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To Study the Colloidal Properties of

Semiconductor Nanoparticles using Dynamic


Light Scattering

Research Report (Chem 751)


Pushpa Chhetri
May 9, 2014

Importance of DLS in the scientific world


DLS
Study the properties of colloids
Particle size distribution of particles
Observing aggregation effects in colloids
Application in observe the stability with time eg. Emulsion

Why and when DLS is used


Polymer and particle science: routine characterization
Experimental physicist and physical chemist: study gels, networks,
liquid crystals, hydrodynamic interactions
Obtaining precise particle size

Schematic of DLS Instrument

Lente

LASER

Abertura

PMT

Autocorrelacin
digital y
microcomputadora
Video Display

Brownian
motion
Particles move or diffuse in random walk
fashion
Collision of neighboring solvent molecules
It Probes density or conc. fluctuations
The fluctuation in scattering intensity of
laser due to the Brownian motion of
particles in liquid can be recorded and
particle size can be calculated using
Stokes-Einstein relation.

+ +
- +
++
+
+

+ +
- +
++
+
+

Effect of Diffusion
Intensity Vs time plot
Pequeo

Ia (t)

Mediano

Phases of the each of the


scattered wave arriving at
PMT
Fluctuates randomly due to
the fluctuation in position of
particles
that scatter the wave.
Because these waves
interfere at the detector,
the net intensity fluctuates.

Largo

Tiempo, t

How well a particle can scatter depends on


MW or V
Polarizability of the particle which is related to refraction of the
particle relative to the solvent.
Is = f(np,ns) .(MW)2.I0

Obtaining particle size


Step 1. Obtaining raw data as intensity of scattered signal
Step 2. diffusion coefficient from fluctuating light scattering signal
25 nM DSNPs in MeOH

0.8

0.6

0.4

0.2

Diameter (nm)

500

376.95

284.19

214.25

161.53

121.78

91.81

69.22

52.18

39.34

29.66

22.36

16.86

12.71

9.58

7.22

5.45

4.11

3.1

2.33

1.76

1.33

0
1

T = Temperature
= viscosity of solvent
R = particle radius
Step 3. obtaining autocorrelation function

Relative intensity of scattered signal

1.2

Autocorrelation function: definition


C(t) = <Is(t)*Is(t-t)>
C(t) = averaged over many wiggles
of the fluctuating intensity Is
Is(t) = Intensity at given time t
Is(t-t) = Intensity at earlier time t-t
Study of similarity between the values
of Is(t) and Is(t-t)

800000
700000

C(t')

600000
500000
400000
300000
200000

5 min duration on 200 nm particles


DLS module performs approximately 15 million
multiplications
And obtains C(t) for one value of t (eg. t=20
microsecond for channel #1)
The instrument makes 64 such sets of calculations
simultaneously for 64 different values of t.
100000

-6

14

24

34

# of channel

44

54

64

Obtaining particle size


Step 1. Obtaining raw data as intensity of scattered signal
Step 2. diffusion coefficient from fluctuating light scattering signal

T = Temperature
= viscosity of solvent
R = particle radius
Step 3. obtaining autocorrelation function
1/ = 2DK2
Or D = (1/2K2)*(1/ )

decay

t
Channel width

Challenges
Challenges in collecting data
- Sample preparation: sonication
- Sample purification: dust is big enemy
- Right use of cuvette
Challenges in interpreting data
Intensity weight
Volume weight
Number weight
Distribution of particle size manipulations depends on: x axis scale bar

Advantages

disadvantages

Simple experimental set up

Clean samples required


Only transparent samples
Does not work for Settling
samples
Gives data for everything

Less expensive

Hydrodynamic size range 1nm to 1m


Eg
micro-emulsion
Peptides
Micelles
Macromolecules
Polymer

Paint pigments

Experimental data
interpretations
No TBAP run 102 before EC
Autocorrelation function

800000

25 nM DSNPs in MeOH

700000

600000
500000

C(t')

0.8

0.6

400000
300000
200000

0.4

100000
0.2

0
-6

14

24

34

# of channel

Diameter (nm)

500

376.95

284.19

214.25

161.53

121.78

91.81

69.22

52.18

39.34

29.66

22.36

16.86

12.71

9.58

7.22

5.45

4.11

3.1

2.33

1.76

1.33

0
1

Relative intensity of scattered signal

1.2

44

54

64

My observations as a DLS data user


The main goal is to determine diffusion coefficient D of particles from
raw data of scattered light intensity signal using decay constant .
DLS is highly sensitive to aggregation.
Effect of Migration is none.
Brownian motion induced diffusion as well as the natural convection
is prevalent which constantly fluctuates the net intensity.
Mathematic behind calculations is quite complicated.

References:
PSS Nicomp ZLS 380 manual
Experimental Data obtained using PSS Nicomp ZLS 380 in Dr. Alpuche
lab, UNR.

Thank You

C(0) = <Is2(t)>
C() = <Is (t)>2
<Is2(t)> > <Is (t)>2
Now the function C(t) for diffusing particles must fall from the value
<Is2(t)> at t=0 to the baseline value <Is (t)>2 at

very large t
Ideal case of uniform particle size: exponential