their intrinsic wave-like nature, electrons can tunnel quantum rr.e.
cluu\ICl\1ly between two closely adjacent nanostructures. If a voltage is applied between
lwo flJUl08truct ures 1 the discrete energy levels in the density of states are aligned. Thi!
nlignmcnl increa.~e8 resonant tunneling which abruptly increases the tunneling current.
ConducLion in highly confined structures, such as quantum dots, is very sensitive to thr
pr nee of other charge carriers and hence the charge state of the dot. Coulomb blockade
<:ffect i8 one such charge state. This results in conduction processes involving single
<:l~Lrons and as a result they require only a small amount of energy to operate a switch.
t.r&Mi3Lor or memory element. All these phenomena can be utilized to produce radically
dHf •rcmt, t.ypes of components for electronic, optoelectronic and information proc~
3-}Jplicalion.tJ, auch as nmonant tunneling transistors and single-electron transistors.

7 Applications of the nanomaterials

Nrmu(;1y11tallluc wutcrl1:1l8 po8~l't>~ vory fi11c grui11 !:>i~L·::;. A::; u result, they exhibit a varidY
1Jf JJTOf)CJtk-tt th.at arc <liffcrcut tllH.l ufLL'll w11si<lcrnbly irnprovcJ iu comparison with those of
<:.tJ11V«mUcmal C41ansc-~u.iuc<l pulyc.;ry8tullim.: 1110.tcriuls . The fosdnu.tiug fidtl of 11a11utcd1110lo1P'
liUH wltlc rtuJS)4' uf ti.ppHcuLiow;. U1;L1 uf 11u11oscalu muturinls muy i111pruw the pl'rfonutUlce
()f J1f<'HC11tly u.vuilu.blu <lcvict.:8. Thu 11miuwr:;iun uf :;ilku, titnuium Jiuxitk:, days, pow<ler<-.J
iw:Lt.1111, poly111crH UHU clu:mkul prutluct1:1 urn ulrcutly iu usl' iu thl· society. Nc:w materials with
dHJ'c,m:m;.c J'cl'fon11uucc chuni.ctcristicM nru also bci11g tkvclopctl from mmostructure<l matcrialS·
Ou the otlic1· hum.f 1101uu ucw pt·uJucti:; huve curnc up iu the market using nauotubcs, buck~
ballH, <l ·11c.lrluu.:r1J, qnu11tu1u Jut.1> etc. Su1uu of the npplicatious of 11m10matcrials arc rncutioiw
l><:JlJW.

12
Nnnom atcrials: Theory Problc111:-; 1uH.I Solut.lo11H Introduction

1. Tough r nnd h nrd r ruttln~ toolH: C ut I i11µ, I oolH 111ndf• of 111\11ocryHtalli11c materials,
such ''~ hmb~tl'l\ enrhidl', t1\nt.1tl11111 l'11 rl>ld1 1 1111d 1.111111 111111 « HI bid,·, a m 11111clt ha rder , much
m<.m .' W<.'m'-l'<.'sistnnt.. t'rn~in11 l'l'HiKtn11t.1 n11d l11"il. lw1gl'I' t.1 11111 1,J11·ir ccJ11vcntiona l (la rge-
grain<.'(l) ('()\\l\h'rp1u·t ~. 'l'\H'Y nlHo P11nhlt1 t.lit1 111111111fn(' l,111'N t,o 1wtdil11<: vario111:1 materia ls
lUUt'h f~tt'l'. l'his illl'\'l' t\S\'S p n>dltt'l \v il y l\lld t-1i1t,111fil'n11t.ly n•cJ m•<t1 tJw ina nufact uring
1

~t.s. Also, for t.lw mini1,t.miznt.lo11 of' 111lcnH'l<·<·t.rouic cil'C:11lt,H, t,h<: i11d11Htry necdH micro-
drHl · wit h c.' nhalH'l'd <.'d gc r •tcntiou ttud l'nr bet.I.or wcn.r rcsiHl.1rncc. Si 11cc nanocryHtall ine
rtu·bidt'~ ~U'l' nmd1 stronger, hnrdcr, n.ud wciu·- rcHiHl.1.1.11t 1 t,hcy arc c11rrc11Lly being used in
t h~ ..~ mkt'l..>drills.

Ductil m achinnble cer a mics: Ceramic~ Mc Vt'ry hard , bri t t le, and difficult to ma-
chine. The::,'(' characteristics of ceramics h uvc discouraged the potentia l users from exploi t-
htg thdr Ul'lK11dal properties. However, with a rn lttctiu11 i11 g rni11 size, these ccrnmi<.-s
have increasing ly b een used. Zirconia, a hard , brittle ceramic, has even been rendered
superplast ic. i. e ., it can b~ deformed to great lengths (up to 3003 of its original length).
Howe,-ei:·, these ceramics must possess nanocrystalline grains to be s uperplastic. In fact ,
nanocryst.alline ceramics, such as silicon nitride (Si3N4 ) and s ilicon carbide (SiC) have
been used in a utomotive applications as high-strength spri ngs, ball bearings, and valve
lifters, b ecause they possess good formability and machinabilty combined with excellent
physical, chemical, and mechanical properties. They are also used as components in
h.igh-temperatw·e fw·naces. Nanocrystalline ceramics 9an be pressed and sintered into
\-arious shapes at significC\ntly lower temperatures, whereas it would be very difficult, if
not impossible , to press a nd sinter conventional ceram ics even at high temperatures.

3. Optical filters a nd atte nuators: Optical transparency of na nocrystalline ceramics can

be controlled by grni11 size. By clianging the size, optical filt ers for d ifferent colors cnn
be made. These arc ubo u:;eful for sunscrecm;.

4. Lasers with low threshold current: Double heterostructure lasers made from quan-
tum well and qua11tum dot:; can be operated o.t extro. low threshold current. These ru·e
used in compact dh;k players, optical co111111unicutions etc.
5. Elimination of pollutants: Nunocrystallino materials possess extremely large grain
boun<larit.!8 relative to their grai11 size. Hc11cc 1 nunonrntcriub tU'e very active in terms
of their chemical , phy:>ica l, und mechanical properties. Due to their enhanced chemical
activity, nauomatcriuls can be used u.s catulysls to rcuct with such 1~oxious and toxic
gasei; as carbon inonoxidc and nitrogc11 oxide in uutomobile catulyt1c converters ~nd
power generation equipment to prcvc11t c11viron111e11tal pollution nrisi11g from burning
gasoline a11<l coal.
6. High- power magnets: The strength of a nu,\g11ct is measured in terms ~f coercivi~y
· value8. Tl1csc vn Iues· 111c1
and saturation magnetization · ·ea::;e with a decrease m the gram

13
 Introduction
. J>1nhll•11111 n11d ~ll!lo~1~1s~--------------==------
. 'fhl'01Y ::.:
_ :.:.:.;...- -
1\ll'l'lld!! .
. . per unit volume of the
I . ( 11 rlncc a.t c.>a
i·n·11su 111 t lw tilH'<' ifl1• 11111 o.ro na < n " . f na.nocrystalline yttrium-
s11e t\IHI n11 "' . I . • It. hl\H h 1•1•11 tihuw11 tho.I i11og 111'tH uaa.do o. d t their extremely
) •I t hl' ~ 11' iii; ·rtH.'S ue o
~,ull!' l l Jt ur{lll\t:l }WSHt.'tlll Vl'I Y 1111\ISllltl 111og 111•l1C' propt: ·t h magnets .
1111H"t' >A ~ I. I er ra.ro-ear in-
:-<u1uu 1 • \ Tyt>kal nppllco.tious for l lu·sc ug i-pow
11\1~n• surfol'C tu l't · <l b ·d QWer gtmerators, motors
·l'tl'r 11ul>mo1 inl'S, o.utomouilc ultl't no.ton~, la.a • asc P . . MRI
dnut> qua . . 1 •t' c resonance 1magmg ( )
fur ships, ultnl-Sl'J1s1tiVl' analyt1ca.l instr11me11ts, auc magne l
111 mediclll diagnostics.

Phosphors for high-defin ition TV and fiat-panel d ispl.ays: The rcs~lution of a

television, or n monitor, depends greatly on the si7.e of the pixel. These pixels arc cs-
St'ntia.lly made of mnterials called " phosphors," which glow when struck by a stream of
electrons inside the cathode ray tube (CRT). The resolution improves with a reduction
in the size of t he pixel, or the phosphors. Nanocrystallinc zinc selenidc, zinc sulfide, cad-
mium sulfide, and lead tdluride synthesized by the sol-gel technique are candidates for
improving the resolution of monitors. The use of nanophosphors is envisioned to reduce
the cost. of these displays so a.ci to render high-definition televisions (HDTVs) and per-
sonal computers affordable to be purchased by an average household. Also, the fiat-panel
displays constructed out of nanomaterials possess much higher brightness, contrast and
fa.5t response than the conventional ones owing to their enhanced electrical and magnetic
properties.

8. Nanoelectromechanical systems (NEMS) show great promise in many applications such

as ultrasensitive sensors and components for radio frequency communication systems.
But so far, their performance has been limited due to t he use of heavy and thick metal
electrodes that dampen t he vibration of resonators. To overcome this issue, academics
have developed nano-resonat ors that utilize graphene as an ultra-thin, ultra-light elec-
trode. The researchers have observed a striking increase in device performance, including E
greater detection speeds, higher sensitivity and greater limits of detection. t
(\

n.
cc
8 About the book w
th
The.co~tents of the book Nanomaterla ls: Theory, P roulems a nd Solu t ions are as follows: ar
a.bn~f mtrQduction nbout nanomaterials nnd nanotechnology is presented in Chapter 1. The of
highlight~ on. the subject "Nanomaterials" including classification, synthesis, characterization sol
and apphcations ar~ presented in short in t his chapter. In Chapter 2 the common crystal I W1

struct~res of solids are discussed in or<ler to have nn understanding of the structures of nano- fret
matenals. Solids nppenr in a number of forms, from amorphous (glass-like) to polycrystalline (DI
bol
~multip~e <lo~ains) to crystalline. Much of nanosdence and nanotechnology focuses on the
rystalhne sohds of nanometer size. The crystal structure is described in brief in Chapter 2. fJ1

14

:llf" .
Nunomntcrinls: Tlwory Prohll'ltl~ 1\11d Hul11t lo11"
- - - - - - - - - - - - - - - lntrod 11r.tlcm

n<l<~it\(\l\ to tlw d,·M:ri\ tlnn ,,t '""'"I l111c•t111 111t, 1•1l1·1·t 1,f hw11m-.i• 111 tho ,111 1'fn<'o 10 volt1uw ~
rnt10 flw tll\lH'\\\(\ll'1·rnls '''"'hulk I lllrnt111t1·d 111d1•t1lh~ 111 tltl i rlinpt' 1• ·11,,. 111.1,1,, ~ lllrrcMt:H
t~·nu'1' up t1' M)" ''' tlw 11tn111s 111 11 111111111111•!1•1 •111.1' Hy11t1•111 111• 111. 1.li1• Hiil ( 11.u ,1( th<• ru1110,.._
tf\ll'l\m' l'ht~ , . . m 1l\\1'1' t ( 01\111\Sf I II 11111\'l'CIHC'Opll· H11lldH wliNt• Hllf Ii 1111111l1l'fH llrf typlr111ly
nmcll ....n\.\H t H1'l\\'''' th1• s111la1•1• of n 1111110Hl.111 C'l .1111•d 111nt1 1 rlnl In pot.1>11t.inlly n1 t.iw• lr1 rlirtlltui;.<
th ''l t \.1 ~n,l \'11 ·tt l\':\\ p1 n1w1 t h•s l•'l11 I lt(•1·111m fl 1 H11rh 1u1 lr1C'1011"'' 111 1111rforr• "'''ll pJ.1.yA n
mt l'\ m ~'llll' ,\pplk:\tinlll-1 ll"t' rn lnlyHiH 1u11l phot,ovolt.11ic1t UY' of Ht1rh FL nac1r1rnRtninl
~ • l t" ru1 mct\.'l\..''-' in t lw dlkil'IH')' of solnr r<'lls fHld 1 ns tl11• GrnLrA·I c• II. Tb1• el ·r.t rornc
t- • ~truct\ll'\.' iue t 0 the }Wriodic' pol c•11l.il\I formt•cl hy the• ordered nrrnngf•ment o( the RtorrJ.if
, 1 lllustnted in tlrn~ Chl\pt er 2. Th ls will help I.he render to rompnrf' and contrn."lt the

:-U\.")nk h3.nd ~tnlC'ture bet.ween the cry8tal structure und the nanomatcrinl. The concept of
~ li :- , les rel~\'Rllt to mrnomatcrials is also presented in this chapter. Thf! relevant physic.al
~th sc-.a!es are actuall~· relative to the natural electron or hole length scales in the parent bulk
ma.."-eri31. These natural length scales can either be referred to by their de Uroglie wavelength
orb~ the exciton Bohr radius. Thus, while a given nanometer sized object of one material may
q~· fox nano. a similar sized object of another material may not.
Vl1tb the reduction in dimensions in nanomaterials, quantum effects become prominent rutd
~·c-.i::nement of particles occur. To deal with such confinement of particles in various dimension!),
SchrOd.inger \\""a\'e equation and related concepts of quantum mechanics a.re bnefiy discus::;ed
in Chapt,cr 2. The concept of quantum confincnicnt is thereby introduced through tltc struplc
q'J.an.Lum mecharucal analogy of a particle in a one dimensional , two dimensional and three
dimensional box Quantum confinement is most commonly associated with the nnnoruaterinls
:... the sense that upon reaching a physical length scale equivalent to or lesl> than either the
exciton Bohr radius or de Broglie wavelength, both optical and electronic spectra hecome
dibCret.e and more atomic-like. Out bulk materiab generally exhibit continuous abN>rption
and <dectron.ic spectra. In the extreme case of quantum dots, confint-mt•ut occtu-s ruong all
three pbyb"ical dimen.sion.s, x, y, and z 1»uch thnt the opticnl and ekictrical spectra become truly
~lvwic~likc This is uuc n .•cu;u11 why qm111t u111 tluts or 1uu10c1ystols nrl' uftL'll cnllt.:<l tu·tilit:hJ
atoms. A.nalogi~ provide only half L11e 1:>0lut.ion when n pnrticlo in n 011c <liniensionul bo."'C is
U)mparoo to a quantum well, u particle in a two di111011sionn.l box is compared to a qum~tuo1
win: and a particle in a three dimensional box ii; compnre<l to n qunutum dot. If one colliiiders
tL.a.t. iu a quwitrnn well ouly 011e <lin1cn~1on iii confi11u<l nntl thnt two oth.t't'S ~\lL' _fn'C, then·
an: dcctronic i;t.awts rusi,ociated with tlie::;e CX Ll'll two d (•grct!s of frc •dom. Likcwtso m the ct~
of a qu&.nt.lllll win:, wit.Ii two d~g 1 I'\!:> ol coufit1tmit>11t, tlww t.'Xists 01w tllog1:L'll of fn:•e<lom. So
b<Jlving the part.iclc in a two diut<msionn.l box problem 111odol~ t.llu dectrouu· s~t,~cs along the
two oonfint-d dir(;CtioHri but dues nut nddr1.~ss s lall•s t\b.')()ci1\lcd with tltt- l't.'11U\lllt1.\g dcgrt'<J of
froodom. To gniu bc:t.L<•r im;i~lit. iuw Lhc."l>c adcliLioul:\l stn1.t•s, tltt• co.11c:oµt of dc11s1ty of ~tt,tes
(DOS) . . . t d d . C l nptcr 2. Tlte idt•a of tho 1.knsity of i>tntcs is sul>i:it'QUOntly upphed to
. IS Ill ro ucc Ill I '" I r t,"11. togotlwr both vulc11ce tUld
hoth the valence; band uud co11duct ion born.1 of 1\ 111t\tt 111:\ · ut 1 g

15
 Introd ur.t10
cl Solut ions
p ohlc01S t\11
. .. T hrorY ~r;_:..--­
Nanoml\tl'rit\1l'j. . . t d e nsity of states ( JDOS
0f t h e JOIO . •
. . \uccs the concept .· This is discussed m detail
r t I l'l3 11111 ()( f mateua1.
. luctiou b11111l density o s t\. t\b~orptiou coefficient o a. .
(:Ot~t . t ur11. •Hrdnt t•d lo tlu: . . g the optoelectronic prop.
whu:h. 1n 1 in <lcterrrurun .
m this rhoptl'r ' l•xtn•111L•ly importont ro c 11 determines what colors o f hght is
Tlw b1md ~t'P p\1\ys m . lt• ti1l' bl\t1d ga.p gcnNa ~ l . t tm determine its usefulness
1 Hw l'X1\111p • ,. l wh1c i, in t ' .
l'rl•l~ ol I\ tm,tl•111\ . '' sl'111icouducti11g niatl•11a d t to1·s or laser. An exploration of
·\ • 1hy 1\ tJ,IVl' • • hoto c ec •
l'""t \l'\\ lll' n\l$OI l t' · . • \ur energy couvcnuon, P d. o f the quantum confinement
. 1 \1 ,1'' t0ns Ill l'iO ~· • h derstan mg
1n pt.\l' t tt't\ l\PP \; \timatcly l•nha nces t e un rt properties. It has been o~
1 f \){\l\ll gl\P u l t ·cal trans po
tht• ~nl'\'P o , .. al . l'l.ml their optical a nd t• ec n . l The idea of size dependent band
dT"'"' in n<'nolnu,bt1.:11<l :sgap depends on size in nanomate.na . dis·cussed in Chapter 2. Such
..J thnt l \l' nn · l ·op ert1es are
~r\'\: d its consrquent effect. on the phys1ca pr -· nee research ers have envisioned that
~P rul . d f another reason s1 .
d l'!SCnpt t·ot' of band gap is reqmre or wires or dots, muc 1
h l"ke the arrangement of atoms ID a
.
ordt>red arrays of quantum wells, or . . ' . "th artificial bands and corresponding band
1 1 d t new art1fic1al solids w1 f · · his
cn-sU\l. can ultimate y ea o . d f. the de localization o earners m t
· · d - are forme rom
gaps. These bands and associate gaps d ment of quantum dots , quantum wires,
new periodic potential defined by the ordere arrange
or quantum wells. . . d wn and bottom up approaches are dis-
Synthesis of nanostructured materials usmg top o . . . as hase
cussed in Chapter 3. Various synthesis techniques are photohthography, ball milling, g . P
ndensa.tion vacuum deposition, physical vapor deposition (PVD ), thermal evaporation, E-
~eam evapor~tion, pulsed laser deposition, chemical vapor deposition (CVD).• Sol-Gel, electr~
deposition, spray pyrolysis, hydrothermal synthesis, preparat ion through colloidal methods~
M.BE growth of quantum dots. These techniques are described in details in Chapter 3 WJth
corresponding schematic diagrams and figures. .
Once created, tools are needed to study as well as manipulate nanoscale objects. It is qwte
natural that characterization of nanomaterials is essential before the measurements of physi-
cal properties and extraction of possible scopes of their applications. Vru·ious characterization
techniqu.es using X-ray diffraction, optical microscopy, scanning electron microscopy (SEM),
transmission electron microscopy (TEM), atomic force microscony (AFM) and scanning tun-
neling microscopy (STM) a re described in details in Chapter 4 .
Nanomaterials exhibit various interesting physical propt!rties such as optical, electrical, and
magnetic. The optical property of nanomaterials is highlighted in Chapter s. Some basic con-
cepts in nanomatttrials such as Coulomb interaction, dielectric constant, quasi-particles and
excitons am introduced in this Chapter 5. Excitons in direct and indirect band semiconductor
nanocrystaL-; a nd their quantitative treatment with charging effects are elaborated. Optical
properties of he~crnslru.ct~res and nanostruclures with emphasis on the general formalizatio~
such as absorption, c.m1ss1.on and lum.im-scence are also discussed in Chapter 5. The electri·
cal transport propertws ot nanomatenals is distinctly different from their bulk counterpart 85
stwcral new effects appear in nanomaterials. Coulomb blockade effect is one them. Coulotilb

16
Nanomaterials: Theory Problems and So lut.ions Introduction

blockade a nd Coulomb staircase problo111~ for m t he lmHi!:! of potential in single electron tran-
sistors which ~u·e expected to excel in next gc11crntio11 elcct,ronic!:!. These Coulomb blockade
effects are discnsse<l iu Chl\ptcr 0 with spedn1 l 1111p li aHiH.
The clectricl\.l trunsport in mrnonmterials Is elm: to tunneling and/or hopping and via the
procE*>s of thermionic 'l1lit'::;iou. These trnnspOLt J)l'Occsse8 a re de:-;cl'ibc<l in details in Chap-
ter 6. Deep lt'\'cl and surfo<'c defect~ d11<' to impurity play dominant role in determining the
electric~\! t.rnn:-;port. prupert.ics. These transport prop erties take ccmter stage in the realm of
devices where one de ·ire· to apply qu;111tum dots , quanturn wells, and quantum wires within
optoele<:tronic devices such ns single electron transistors. The concept of tunneling is intro-
duce<! in Chapter 6 to understand cHrrier transport in nanometer-sized materials. Tunneling is
I\ quantm11 mechanicru effect where carriers rnn have non-zero probability of being located in
energetically forbidde n classical regious of a system. This b ecomes important when one consid-
ers the discreteness of states in confined systems with substantial barriers for canier transport
along certain physical directions of t he material. Nanrn:;ystems show nonOhmic C'urrent-voltage
characll'ristics with t.hl' l'Xistcuce uf m1 uusct vultage at. a fi..xe<l tempera.tun.· or at a fixc<l <lh;ur-
der. This onset voltage follows a scaling behaviour with Ohmic conductance with an exponeut.
Such e."\.-ponent is found to be negative in most cases. These are a lso highlighted in Chapt.er 6.
Finally, applications of na nomaterials such as quant um dots, nanowires, quantum wells and
thin films for photonic devices (LED. solar cells), single electron transfer devices, carbon nan-
otube based transistors, microelectromechanical systems (MEMS) and na noelectromechanical
systems (NEMS) in diverse technological fields are presented in d etails in Chapter 7.

17
~~~~~~~~r..!~~~~~~~~~~~~~~~~~~~
~anomaterials: Theory Problems and Solutions N_a_n_o_sc_a_le__Sy:...:~
8 ~~

Chapter 2 - Nanoscale Systems

S llabus· Length st'rucs m . P1iys1 . . Na nostructures: lD , 2D and 3D. nanostructures (nan.

.· cs,
y · . ds) Band structures a nd density of states of materials at
odots, thin films, iurnownTS, nanoro ' . . ...
. ffc ·t~ nt nanosystems Quantum confinement: Applications of S chrodinger
nanoscales, ize e :c s 0
' • •

equation, Infinite potential well, potential step, potential box, quantum confinement of earners
in 3D, 20 and l D nanostfl'.ctures and its consequences.

1 Introduction
.Xanotechnology is the most widely used term in the modern scientific and technological litera-
ture. The concept of nanotechnology appeared for the first time in the famous talk " T HERE IS
PLEXTY O F ROOM AT THE BOTTOM" delivered by the great physicist Richard Feynman at the
American Physical Society meeting at Caltech on December 29, 1959. In his lecture, Feynman
described how individual atoms and molecules couid be manipulated to prepare low dimensional
materials and to develop nano-machines for technological applications. He stressed further that
scaling issues would arise from changing the magnitude of various· physical phenomena; gravity
would become less important but the surface effects would become increasingly more significant.
The term nanotechnology was originally defined by Norio Taniguchi in 1974 in the following way:
"Nanotechnology mainly consists of the processing of separation, consolidation and deformatiO'fl
of materials by one atom or by one molecule". Since then nanotechnology and nanoscience got an
upsurge and many new scientific developments came into reality. Two such major developments
are: the advances in computing power an<l matel'ial mo<leling and significant improvements in
characterization of nanomaterials with the use 0f scanning tunneling microscope (STM) and the
atomic force microscope (AFM). These lead new directions to the study of nanomaterials,
The field of nanotechnology is now growing very rapidly. It is the collaboration of the
physics, chemistry, biology, computer and material sciences integrated with nanoscale engineer·
ing. Hence it is truly an interdisciplinary subject. In nanotechnology, scientists focus on the
study of phenomena and manipulation of particles, things and devices at atomic molecular, and
macromolecular scales where properties differ significantly from those at mac:oscopic (larger)
scales. The difference in microscopic and macroscopic properties mainly arises due to the bi~h
surface to volume ratio (aspect ratio) and the appearance of quantum effects at the microscoP1c
(nauo) scaks. Nanot<:chuology <leals with design, d1ara<..:tt"rization, pro<luction, an<l appliciiti0 115
of nanomaterial-based devices in industry and technology. Nanomaterials are used in a.Jmost iJI
commercial products me . 1u d.mg med'icaI eqmpmen
. t , text1·1es, f uel additives, cosmetics, P1astit::i
Nanomaterials: Theory Problems and Solutions N a noscale Systems

and more. In such applications, shtipo o.nd slzo o f tho mnterinls at the nanoscale play dominant
role. These materials tu·o cunenlly produced ill met.ric Lom1 per year and m·e expected to increase
exponentially ru> now Rdvn.nces mnorgo out. ftesoarchcrH nro rolentlcssly pursuing from differ-
ent routes to create nauoma.terit.t ls nnd t o unde1·8tand their physical and chemica l relation.ship
between composition, size, and morphology t;o incorporate nanomatcriuls into everyday life.
Na.uomateria.ls exhibit various phy::iical properties such as electrical, optical and magnetic.
f\1a.gnetic ntwopa.rticles are used in a range of applications like imaging, bioprocessing, refrig-
eration as well as high storage density magnetic memory media. The large surface area to
,-ohune ratio results in a substantial proportion of atoms having different magnetic coupling
";th neighboring atoms leading to differing magnetic properties. Bulk gold and platinum are
non magnetic but at the nano size they act as magnetic particles. Au nanoparticles become
furrornaoonetic when they a.re capped ·with the appr~priate molecules such as thiol. Giant mag-
netoresistance (GMR) is a phenomenon observed in nanoscale multilayers consisting of strong
ferromagnet (Fe, Co, Ni) and a weaker magnetic or non magnetic buffer (Cr, Cu). It is usually
employed in data storage and sensing.
Dimension at the nanoscale plays a significant role in the aµ pearance of physical properties
of nanomaterials. For example, the redijced dimensionality has the most profound effect on the
energies of highest occupied molecular orbital (HOMO) [valence band] and the lowest unoccupied
molecular orbital (LUMO) [conduction band] . T he optical emi.ssion and adsorption occurs when
the transition of the electrons occur between these two states. Semiconductors and many metals
show large changes in optical properties such as color, as a function of particle size. Colloidal
suspenses of gold nano particles have a deep red color which becomes progressively more yellow
as the particle size increases. Gold spheres of diameter 10-20 nm exhibit red color. But the
gold spheres of diameter 2-5 nm exhibit yellow color while that of diameter > 20 nm exhibit
purple color. Similarly, silver particles of 40 nm size exhibit blue color while such silver particles
of lOOnm size exhibit yellow color. Prism shaped silver particles show red color. Reduced
dimensionality also affects other optical properties such ns photocatruysis, photoconductivity,
photoemission and electroluminescence.
The reduced dimensionality changes the electronic structure of nanomaterinls. Such changes
in electronic properties occur mainly due to the incrensing influence of the wnve-like property
of the electrons (qu~ntum mechanical effects) A.nd the scnrcity of scattering centers. As the
size of the system becomes comparable with the de Broglie wavelength (>..dB = ~· h is Planck's
constant and p is the momentum) of the electrons, the discrete nature of the energy states
becomes obvious, although a fully discrete energy spectrum is only observed in systems which are
confined in nll three rlimensions. In certain ca.')es, conch1ct.ing m11.teriaJ:.; become insulators below
a critical length scale, as the energy bands cease to overlap. Owing to their intrinsic wave-like
nature, electrons can tunnel quantum mechanically between two closely adjacent nanostructures.

19
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what comes o’ steamer trainin’. I’d sooner trust Sue to sail her nor him.
[Waves his arm and shouts.] Come about!
Nat—[Bitterly.] He seems to be heading straight for the open sea. He’s
taking quite a sail, it seems to me.
Bartlett—[As if he couldn’t believe his eyes.] He’s passed the p’int—
and now—headin’ her out to sea—so’east by east. By God, that be the
course I charted for her! [Sue bursts out sobbing. He wheels on her, his
mouth fallen open, his face full of a stupid despair.] They be somethin’
wrong here. What be it, Sue? What be it, Nat? [His voice has begun to
quiver with passion.] That schooner—she’s sailin’ without me—— [He
suddenly springs at Nat and grabs him by the throat—with hoarse fury,
shaking him.] What be it, ye whelp? It’s your doin’—because I wouldn’t let
ye go. Answer me!
Sue—[Rushing to them with a scream.] Pa! [She tugs frantically at his
hands. Bartlett lets them fall to his side, stepping back from Nat who
sinks weakly to the ground, gasping for breath. Bartlett stands looking at
him wildly.]
Sue—Nat didn’t know, Pa. It’s all my fault. I had to do it. There was no
other way——
Bartlett—[Raging.] What d’ye mean, girl? What is it ye’ve done? Tell
me, I say! Tell me or I’ll——
Sue—[Unflinchingly.] You had to be stopped from going someway. You
wouldn’t listen to reason. So I asked Danny if he wouldn’t make the trip in
your place. He’s just got his captain’s papers—and oh, Pa, you can trust
him, you know that! That man Horne said he knows about everything you
wanted done, and he promised to tell Danny, and Danny’ll come back——
Bartlett—[Chokingly.] So—that be it—— [Shaking his clenched fist at
the sky as if visualizing the fate he feels in all of this.] Curse ye! Curse ye!
[He subsides weakly, his strength spent, his hand falls limply at his side.]
Mrs. Bartlett—[Appears in the doorway. Her face is pale with
anguish. She gives a cry of joy when she sees her son.] Nat! [Then with a
start of horror at her eyes fall on her husband.] Isaiah! [He doesn’t seem to
hear.] Then—you ain’t sailed yet?
Sue—[Going to her—gently.] No, Ma, he isn’t going to sail. He’s going
to stay home with you. But the schooner’s gone. See. [She points and her
mother’s eyes turn seaward.]
 Bartlett—[Aloud to himself—in a tone of groping superstitious awe
and bewildered fear.] They be somethin’ queer—somethin’ wrong—they be
a curse in this somewhere——
Mrs. Bartlett—[Turning accusing eyes on him—with a sort of
fanatical triumph.] I’m glad to hear you confess that, Isaiah. Yes, there be a
curse—God’s curse on the wicked sinfulness o’ men—and I thank God
He’s saved you from the evil of that voyage, and I’ll pray Him to visit His
punishment and His curse on them three men on that craft you forced me to
give my name—— [She has raised her hand as if calling down retribution
on the schooner she can dimly see.]
Sue—[Terrified.] Ma!
Bartlett—[Starting toward his wife with an insane yell of fury.] Stop it,
I tell ye! [He towers over her with upraised fist as if to crush her.]
Sue—Pa!
Nat—[Starting to his feet from where he has been sitting on the ground
—hoarsely.] Pa! For God’s sake!
Mrs. Bartlett—[Gives a weak, frightened gasp.] Would you murder
me too, Isaiah? [She closes her eyes and collapses in Sue’s arms.]
Sue—[Tremblingly.] Nat! Help me! Quick! We must carry her to bed.
[They take their mother in their arms, carrying her inside the house.]
Bartlett—[While they are doing this, rushes in his mad frenzy to the
platform over the edge of the cliff. He puts his hands to his mouth,
megaphone-fashion, and yells with despairing rage.] Ahoy! Ahoy! Sarah
Allen! Put back! Put back! [as

[The Curtain Falls]

ACT FOUR
Scene—About nine o’clock of a moonlight night one year later—Captain
Bartlett’s “cabin,” a room erected on the top of his house as a lookout
post. The interior is fitted up like the cabin of a sailing vessel. On the left,
forward, a porthole. Farther back, the stairs of the companionway. Still
farther, two more portholes. In the rear, left, a marble-topped sideboard.
In the rear, center, a door opening on stairs which lead to the lower house.
A cot with a blanket is placed against the wall to the right of door. In the
right wall, five portholes. Directly under them, a wooden bench. In front of
the bench, a long table with two chairs placed, one in front, one to the left
of it. A cheap, dark-colored rug is on the floor. In the ceiling, midway from
front to rear, a skylight extending from opposite the door to above the left
edge of the table. In the right extremity of the skylight is placed a floating
ship’s compass. The light from the binnacle sheds down over this and
seeps into the room, casting a vague globular shadow of the compass on
the floor. Moonlight creeps in through the portholes on the right. A lighted
lantern is on the table.
As the curtain rises, Sue and Doctor Berry are discovered sitting by
the table. The doctor is a man of sixty or so, hale and hearty-looking, his
white hair and mustache setting off his ruddy completion. His blue eyes
have a gentle expression, his smile is kindly and sympathetic. His whole
manner toward Sue is that of the old family doctor and friend, not the least
of whose duties is to play father-confessor to his patients. She is dressed in
deep mourning. She looks much older. Her face is pale and plainly marked
by the ravages of suffering and grief. But there is an excited elation in her
face at present, her eyes are alight with some unexpected joy.
Sue—[Excitedly.] And here is Danny’s letter, Doctor—to prove it’s all
true. [She takes a letter from the bosom of her dress and holds it out to him.]
Doctor—[Takes it with a smile, patting her hand.] I can’t say how glad
I am, Susan. Coming after we’d all given him up for lost—it’s like a
miracle. Eh, well, I can hardly believe——
Sue—[Smiling happily.] Read what he says. Then you won’t doubt.
Doctor—[Hesitating—playfully.] I don’t know that it’s right for me—
love letters at my age!
Sue—Go ahead. I want you to read it. [He reaches in his pocket for his
spectacles. Sue continues gratefully.] As if I could have any secrets from
you after all you’ve done for us since Ma died. You’ve been the only friend
—— [She stops, her lips trembling.]
Doctor—Tut-tut. [He adjusts his spectacles and peers at her over
them.] Who wouldn’t be of all the service he could to a brave girl like you
—and I who’ve known you since you were so high! Eh, well, my dear girl,
this past year—with your mother’s death—the state your father’s in—and
then the news of the schooner being reported lost—one damn thing on top
of another! You’ve borne the whole brunt of it on your shoulders and stood
up like a major. I’ll tell Danny when he comes he ought to get down on his
knees and thank God for getting such a wife!
Sue—[Flushing.] You’re too good. I don’t deserve it. It was just a case
where someone had to carry things on.
Doctor—Not many could have stood it—living in this house with him
the way he is—even if he was their father.
Sue—[Glancing up at the skylight—apprehensively.] Ssshh! He might
hear you.
Doctor—[Listening intently.] Not him. There he goes pacing up and
down up there in the night, looking out to sea for that ship that will never
come back! And your brother Nat is getting just as bad. [Shaking himself.]
Brrr! This house of mad dreams! It’s the crowning wonder to me you
haven’t lost your balance too—spending nearly all of your time in this crazy
cabin—afraid to go out—afraid of what he might do——
Sue—Don’t you think Pa’ll come to realize the schooner is lost as time
goes by and she doesn’t come back?
Doctor—If he was going to realize that, the report of the facts five
months ago would have convinced him. There it was, plain as the nose on
your face. British freighter reports finding derelict schooner. Steams near
enough to read the name on the stern—Sarah Allen, Harborport. Well, who
could get around that evidence except a man with an obsession? No, your
father won’t let himself look the facts in the face. If he did, probably the
shock of it would kill him. That darn dream of his has become his life. No,
Susan, as time goes on he’ll believe in it harder and harder. After observing
him for the past year—and I speak for his own sake, too, as his good friend
for twenty years or more—my final advice is the same: Send him to an
asylum.
Sue—[With a shudder.] No, Doctor.
 Doctor—[Shaking his head.] You’ll have to come to it in time. He’s
getting worse. No one can tell—he might get violent——
Sue—How can you say that? You know how gentle and sane he is with
me—just like he used to be in the old days.
Doctor—You’re his last connecting link with things as they are—but
that can’t last. On the other hand, I think that if we got him away from the
sea, from this house, especially from this crazy cabin and the ship’s deck he
had built up there—[He nods upward.]—that perhaps——
Sue—[With conviction.] No. It would kill him to leave it.
Doctor—Eh, well, my dear, one thing you’ve got to realize: Your father
and Nat must be separated somehow. Nat’s going to pieces. He’s lost his
job, he moons about this house, he takes no interest in anything but this
craziness. I’ll bet he doesn’t believe that schooner is lost any more than
your father does.
Sue—You mean he still hopes it may not be true. That’s only natural.
He’s in San Francisco now tracing down the report again. He saw in the
papers where the British freighter that found the derelict was in port again
and he went to talk with the people on board. I’m hoping he’ll come back
fully convinced, with the whole thing out of his mind.
Doctor—[Shaking his head—gravely.] I’ve watched him and talked
with him—— Why, even your father seems to realize, in his twisted way,
that he has a bad effect on Nat.
Sue—Yes, as I’ve told you before, he hasn’t spoken to Nat alone since
the schooner sailed a year ago. And Nat sneaks about trying to spy on him
—and I have to be always on the watch to keep them apart—— It’s terrible.
Doctor—You’ve got to persuade Nat to go away, Susan.
Sue—He won’t heed me—but I was thinking that now Danny is coming
back, I’d get him——
Doctor—There’s another thing. You can’t continue to play slave to
these two after you’re married.
Sue—[Miserably.] We’ll have to wait a while longer——
Doctor—[Roughly.] Rats! You can’t sacrifice any more of your life and
Danny’s to mad dreams.
Sue—[Helplessly.] I don’t know—— [Then brightening.] That’ll all be
decided when the time comes. Just now it’s enough to know Danny’s alive
and coming back. Read his letter, Doctor. You’ve been holding it in your
hand all this time.
Doctor—Yes, yes, let’s see. [He takes the letter from the envelope.]
Sue—Poor Danny! He’s been through terrible things.
Doctor—Hmm! Rangoon.
Sue—Yes, he’s still in the hospital there. You’ll see.
Doctor—[Reads the letter—grunts with astonishment—angrily.] By
Gad! The damn scoundrels!
Sue—[Shuddering.] Yes, wasn’t it hideous—those awful men stabbing
him and leaving him for dead in that out of the way native settlement! The
natives nursed him back to life, have you got that far yet? And then he was
laid up for four months there waiting for a vessel to touch and take him
back to civilization. And then, think of it, getting the fever on top of all that
and nearly dying in the hospital in Rangoon!
Doctor—A terrible time of it! He’s lucky to be alive. Hmm. I see he
foresaw the wreck of the schooner. Those brutes couldn’t navigate. [Folding
the letter and putting it back.] He doesn’t seem to have found out what the
purpose of that mad trip was. Horne hid it from him to the last, he says.
Well, it’s queer—damn queer. But I’m glad to know those wretches have
gone to their final accounting.
Sue—[With a shudder.] I was always afraid of them. They looked like—
murderers. [At a noise from below they both start. Steps can be heard
climbing the stairs. Sue jumps to her feet frightenedly.] Why—do you hear
—who can that be? [There is a soft rap on the door. The Doctor jumps to
his feet. Sue turns to him with a half-hysterical laugh.] Shall I open? I don’t
know why—but I’m afraid.
Doctor—Tut-tut! I’ll see who it is. [He opens the door and Nat is
discovered on the stairs outside.] Why hello, boy. You gave us a scare.
Susan thought it was a ghost knocking.
Nat—[Comes into the room. He has aged, grown thin, his face gaunt
and drawn from continual mental strain, his eyes moody and preoccupied.
He glances up at the skylight apprehensively, then turns to Sue.] I didn’t
find you downstairs so I—— [Then to the Doctor.] Yes, you do grow to
look for ghosts in this house, don’t you? [Again glancing upward.] He’s up
there as usual, I suppose—looking for a ship that’ll never, never come now!
 Doctor—[With a grunt of approval.] I’m glad to hear you acknowledge
that.
Sue—[Who is just recovering from her fright.] But, Nat, I didn’t expect
you—— Did you find out——?
Nat—Yes, I talked with several of the men who were on board at the
time. They said they steamed in so close to the schooner it was easy to read
the name with the naked eye. All agreed—Sarah Allen, Harborport. They
even remembered how her tafrail was painted. There’s no chance for
mistake. The Sarah Allen is gone. [With great emphasis.] And I’m glad—
damn glad! I feel as if a weight of lead had been taken off my brain. I feel
free again, and I can go back to work—but not here. I’ve got to go away—
start new altogether.
Sue—[Happily, coming and putting her arms around him.] It’s so good
to hear you talk like your old self again.
Doctor—[Earnestly.] Yes, Nat, by Gad, that’s sound sense. Get out of
this.
Nat—[Giving him a queer look.] I suppose you thought I was doomed,
eh?—like him. [He makes a motion upward—then with an uncertain laugh.]
A doctor’s always looking for trouble where there isn’t any. [In a tone of
finality.] Well, it’s all over, anyway.
Sue—[Snatching the letter from the table.] Oh, I was forgetting, Nat.
Read this. I got it yesterday.
Nat—[Turns it over in his hands suspiciously.] Who from?
Sue—Open it and see.
Nat—[Does so and turns over the pages to read the signature—he gives
a start—hoarsely.] Danny! It can’t be! But it’s his writing sure enough! [He
exclaims with a sudden wild exultation.] Then they must have been lying to
me!
Sue—No, the Sarah Allen was wrecked all right, but that was
afterwards. He wasn’t on board then. Read it. You’ll see. [Nat sinks back on
a chair, evidently depressed by this information. He starts to read the letter
with unconcealed indifference, then becomes engrossed, excited, the paper
trembling in his hands. The Doctor shakes his head at Sue indicating his
disapproval of her giving him the letter. Nat finishes and springs to his feet
—angrily.]
 Nat—The stupid fool! He let Horne pull the wool over his eyes in fine
shape. He deserved all he got for being so dumb!
Sue—[Indignantly.] Nat!
Nat—[Unheedingly.] Oh, if I could only have gone in his place! I knew
the kind Horne was. He couldn’t have played that trick on me. I’d have
forced the secret out of him if I had to—— [He raises his clenched fist in a
gesture of threat like his father’s—then lets it fall and sits down again—
disgustedly.] But what’s the use? And what’s the use of this? [Tosses the
letter contemptuously on the table.] He might just as well not have written.
We’re no wiser than we were before.
Sue—[Snatching up the letter—deeply hurt.] Aren’t you even glad to
hear Danny’s alive?
Nat—[Turning to her at once—with remorseful confusion.] Yes—yes—
of course, Sue—I don’t have to say that, do I? What I mean is, he never
found out from Horne—and we’re no wiser.
Doctor—[Briskly—with a significant glance at Sue.] Well, Susan—Nat
—I’ve got to run along—[Meaningly.] I’ll be over again tomorrow, Susan.
Sue—Yes, do come. [Goes with him to the door.] Can you see your way?
Doctor—Yes. Good night.
Sue—Good night. [She closes the door and comes back to Nat. The
Doctor’s footsteps die out.]
Nat—[Savagely.] That damned old fool! What is he doing, sneaking
around here all the time? I’ve grown to hate the sight of him.
Sue—Nat! You can’t mean that. Think of how kind he’s been.
Nat—Yes—kindness with a purpose.
Sue—Don’t be silly. What purpose could he have except wanting to help
us?
Nat—To find out things, of course, you simpleton. To pump Pa when
he’s not responsible for what he’s saying.
Sue—[Indignantly.] Nat!
Nat—Much good it’s done him! I know Pa. Sane or not, he won’t tell
that to anyone—not even you or me, Sue. [With sudden fury.] I’m going
away—but before I go I’m going to make him tell me! He won’t refuse this
time when he knows I’m leaving for good. He’ll be glad then. He’s been so
afraid I’d find out, so scared to speak to me even—locking himself up here.
But I’ll make him tell—yes, I will!
Sue—Careful, Nat. He’ll hear you if you shout like that.
Nat—But we have a right to know—his own children. What if he dies
without ever speaking?
Sue—[Uneasily.] Be sensible, Nat. There’s nothing to tell except in your
imagination. [Taking his arm—persuasively.] Come on downstairs. I’ll get
you something to eat. You must be starved, aren’t you?
Nat—No—I don’t know—I suppose I ought to be. [He gets to his feet
and glances around with a shudder.] What a place for him to build to wait
in—like the cabin of a ship sunk deep under the sea—like the Sarah Allen’s
cabin as it is now, probably. [With a shiver.] There’s a chill comes over you.
No wonder he’s mad. [He listens.] Hear him. A year ago today she sailed. I
wonder if he knows that. Back and forth, always staring out to sea for the
Sarah Allen. Ha-ha! God! It would be funny if it didn’t make your flesh
creep. [Brusquely.] Come on. Let’s leave him and go down where there’s
light and warmth. [They go down the stairs, closing the door behind them.
There is a pause. Then the door of the companionway above is heard being
opened and shut. A gust of wind sweeps down into the room. Bartlett
stamps down the stairs. The madness which has taken almost complete
possession of him in the past year is clearly stamped on his face,
particularly in his eyes which seem to stare through and beyond objects
with a hunted, haunted expression. His movements suggest an automaton
obeying invisible wires. They are quick, jerky, spasmodic. He appears to be
laboring under a state of extraordinary excitement. He stands for a second
at the foot of the stairs, peering about him suspiciously. Then he goes to the
table and sits down on the edge of a chair, his chin supported on his hands.]
Bartlett—[Takes a folded piece of paper from his pocket and spreads it
out on the table in the light of the lantern—pointing with his finger—
mumblingly.] Where the cross be—ye’ll not forget that, Silas Horne. Ye had
a copy o’ this—no chance for a mistake, bullies—the gold’s there, restin’
safe—back to me and we’ll share it fair and square. A year ago today—ye
remember the orders I wrote ye, Horne. [Threateningly.] Ye’ll not be gone
more nor a year or I’ll—and if ye make port to home here at night, hang a
red and a green light at the mainm’st head so I’ll see ye comin.’ A red and a
green—— [He springs up suddenly and goes to a porthole to look out at the
sea—disappointedly.] No light be there—but they’ll come. The year be up
today and ye’ve got to come or I’ll—— [He sinks back on the chair, his
head in his hands. Suddenly he starts and stares straight in front of him as if
he saw something in the air—with angry defiance.] Aye, there ye be again
—the two o’ ye! Makin’ a mock o’ me! Brass and junk, ye say, not worth a
damn! Ye don’t believe, do ye? I’ll show ye! [He springs to his feet and
makes a motion as if grabbing someone by the throat and shaking them—
savagely.] Ye lie! Is it gold or no? Answer me! [With a mocking laugh.]
Aye, ye own up to it now, right enough. Too late, ye swabs! No share for ye!
[He sinks back on the chair again—after a pause, dully.] Jimmy’s gone. Let
them rot. But I spoke no word, Silas Horne, remember! [Then in a tone of
fear.] Be ye dyin’, Sarah? No, ye must live—live to see your ship come
home with the gold—and I’ll buy ye all in the world ye set your heart on.
No, not ambergris, Sarah—gold and diamonds and sech! We’re rich at last!
[Then with great anguish.] What woman’s stubborn talk be this? Confess,
ye say? But I spoke no word, I swear to ye! Why will ye hound me and
think evil o’ what I done? Men’s business, I tell ye. They would have killed
us and stolen the gold, can’t ye see? [Wildly.] Enough o’ talk, Sarah! I’ll sail
out in spite o’ ye! [He gets to his feet and paces up and down the room. The
door in the rear is opened and Nat re-enters. He glances at his father, then
looks down the stairs behind him cautiously to see if he is followed. He
comes in and closes the door behind him carefully.]
Nat—[In a low voice.] Pa! [Then as his father does not appear to notice
his presence—louder.] Pa!
Bartlett—[Stops short and stares at his son as if he were gradually
awakening from a dream—slowly.] Be that ye, Nat?
Nat—[Coming forward.] Yes. I want to talk with you.
Bartlett—[Struggling to bring his thoughts under control.] Talk? Ye
want to talk—to me? Men’s business—no room for a boy in it—keep clear
o’ this.
Nat—[Defiantly.] That’s what you’ve always said. But I won’t be put off
any longer. I won’t, do you hear?
Bartlett—[Angrily.] I’ve ordered ye not to set foot in this cabin o’
mine. Git below where ye belong. Where’s Sue? I told her to keep ye away.
Nat—She can’t prevent me this time. I’ve made up my mind. Listen, Pa.
I’m going away tomorrow.
 Bartlett—[Uncertainly.] Goin’ away?
Nat—Yes, and I’m never coming back. I’m going to start a new life.
That’s why I want a final talk with you—before I go.
Bartlett—[Dully.] I’ve naught to say to ye.
Nat—You will have. Listen. I’ve absolute proof the Sarah Allen is lost.
Bartlett—[Fiercely.] Ye lie!
Nat—[Curiously.] Why do you say that? You know it’s true. It’s just that
you won’t believe.
Bartlett—[Wanderingly—the word heading his mind into another
channel.] Believe? Aye, he wouldn’t believe. Brass and junk, he said, not
worth a damn—but in the end I made him own up ’twas gold.
Nat—[Repeating the word fascinatedly.] Gold?
Bartlett—A year ago today she sailed. Ye lie! Ye don’t believe either,
do ye?—like him. But I’ll show ye! I’ll make ye own up as I made him!
[With mad exultation.] She’s comin’ home tonight as I ordered Horne she
must! I kin feel her makin’ for home, I tell ye! A red an’ a green at the
mainm’sthead if ye make port o’ night, I ordered Horne. Ye’ll see! [He goes
to look out of a porthole. Nat, as if under a spell, goes to another.]
Nat—[Turning away disappointedly—making an effort to throw off his
thoughts—without conviction.] Nonsense. There’s nothing there—no lights
—and I don’t believe there ever will be.
Bartlett—[His wild eyes fixed on his son’s with an intense effort of will
as if he were trying to break down his resistance.] Ye’ll see, I tell ye—a red
and a green! It ain’t time yet, boy, but when it be they’ll be plain in the
night afore your eyes. [He goes and sits down by the table. Nat follows him
and sits down in the other chair. He sees the map and stares at it
fascinatedly.]
Nat—What is this—the map of the island? [He reaches out his hand for
it.]
Bartlett—[Snatching it up—with a momentary return to reason—
frightenedly.] Not for ye, boy. Keep clear o’ this for your own good. [Then
with a crazed triumph.] Aye! Ye’d believe this soon enough, wouldn’t ye?
Nat—[Intensely.] I’ve always believed there was something—and a
moment ago you mentioned gold. [Triumphant in his turn.] So you needn’t
try to hide the secret any longer. I know now. It’s gold—gold you found on
that island—gold you fitted out the Sarah Allen to sail back for—gold you
buried where I saw that cross marked on the map! [Passionately.] Why have
you been afraid to confide in me, your own son? Why didn’t you let me sail
back in your place? Were you afraid I’d give the secret away? Did you think
I wouldn’t believe——?
Bartlett—[With a mad chuckle.] Aye, ye believe now, right enough.
Nat—I always believed, I tell you. [Pleadingly.] And now that I know so
much why can’t you tell me the rest? I must know! I have a right to be heir
to the secret. Why don’t you confess——
Bartlett—[Interrupting—his brain catching at the word.] Confess?
Confess, did ye say, Sarah? To Nat, did ye mean? Aye, Sarah, I’ll tell him
all and leave it to him to say if I did wrong. [His gleaming eyes fixed on his
son’s.] I’ll tell ye, boy, from start to finish o’ it. I been eatin’ my heart to tell
someone—someone who’d believe—someone that’d say I did no wrong.
Listen, boy, ye know o’ our four days in an open boat after the Triton went
down. I told ye o’ that when I come home. But what I didn’t tell ye was
they was six o’ us in that boat, not four.
Nat—Six? There were you and Horne and Cates and Jimmy——
Bartlett—The cook o’ the Triton and the ship’s boy. We’d been on the
island two days—an island barren as hell, mind—without food or drink. We
was roasted by the sun and nigh mad with thirst. Then, on the second day, I
seed a Malay canoe—a proper war canoe such as the pirates use—sunk
down inside the reef. I sent Jimmy down to go over her thinkin’ they might
be some cask o’ water in her the sea’d not got to. [With impressive
emphasis.] He found no water, boy, but he did find—d’ye know what, boy?
Nat—[Exultantly.] The gold, of course!
Bartlett—[Laughing harshly.] Ha-ha! Ye do believe right enough,
don’t ye! Aye, the gold—in a chest. We hauled her up ashore and forced the
lid open. [Gloatingly.] And there it was afore our eyes in the sun—gold
bracelets and rings and ornaments o’ all sorts fixed up fancy with diamonds
and emeralds and rubies and sech—red and green—shinin’ in the sun! [He
stops impressively.]
Nat—[Fascinatedly.] Diamonds and—— But how did they get there?
Bartlett—Looted treasure o’ some Chinese junk, likely. What matter
how it come about? There it was afore our eyes. And then, mind ye, that
thief o’ a cook came runnin’ up from where he’d been shirkin’ to look at
what we’d found. “No share for ye, ye swab,” I yelled at him; and then he
says: “It ain’t gold—brass and junk,” he says and run off for fear o’ me.
Aye, he run off to the boy and told him to jine with his sneakin’ plan to steal
the gold from us!
Nat—[Savagely.] But why didn’t you stop him? Why didn’t you——?
Bartlett—I be comin’ to that, boy, and ye’ll see if I did wrong. We
carried the chest to the shade o’ a palm and there was that thief o’ a cook
an’ the boy waitin’. I collared ’em both and made ’em look at the gold.
“Look and tell me if it’s gold or no,” I says. [Triumphantly.] They was
afeerd to lie. Even that thief o’ a cook owned up ’twas gold. Then when I
turned ’em loose, because he knowed he’d git no share, he shouted again:
“Brass and junk. Not worth a damn.”
Nat—[Furiously.] But why did you allow—— Why didn’t you——
Bartlett—[With mad satisfaction.] Aye, ye be seein’ the way o’ it, boy.
It was just then we sighted the schooner that picked us up after. We made a
map and was burryin’ the gold when we noticed them two thieves sneakin’
about to see where we’d hide it. I saw ’em plain, the scum! That thief o’ a
cook was thinkin’ he’d tell the folks on the schooner and go shares with
them—and leave us on the island to rot; or he was thinkin’ he and the boy’d
be able to come back and dig it up afore I could. We had to do somethin’
quick to spile their plan afore the schooner come. [In a tone of savage
satisfaction.] And so—though I spoke no word to him—Jimmy knifed ’em
both and covered ’em up with sand. But I spoke no word, d’ye hear? Their
deaths be on Jimmy’s head alone.
Nat—[Passionately.] And what if you had? They deserved what they
got.
Bartlett—Then ye think I did no wrong?
Nat—No! Any man—I’d have done the same myself.
Bartlett—[Gripping his son’s hand tensely.] Ye be true son o’ mine,
Nat. I ought to told ye before. [Exultantly.] Ye hear, Sarah? Nat says I done
no wrong.
Nat—The map! Can I see it?
Bartlett—Aye. [He hands it to Nat who spreads it out on the table and
pores over it.]
 Nat—[Excitedly.] Why, with this I—we—can go back—even if the
Sarah Allen is lost.
Bartlett—She ain’t lost, boy—not her. Don’t heed them lies ye been
hearin’. She’s due now. I’ll go up and look. [He goes up the companionway
stairs. Nat does not seem to notice his going, absorbed in the map. Then
there is a loud muffled hail in Bartlett’s voice.] “Sarah Allen, ahoy!”
[Nat starts, transfixed—then rushes to one of the portholes to look. He
turns back, passing his hand over his eyes, frowning bewilderedly. The door
above is flung open and slammed shut and Bartlett stamps down the
stairs.]
Bartlett—[Fixing Nat hypnotically with his eyes—triumphantly.]
What did I tell ye? D’ye believe now she’ll come back? D’ye credit your
own eyes?
Nat—[Vaguely.] Eyes? I looked. I didn’t see——
Bartlett—Ye lie! The Sarah Allen, ye blind fool, come back from the
Southern Seas as I swore she must! Loaded with gold as I swore she would
be!—makin’ port!—droppin’ her anchor just when I hailed her.
Nat—[Feebly, his will crumbling.] But—how do you know?—some
other schooner——
Bartlett—Not know my own ship—and the signal I’d ordered Horne
to make!
Nat—[Mechanically.] I know—a red and a green at the mainm’sthead.
Bartlett—Then look out if ye dare! [He goes to a porthole.] Ye kin see
it plain from here. [Commandingly.] Will ye believe your eyes? Look! [Nat
comes to him slowly—looks through the porthole—and starts back, a
possessed expression coming over his face.]
Nat—[Slowly.] A red and a green—clear as day!
Bartlett—[His face is now transfigured by the ecstasy of a dream
come true.] They’ve lowered a boat—the three—Horne an’ Cates and
Jimmy Kanaka. They’re rowin’ ashore. Listen. I hear the oars in the locks.
Listen!
Nat—[Staring into his father’s eyes—after a pause during which he
appears to be straining his hearing to the breaking point—excitedly.] I hear!
Bartlett—Listen! They’ve landed. They’ll be comin’ up the path now.
[In a crooning, monotonous tone.] They move slowly—slowly. It be heavy,
I know—that chest. [After a pause.] Hark! They’re below at the door in
front.
Nat—I hear!
Bartlett—Ye’ll see it now in a moment, boy—the gold. Up with it,
bullies! Up ye come! Up, bullies! It’s heavy, heavy!
Nat—[Madly.] I hear them! They’re on the floor below! They’re
coming! I’ll open the door. [He springs to the door and flings it open,
shouting.] Welcome home, boys! [Sue is discovered outside just climbing
up the stairs from below. She steps inside, then stops, looking with
amazement and horror from father to brother. Nat pushes her roughly aside
to look behind her down the stairs.]
Sue—Nat!
Nat—[Turning to his father.] I’ll go down to the wharf. They must be
there or—— [The rest of his words are lost as he hurries down the stairs.
Bartlett steps back, shrinking away from his daughter, and sinks on a
chair by the table with a groan, his hands over his eyes.]
Sue—[Comes to him and shakes him by the shoulder—alarmed.] Pa!
What has happened? What is the matter with Nat? What have you told him?
[With bitter despair.] Oh, can’t you see you’re driving him mad, too?
Bartlett—[Letting his hands fall and staring at her haggardly—
falteringly, as if reason were slowly filtering back into his brain.] Sue—ye
said—drivin’ him mad, too! Then ye think I be——? [He staggers to his
feet. Sue breaks down, sobbing. Bartlett falters on.] But I seen her—the
Sarah Allen—the signal lights——
Sue—Oh, Pa, there’s nothing there! You know it! She was lost months
ago.
Bartlett—Lost? [He stumbles over to a porthole and looks out. His
body sags as if he were going to fall. He turns away and cries hopelessly in
a tone of heart-rending grief.] Lost! Aye, they be no Sarah Allen there—no
lights—nothin’!
Sue—[Pleading fiercely.] Pa, you’ve got to save Nat! He won’t heed
anyone else. Can’t you tell him the truth—the whole truth whatever it is—
now when I’m here and you’re yourself again—and set him free from this
crazy dream!
 Bartlett—[With wild grief.] Confess, ye mean? Sue, ye be houndin’
me like your Ma did to her dyin’ hour! Confess—that I spoke the word to
Jimmy—in my mind! Confess—brass and junk—not worth a damn! [In
frenzied protest.] No! Ye lie!
Sue—Oh, Pa, I don’t know what you mean. Tell Nat the truth! Save him!
Bartlett—The truth? It’s a lie! [As Sue tries to bar his way to the
companionway—sternly.] Out o’ my way, girl! [He pulls himself feebly up
the stairs. The door is heard slamming above. Sue sits down in a chair in a
hopeless, exhausted attitude. After a pause Nat re-enters. He is panting
heavily from his exertions. His pale face is set in an expression of despair.]
Nat—[Looking about the room wildly.] Where is he? Sue! [He comes
forward and falls on his knees beside her chair, hiding his face in her lap
like a frightened child. He sobs hoarsely.] Sue! What does it all mean? I
looked. There was nothing there—no schooner—nothing.
Sue—[Soothing him as if he were a little boy.] Of course there wasn’t.
Did you expect there would be, you foolish boy? Come, you know better
than that. Why, Nat, you told the doctor and I that you were absolutely
convinced the Sarah Allen was lost.
Nat—[Dully.] Yes, I know—but I don’t believe—like him——
Sue—Sshhhh! You know the state Pa is in. He doesn’t realize what he’s
saying half the time. You ought to have better sense than to pay any
attention——
Nat—[Excitedly.] But he told me all he’s been hiding from us—all about
the gold!
Sue—[Looking at him with alarm—mystified.] Gold? [Then forcing a
smile.] Don’t be silly, Nat. It doesn’t exist except in his poor, deranged
mind.
Nat—[Fiercely.] That’s a lie, Sue! I saw the map, I tell you—the map of
the island with a cross marked on it where they buried the gold.
Sue—He showed a map to you—a real map? [Gently.] Are you sure
you’re not just imagining that, too?
Nat—I had it in my hands, you fool, you! There—on the table. [He
springs to his feet, sees the map on the table, and snatches it up with an
exclamation of joy—showing it to Sue.] See! Now will you believe me!
[She examines the map perplexedly. Nat paces up and down—excitedly.] I
tell you it’s all true. You can’t deny it now. It’s lucky for us I forced him to
confess. He might have died keeping the secret and then we’d have lost—
I’ll tell you what I’m going to do now, Sue. I’m going to raise the money
somewhere, somehow, and fit out another schooner and this time I’ll sail on
her myself. No trusting to Danny or anyone else! Yes, Sue, we’ll come into
our own yet, even if the Sarah Allen is lost—— [He stops—then in accents
of bewildered fear.] But—she can’t be lost—I saw the lights, Sue—red and
green—as plain as I see you now—— [He goes to one of the portholes
again.]
Sue—[Who has been watching him worriedly, puts the map back on the
table, gets up and, assuming a brisk, matter-of-fact tone, she goes over and
takes him by the arm.] Come downstairs, Nat. Don’t think any more about it
tonight. It’s late and you’re worn out. You need rest and a good sleep.
Nat—[Following her toward the door—confusedly.] But Sue—I saw
them—— [From above in the night comes the muffled hail in Bartlett’s
voice.] Sarah Allen, ahoy! [Nat stops, tortured, his hands instinctively
raised up to cover his ears. Sue gives a startled cry. The door above is
slammed and Bartlett comes down the stairs, his face revealing that the
delusion has again full possession of his mind.]
Bartlett—[Pointing his finger at his son and fixing him with his eyes—
in ringing, triumphant tones.] The Sarah Allen, boy—in the harbor below—
a red and a green plain afore my eyes! What did I tell ye, boy? Come back
from the Southern Seas as I swore she must! Loaded with gold as I swore
she would be! [Nat again seems to crumble—to give way to the stronger
will. He takes a step toward his father, his eyes lighting up. Sue looks at his
face—then rushes to her father.]
Sue—[Putting her hands to her father’s head and forcing him to look
down into her face—intensely.] Pa! Stop, do you hear me! It’s all mad!
You’re driving Nat mad, too! [As she sees her father hesitate, the wild light
dying out of his eyes, she summons all her power to a fierce pleading.] For
my sake, Pa! For Ma’s sake! Think of how she would feel if she were alive
and saw you acting this way with Nat! Tell him! Tell him now—before me
—tell him it’s all a lie!
Bartlett—[Trying in an agony of conflict to get hold of his reason—
incoherently.] Yes, Sue—I hear ye—confess—aye, Sarah, your dyin’ words
—keep Nat clear o’ this—but—red and green—I seen ’em plain—— [Then
suddenly after a tremendous struggle, lifting his tortured face to Nat’s—in
tones of despair.] Nothin’ there, boy! Don’t ye believe! No red and green!
She’ll never come! Derelict and lost, boy, the Sarah Allen. [After another
struggle with himself.] And I lied to ye, boy. I gave the word—in my mind
—to kill them two. I murdered ’em in cold blood.
Sue—[Shrinking from him in horror.] Pa! You don’t know what you’re
saying.
Bartlett—The truth, girl. Ye said—confess——
Nat—[Bewilderedly.] But—it was right. They were trying to steal——
Bartlett—[Overcome by the old obsession for a moment—savagely.]
Aye, that’s it! The thievin’ scum! They was tryin’—— [He stays short,
throwing his head back, his whole body tense and quivering with the effort
he makes to force this sustaining lie out of his brain—then, broken but self-
conquering, he looks again at Nat—gently.] No, Nat. That be the lie I been
tellin’ myself ever since. That cook—he said ’twas brass—— But I’d been
lookin’ for ambergris—gold—the whole o’ my life—and when we found
that chest—I had to believe, I tell ye! I’d been dreamin’ o’ it all my days!
But he said brass and junk, and told the boy—and I give the word to murder
’em both and cover ’em up with sand.
Nat—[Very pale—despairingly.] But he lied, didn’t he? It is gold—real
gold—isn’t it?
Bartlett—[Slowly takes the studded anklet from his pocket and holds it
out to Nat. The latter brings it to the light of the lantern. Bartlett sits on a
chair, covering his face with his hands—in a tone of terrible suffering.]
Ye’ll tell me, boy—if it’s gold or no. I’ve had it by me all this time—but
I’ve been afeerd to show——
Nat—[In a tone of wild scorn.] Why, it’s brass, of course! The cheapest
kind of junk—not worth a damn! [He flings it savagely into a corner of the
room. Bartlett groans and seems to shrink up and turn into a figure of
pitiable feebleness.]
Sue—[Pityingly.] Don’t, Nat. [She puts her arms around her father’s
shoulders protectingly.]
Nat—[In a stifled voice.] What a damned fool I’ve been! [He flings
himself down on the cot, his shoulders heaving.]
 Bartlett—[Uncovers his grey face on which there is now settling an
expression of strange peace—stroking his daughter’s hand.] Sue—don’t
think hard o’ me. [He takes the map.] An end to this! [He slowly tears it
into small pieces, seeming to grow weaker and weaker as he does so.
Finally as he lets the fragments filter through his fingers, his whole frame
suddenly relaxes. He sighs, his eyes shut, and sags back in his chair, his
head bent forward limply on his chest.]
Sue—[Alarmed.] Pa! [She sinks to her knees beside him and looks up
into his face.] Pa! Speak to me! It’s Sue! [Then turning toward her brother
—terrifiedly.] Nat! Run—get the doctor—— [Nat starts to a sitting
position. Sue tries with trembling hands to feel of her father’s pulse, his
heart—then begins to sob hysterically.] Oh, Nat—he’s dead, I think—he’s
dead!

[The Curtain Falls]