Synthesis,

characteriza/on and
applica/ons of some quantum dots

Dr. Ashutosh Pandey

Chemistry Department
MNNIT Allahabad

 II-VI Nanopar/cles
•  A. Henglein (Ber. Bunsenges,. Phys. Chem, 1982,86,301) was the very first work
revealing the absorp/on spectrum of a colloidal solu/on of size quan/zed CdS
nanocrystals. These were prepared by reac/on of cadmium chlorate and Na2S on
the surface of silica par/cles. The absorp/on onset is shiRed considerably to
higher energies with respect to the bulk band gap of CdS (515 nm). In addi/on the
sol emits light upon excita/on at 390 nm.
•  Another milestone is the work by Murray et.al. ( J. Am. Chem. Soc. 1993, 115,
8706) wherein the pyrolysis of organometallic reagents like dimethyl cadmium
and trioctyl phosphene selenide . Figure shows the evolu/on of the absorp/on
spectra of CdSe crystallites ranging from 1.2 to 11.5 nm.
•  RosseZ et al reported quantum size effects in the redox poten/als and electronic
spectra of CdS nanocrystals. [J. Chem. Phy. 1983, 79, 1086]. Henglien and
coworkers enlarged the field [Ber. Bunsenges,. Phys. Chem, 1982,86,301]by
prepara/on of ZnS and ZnS/CdS co-colloids.
•  Ramsden et al prepared CdS nanocrystals by reac/ng cadmium nitrate and sodium
sulphide[J. Chem.Soc. Farady Trans. 1984, 80,819].
 Sol gel condensa/on with metal alkoxides

—  --- M---OR + HOH-----> M---OH +ROH

—  --- M---OR + HOH-----> M--O--M +ROH

—  M---O--M--O--M

31/01/18 7
 Synthesis of colloidal
nanocrystals
Ar

P=O
Ar

P=O
P=O
P=O

P=O Cd

thermocouple

P=O
Inject
organometallic
precursors Highly crystalline

Explosive nucleation structure
Narrow size
Followed by temp. drop and slow growth
Of pre formed nuclei distribution
Heating mantle 350 set
348 cur
temperature
controller
Mixture of
Surfactants/stabilizing agents
 Polymer Coa+ng: Surface Chemistry
thickness of shell: approx. 2 - 3 nm

poly(maleic anhydride alt-1-tetradecene)

crosslinker
•  Carboxyl groups

•  Nega/ve charge ⇒ Coulomb

repulsion
•  EDC chemistry for binding of
primary amines
•  Limita/ons:
–  stable to ~ 150 mM NaCl
–  not good at acidic pH
(protona/on)
 Polymer Coa+ng
Transfer of hydrophobic nanocrystals into water

Comb-like polymer:
+ hydrophobic sidechaines,
hydrophilic backbone

+ Cross linker

Nanocrystal with Nanocrystal wrapped

hydrophobic surfactant in a
closed hydrophilic
shell
 Func+onaliza+on of the quantum
dots
EDC activated hydrophilic nanocrystals now can subsequently react with free amine groups
from enzymes, antibodies, or ligands such as streptavidin and protein A.

EDC = 1-ethyl-3, 3’ (dimethyl amino propyl) carbodiimide

Coupling of amine-containing
methoxy-PEG-amine
PEG by means of EDC
(‘‘crosslinker‘‘)

homo- and heterobifunctional PEG COO- X

commercially available
NH2
⇒ modification of particles with
new functional groups
X X
Principle of operation of the dye-sensitized nanocrystalline solar cell. Photoexcitation of
the sensitizer (S) is followed by electron injection into the conduction band of a
semiconductor oxide film. The dye molecule is regenerated by the redox system, which
itself is regenerated at the counterelectrode by electrons passed through the load.
 1.sensitizer(S) excitation by light;
2.radiative and nonradiative deactivation of the sensitizer;
3electron injection in the conduction band, followed by electron trapping and diffusion to the particle surface;
4recapture of the conduction band electron by the oxidized sensitizer (S+);
5recapture of the conduction band electrons by the oxidized form of the redox couple regenerating the sensitizer and transporting the positive charge to the
counter electrode.
Grayspheres: titania nanoparticles. Red dots: sensitizer. Green and blue dots: oxidized and reduced forms of the redox couple.