Synthesis and Optical Characterization of CdS Nanoparticles

Background:
Nanoparticles or quantum dots are receiving considerable attention because of their
potential applications in several areas of great commercial value1. The vast majority of the
research has focused on materials which are semiconductors. These material generate electron-
hole pairs when excited by photons or appropriate electrical bias voltages. The recombination of
these electron-hole pairs can result in light emission or luminescence. While the color of light
emitted is strongly influenced by the band gap of the semiconductor, it is also possible to tune the
color of light produced by controlling the size of the particle. The trick is to make the particles
small enough that quantum confinement is operative and the energy levels are influenced or even
dictated by the particle size. This usually requires that the particles have nanometer dimensions.

This Experiment:
In this experiment we will attempt to make nanometer sized particles of CdS, a semi-
conducting material. Making CdS particles is not hard at all. The material is rather insoluble in
many solvents and so a simple metathesis reaction can be employed:

Cd(NO3)2 + Na2S -----> CdS + 2 NaNO3

The trick is to keep the newly formed CdS molecules from aggregating to form particles in
the 10's of nm or larger size range which display the properties of bulk CdS and for which
quantum confinement is not important. Further, if particle growth is not restrained
precipitation will quickly occur.

Recent literature suggests that it is possible to cap or coat the newly formed CdS particles
with a polymer which renders further aggregation unlikely.2 This process is called passivation.
The initial work used a star dendrimeric polymer as the capping agent. These materials are very
expensive and so a less costly alternative was sought. Work in Prof. Augustine’s laboratory at

1
JMU suggested that certain other polymers with prosthetic functional groups such as -NH- or -
COOH might be almost as efficient in protecting the nascent CdS from further aggregation3. Our
initial trials with this approach were quite encouraging. However, this experiment is a work in
progress.

In this experiment your group will synthesize CdS by two methods. One preparation is a
control in which the CdS particles generated are colloidal and too large to show much quantum
confinement. The second preparation employs conditions which trap the nascent CdS aggregates
earlier in their growth and produces nanometer-sized particles.

PROCEDURE:
Several of the materials you will use are toxic and the use of gloves is required. The
solvent system is also toxic and the experiment must be conducted in a hood. Dispose of
waste reagents in the containers labeled for such.

Nanometer particle synthesis:

A 50 ml three neck round bottom flask equipped with stir bar and placed in a suitable cooling
bath is used for the synthesis. Two of the necks are fitted with septa and the other with a Teflon
plug. The cooling bath should be prepared using ice/water and be at ~ 10oC. After allowing the
flask to cool for at least 2 minutes in the bath, start the stirrer at a moderately vigorous rate and
pipette in 10 ml of the working polymer solution in CH3OH. Again, let the solution cool for
about 2 minutes and then begin the alternate addition using syringes of 0.5 ml portions of the
Cd+2 ion solution, followed by the S-2 ion solution. To keep the addition rate approximately
constant, count to 5 slowly between each addition. After a total of 5.0 ml of each reagent has
been added, allow the solution to stir for an additional 5 min. At this point, if you shine a “black”
light on the flask you should observe luminescence from the solution.

Stock Solution Working Solutions Amount Added - Working Solution

0.02 M Cd(NO3)2 2.0 * 10-3 M 5.0 ml in 0.5 ml increments/syringe
0.02 M Na2S 2.0 * 10-3 M 5.0 ml in 0.5 ml increments/syringe
1.5*10-3 M polymer - high 4.5*10-4 M 10.0 ml at start of procedure in flask
MW, branched

Carefully transfer the contents of the flask to a labeled bottle for subsequent physical
measurements. Rinse the flask with CH3OH and remount in cooling bath for the next synthesis.
Keep the syringes.

2
Colloidal (bulk) particle synthesis.
This synthesis is very similar to the first one, but here we will place the capping polymer and the
Cd2+ solution together in the flask at the start. Then we will add the S2- solution via 0.5 ml
aliquots with a syringe, just as we did in the first preparation.

Stock Solution Working Solutions Amount Added - Working Solution

0.02 M Cd(NO3)2 2.0 * 10-3 M 5.0 ml at start of procedure in flask
0.02 M Na2S 2.0 * 10-3 M 5.0 ml in 0.5 ml increments/syringe
1.5*10-3 M polymer - high 4.5*10-4 M 10.0 ml at start of procedure in flask
MW, branched
The other aspects of this preparation are identical to that above. When the addition of the NaS
solution is complete, let the mixture stir for an additional 5 minutes, as above. Again, transfer
the reaction mixture to an appropriately labeled bottle for later physical characterization.
[Note]: While the exact mechanism by which this procedure generates colloidal CdS is
uncertain. The effect is almost certainly a kinetic one with higher aggregates forming before
capping can occur. The initial concentration of Cd2+ ion “seen” by the injected S2- ion is 10 times
greater than for the 1st procedure. This may result in a high local concentration of CdS as the S2-
drops hit the polymer/Cd2+ solution and lead to larger aggregates before passivation by the
polymer can occur.

Optical Characterization:

UV-VIS SPECTRA:
Transfer several ml of the prep solutions to quartz fluorescence cuvettes. Obtain a uv/vis
spectrum of each solution and overlay the two spectra. Are there any obvious differences in the
absorption spectra of the nanoparticle and colloidal particle solutions. Save the two spectra on
disk as .csv files.

EMISSION SPECTRA:
Using the Spex fluorimeter, obtain emission spectra of the two solutions. Instructions for use of
the fluorimeter will be available on site. Excite the materials using 340 nm light and scan the
emission from 400 nm -> 700 nm. Be sure to transfer your spectra in ASCII format to disk for
later processing.

COMMERCIAL QUANTUM DOTS:

A sample of commercial quantum dots using CdSe will be available. These materials were
synthesized under conditions which allow very precise control of the particle size. Instructions
will be available on site for the parameters to be used in obtaining their emission spectra. As
with your own preps, obtain the emission spectra and save in a suitable ASCII format file.

3
 REPORT
DATA:
Plot your absorption and emission data as overlays. That is, plot the absorption spectra from
both preparations on a common graph. Determine λmax for the lowest energy transition of each
material. Make a similar plot for the emission spectra of your preparations. Determine the λmax
for each solution. Finally, make a 3rd plot showing the emission spectra of the commercial
quantum dots.

DISCUSSION QUESTIONS:

1. The emission energy taken at λmax for the nanoparticulate CdS can be thought of as
composed of the band gap energy (bulk property, coulombic), Ebandgap, and the quantum
confinement energy, ∆E (here we simplify by ignoring the solvation effects). Thus

Ephoton (λmax) = hc/λmax = Ebandgap + ∆E (1)

This additional energy resulting from quantum confinement, ∆E, can be related to the
average particle radius through the expression4

∆E = h2
8R 2 (1 / m*
e + 1 / mh* ) (2)

Where R is the particle radius, me* is the effective mass of the electron and mh* is the
effective mass of the hole. Using your experimental value for λmax for the
nanoparticulate material, calculate ∆E. The band gap for CdS is given below.
Using the values of me* and mh* provided below, calculate the average particle radius for
the nanoparticulate CdS.

2. The recombination of an electron-hole pair will result in the emission of light, which is
the mechanism for the emission that you observed. An electron-hole pair is known as an
exciton. One can model an exciton as similar to a hydrogen atom, consisting of a positive
and negatively charged species bound to one another electrostatically. We can estimate
how far apart the two charges are on average by calculating the effective Bohr radius of
the exciton, ab.

h 2ε
ab = 2 (1 / me* + 1 / mh* ) (3)
πe

Here ε = εCdS εo, the dielectric constant of CdS, and e is the charge on the electron.
Calculate ab . A suitable value for εCdS is given below. Is the calculated distance of
electron-hole separation consistent with the calculated particle size?

4
3. Based on the value of R found in 1, calculate the volume of the nanoparticles responsible
for the most intense emission (i.e. λmax). Now find the ionic radii for Cd2+ and S=.
Assume that the CdS ion pair is a sphere with radius RCd + RS , the sum of the ionic radii
for the two ions. How many CdS ion pairs (molecules) are in the nanoparticle? How
many CdS ion pair would it take to span the diameter of the particle?

4. Using your absorption spectra, estimate the transition energy for the lowest energy
transition (longest λ peak, use λmax) for both the nano and colloidal CdS. Calculate the
∆E between the two transitions in eV. This will be less than 1 eV. How does the ∆E for
absorption compare to the ∆E for emission. The latter was obtained in Question 1, Eq
(1).

5. Comparing the emission spectra of our preparations and the commercial quantum dots,
explain how we know that our preparation has a much greater dispersion of particle sizes.

6. Using the Mathcad document provided, alter the various parameters as required for our
experiment. Print a copy of the revised document to be turned in with your report.
Answer the question posed regarding the 3 graphs and what they tell us regarding the
range of particle radii for which quantum confinement is important.

Useful Information:
1. Note that me* = 0.19 me and mh* = 0.80 me where me is the mass of the electron.
2. Band gap for CdS at room temperature ~ 2.42 eV
3. The dielectric constant for CdS at optical frequencies is ~ 5.7

References:
1. C. Murphy, J. L. Coffer, Applied Spectroscopy, 2002, 56, 16A - 27A.
2. J. Huang, K. Sookal, C. J. Murphy, H. J. Ploehn, Chem. Mater.,1999, 11, 3595.
3. J. F. Arceo, L. Daily , W. C. Hughes, B. A. DeGraff, B. H. Augustine, 2004 , J. Chem.
Ed. (submitted).
4. Brus, L. E., J. Chem. Phys., 1983, 79, 5566-71. Brus, L. E., J. Chem. Phys., 1984, 80,
403-9.

5
 [Student Writeup]

SYNTHESIS

AND

OPTICAL CHARACTERIZATION

OF

CdS NANOPARTICLES
This worksheet calculates the expected emission energy and
wavelength for semiconductor particles which show quantum
confinement features.
− 19 This is the bulk band gap of the material
E := 4.000 ⋅10
Supply appropriate value. Unit = Joules

These are the various constants needed to calculate the

change in band gap energy as a result of quantum confinement
− 34 − 31 − 31
h := 6.626 ⋅10 me := 0.19 ⋅ 9.109 ⋅10 mh := 0.80 ⋅9.109 ⋅ 10
This is our guess as to the size range of particles.
Supply appropriate range for our experiment. Unit = m
− 10 − 10 − 10
R := 100 ⋅10 , 110 ⋅10 .. 1000 ⋅10

This is the expression for the change in band gap due to

quantum confinement

2
⎛ h ⎞ ⋅π 2
⎜ ⎟
⎝ 2 ⋅π ⎠ ⎛ 1 + 1 ⎞
∆E ( R) := ⋅⎜ ⎟
2 ⋅R
2 ⎝ me mh ⎠

The total band gap energy is the sum of the bulk band
gap and the incremental change due to confinement

Et( R) := E + ∆E ( R)

We also formulate an expression for the λ of light that

will be emitted for a particular total band gap.

8 c
c := 3 ⋅ 10 λ ( R) := h ⋅
Et ( R)
 3 .10
21

2 .10
21

∆E ( R)

1 .10
21

0
2 .10 4 .10 6 .10 8 .10 1 .10
8 8 8 8 7
0
R

What do these three graphs tell us about the range of particle

radii for which quantum confinement is significant? That is, what
range of R is required for the ∆E to be a significant fraction of the
total excitation energy and to cause a significant blue shift in the
observed emission?

0.01

∆E ( R)
0.005
E t ( R)

0
0 2 .10 4 .10 6 .10 8 .10 1 .10
8 8 8 8 7

R
 4.98 .10
7

4.96 .10
7

λ ( R)

4.94 .10
7

4.92 .10
7

2 .10 4 .10 6 .10 8 .10

8 8 8 8

Next we turn to the question of how far apart are the two
charges (electron and hole) separated when an exciton is
created. We approximate this by using a modified calculation
for the Bohr radius
− 19 dielectric constant for your
e := 1.602 ⋅ 10 Charge on electron Dr := 20 material. Supply correct
value.
− 12
D := Dr ⋅8.854 ⋅10 dielectric constant for material in mks units.

⎛ h2 ⎞ D ⎛ 1 1 ⎞
ab := ⎜ ⎟ ⋅ ⋅ ⎜ + ⎟
⎝ π ⎠ e2 ⎝ mh me ⎠
−9
ab = 6.895 × 10

We calculate that the distance of separation for the exciton

or e/hole pair is about ___ nm (proved results of your caln.)
Finally we estimate (order of magnitude) the number of CdS
molecules in our "average" nanoparticle.

− 10 − 10 − 10
R := 5 ⋅ 10 , 10 ⋅10 .. 60 ⋅ 10 radius of the nanoparticle

4 3 volume of the nanoparticle

Vn ( R) := ⋅ π ⋅R
3
−9 −9
r1 := 0.200 ⋅10 radius of the 1st ion r2 := 0.200 ⋅10 radius of the 2nd ion

(You must supply appropriate values for your two ions)

4
⋅π ⋅( r1 + r2)
3
Vp := volume of the ion pair approximated as a sphere
3

Vn ( R)
N ( R) :=
Vp

R= N ( R) = Thus, if our particles are __nm

5·10 -10 1.953 in radius or above, we have 100's
1·10 -9 15.625 to 1,000's of ion pairs in each
1.5·10 -9 52.734 particle. (fill in the results of your
2·10 -9 125 calculation)
2.5·10 -9 244.141
3·10 -9 421.875
3.5·10 -9 669.922
4·10 -9 1·10 3
4.5·10 -9 1.424·10 3
5·10 -9 1.953·10 3
5.5·10 -9 2.6·10 3
6·10 -9 3.375·10 3

file is nanopart.mcd

revised 07/22/04
Instructor Notes

Chemicals:

Chemical CAS Hazard

Registry
Methanol, CH3OH 67-56-1 Toxic liquid, toxic vapor
Cadmium Nitrate, Cd(NO3)2*4H2O 10022-68-1 Toxic solid
Sodium Sulfide, Na2S*9H2O 1313-84-4 Toxic, corrosive solid
Polyethylenimine, Mw~7.5*105 (branched) 68130-97-2 Irritant
Polyethyleneimine, Mw~2.5*104 (branched) 9002-98-6 Irritant
Polyethyleneimine, Mn~423 (linear) 26913-06-4 Strong irritant
Polyethyleneimine, low MW, branched 25987-06-8 Irritant

1. The higher MW polymers require some time to dissolve in methanol, so prep ahead of
use.

2. The Cd2+ and polymer solutions are stable for at least 1 year. The Na2S solution
should be made fresh, not more than a few days prior to use.

3. We observed little difference in the durability of the product nanoparticle suspensions

with temperature (room vs 4oC) or air vs Ar purge. The solutions are good for a week
with some slight deterioration in emission intensity. We routinely stored the suspensions
in brown bottles in the dark.

Preparation:

1. The two preparations are amazingly tolerant. We have investigated the effect of drip
rate using various delays with the syringe addition and also use of addition funnels. All
seemed to have only minor effects. We experimented with ultrasonic agitation, but found
little difference in the results. Any reasonable stirring rate with a simple magnetic stirrer
will give acceptable results.

2. The reaction temperature does not seem to have a big impact on the outcome. We find
that the emission intensity is greater for preparations done at about 10oC, but useful
suspensions can be made in the range 0 ->25oC.

3. The emission intensity observed with a common black light clearly shows that
luminescence is occurring and that there is a real color difference between the two
preparations. However, the intensity is sub-optimal as both the nano- and colloidal
materials do not absorb well at 366 nm.

Optical Measurements:

1. The blue shift observed between the nanoparticles' lowest energy absorption and the
colloidal material is typically 340 nm vs 360 nm. This gives a crude value for ∆E of
about 3.2*10-20 J, or about 30% smaller than that estimated from emission measurements.
However, inevitable small errors in estimating λmax for absorption result in much larger
energy errors than a comparable error in λmax estimation for emission (i.e. a 1 nm error at
300 nm is a much greater energy error than at 550 nm). It is useful to point this
difference in potential error out to students.

2. For reasons we do not understand, the emission intensity of the colloidal preparation is
typically a factor of 2 or more brighter than for the nanoparticle suspension, even when
differences is absorption of the exciting light are factored in. The absorption at the first
λmax for both preparations is quite similar, but the quantum yield for emission of the
colloidal material is greater.

3. Sample spectra comparing the emission intensities of both the nanoparticulate and
colloidal CdS are provided (Figures 1 and 2). Also, a emission spectrum for a
commercial CdSe quantum dot preparation is included (Figure 3).

4. The polymers are somewhat luminescent due to various impurities. Typically, the
background luminescence from the polymers is ~ 4->7% of the total. It is up to the
instructor as to whether a blank correction is warranted.

5. The higher MW polymers also scatter light. Since the polymer concentration is
significantly greater than the particle concentration, assuming an aggregation number of
1,000, it is the major contributor to the observed light scattering. We have the students
visually observe that the solutions scatter light and explain that it is primarily due to
excess polymer. However, with quantitative measurements using a photodiode detector
one can show a scattering difference between the nano and colloidal preparations. This
part of the experiment is a bit fussy and should not be attempted without some experience
in light scattering detection.

6. The emission spectra shown in the article have been corrected for detector response.
Use of uncorrected data will give slightly different appearing spectra.

Calculations and Report:

1. In the original work of Brus1, the excitation energy expression also contains a term
that gives the polarization effects on the energy. Though this term can be estimated
reasonably well, it is usually small compared to the other contributions (i.e. the
Coulombic and confinement terms). We omit this term in our implementation so that
students can focus on the main point of the experiment, changes in energy levels with
particle size.

2. One would expect that colloidal CdS would show a λmax ~ 520 nm for Ebandgap ~ 2.42
eV. The λmax ~ 525 nm observed for our "colloidal" preparation is quite close, but a
spread of emission wavelengths is observed. However, surface states often shift the
emission energy of semiconductor materials and these particles are polymer encapsulated
so this result is not too surprising. Pure colloidal (5µ) CdS is available from Aldrich, but
this material is totally insoluble and suspensions of it are non-emissive.

3. Unfortunately, there is range of reported values for Ebandgap for CdS (2.42 -> 2.53) .
Also, students may well use the static dielectric constant for CdS rather than the optical
frequency value. The static is over 50% higher.

4. The calculation of the number of CdS pairs in a typical nanoparticle can be done to
varying degrees of approximation. We assume no void volume, which gives the largest
number of particles. Lattice constants and crystal structure are known for CdS and so a
more accurate model can be used.
1
Brus, L. E., J. Chem. Phys.1983, 79, 5566-71. Brus, L. E., J. Chem. Phys., 1984, 80, 4403-09.

Emission Intensity for Nanoparticulate CdS in CH3OH

Immediate __________ After 24 hrs _ _ _ _ _ _

nano_c.PDW
2.00E6
Emission Intensity (cps)

1.50E6

1.00E6

5.00E5

0.00E0
400 450 500 550 600 650 700
Wavelength(nm)
Figure 1
 Emission Intensity for Colloidal CdS in CH3OH
Immediate __________ After 24 hrs. _ _ _ _ _ _
Colloidc.dat
2.50E6
Emission Intensity (cps)

2.00E6

1.50E6

1.00E6

5.00E5

0.00E0
400 450 500 550 600 650 700
Wavelength (nm)

Figure 2

Commer.dat

1.20E6

1.00E6
Emission Intensity (cps)

8.00E5

6.00E5

4.00E5

2.00E5

0.00E0
520 540 560 580 600 620 640 660
Wavelength (nm)

Figure 3 Spectrum of nanoparticulate CdSe (Evident Technology)