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Heinrich Hofmann
Swiss Federal Institute of Technology,EPFL
Lausanne, Switerland
heinrich.hofmann@epfl.ch
“Nanochemistry and Nanophysics”
2D. Myers Surfaces and Interfaces, VCH Publishers Inc., New York, 1991.
3J. P. Spatz, A. Roescher, M. Möller Adv. Mater. 8/4 (1996)
Nucleation and Growth (La Mer)
The influence of the counter-ion on the particle size is again a kinetic one. The
Zn2+-ion forms complexes with the above mentioned acetate, acetylacetonate, or
trifluoromethane-sulfonate anions. Depending on the complexation, less „free“
cations are available for reaction, the crystallite growth is suppressed.
Lit.: R. Vacassy, S. M. Scholz, J. Dutta, H. Hofmann et al., J. Am. Chem. Soc. 81/10 (1998)
2669ff.
Quantum-dots
Size- and material-dependent emission spectra of
several surfactant -coated semiconductor nanocrystals
in a variety of sizes (A).
Blue series: different sizes of CdSe (Diameter :
2.1, 2.4, 3.1, 3.6, 4.6 nm)
Green series: InP nanocrystals (Diameter: 3.0, 3.5, and
4.6 nm)
Red series: InAs nanocrystals (Diameter:
2.8, 3.6, 4.6, 6.0 nm)
(B) A true-color image of a series of silica-coated core
(CdSe)-shell (ZnS or CdS) nanocrystal probes in
aqueous buffer, all illuminated simultaneously with a
handheld ultraviolet lamp
Synthesis: There are many wet chemical methods of synthesis for semiconductor nanoparticles, a organic and an inorganic method are
presented here:
TOP/TOPO
Cd2+ + Se2- CdSeLn [Me2Cd] + [(TMS)2Se] CdSe
Stabilizer Ln
Optimized synthesis
Optimized synthesis parameters:
parameters:
9<pH<12.5
230 < T < 260°C
Surfactant: Thioalcohols/Thioacids
Surfactant: TOP/TOPO
Atmosphere: inert gas Transmission electron micrograph
Atmosphere: inert gas
of CdSe
A. P. Alivisatos J.Phys.Chem. 100/31 (1996) 13226ff.
Brus and co-workers suggested that sulfur
vacancies, located at the surface of the
material, might be important in mediating
low-energy emissions. There are several
reasons for this, one of which is the
considerable size of such shallow traps.
Moreover, as the size of these traps
approaches that of the nanoparticle, the
wave functions of the trap and excited state
overlap. Transfer to these levels, in the form
of a separate event, should subsequently
be minimized, and the possibility of electron-
hole recombination, with emission close to
the absorption peak of the bound exciton,
can become the predominant
event.
Small crystallites are less stable than larger ones and tend to dissolve into their
respective ions. Subsequently, the dissolved ions can recrystallize on larger
crystallites, which are thermodynamically more stable (Ostwald ripening). The
use of acetonitrile, as a solvent, or the addition of styrene/maleic anhydride
copolymer allowed the preparation of stable CdS nanoparticles, with an
average size of 34 and 43 Å, respectively.Cubic ZnS and CdS nanocrystallites
were synthesized in aqueous and methanolic solutions without organic
surfactant (capping agent).
C. B. Murray and C. R. Kagan and M. G. Bawendi Annu. Rev. Mater. Sci. 2000. 30:545–610
ZnS:Mn (Me) Photoluminescence
L-cysteine
ZnSO4 + Na2S + (MnCl2) ZnS(:Mn2+) + 2 Na+ + SO42- + (Cl-)
Absorption Spectrum
1.8
30 min
1.6 1h
1.4 1h 30 min
2h
1.2
1
0.8
0.6
0.4
0.2
0
260.0 280.0 300.0 320.0 340.0
wavelength (nm)
ZnS:Mn (Me) Photoluminescence
wavenumber (cm-1)
3400.0 2400.0 1400.0 400.0
O 0.0
O
20.0
H2N
O NH2 2090 cm -1 40.0
S
H2N 60.0
O S O 2559 cm -1
80.0
S 1581 cm -1 1531 cm -1
O Cysteine
100.0
Cysteine on particles
120.0
O S
S
O NH2
2559 cm-1: S-H stretch band
H2N O • 2090 cm-1: NH3+ stretch band
• 1581 cm-1: COO- stretch band
O • 1531 cm-1: NH3+ deformation band
R. Vacassy, R. J. Flatt, H. Hofmann, K. S. Choi, and R. K. Singh ,Journal of Colloid and Interface
Science 227, 302–315 (2000)
SiO2 nanoparticles formed by the
co-hydrolysis of TEOS in ethanol
containing ammonia at an
intermediate stage of the synthesis
(4 h reaction time, SiO2 100/0).
Evolution of the particle size and particle size distribution of silica during the
hydrolysis precipitation of TEOS (SiO2 100/0). The results were determined using
PCS, and error bars indicate the spread of the particle size distribution.
The total pair interaction energy V for
particles of masses i and j and for the
center-to-center separation R is the sum of
Van der Waals,VA, electrostatic, VE, and
solvation, VS, interactions.
R-ri-rj (nm)
Evolution of the maximum of the total particle interaction energy
(potential barrier) during the early stage of the silica nanoparticle synthesis,
considering the interaction between primary and growing particles. Dashed
lines present linear corrections due to particle density variations.
Side Reactions
Very often, syntheses, which seem straight forward are in fact very complicated
and result in various reaction products. A very good example is the well known
iron oxide Fe2O3 .
Overall reaction: 2Fe3+ + 6OH- ⇔ Fe2O3 + 3H2O
In detail:
[Fe(H2O)6]3+ [Fe(OH)(H2O)5]2+ + H+ pH: 0-2
Fe2O3·xH2O
Jean-Pierre Jolivet et al. C h e m . C o m m u n . , 2 0 0 4 , 4 8 1 – 4 8 7
Nanosized particles in a biological environment
are complex systems
Nanoparticles Beads
Typical Functionalisation and Derivatisation
Physics Chemistry Colloidal chemistry Biology
OH OH
Iron oxide-PVA-Linker-Transferrin Avidin
8 nm 10 nm 2 – 30 nm
Synthesis of
Maghemite
Wet chemical co-
precipitation
Base
Sedimentation
Fe2+
Fe3+ 30 nm
HRTEM Oxidation/Redispersion
Fe3O4
γ- + Polymer
Fe2O3
Bare
particles
PRODUCT
2 nm
+
NH2 NH2
NH2 NH2
Bare particle with
double layer + PVA
PVA coated particle PVA coated & functionalized PARTICLE & BEAD
Nanocrystalline Semiconductors: Synthesis, Properties, and Perspectives (review) Tito Trindade et al. Chem. Mater.
2001, 13, 3843-3858
Segmented Flow Tubular Reactor
Mixer
-segmenter Tubular section
Reactant 1
Immiscible Fluid
Parobolic flow
Quasi - Plug Flow
• Temperatures 5
- 95°C
Perfect Segmentation –no fouling
• Flow rates 1.4 L/hr
• Residence times 1-60 mins
• pH 1-14 In
30 m long
Segmenting
10 cm
Fluid
Dodecane
Out
Previous Results- Narrower size distributions
Batch SFTR
Frequency
Frequency
σg = 4.3 σg = 1.7
Freq vol %
10
0
0.01 0.1 1 10
d [µm]
Crystallographic Control Seeding(25°C)- CaCO3
Seed Powder
Calcite H Calcite
Vaterite H Vaterite
Aragonite H Calcite
BaTiO3 synthesis – Batch vs SFTR
Low Temperature Aqueous Synthesis (LTAS) developed at Genoa
Reactants 0.6 M pH 12-14
Ba(OH) 2 + TiCl4 + 4NaOH → BaTiO3 + 4NaCl + 3H 2 O
• SFTR
• Batch 6 litre reactor
• 95°C
• 85°C
• Nitrogen segmenting fluid
• Nitrogen atmosphere
• 4mm φ tube PTFE
• 5hrs ageing
• Residence time 10 mins
• Washing • Washing
• Freeze drying • Freeze Drying
A.Testino, M.Viviani, M.T.Buscaglia, V.Buscaglia, P.Nanni
Institute for Physical Chemistry of Materials - CRN, Genoa, Italy
Chemical and Process Engineering Department - University of Genoa, Italy
Powder Characterisation (1)
Powder Ba/Ti (±1%) BaCO3
nominal experim. %
80
• SFTR powder
% Volume
60
• Finer,
• High surface area, 40 Batch
20 SFTR
0
0 0.05 0.1 0.15 0.2 0.25 0.3
Diameter (µm)
• Initial powders
primary particles
22-40 nm
•Sintering SPS
- 50 MPa, Batch
- vacuum – N2 - 50% < 100 nm
- 800-1000°C - density - 96%
- grain size 150 nm
Dr.Zhao Zhe,
Prof. Mats Nygren,
Dr. Zhijian Shen SFTR
Dept. of Inorg. Chem., - 90% < 100 nm
Arrhenius Lab., - density – 97 %
Stockholm Univ. S106 - grain size 80 nm
91, Sweden
B10 Paper 659 Tuesday
14.50, Dolmabahce C