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Lecture 2
Silicon Germanium Quantum
Dots
200
nm
Precise Placement of Quantum Dots
Synthesis and Characterization of
Monodisperse Nanoparticles
C. B. Murray IBM
M+ M+
M+
M +
M + + ne- M
M+
Hayat, M. A. , Ed., Colloidal Gold: Principles, Methods, and Applications; Academic Press: San Diego, 1989; Vol 1.
Functionalized Reductions
M+ Functionalized
+ Reductant
Surfactant Nanoparticle
X
X
X
X
Y Y
Y
Y X
X Y
Y
Y
Y Y
Y
X
X
M1+ + Reductant M1
M1 + M2+ + Reductant M1
M2
Mixed Alloy
Cd 2+ CdS
Mix Intermicelle
S 2- CdS
S 2- exchange
Thiol capping
X
from emulsifier
X
X X
X
X
X X
X Monomer X
X
Polymer
X
X
X
X
Stability Sphere
X X
X X
X X
X
X X X
•Colloid Science, Kruyt, H. R., Ed.; Elsevier: New York, New York, 1952; Vol. 1
•Mysels, K. J. Introduction to Colloid Chemistry; Interscience: New York, 1959
•Irja Piirma, Ed., Emulsion Polymerization; Academic Press: New York, 1982
Initiator
•Eliseeva, V. I.; Ivanchev, S. S.; Kuckanov, S. I.; Lebedev, A. V. Emulsion Polymerization and its
Applications in Industry; Plenum: New York, 1981
•Bovey, F. A.; Kolthoff, I. M.; Medalia, A. I.; Meehan, E. J. In High Polymers; Mark, H., Melville, H. W.,
Marvel, C. S., Whitby, G. S., Eds.; Interscience: New York, 1955; Vol. IX
A
Monodisperse Colloid Growth (La Mer)
Nucleation
Concentration of Precursors
(arbitrary units)
10 0 G ro w th S o lutio n A C
R
0/\=//\P/\/\/\
37Å M ajor D ia.
0/\=//\P/\/\/\
\/\/\/\/ =0 /\/\/\/\
\/\/\/\/\
\/\/\/\/ =0
0=/\/\/\/\
\/\/\ \/\
0=/\/\/\/\
/\/\ \/\
\/\/\/ /\/
/\/\
\/\/\/ /\/
/\/\
/\/ P \
\/\/
/\/ P \
\/\/
/
σ = 12%
\/\/
/
/\//\\//\\/\
80
\/\/
/\/\
/\//\\//\\/\
0=P /\/\
/\/\
Normalized Counts
/\/\
\/\/
0=P
\/\/
\/
\/\/ \/\/\/\/\
\/
\/
/\/\ /\/
\/\/ \/\/\/\/\
/ \
\/\/
P
\//\\//\/\/\
/ /\
P
/
P 00==\P/P
\
P 00==\P/P
\
\ \
P= =0 \/\/ P= =0
\/\/ \
\/\/
\ /\/\/\/\/\/
\/\/
/\/\/\/\/\/
/\/\
Se=P \/\
/\/\
Se=P \/\ 60
O \/\/P=0 O
\/\/P=0 r /\/
\
r /\/
\
0=P
/\/
0=P \/\/ /\//\\/\
/\/\
/\/
\/\/ /\//\\/\
/\/\
\ \
\/\/ \/\/ 0=P /\
/\//\/\//\/\/\/\\/\//\/\
0=P /\
/\//\/\//\/\/\/\\/\//\/\
P=Se
/\/\/\ P=Se
/\/\/\ M eOH
/\/\/\/\
/\/\
/\/\/\/\
/\/\
/\/ /\/ /\
/\
P=0 0=\/\/\/\/
P P=0 0=\/\/\/\/
P 40
/\/\
0=\/P
/\/\
\/\/
0=\/P
\/\/
/\/\/\/\ =0 \/ /\/\/\/\ =0 \/
P/\/\\//\/ \
\/\/\/\/
P \/\/ \ 0\=//\/\/\/\
\/\/\/\/
0\=//\/\/\/\
P/=\ =0
P==00
P P
\/\P\/\
/\/\\//\\///\\\// P 0
\/\P\/\
P=0
P/\ =
\
P=0
\//\\//\/\/\
P==0
\//\\//\/\/\ /\/\/\//\\/
Se \/\\/\ /
P= 0
0
Se/\ /\\/ \/
\//\\=//P\/\/
0
\//\\=//P\/\/
20
/\/\/\/\
\/\/\/\/\
/\/\/\/\
\/\/\/\/\
\/\
\/\/ /\/\
\/\/\/\/
/\/\
\/\/
/ /\/\/
\/ \
\/ \
/\/
/\/
\
\
0
0 10 20 30 40 50 60
M ajor D iam e te r < 0 02 >
Energy (arbitrary units)
-12
Steric Repulsion (R )
10 0 S ize S e lecte d B
a
Normalized Counts
80 39Å M ajor D ia.
b
σ = 4.5%
c 60
d
40
H e xa ne
-6 B uO H
van der Waals (R ) 20
Attraction
0
0 10 20 30 40 50 60
Center to Center Distance R M ajor D iam e te r < 002 >
(arbitrary units)
Results of size selected Percipitation
A B
(e) 39Å+11%
(b) 39Å+8%
(f) 41Å+6%
(c) 40Å+5%
(d) 42Å+<4%
(g) 45Å+<4%
400 500 600 700 800 400 500 600 700 800
This is an old method (refereed as Turkevich method) which yields fairly uniform size colloids
with diameter of 15-20 nm. See reference Turkevich, J.;Stevenson, P. L.;Hillier, J.Discuss.
Faraday Soc. 1951, 11, 55
Preparation of 1.0 x 10-3M Ag Colloids (Sodium Citrate Reduction Method)
1.Make a solution of ~ 5.0 x 10-3M AgNO3 in water. (0.0425 g in 50 mL deionized H2O).
2.Take 25 mL of that solution and add it to another 100 mL of H2O (now ~1.0 x 10-3M).
3.Make a solution of 1% sodium citrate (0.5 g in 50 mL of H2O).
4.Heat the 125 mL solution of AgNO3 until it begins to boil.
5.Add 5 mL of 1% sodium citrate solution, as soon as boiling commences.
6.Continue heating until a colour change is evident (pale yellow).
7.Remove the solution from the heating element and continue to stir until it has cooled to
room temperature.
8.Top the solution up to 125 mL to account for boiling.
This method yields relatively large size silver nanocrystallites with a diameter of 60-80 nm and exhibits abs.
max. ~420 nm. See reference J. Phys. Chem. B, 1998, 102, 3123
(Note: Use of Sodium Borohydride as a reductant can give smaller size silver nanoparticles with plasmon
absorption around 380 nm. Presence of citric acid or polyvinyl alcohol can provide additional stability to
these colloids)
Preparation of Gold Particles in Toluene:
A.Hydrogen tetrachloroaurate (30 mL of 30 mM, in water).
Mass = 393g/mol ´ 0.03 M ´ 30mL/1000mL = 0.3537g of HAuCl4 in 30mL of H2O
B. Tetraoctyl ammonium bromide (80 mL in 50 mM, in toluene).
Mass = 546.8g/mol ´ 0.05 M ´ 80ml/1000mL = 2.187g of TOAB in 80mL of toluene
2.Heat this solution until it comes to a boil and then add the
appropriate amount of 5.0 x 10-3M HAuCl4. (For example: 50µ L,
100µ L, 150µ L, 300µ L, and 500µ L)
Synthesis of Transition Metal Nanocrystals
Co 8 nm Ni 9 nm Co/Ni 9 nm FePt 4 nm
CobaltNanocrystal Synthesized by
decomposition of Cobalt Carbonyls
Organometallic syntheis of the II-VI Semiconductor Nanocrystals
\/\
/\/
R 2 M + (T M S ) 2 E
\/\
R 2 M + \/\/\/\/P = E
\/\
/\/
\/ \
o E=S, Se, Te
E=Se, Te ∆ 300 C
M =Zn, Cd, Hg
M =Zn, Cd, Hg
\/\
/\/
/\/\/\/\/P = 0 TOPO
/ \/\/\
\ /\
\/ \
\ /\
/\ /
\/\
\/\/\/\/\P : TOP
\/ \
/ \/
\ /\
0=P/\ /\/\/\/\
\/\/\/\/
\/\/\/\/\/\
/\
P /\/\/\/\
/\
\ /\
/\ /\ /
\/\/
/\/\/\/\/\
/\/\
/ \/
/\/\ \/\/
0 =P
/\
/\
/\/\
\/\/
\ /\
/\/\
\/
\/\/
/\ /\
/\/
P=
\/ \/ \/
0=
\/ /
/\/ P \/\\ / \ / \ / \
/\/\
0= P
0
P= \/\
\/
/\/
0 0=
/\ /
\/
P=
/\ /\
\ /\
O E=P /\
\/\/\
/\ /\ /\ /\
/\/\
\/\/\
0=P/
\/\
/ \ /P = 0
/ / \/\ /
/\/\ ME
/\/\ S e m ic o n d u c to r 0 = P/\ /\ /\ /\
P=E \
/ \/\
\/\/\/
\/ \/\ /\
N a n o c ry s ta llite 0=P /
/\/\
/\ /\ /\ /\
P=0
0 = P\/\/\/\/\/
/\/\/\/\
/\/\/\ 0 \/\
/\ P = /\/
P= 0
0 = P /\/\/\/\
\/\/\/\/
/\/\
P=
\
\ /\ \
\ /
0
/ \ / / \/\/\/
\/ /
/ \ /\\//\\/ \ /
E
0
P=0
/\
/\
= P \/
P=
\/\ / \ / \ / \ /\
P=
\//\/
\ /\/
/\/\/\/\
\/\/
/\/
//\\//\\/\/
\/
/\/\/\/\
\/\/\/\/
\/
\/\
\/\ /
/\/\\
FIG. 2.1 Cartoon of the reaction scheme for the production of monodisperse II-VI nanocrystallites by rapid pyrolysis in coordinating solvents.
Colloidal CdSe Nanocrystals (Quantum dots).
15nm
2R ⎣me mh ⎦ εR
1.7nm
Wavelength, nm
Atomistic approach to structural characterization
• Nanoparticles are measured using a wide variety of techniques
• Standard approach
– Specific modeling for each measurement.
– Difficult to produce single unified model.
• Atomistic approach
– Model of nanoparticle built up atom-by-atom.
– Single model used for each technique.
– Self-consistent, systematic and extensible methodology.
High Resolution TEM Images reveal internal lattice.
A & B CdSe
C CdTe
D Cobalt
Low Mag TEM allows determination
of average size and shape:
CdSe
Cobalt
Cap exchange to modify surface:
/\/\/\\//\\/
/\/\/\/\
/\/\/\
A
/\/
\\/
/\/\
/\
/\\//\/\/
0=P\
\/\/
/\
/\/\
\/\/
/\/\ \/\
\/\/\/ P P \
0=Se=P
/\/\ /\/
\/ = /\/\
/\/\/\/ 0 /\/
\/\\/\
\
P=0 0=P /\/ /\/\/\
/\
/\/\/\ =Se
/
/\ P 0=P \/\/\/\/
\
\\/\
/\/\/ \/\/\/
/\//\/
Se
\/\/
/\/ \
/\/\
/\/\/\/\/\/\
/\P=0
/\/\/\ =0
\/\/\/\/ /
=P /
\/
P
\/\/\/\/\
/\
/\/\
/\/\
/\/\/\ \/\/
/\/\/\/\
/\/\
/\
\
N
Pyridine
o
∆ 60 C
N
C N N N
B
N N V ac uu m
PO N
/ TB N
N
/\/\/
∆ 15 0 o
/\/\/
/\/
/\/\/
T BP o N
C
F
0=P\
/\/\/\ C N
/\/\
\
\/\/ P\/\/ ∆ 60 N
N N
/
\/\/\ P
/ \
/
/\/\/ ra
/
0=\P N
P=0 /\/\ N ∆ z
80 o ene
/
/\/\/ e
/\/\/
Tricetylphosphate
=S 0=P \/\/\ C
/\/\/ P
\\/\
/\//\
/\/\
o
0
\/\/ \/\/
∆ 80 C N
/\/\ P=
Se /\/\/
\
\ \
0
/
\/\P=0
/\/\/
P=
\/\/\
=P/\ /
\/\/\
/\/\/
N N N
\/\/\/
/
/\/\/\/\/\/\/\/\/\/ N
/\/\/\/\/\/\
/\/\
/\/\
N N
/\/
/ /\/\
//\/\/\/\/\/\/\/\/\/
\/\/
N N N
/\/\/\/\/\/\/\/\/\/
/
N
/
N N
\/\/
N N
/\/
N N
\ /
\/\
N N
/
/\/
/\/\
N N
/\/
/\/\/\/
\/\
N N N
\/\
/ N
/\/
\/\
/\/\
/\ / N
/\/
\/\
N
/\/
N N
0=P
\/\
N
\
/\ /
/
/\/\/\/\/\/\/\/\/\/ N NN
\/\
/\ N
0=P /\/\/\
\/\
/\/\/\/\/\/\/\/\/\/ P
/\/
N
=0 N N
/
\/ \
/\/
N
/\ E
/\/
\/ \
/\/
/\/\/\/\/\/\/\/\/\/
/
/\/
/\/\/\/
\/\
\/\/\/\ e \/\
P= S 0=P /\/\/\/\/\/\/\/\/\/
/\/
/
/\/
\/\/
/\/\ \/\/ =0
\/\
/\/\ \/\ /\/
0
/\/\ /\\//\\//\\//\/\/ /\/\/ /
/\/\/\/\/\/\/\/\/\/ P=0 Se
/\/
/\/\ /\/ \/\
/ \ /\
/\/\
/\/\ \/\/ /\/\/P
/\/\ P=
/\/\/\/\/\/\/\/\/\/\/
\ /\
/\/\ \/\/\ /\/\/
=P/\/\
/\/\
/\/\
/\/\
\/ /\
/\/\ /\
/\/
/\/ \/\/\
/\/\ /\/\/\
/\/\
\
/\/\
/\/\ /
/
/\/ \/\/
\
/\/\
/\/\
D
/\/\
/
/\//\\/
/\/
Wet Chemical Synthesis of PbSe
Nanocrystals and Superlattices
oleic acid,
Synthesis Pb(OAc)2 + R3PSe
R3P, T=150 C
R= octyl PbSe
12 nm
IR Absorption (Arb. Unit)
4.0 nm
5.0 nm
8 nm
3.0 nm
4.0 nm
3.5 nm
3.0 nm
800 1200 1600 2000 2400 2800 800 1200 1600 2000 800 1200 1600 2000 2400
Wavelength (nm) Wavelength (nm)
Wavelength (nm)
PbSe PbS PbTe
T. J. Watson Research Center
Shape Change from Sphere to Cubic
and SAXS in Polymer Matrix
5
10
4
10
3
10
1 2 3 4 5 6
2θ (Degree)
5
10
4
10
3
10
1 2 3 4 5 6
2θ (Degree)
K.-S. Cho, W. Gaschler
Ferroic Nanoparticles: synthesis and self-
assembly into Ferroic Nanocomposites
Target ferroelectrics:
BaTiO3
SrTiO3
BaSrTiO3
Future targets Niobdates
average size 8 nm
Bimodal population
(Most runs look worse)
Fe3O4 Nanocrystals
(Sun and Zeng)
IR Absorption of Lead Chalcogenides NCs
12 nm
IR Absorption (Arb. Unit)
4.0 nm
5.0 nm
8 nm
3.0 nm
4.0 nm
3.5 nm
3.0 nm
800 1200 1600 2000 2400 2800 800 1200 1600 2000 800 1200 1600 2000 2400
Wavelength (nm) Wavelength (nm)
Wavelength (nm)
PbSe PbS PbTe
Shape selective synthesis of wuestite
oleic acid
Substitute dioctyl ether
Fe(CO)5 FeO-NC
trimetylamine N-oxide or trioctylamine
∆T N O
with pyridin N-oxide
Graduate Seminar
Ag Nanocubes contd…
Fig.1
(A) Low &
(B) High
magnification
SEM images (B)
was taken at a
tilting angle of
20°
(C)TEM image
(D) XRD
pattern
Gold nanoboxes: