Nanoparticles

Synthesis: metal,
magnetic and QDs
Carlos Baleizão

Department of Chemical Engineering / Instituto Superior Técnico / Universidade de Lisboa

carlos.baleizao@tecnico.ulisboa.pt http://web.tecnico.ulisboa.pt/carlos.baleizao/
Types of chemical bounds

Both atoms with high electronegativity,

and small (or 0) D
Covalent

Atoms with large D

Ionic

Both atoms with small

electronegativity, and
Metallic small (or 0) D

2
Standard organic reactions

Low molecular weight reactants

Homogeneous liquid system

(all reactants dissolved in the solvent)

Diffusion is not a limitation

Catalyst and temperature: can help

At the end what matters: conversion

and selectivity

Major changes?

hybridization

oxidation state (CO2 vs. CH4)

valid for (bio)macromolecules 3

For Nanostructures …

3D structure

Grow over time (anisotropic)

Reduce mobility

Assembling of the atoms in their

crystal structure

Changes in the oxidation state

Stability over time depends of the

- type of bound (covalent > metallic > ionic)

- E0 (standard reduction potencial)

- medium 4
Metal Nanoparticles

Au and Ag colloidal particles

usually prepared in aqueous
dispersion from HAuCl4 and Nucleation
AgNO3, under smooth conditions,
in the presence of a reducer, for
example of citrate Supersaturation

Au0 Growth

Other reducers: Au+3

ascorbic acic Time
hydroxylamine
sodium borohydride (NaBH4) Addition of reducer

5
Gold Nanorods – Anisotropic Grow

Nanorods
seed-mediated growth

Bilayer packing density is lower near the tip

CTAB due to its curvature
The probability for micellized gold ions to
approach the tips is higher compared to the
sides

Murphy et al, 2011 https://doi.org/10.1016/j.cocis.2011.01.001 6

Gold Nanostructures surface modification

Thiol-Gold interaction very strong (amines also used)

Solvent exchange (hydrophilic vs. hydrophobic ligands)

Specific functional ligands for SERS, fluorescence sensing, etc.

7
Magnetic Nanoparticles

Most magnetic nanoparticles

are prepared from iron oxides

Iron oxides Magnetite nanoparticles are the most used

because they are biocompatible and
Hematite α-Fe2O3 inexpensive
Magnetite Fe3O4 (FeIIFeIII2O4)
Maghemite γ-Fe2O3
β-Fe2O3
ε-Fe2O3 Co and Ni are also highly magnetic
Würstite FeO materials, but they are toxic and easily
oxidized

8
 Magnetic Nanoparticles

Nanomaterials 2018, 8(10), 810;  https://doi.org/10.3390/nano8100810 9

Magnetic Nanoparticles

10
Magnetic Nanoparticles: co-precipitation

Stoichiometric mixtures of ferrous and ferric hydroxides in aqueous media,

yielding spherical magnetite particles homogeneous in size

2Fe3+ + Fe2+ + 8OH− Fe3O4 + 4H2O

oleic acid
6 nm 7 nm 8 nm 9 nm

 Simple and efficient

 Poor crystallinity
 Aggregation

10 nm 11 nm 12 nm 13 nm
J. Mater. Chem., 2008, 18, 1171 11
Magnetic Nanoparticles: thermal decomposition
High-temperature (ca. 300ºC) decomposition of iron organic precursors, using
organic solvents and surfactants

Precursor: e.g. Fe(Cup)3, Fe(CO)5, or Fe(acac)3

Surfactant: e.g. fatty acids, oleic acid,
hexadecylamine

Size control through precursor concentration,

ratio and nature; temperature and reaction time

 Magnetite with high crystallinity

 Good control of size dispersion

 Low yields
 Hydrophobic magnetite

JACS, 2009, 131, 454 12

Magnetic Nanoparticles: surface modification

Avoid oxidation in air

Avoid aggregation (improve colloidal stability)

Tetraethoxysilane
(TEOS)

Functionalization (for biological applications,

introduction of specific chemical functionalities,
etc.)

Nanomaterials 2018, 8(10), 810;
 https://doi.org/10.3390/nano8100810 13
 Quantum Dots: colloidal synthesis

The synthetic method of choice is by

arrested nucleation and growth capping
Reagents are depleted
Essential elements and capping agent
metallic or organometallic precursor coordinates to surfaces
such as Zn, Cd, Hg, with a
corresponding chalcogen precursor growth
such as S, Se Te in a coordinating
solvent at high temperature
Decrease reaction temperature to
induce slow growth
nucleation
I Supersaturation
II burst nucleation
III growth controlled by diffusion
of monomer
Small nanocrystals are rapidly
nucleated and capped by an
organic monolayer

Injection of reagents
Quantum Dots: easy monitoring

CdSe QDs

In CdSe, the fact that some peaks decrease

while others increase is indicative of a
system that is not undergoing Ostwald
ripening.

Ostwald ripening would lead to slow peak

red-shifts with time rather than loose
intensity.

Instead, the system is undergoing a series

of growth steps (magic NCs) where one size
concentration increases with time while
other diminishes, tending toward larger
sizes.
Quantum Dots: colloidal synthesis
Preparation of Trioctylphosphine oxide (TOPO) capped CdSe QDs by
arrested nucleation and growth

Tributylphosphine selenide is rapidly injected into a

stirring 300ºC solution of dimethyl cadmium in TOPO
(surfactant–ligand–solvent)

CdSe nanocrystals nucleate and the temperature is

dropped so that they grow to become QDs with the
diameter determined by the amount of precursors
After the synthesis, the QDs are precipitated,
filtered and washed Other ligands that can be used instead of TOPO, include
long chain amines, phosphines, carboxylic acids, thiols,
Re-dispersing in toluene and gradually adding etc.
a non-solvent (eg. acetone) causes size-
selective QD precipitation (separated by
centrifugation)
Quantum Dots: capping layer

Stabilize the QDs at a particular size

Act as a dielectric shell to
prevent surface traps
(defects)
Act as a
diffusion barrier
to promote
uniform particle
size distribution Contain functional
groups to disperse
the particles in
different solvents

Prevent oxidation of the

particles Allow direct
assembly into
different morphologies

The molecules of the capping layer are attached to the particle surface by coordination bonds,
weak enough to allow exchange by other molecules
Quantum Dots: functionalization

QDs surface modification

and functionalization

shell

Sensors 2007, 7, 3489

Quantum Dots

Direct electrodeposition of semiconductor pillars

Spin-coating of bilayer e-beam resist

Exposure to focused electron beam Chemical electrodeposition of

CdSe CdSO4, H2SO4 and SeO2

Development of exposed pattern

Chemical etching Polymer resist removal

Oxygen reactive ion-bean cleaning

Su et al, Adv. Mater. 2003, 15(1)49

Quantum Dots: Epitaxial Deposition

Epitaxial deposition by patterned growth

Epitaxy is the process of growing a crystal of a particular orientation, where this
orientation is determined by an underlying crystal

Photolithography and wet

Semiconducting compounds with a small chemical etching
bandgap (GaAs) are grown on the patterned
surface of a compound with a larger bandgap metalorganic vapor phase
(example: GaAs on AlGaAs) epitaxy (MOVPE)

Growth is restricted by coating with a

masking compound (SiO2) and etching
that mask with the shape of the required
crystal cell wall

Appl. Phys. Lett. May, 1991

Density and size of quantum dots limited

by the mask pattern
MAP5