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No. 26, are f85% (Fig. 6) [21]. Although absolute PL QY measurements arerequired to confirm this remarkable figure, PbSe NQDs are, in the very least,substantially more efficient IR emitters than their organic dye counterparts.Further, the inorganic semiconductor offers enhanced stability compared toexisting IR fluorophores.In addition to the moderate (f150jC) and high-temperature (>200jC)preparations discussed earlier, many room-temperature reactions have beendeveloped. The two most prevalent schemes entail thiol-stabilized aqueousphasegrowth and inverse-micelle methods. We will briefly consider theseapproaches here, and the former is discussed in some detail in Section III as itpertains to core–shell nanoparticle growth, whereas the latter is revisited inSection VI with respect to its application to NQD doping. In general, the lowtemperaturemethods suffer from relatively poor size dispersions (j > 20%)and often exhibit significant, if not exclusively, trap-state PL. The latter isinherently weak and broad compared to band-edge PL, and it is less sensitiveto quantum-size effects and particle-size control. Further, low-temperatureaqueous preparations are limited in their applicability to relatively ionicmaterials. Higher temperatures are required to prepare crystalline covalentcompounds [barring reaction conditions that may reduce the energeticbarriers to crystalline growth (e.g., catalysts and templating structures)].Figure 6 PbSe NQD size-dependent room-temperature fluorescence (excitationsource: 1.064 Am laser pulse). Sharp features at f1.7 and 1.85 Am correspond tosolvent (chloroform) absorption. (From Ref. 21, reprinted with permission.)Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Thus, II–VI compounds, which are more ionic compared to III–V compounds,have been successfully prepared at low temperatures (room temperatureor less), whereas III–V compound semiconductors have not [22].The processes of nucleation and growth in aqueous systems are conceptuallysimilar to those observed in their higher-temperature counterparts.Typically, the metal perchlorate salt is dissolved in water, and the thiolstabilizer is added (commonly, 1-thioglycerol). After the pH is adjusted to>11 (or from 5 to 6 if the ligand is a mercaptoamine [23]) and the solution isdeaerated, the chalcogenide is added as the hydrogen chalcogenide gas [23–25]. The addition of the chalcogenide induces particle nucleation. Thenucleation process appears not to be an ideal, temporally discrete event, asthe initial particle-size dispersion is large, as evidenced, for example in broadPL spectra. Growth, or ‘‘ripening,’’ is allowed to proceed over several days,after which a red shift in the PL spectrum is observed, and the spectrum is stillbroad [22]. For example, fractional precipitation of an aged CdTe growthsolution yields a size series exhibiting emission spectra centered from 540 to695 nm, where the full width at half-maximum (FWHM) of the size-selectedsamples are at best 50 nm [22], compared to f25 nm for the best high-temperaturereactions. In Cd-based systems, the ripening process can be acceleratedby warming the solution; however, in Hg-based systems, heating thesolution results in particle instability and degradation [22]. The initial particlesize can be roughly ‘‘tuned’’ by changing the identity of the thiol ligand. Thethiol binds to metal ions in solution prior to particle nucleation, and extendedx-ray absorption fine structure (EXAFS) studies have demonstrated that thethiol stabilizer binds exclusively to metal surface sites in the formed particles[26]. By changing the strength of this metal–thiol interaction, larger or smallerparticle sizes can be obtained. For example, decreasing the bond strength byintroducing an electron-withdrawing group adjacent to the sulfur atom leadsto larger particles [23,26].The advantage of room-temperature, aqueous-based reactions lies intheir ability to produce nanocrystal compositions that are, as yet, unattainableby higher-temperature pyrolysis methods. Of the II–VI compounds, Hgbasedmaterials are thus far restricted to the temperature–ligand combinationafforded by the aqueous thiol-stabilized preparations. The nucleation andgrowth of mercury chalcogenides have proven difficult to control in highertemperature,nonaqueous reactions. Relatively weak ligands, fatty acids andamines (stability constant K10 17 ), promote reductiveelimination of metallic mercury at elevated temperatures [13]. Very high PLefficiencies (up to 50%) are reported for HgTe NQDs prepared in water [25].However, the as-prepared samples yield approximately featureless absorp-Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Page 1: Copyright 2004 by Marcel Dekker, In
Page 4 and 5: Copyright 2004 by Marcel Dekker, In
Page 6 and 7: Copyright 2004 by Marcel Dekker, In
Page 8 and 9: This book covers several topics of
Page 10 and 11: esult, some exciting topics were no
Page 12 and 13: 3. Fine Structure and Polarization
Page 14 and 15: 9. III-V Quantum Dots and Quantum D
Page 16 and 17: ContributorsUri BaninThe Hebrew Uni
Page 18 and 19: 1‘‘Soft’’ Chemical Synthesi
Page 20 and 21: structure of energy states leads to
Page 22 and 23: growth can proceed by Ostwald ripen
Page 24 and 25: Figure 3 Transmission electron micr
Page 26 and 27: Figure 4 Temporal evolution of the
Page 30 and 31: tion spectra and broad PL spectra.
Page 32 and 33: ing surface-to-volume ratio with di
Page 34 and 35: Figure 8 Photoluminescence spectra
Page 36 and 37: lattice mismatch. Such a large latt
Page 38 and 39: match between InAs and ZnS of f11%.
Page 40 and 41: successfully repeated for up to thr
Page 42 and 43: Under a different growth regime, on
Page 44 and 45: Figure 14 Atomic model of the CdSe
Page 46 and 47: ‘‘Teardrop-shaped’’ particl
Page 48 and 49: Figure 17 High-resolution TEMs of C
Page 50 and 51: allows isolation of tetrapods in f8
Page 52 and 53: ligand concentrations yield a reduc
Page 54 and 55: een determined and quantitatively c
Page 56 and 57: tion volumes were also shown to be
Page 58 and 59: synthesis temperatures of z400jC ar
Page 60 and 61: Figure 23 (a) Photoluminescence spe
Page 62 and 63: levels (fV1 Mn per NQD). Despite in
Page 64 and 65: Figure 25 X-ray diffraction pattern
Page 66 and 67: Figure 27 Transmission electron mic
Page 68 and 69: An additional factor that strongly
Page 70 and 71: Figure 30 (a,b) Schematics illustra
Page 72 and 73: Slow, controlled precipitation of h
Page 74 and 75: Figure 34 Schematic illustrating th
Page 76 and 77: Figure 36 Transmission electron mic
Page 78 and 79:
achieving biological compatibility
Page 80 and 81:
47. Yu H.; Gibbons P.C.; Kelton K.F
Page 82 and 83:
2Electronic Structure inSemiconduct
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Figure 2 (a) Simple model of a nano
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electron and hole to be treated as
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independently, Eq. (13) is commonly
Page 92:
a better description of the bulk ba
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investigated. For optical experimen
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Figure 4 (a) Absorption (solid line
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Figure 6 Normalized PLE scans for s
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Figure 8 A simplistic model for des
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Figure 10 Theoretically predicted p
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Figure 12 Schematics depicting the
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Figure 14 Calculated band-edge exci
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Figure 15 Absorption (solid line) a
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Figure 18 (a) Calculated band-edge
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IV.BEYOND CdSeA. Indium Arsenide Na
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the six-band Luttinger Hamiltonian.
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11. Norris, D.J.; Efros, Al.L.; Ros
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69. Gaponenko, S.V.; Woggon, U.; Sa
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formation of a long-lived dark exci
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where the constant A is determined
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In crystals for which the function
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The respective wave functions areC
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passive, as was shown in Ref. 12. T
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square of the matrix element of the
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where e F = e F ieV and e F F = e x
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see that for all nanocrystal shapes
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optical recombination of the excito
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B. Recombination of the Dark Excito
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where x = cos h and f = l B g e H/3
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The theory of the polarization memo
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Figure 7 The size dependence of the
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state would have an infinite lifeti
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crystal axis [see Eq. (40)]. As a r
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time of the exciton momentum relaxa
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One must also account for the influ
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observed in one of the first studie
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REFERENCES1. Bawendi, M.G.; Wilson,
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4Intraband Spectroscopyand Dynamics
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The solid line in Fig. 1 shows the
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Figure 2 FTIR spectra of n-type CdS
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of the center frequency. The experi
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limit given by radiative relaxation
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from a long lifetime due to the pho
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are two natural approaches to study
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32. Inoshita, T.; Sakaki, H. Physic
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continuous spectral tunability over
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function and envelope function mome
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ottleneck’’ [14,28]. Further re
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in NQDs is dominated by nonphonon e
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Figure 4 Dynamics of the IR postpum
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Figure 5 (a) Time-resolved PL spect
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Figure 6 (a) The time delay of the
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and due to Auger-type e-h interacti
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Figure 9 Dynamics of the 1S bleachi
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significantly greater than the fast
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Figure 11 (a) Pump-intensity-depend
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NQD size. For small NQD sizes (R =
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Figure 14 Nonlinear absorption/gain
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sorption change associated with a s
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where n h em is the hole ‘‘emit
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ultrafast (subpicosecond to picosec
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Figure 18 Schematic of transitions
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Figure 19 Dynamics of pump-induced
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where n i (i=1, 2 . . . , N ) is th
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Figure 21 (a) Two-e-h-pair (biexcit
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the volume fraction (filling factor
Page 217 and 218:
intensity dependence of this peak (
Page 219 and 220:
Copyright 2004 by Marcel Dekker, In
Page 221 and 222:
can contribute to the saturation of
Page 223 and 224:
Page 225 and 226:
coupling between ‘‘volume’’
Page 227 and 228:
numerous discussions on the photoph
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53. Kang, K.; Kepner, A.; Gaponenko
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the ‘‘on-off ’’ emission in
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parallel form of data acquisition i
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Figure 3 (a) Spectral time trace of
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transition energies. In fact, these
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distribution (dark line) does not d
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exposure to only room light. In our
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statistics for the off times are in
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230Shimizu and BawendiCopyright 200
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Figure 10 (a) Time trace of a CdSe(
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and excited QD core states to fluct
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arrows indicate the on-time truncat
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W. K. Woo and V. C. Sundar for assi
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size allows the electron affinity a
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II.THEORY OF ELECTRON TRANSFER BETW
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For the specific case of charge tra
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dominates, the mobility is often fi
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where the constant A and the temper
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components of modulation which are
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nanocrystals [41], understanding ph
Page 269 and 270:
and ionization potential through tw
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quantum dots. Furthermore, because
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For many applications, a host mater
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form blends with morphologies that
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Figure 11 Photoluminescence efficie
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Figure 12 (a) Room-temperature PIA
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discussed briefly in Section IV. Ch
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dithiolates to thiol-terminated DNA
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Films of passivated CdSe nanocrysta
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Figure 16 Photocurrent action spect
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decay with stretched exponential ki
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siderably larger than might be esti
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dispersing CdSe nanocrystal chromop
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memory and charge storage effects [
Page 297 and 298:
all) of the optically excited elect
Page 299 and 300:
composites of nanocrystals and conj
Page 301 and 302:
55. Asbury, J.B.; Hao, E.C.; Wang,
Page 303 and 304:
108. Morgan, N.Y.; Leatherdale, C.A
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The approaches to fabrication of se
Page 307 and 308:
Figure 1 Experimental realization o
Page 309 and 310:
Due to this voltage division, the m
Page 311 and 312:
Figure 3 Simulated tunneling spectr
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electron charging. In both positive
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Figure 5 shows the typical features
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Figure 7 Map of levels for InAs nan
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Figure 8 Scanning electron microsco
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D CB = 0.31 eV is thus obtained. On
Page 323 and 324:
Figure 11 Correlation of optical an
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atomistic approach based on pseudop
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charging indicated that the tunneli
Page 329 and 330:
capacitance values were also kept t
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could not be detected in the QD/DT/
Page 333 and 334:
Figure 18 Tunneling conductanceF sp
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data in the inset of Fig. 19 repres
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corresponding to the s-like wave fu
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7. Grabert, H.; Devoret, M.H., Eds.
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66. Su, B.; Goldman, V.J.; Cunningh
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dimensional confinement are created
Page 345 and 346:
Figure 1 Transmission electron micr
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The room-temperature absorption and
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narrower in samples with larger mea
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GaInP 2 QDs from a plot of the squa
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crystal, indicating lattice-matched
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Figure 5 Evolution of Stranski-Kras
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Figure 7 Photoluminescence spectra
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Figure 8 Photoluminescence spectra
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C. Efficient Anti-Stokes Photolumin
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Because HF treatment has been shown
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Page 367 and 368:
intensity of the PL when it is on a
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eV stems from recombining carriers
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Figure 16 Model to explain two-colo
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although this term is not rigorousl
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10 ps (about an order of magnitude
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electron relaxation is inhibited an
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Figure 18 Transmission electron mic
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QDs, the nature of the QD capping s
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QD solution. For an interdot distan
Page 385 and 386:
emission spectra of the two individ
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Figure 23 Change of the PL intensit
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(viz. the absorbed light intensity)
Page 391 and 392:
Figure 25Impact ionization in QDs.m
Page 393 and 394:
prevent electron-hole recombination
Page 395 and 396:
36. Miller, R.D.J.; McLendon, G.; N
Page 397 and 398:
91. Vurgaftman, I.; Singh, J. Appl.
Page 399 and 400:
139. Mićić, O.I.; Ahrenkiel, S.P.
Page 401 and 402:
10Synthesis and Fabrication of Meta
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Figure 2 (A-C) Progression of HR-TE
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Figure 3 Schematic for gold nanocry
Page 407 and 408:
Nanocrystal growth can occur by two
Page 409 and 410:
on the other hand, provide an ensem
Page 411 and 412:
Figure 6 (a) SAXS patterns for disp
Page 413 and 414:
Figure 8 The gold nanocrystal film
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of the stabilizing ligand, and the
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successfully modeled the 2D island
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2. Steric Stabilization and a Soft
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are fully extended. Moving away fro
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Figure 11 High-resolution SEM image
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Figure 13 (A) Transmission electron
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function of the density of localize
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Figure 15 High-resolution SEM image
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thiol-capped nanocrystals [2]. The
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41. Ackerson, B.J. Nature 1993, 365
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with the effect of the particle com
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Figure 1a shows the surface plasmon
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Figure 2 (a) Ultraviolet-visible ab
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agents [34]. The short-wavelength b
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Figure 4 (a) Plot of the plasmon ab
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the framework of traditional Mie’
Page 447 and 448:
show that effects due to the surrou
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is located at the position of the g
Page 451 and 452:
Page 453 and 454:
Figure 8 Ultraviolet-visible absorp
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laser pulses while being mixed in t
Page 457 and 458:
Figure 10 shows HR-TEM images of go
Page 459 and 460:
Figure 11 Transmission electron mic
Page 461 and 462:
final irradiation product. At the s
Page 463 and 464:
following the laser excitation appe
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36. Papavassiliou, G.C. Prog. Solid
Page 467 and 468:
particles to expand. Because the he
Page 469 and 470:
was frequency doubled in a 1-mm B-
Page 471 and 472:
Figure 2 Frequency of the acoustic
Page 473 and 474:
Figure 3 Change in radius (DR/R) ve
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In this model, the electrons couple
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Figure 5 Transient bleach data for
Page 479 and 480:
Figure 7 (a) Transient bleach data
Page 481 and 482:
that the particles with >80% Au hav
Page 483 and 484:
3. Del Fatti, N.; Valle´e, F.; Fly
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