Professional Documents
Culture Documents
Bawendi1990 - The Quantum Mechanics of Larger Semiconductor Clusters (Quantum Dots)
Bawendi1990 - The Quantum Mechanics of Larger Semiconductor Clusters (Quantum Dots)
REVIEWS Further
Annu.Rev. Phys. Chem.1990. 41:477-96 Quick links to online content
Copyright©1990by AnnualReviewsInc. All rights reserved
Louis E. Brus
AT&T
Bell Laboratories, Murray Hill, NewJersey 07974
INTRODUCTION
spectroscopy of CdSecrystallites.
e+ 2/L However,since this MOhas nodes on the chain ends, its energy is
shifted higher than the band edge: This is in essence the "quantum size
effect." Higher MOshave an increasing numberof internal nodes. States
near e have a node on ever) other atom and are essentially nonbonding
by University of Sussex on 12/20/12. For personal use only.
2’8
POLYENECHAIN
E = e + 2/~cos(Kja)
j~r
Kj= (N+l)a
oN=11
oN=15
-2’80 Tr/a
k WAVEVECTOR
Figure 1 Polyene chain band structure (adapted from Ref. 6). Discrete eigenvalues for
N - 13 and N = 11 chains are also shown. (e = ~b)
480 BAWENDI, STEIGERWALD & BRUS
2~k~a2 _ 2rc
E(km)= (e + 2fl) 2~
~ a2m2
E°+(~7)
where
L = (U+ 1)a.
Annu. Rev. Phys. Chem. 1990.41:477-496. Downloaded from www.annualreviews.org
Ep(n) - 2 m*" 4.
LOCALIZED ~
Si ATOM ORBITAL CLUSTER ~ OF
MOLECULAR DENSITY
ATOMIC DEGENERATE STATES ~
ORBI TALS BASIS ORBITALS
Figure2 Molecularorbital modelfor evolutionof discrete MOsinto continuousbands
(adaptedfromRef. 6).
energy orbital in the sigma star (i.e. conduction) band is the crystallite
LUMO.In the limit of the bulk crystalline solid, the HOMO-LUMO
spacing becomes the band gap, and the bands become separately con-
tinuous in energy.
In a II-VI or III-V zinc blende crystal such as GaAs, each Ga atom is
surrounded tetrahedrally by four As atoms, and vice versa. With a minimal
atomic basis of three P and one S atomic orbital (AO) on each cation and
each anion, there will be four occupied electronic bands (analogous to
sigma above) and four unoccupied electronic bands (9). The bands have
the Bloch form
eie’~Z,,(F
)
where %~is a symmetrized combination of bond orbitals within one unit
cell. The bands have a complex structure as a function of K inside the
Brillouin zone and cannot be characterized by one scalar effective mass
valid over the entire zone. However,for crystallites of diameter D, the
HOMO and LUMOare principally formed from regions of IKI < ~/D
around the top of the highest occupied band and the bottom of lowest
482 BAWENDI, STEIGERWALD & BRUS
and is designated a "Is" state. Note that the allowed quantum numbers,
and energetic ordering of states, are different from those of hydrogen
because the radial potential is a square well and not Coulombic.
by University of Sussex on 12/20/12. For personal use only.
Discrete occupied MOsnear the top of the valence band have a far more
complex structure. Three of the four occupied valence bands of the bulk
crystal are degenerate at K = 0, due to the underlying three-fold degener-
acy of p AOs. Awayfrom K= 0 these bands split and can be described
by a 6 x 6 tensor "hole" Hamiltonian (13) that, in a spherical harmonic
ID
--tP -
- -- tS LUMO
£9 ....... CONDUCTION
EDGE
I’~: ~. V..,~__AL,
ENCEEDGE-
°RB’TI £~’~:,S: [ ~ Is HOMO
SP’N~
,~.- Ip -
-1 ~tD
Figure 3 Molecular orbital energy levels for a 45 ~. diameter ZnSe crystallile (from ReC
12). The lowest two allowed transitions are indicated.
QUANTUMDOTS 483
basis, can be written
method has been applied to ZnO and CdS, with the result that the ls
electron shift is only about half that estimated by the effective mass model
for intermediate sizes (18). The independenceof this important result
surface bonding and model approximations needs to be examined; the
effective mass model is knownto be a quite adequate approximation for
zinc blende materials in superlattice physics.
ELECTRON-HOLE CORRELATION
Annu. Rev. Phys. Chem. 1990.41:477-496. Downloaded from www.annualreviews.org
electron and hole attract each other via (shielded) Coulombforces. This
suggests a model Hamiltonianfor the lowest ls-ls excited state (19):
2
_h h 2 2e
/~ = ~Vc 2 - ~Vh 2 6.
zrnc Zmh ~IL--~hI"
Equation 6 describes internally correlated, bound "excitons" in bulk crys-
tals and in superlattices quite well. In crystallites, the Coulombterm
induces electron-hole correlation and is relatively more important at large
diameters, because the kinetic energies vary as (1/R2) and the Coulomb
term as (I/R) (19), where R is the crystallite radius. The Coulomb
mixeshigher lying states into the Is-Is state. In the limit of small R, mixing
is minor due to large state splittings in zero order, and the wavefunction
approaches ls-ls. This is the molecular limit.
Only in the limit of large R does an internally correlated, hydrogenic
electron-hole "exciton" form. The electronic polarizability becomesquite
high as the eigenspectrum becomes dense. In the limit of continuous
band structure near the band edges, such large crystallites could conduct
electricity in an excited state with an electron and hole present in the
presenceof an electric field.
In the small crystallite, Is-Is limit, the energyis (19, 20)
h2rc2F 1 1I 1"8e2
¯ E(R) -- Eg+ ~-[_~ + m, 7.
GoR"
APPROACHOF CLUSTERLOWESTEXCITED
5.0 ELECTRICSTATETO THEBULKBANDGAP
4.5--
\~ -- ZnO
BANDGAP
w 2.0
1.5 ~ GaAs
0.5 ~ InSb-
O I I I I ~ I
30 5o too 200300 50o
DtAWETER
(~)
Figure 4 Lowestallowed electronic transition energy versus size (from Ref. 19).
486 BAWENDI, STEIGERWALD & BRUS
and reacts with the Cd rich surface. Whenphenyl groups are chemically
bonded to the crystallite, it becomes hydrophobic. This surface deri-
vatization prevents fusion of crystallites, and enables recovery of macro-
by University of Sussex on 12/20/12. For personal use only.
~ PhSeTMS
~ = SURFACTANT MOLECULE
Figure 5 Schematic diagram of synthetic process that "caps" a CdSecrystallite with phenyl
groups (Ref. 1).
QUANTUM DOTS 489
(a)
INTERMEDIATE BETWEEN
ZINC BLENDE
AND WUR]’ZITE
0
~]~ --EXPERIMENT
Annu. Rev. Phys. Chem. 1990.41:477-496. Downloaded from www.annualreviews.org
20 30 40 50 60
by University of Sussex on 12/20/12. For personal use only.
20
(b)
NEAR WURTZITE
I-
z
::D
o
(J
0 10 20 30 40 ,.50 60
2e
Figure 6 Bragg powderX-ray scattering spectra of CdSecrystallites (from Ref. 57).
tion for two different ca. 35 ~ CdSesyntheses (57). One reaction yields
essentially wurtzite single crystallites, whereasthe other yields particles
that switch between wurtzite and zinc blende, apparently randomly, as
growth occurs. Modeling shows that powder patterns measure average
long range structure, and are relatively insensitive to deviations from the
average. Such deviations can be either random (thermal motion and/or
defects) or systematic (position dependent strain and/or surface recon-
struction). NMRand EXAFSmeasurements, however, do provide partial
information about surface bonding and structure (P. R. Reynders and M.
Marcus, unpublished results).
490 BAWENDI, STEIGERWALD & BRUS
geneous broadening.
The upper panel of Figure 7 shows the 10 K absorption spectrum of
by University of Sussex on 12/20/12. For personal use only.
ENERGY
(eV)
2.5 2.0
0.6 1I , I I I I i I
0.3
0.0
0.:3
0.0 --
25K
~ LUMINESCENCE
Annu. Rev. Phys. Chem. 1990.41:477-496. Downloaded from www.annualreviews.org
LUMINESCENCE EXCITATION /~
by University of Sussex on 12/20/12. For personal use only.
ls-Is(A) /ls-ls
~ ~s-lp /
EMISSION
I
spectrum. The bumpat ca. 500 nm may be the ls-lp transition, and the
weak feature at 460 nm may be the ls-2s transition. The stronger and
broader feature at 440 nm, also seen directly in absorption, is probably
the higher spin orbit component of ls-ls. The broad continuum in the
ultraviolet corresponds to higher excited states including lp~lp.
In general, quantumcrystallite luminescenceis quite sensitive to surface
composition and structure. Figure 9 schematically illustrates the types
of processes that may occur. The figure compares the discrete MOsof
nanometer crystallites with the standard band diagram of a bulk semicon-
ductor. The CdSeluminescence observed in Figure 8 appears to be the ls-
ls state in fluorescence, although a complete understanding of vibrational
and electronic reorganization between absorption and fluorescence has
not yet been workedout. In this state, the electron and hole are inside the
crystailite; recall that the ls wavefunction has a node on the surface (in
the limit of an infinite barrier).
QUANTUM DOTS 493
SPATIAL ELECTRONICSTATE CORRELATIONDIAGRAM
CLUSTER
BULK SEMICONDUCTOR
LUMO
CONDUCTION
BAND
/////////%)---;/’
l i SHALLOW
TRAP.....
Annu. Rev. Phys. Chem. 1990.41:477-496. Downloaded from www.annualreviews.org
ADSORBED
BULKig MOLECULE
by University of Sussex on 12/20/12. For personal use only.
~’--SURFACE
"//////////
....
} ,,,
STATE
VALENCEBAND
~’ ~ HOMO
~" DISTANCE
"-=" ~
CLUSTERDIAMETER
SUMMARY
by University of Sussex on 12/20/12. For personal use only.
Literature Cited
Ch. 3. San Francisco: Freeman 40. Hache, F., Richard, D., Flytzanis, C.
10. Rossetti, R., Hull, R., Gibson, J. M., 1989. Appl. Phys. Left. 55:1504
Brus, L. E. 1985. J. Chem. Phys. 83: 41. Arai, T., Fujumura, H., Umezu, I.,
1406 Ogawa,T., Fujii, A. 1989. Jpn. J. Appl.
11. Efros, A1. L., Efros, A. L. 1982. Soy. Phys. 28:484
by University of Sussex on 12/20/12. For personal use only.