Read More about - Introducing a 10-nm Particle Counter for Ultrapure Water

1. Fluid Measurement
Technologies, Inc.
Introducing a 10-nm Particle
Counter for Ultrapure Water
Derek Oberreit PhD, David Blackford PhD
Fluid Measurement Technologies, Inc.
Gary VanSchooneveld, Mark Litchy, Don Grant
CT Associates, Inc.

2. Outline
• Overview of the state of the art in in-situ
particle counting
• Overview of particle counting in the gas
phase
• Description of threshold particle counting
• Description of the Scanning Threshold
Particle Counter (Scanning TPC)
• Review of sample data

3. Can
existing
technology
get us
here?

4. Liquid Particle Counting
Technologies
• Dynamic light scattering
– Requires high concentrations
• Optical particle counting
– Specified down to 25nm with 3-5% detection efficiency
– Sensitive to particle composition
• Acoustic Coaxing Induced Microcavitation
– Able to detect 20nm particles
– Commercial availability unknown
• Nebulization – Aerosolization – Condensation
Particle Counting
– Promising new technology to provide measurements at
previously unattainable size thresholds

5. Particle analysis in the gas phase
• John Aitken, in 1888,
showed a method for
detecting and counting
optically invisible,
nanometer size aerosol
particles by enlarging
them via
heterogeneous
condensation of a
supersaturated vapor
http://www.iara.org/AerosolPioneers.htm

6. Condensation particle counting…
the science
• Supersaturated vapors
(relative humidity greater than
100%) are not happy
• The vapor wants to leave the
gas phase and condense onto
a surface
• Curved surfaces are
energetically less favorable
due to added surface tension
work (Kelvin effect)
• Condensation onto
particles is a function of
the surface radius and
the degree of
supersaturation
W=σdA

7. Condensation particle counting
more science
• The particle radius threshold at
which a supersaturated vapor will
condense onto its surface is given
by
where γ is the surface tension and
Vm is the molecular volume of the
condensing liquid. Po is the vapor
pressure above a flat surface of
the condensing vapor and P is the
actual vapor pressure
• P/Po is the Saturation Ratio, S
• Varying the degree of S changes
the minimum enlarged particle
size







P
P
Tk
V
r o
B
vap
ln
2
r
S=Scritical,r

8. Condensation Particle Counting
how it is implemented
• Lewis number is the ratio of the
thermal diffusivity of a gas λ, to
the mass diffusivity of a vapor
D, Le= λ/ D
• Le < 1 (e.g. water in air), cold
saturated gas introduced to
warm wet walls will drive vapor
into gas faster than heat,
leading to S>1
• Le > 1 (e.g. butanol in air),
warm saturated gas introduced
to cold walls will pull heat out of
the gas faster than butanol
vapor, leading to S>1
TSI Incorporated 3772 CPC Brochure

9. A note on detection efficiencies
• OPCs have a
shallow
detection
efficiency curve
• Many OPCs
are specified at
less than 5%
detection
efficiency
• Condensation
Particle
Counters
(CPCs) are
specified at
their 50% cutoff
3772 CPC
50% Detection
Efficiency at
10 nm
OPC data provided by Particle Measuring Systems.
3772 CPC Data by CT Associates
Detection Efficiency Comparison between in-situ OPC and CPC

10. Scanning Threshold Particle Counter
(Scanning TPC)
Principle of Operation
UPW
Nebulization
Large Droplet
Removal
Evaporation
Size Selective
Condensation
Growth
Optical
Detection
Non-volatile
Residue Monitor
Threshold
Particle
Counter

11. ScanningTPC
Principle of Operation
• Size selective growth
– All particles entering Condensation Particle Counter (CPC) are optically ‘invisible’
– Particles larger than a threshold size will grow by orders of magnitude through
vapor condensation
– Threshold size can reach as low as 1 nm!
– Scanning through different threshold diameters leads to a cumulative size
distribution
• Non-volatile residue limits lowest threshold diameter setting
Size Selective
Condensation
Growth
Particle Diameter
Colloid
Particles
Non-Volatile
Residue Particles

12. ScanningTPC
Principle of Operation
• Stepping threshold
diameter range
currently 10 nm to 30
nm
• Lower threshold
diameters possible
with low residue UPW
• Higher threshold
diameters also
possible
Channel 2
Channel 3
Particle Diameter
100%
Detection
Particle Diameter
100%
Detection
Diameter
Cumulative#/mL
Channel 1
Particle Diameter
100%
Detection
Diameter
Cumulative#/mL
Diameter
Cumulative#/mL
Colloid
Particles
Non-Volatile
Residue Particles
AerosolParticleConcentration
Colloid
Particles
Non-Volatile
Residue Particles
Colloid
Particles
Non-Volatile
Residue Particles

13. Predicted particle sizes (150, 300, 600 ppt)
1.E+01
1.E+02
1.E+03
1 10 100
Size (nm)
dN/dlogDp
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Percentdetectedby3772
S TPC
S TPC
S TPC
LNS #6
LNS #6
LNS #6
Det eff
Scanning TPC Nebulizer Design
Upper tail of droplet distribution
removed to minimize dissolved
non-volatile residue particle counts
Secondary large droplet removal incorporated
downstream of nebulization region

14. Scanning TPC
Response to dissolved NVR
• High levels of DNVR
will lead to false
particle counts
• Plot shows little
sensitivity to low
levels of added NVR
(some true colloidal
particles will be
present due to
injection system and
impurities in the
KCL)
Scanning TPC Response to injected KCL
1.E+05
1.E+06
1.E+07
1.E+08
1.E+09
1.E+10
0.1 1 10 100 1000 10000 100000
Dissolved NVR over 150 ppt background (ppt)
Reportedparticlecounts(#/ml)
> 10 nm
> 15 nm
> 20 nm

15. Offline Data Inversion Option
• Monte-Carlo
method may be
used to estimate
the true particle
size distribution
• Accounts for
shape of
detection
efficiency curve
• Accounts for
shape of droplet
size distribution
• Finds best fit of a
defined colloid
size distribution
to match
measurements
Channel 1
Particle Diameter
100%
Detection
Diameter
Cumulative#/mL
D50
TPS Data Inversion Example
0.0E+00
5.0E+05
1.0E+06
1.5E+06
2.0E+06
2.5E+06
3.0E+06
3.5E+06
4.0E+06
0 5 10 15 20 25 30 35
Particle Diameter
#/ml
Measured values
Inverted values
TPS Data Inversion Example
0.0E+00
5.0E+05
1.0E+06
1.5E+06
2.0E+06
2.5E+06
3.0E+06
3.5E+06
4.0E+06
0 5 10 15 20 25 30 35
Particle Diameter
#/ml
Measured values
Inverted values

16. Scanning TPC Sample Data
Colloid Size Standards
• High concentration solutions of
colloidal silica and gold
nanoparticles prepared for testing
• Size distributions of each of the
solutions has been characterized
using Liquid Nanoparticle Sizing
(LNS) technology
– US Patents 8,272,253 and 8,573,034
• Use LiquiTrak ® Precision Diluter to
provide high purity, online dilution.

17. Particle Diameter (nm)
5 10 20 30 40 50
Differentialnumberweighteddistribution
(d(#/mL)/dlog(Dp))
0.0
5.0e+11
1.0e+12
1.5e+12
2.0e+12
2.5e+12
3.0e+12
Particle Diameter (nm)
5 10 20 30 40 50
Differentialnumberweighteddistribution
(d(#/mL)/dlog(Dp))
0.0
2.0e+16
4.0e+16
6.0e+16
8.0e+16
ScanningTPC Sample Data
Colloid Size Standards
Particle Diameter (nm)
5 10 20 30 40 50
Differentialnumberweighteddistribution
(d(#/mL)/dlog(Dp))
0.0
5.0e+14
1.0e+15
1.5e+15
2.0e+15
2.5e+15
Particle Diameter (nm)
5 10 20 30 40 50
Differentialnumberweighteddistribution
(d(#/mL)/dlog(Dp)) 2.0e+16
4.0e+16
6.0e+16
8.0e+16
1.0e+17
1.2e+17
1.4e+17
12 nm Silica 20 nm Silica 30 nm Silica
30 nm Gold
Particle Diameter (nm)
5 10 20 30 40
Differentialnumberweighteddistribution
(d(#/mL)/dlog(Dp))
0.0
1.0e+14
2.0e+14
3.0e+14
4.0e+14
40 nm Gold
Data provided by CT Associates using Liquid
Nanoparticle Sizing methodology

18. ScanningTPC Sample Data
Sensitivity
• Threshold
diameter set to
10nm
• The system
responds to all
particles with an
attenuated
response for the
12 nm particles
10nm Threshold Diameter
1E8 #/mL Colloidal Silica Injections
0.0E+00
2.0E+07
4.0E+07
6.0E+07
8.0E+07
1.0E+08
1.2E+08
1.4E+08
1.6E+08
1.8E+08
2.0E+08
12:21 12:28 12:36 12:43 12:50 12:57 13:04 13:12
Particles/mL
12nm
20nm 30nm

19. ScanningTPC Demonstration
Sensitivity
• Threshold diameter
set to 20nm
• The system shows
little or no response
to the 12nm particles,
attenuated response
to the 20nm particles
and 80% detection of
30 nm particles.
20nm Threshold Diameter
1E8 #/mL Colloidal Silica Injections
0.0E+00
2.0E+07
4.0E+07
6.0E+07
8.0E+07
1.0E+08
1.2E+08
1.4E+08
1.6E+08
1.8E+08
2.0E+08
11:16 11:24 11:31 11:38 11:45
Particles/mL
12nm
20nm
30nm

20. ScanningTPC Sample Data
Scanning Operation
• Operated TPC in
mode that steps
through
threshold particle
diameters
• Mixture of 12,
20, and 30 nm
particles at equal
concentrations
Scanning Mode
1E8 #/mL Mixed Colloidal Silica Injection
0.0E+00
2.0E+07
4.0E+07
6.0E+07
8.0E+07
1.0E+08
1.2E+08
1.4E+08
1.6E+08
1.8E+08
17:25 17:28 17:31 17:34 17:36 17:39 17:42 17:45 17:48 17:51
Particles/mL
10nm
15nm
20nm

21. ScanningTPC Sample Data
UPW Monitoring
• Instrument
installed on small
scale,
semiconductor
grade UPW
system at CT
Associates
• Good stability
observed
• Distribution of
particle sizes
apparent
• Large scale UPW
systems ~4X lower
UPW System Monitoring
1.E+05
1.E+06
1.E+07
0:00:00 2:24:00 4:48:00 7:12:00 9:36:00 12:00:00 14:24:00
Time
ParticleConcentration(#/ml)
> 10 nm
> 15 nm
> 20 nm

22. Scanning TPC Filter Testing
• Single
channel
mode
>10 nm
• Shows
material
dependent
retention of
30 nm
particles
Fractional coverage (Monolayers)
0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200
Retention(%)
0
20
40
60
80
100
Silica
PSL
Gold
30 nm Rated Water Filter Challenged with 2E8 #/ml ( 6ppm) 30nm Particles

23. Scanning TPC
Pros and Cons
• Pros
– Particle composition independence
– No dependence on refractive index or particle shape
– Wide dynamic range
• Cons
– Low sample volume rate (~1 μl / min)
– Requires Butanol as a consumable
– Lower threshold limit is sensitive to amount of
dissolved non volatile residue

24. Further development
• Increase inspection volume
• Further characterization of operating
parameters
• Refinement and automation of optional
offline data inversion software

25. FMT Model 1000
LiquiTrak® Scanning TPC
• Internal data logging
• Touchscreen display
– Set nebulizer
temperatures
– Monitor and log
pressures and
temperatures
– Adjust minimum
detected particle
size
– Display particle
counter
concentration and
trend lines
– Set scan rates
• Patent pending

26. Thank you
Questions?

27. Bibliography
Grant DC (2008). “A New Method for Determining the Size Distribution of the
Working Particles in CMP Slurries,” presented at the 2008 CMP Users
Conference, sponsored by Levitronix.
Don Grant and Uwe Beuscher (2009), “Measurement of Sub-50 nm Particle
Retention by UPW Filters”, Ultrapure Water Journal, 26(11):34-40.
Blackford D and DC Grant (2009). “A proposal for measuring 20-nm particles
in high-purity water using a new technology,” Ultrapure Water, January 2009.
Grant DC, DC Chilcote and U Beuscher (2012). “Removal of 12 nm particles
from UPW by a combination of Ultrafiltration Modules and Microfiltration
Cartridges,” Ultrapure Water Journal, May/June 2012.
Rastegar, A (2013). “Particle Control Challenges in UPW ”, presented at 2013
UPW Micro Conference
Patents US 8,272,253; US 8,573,034; US 7,852,465; Other patents pending

29. Scanning TPC Long Term Stability
System Background - 2014
Date
01/06/14 01/20/14 02/03/14 02/17/14 03/03/14 03/17/14 03/31/14
Concentration(#/mL>10nm)
0
1e+6
2e+6
3e+6
4e+6
5e+6
6e+6
Filter test system
Upper 95% CL
Mean
Lower 95% CL

30. ScanningTPC Sample Data
Material Independence
• Inject 30 and
40 nm
colloidal gold
nanoparticles
• Response
similar to
colloidal silica
20nm Threshold Diameter
Colloidal Gold Injections
0.0E+00
2.0E+07
4.0E+07
6.0E+07
8.0E+07
1.0E+08
1.2E+08
1.4E+08
1.6E+08
1.8E+08
2.0E+08
12:28 12:43 12:57 13:12 13:26 13:40 13:55 14:09 14:24 14:38
Particles/mL
1E7 #/mL
30 nm Gold
1E8 #/mL
40 nm Gold
5E7 #/mL
30 nm Gold
UPW

31. ScanningTPC Sample Data
Linearity
• Dilution ratios
varied over a
16X range
Linearity
30nm Colloidal Silica challenge
y = 3E-07x + 16.846
R2
= 0.9958
0.0E+00
2.0E+01
4.0E+01
6.0E+01
8.0E+01
1.0E+02
1.2E+02
0.0E+00 1.0E+08 2.0E+08 3.0E+08 4.0E+08
Particle Injection concentration (#/mL)
CPCParticles/cm^3

32. Scanning TPC
Single Channel Performance
Installation of Ultra Filters at a Semiconductor Facility

33. Scanning TPC
Single Channel Performance
Resin Rinse Down
Flush Volume (liters UPW)
1 10 100 1000
CumulativeParticleConcentrationAdded
(#/mL>10nm)
1e+5
1e+6
1e+7
1e+8
1e+9
Resin A
Resin B
Resin C
Resin D
Resin E
Resin F
Spool
Flush Volume (liters)
1 10 100 1000
Non-volatileresidueadded(ppt)
10
100
1000
10000
Resin A
Resin B
Resin C
Resin D
Resin E
Resin F
Spool
Particle Rinse Non-volatile Residue Rinse
Data prepared and presented by CT Associates to the
SEMI Ion Exchange Task Force on 02/27/2014