CHEM 146_Experiment #6

A Visual Demonstration of
Particle in a Box theory:
Multicolor CdSe Quantum Dots

Yat Li
Department of Chemistry & Biochemistry
University of California, Santa Cruz

Objective

In this laboratory experiment, we will learn:

1. The principle of interband transition and quantum
confinement effect in zero dimensional quantum dots
2. Synthesis of CdSe nanocrystals
3. Absorption and Emission properties of CdSe
nanocrystals

Semiconductor nanocrystals
Nanocrystals are zero dimensional nanomaterials,
which exhibit strong quantum confinement in all three
dimensions, and thus they are also called quantum
dots.

UV
light

Ambient
light

Size dependent optical

properties!

Particle in a Box theory

The particle is restricted to the region

0 x a; the probability that the
particle is found outside the region is
zero.

(0) = (a) = 0

Free particle in a onedimensional box

Schrdinger
equation:

d2
dx2

2m
2

[E - V(x)](x)
= 0

= h/2E = total energy of the particle; V(x) =

potential energy of the particle; and (x) =
wavefunction of the particles

Free particle: the particle experience no potential energy

V(x) = 0
2mE
d2
+
(x) = 0
dx2
2

Particle in a Box theory

The general solution of Schrdinger
equation:
2(2mE)1/2
(2mE)1/2
k
=
(x) = A cos kx + B sin kx

h
=
when (0) = 0;cos (0) = 1; sin (0) =
0
A=0
when (a) = 0;(a) = B sin ka = 0
B = 0 (rejected) or ka = n n = 1,
2, 3.
Substitute k = n/a back to equation for
k;
h2n2
En =
n = 1, 2, 3.
8ma2
h2

E =
(nf ni)2
8ma2

Quantum dots
A quantum dot is in analogy to the particle in a box model,
where E increases with decreasing a.
h2

E =
(nf ni)2
2
8ma
CdSe has a Bohr exciton radius of ~56 , so for nanocrystals
smaller than 112 in diameter the electron and hole cannot
achieve their desired distance and become particles trapped
in a box.

Free exciton

Synthesis of CdSe nanoparticles

Preparation of Se
precursors:
1.

2.

30 mg of Se and 5 mL octadecene

Preparation of Cd
precursors:
1.

a.
b.

Add 13 mg of CdO
to a 25 mL round
bottom flask
add by pipet 0.6 mL
oleic acid and 10
mL octadecene

3.

0.4 mL trioctylphosphine

completely dissolve the selenium

2.

Heat the cadmium

solution to 225 C

http://mrsec.wisc.edu/Edetc/nanolab/CdSe/index.

Synthesis of CdSe nanoparticles

Preparation of CdSe
nanocrystals:
1.

2.

Transfer 1 mL of the room temperature

Se solution to the 225 C Cd solution and
start timing

Remove approximately 1 mL
samples at 10s intervals (for the
first five samples)

3.

Ten samples should be

removed within 3 minutes of
the initial injection

http://mrsec.wisc.edu/Edetc/nanolab/CdSe/index.

Spectroscopy
Spectroscopic techniques all work on the principle of that, under
certain conditions, materials absorb or emit energy
Quantized energy: photon
E = h

E = h =
hc/
X-axis: Frequency or
wavelength

UV-vis Spectroscopy
Transitions in the electronic energy levels of the bonds of a
molecule and results in excitation of electrons from ground state to
excited state
Energy changes: 104 to 105 cm-1 or 100 to 1000 kJ mol-1
Four types of transitions:
i)

Within the same atom e.g. d-d or f-f

transition

ii) To adjacent atom (charge transfer)

iii) To a delocalized energy band,
conduction band
(photoconductivity)
iv) Promotion of an electron from
valence band to conduction band
(bandgap in semiconductors)

A powerful technique to study the interband electronic transition in semic

Interband absorption
Electrons are excited between the bands of a solid by making
optical transition

Ef = E i +
h

Indirect
bandgap:
Relative position of conduction band and
valence band is not matched

Direct
bandgap:
h < Eg, (h) = 0
h Eg, (h) = (h Eg)

The transition involve phonon to conserve

momentum
Ef = Ei + h +

indirect = (h Eg )2

Beer-Lambert law

log(I0/I) = cl
= A/cl
: extinction coefficient
c: concentration
radiation
l: path length

I0: incident radiation

I: transmitted
A: absorbance

value determine transition is allowed or

forbidden

Luminescence
Spontaneous emission when electron in excited states drop
down to a lower level by radiative emission
Spontaneous emission
rate:

R = A 1

Non-radiative emission:

Electron in excited states will

relax rapidly to lowest level in the
excited band
Sharp emission peak

If R << NR, R 1 (maximum light will

be emitted)

Interband luminescence
Direct bandgap materials

Indirect bandgap
materials

Allowed transition short lifetime

(ns)

Second order process involve

phonon

Narrow emission line close to

bandgap

Low emission efficiency

e.g. GaN, CdS, ZnS

e.g. Si, Ge