Horiba Instruments (S) Pte Ltd

Content
Introduction
Static light scattering
Measurement process
Important instrumental considerations

Applications

Introduction
Static light scattering (SLS) or more commonly known as laser
scattering/diffraction is used for the size determination of micron to
submicron particles. The laser diffraction technique for the
determination of particle size distribution is based on the
phenomenon that particles scatter light in all directions with an
intensity pattern that is dependent on particle size (and shape).

Introduction

Analytical range generally from 10 nm to a few mm

Powders, suspensions, emulsions, creams and pastes are possible
Dry and wet measurement systems are available
Possible to have de-agglomeration mechanism in dry and wet
systems
The whole measurement process can be completed in < 1 minute
Uses Mie theory (needs refractive index) or Fraunhofer
approximation (no need refractive index)
Equivalent spherical diameter is obtained
Volume based distribution
ISO 13320:2009 Particle size analysis Laser diffraction methods

Static light scattering

Characteristics
Theory

Assumptions
Requirements

Characteristics
Particles suspended in a fluid
RI difference between particle and fluid

Large particle
Small/low angle scattering
Large signal/intensity

Small particle
Big/high angle scattering
Small signal/intensity

Scattering pattern

Symmetrical on the axis of incident light

Light wavelength dependent
Particle size dependent
Particle shape dependent

Characteristics
The figure below shows the effect of size on the scattering pattern
detected at different angles. Note that the scattering intensity at the
front of a particle (close to 0 degree) is always the highest and bigger
particle scatters more intensely as compared to a smaller one.

Characteristics

Characteristics
Why you need two light sources of different wavelengths?

Theory
Mie
Rigorous solution valid for all sizes of spherical particles
Requires optical propety (RI) to be known for both
sample and dispersant

Fraunhofer
Approximation for large particles (~> 50 micron) or
opaque particles
Optical property (RI) is not necessary
Limited to forward (low angle) scattering

Theory
Big particle

Theory
Small particle

Assumptions
All particles are spherical and optically homogeneous.
If particles are not spherical, then the scattering pattern obtained is
used to calculate the equivalent spherical diameter for the particles.

Requirements
1. Sample dispersion in a fluid (liquid or air) is necessary.
2. Sample cannot dissolve or react with the fluid it is dispersed in.
3. There must be a difference in refractive index of the sample and
the fluid.
4. Particle concentration cannot be too high (multiple scattering) or
low (low signal).
5. Refractive index of the sample and fluid should be known,
especially for small particles.

Requirements

Real Index (degree of refraction)

Imaginary Index (absorption of light within particle)

Information obtained from ISO 13320:2009

Reflected
Refracted
Absorbed
and
Reradiated

Diffracted

Requirements

Information obtained from ISO 13320:2009

Requirements

Information obtained from ISO 13320:2009

Measurement process
Static/laser light scattering measurement process
Sample is dispersed in a fluid (liquid or air) in a cell
Monochromatic light source(s) illuminate(s) the cell
The light scattered by the particles, at various angles, is measured
by multi-element detectors
The scattering pattern is used to calculate the particle size
distribution

Measurement process

14

100

q(%)

60
40

20
0
0.010

0.100

1.000

10.00
Diameter(m)

100.0

1000

0
5000

Undersize(%)

80

10

Important instrumental considerations

1. Light source

Number of light source(s) (2 is optimal)

Wavelength(s) (Long & short)
State of technology (solid state vs gas laser)

2. Detection system

Number of detectors (> is better but not necessary best)

Detector angular coverage (> is better)

3. Sampling mechanism

Circulation system (centrifugal vs peristaltic)

Dispersion system (ultrasonic probe vs bath)

4. Performance specifications

Accuracy (compared to traceable standard)

Repeatability (< is better)

Important instrumental considerations

5. Maintenance requirements

Cell removable mechanism

Pumping tubing replacement (?)

Important instrumental considerations

Images are obtained from the internet and are copyright of respective owners

Important instrumental considerations

0o

90 o

270 o

180 o

Scattering patterns
for 0.05 and 0.07
micron particles with
650 nm laser and 405
nm LED

Important instrumental considerations

Images obtained from the internet.

Important instrumental considerations

Images obtained from the Cole Parmer website

Important instrumental considerations

Important instrumental considerations

Applications

CMP slurry
Pigment ink

CMP slurry

http://www.horiba.com/semicondu
ctor/products/processes/semicond
uctor-process/cmp-process/

What is a CMP process?

CMP or chemical mechanical planarization is a process used by
semiconductor manufacturers to make wafers flat and smooth using
specially formulated abrasive suspensions

CMP slurry

http://www.horiba.com/scientific/products/particlecharacterization/applications/cmp/

Images from https://www.crystec.com/alpovere.htm

CMP slurry
What is a CMP slurry?
CMP slurry is a special chemical formulation that has abrasive
particles with a specific (narrow) size range and pH value. The
abrasive particles can be silica, alumina, ceria, titania, diamond, etc.
A silica CMP slurry normally has a high pH value that has a certain
weight % of silica abrasives. The alkaline solution helps to soften/etch
the silicon wafer surface while the abrasive particles remove material
from the surface through mechanical action.

CMP slurry
An example of a silica CMP slurry

http://www.fujimico.com/catalog/Chemical%20Mechanical%20Planarization/33

CMP slurry
A certain CMP slurry particle size specification

CMP slurry
Particle size measurements needed by:
CMP slurry producers to control their product quality
End users to confirm specification before use and periodic check to
ensure consistent performance

CMP slurry
Silica CMP slurry

40

100

q (%)

60
20
40
10
0
0.010

20

0.100

1.000
Diameter (m)

0
10.00

Undersize (%)

80

30

CMP slurry
Diamond CMP slurry

45

100

40

q (%)

30

60

20

40

10
0
0.010

20

0.100

1.000
Diameter (m)

0
10.00

Undersize (%)

80

Pigment ink
What are pigments?
Industrially, a pigment is any finely divided
insoluble black, white or colored solid
material, a major function of which is to
improve the appearance of or give color to
the medium in which it is to be used.

Image and information obtained from BASF website:

https://www.dispersionspigments.basf.com/portal/basf/ien/dt.jsp?setCursor=1_561069

Pigment ink
Types of pigments

Table obtained from BASF website:

https://www.dispersionspigments.basf.com/portal/basf/ien/dt.jsp?setCursor=1_
561069

Pigment ink
What are pigment inks?
Pigment inks are complex liquid dispersions of pigments, binding
agent and additives. A binding agent is normally a plastic resin.
Additives commonly consist of anti-foam, waxes, extenders, pHcontrollers and surfactants. Pigment inks can be solvent based or
aqueous based.

Pigment ink

Why do you need to know particle size and distribution for pigment inks?

Pigment ink
Particle size and distribution for pigment inks

Pigment ink
C I pigment blue 15

16

100

10

q (%)

60
40

5
20
0
0.010

0.100
Diameter (m)

0
1.000

Undersize (%)

80

Pigment ink
C I pigment blue 15:3

23

100

20

q (%)

15

60

10

40

5
0
0.010

20

0.100
Diameter (m)

0
1.000

Undersize (%)

80

Gracias

Tack

Danke

Cm n

Grazie

Obrigado