Monitoring and maintaining water purity are important to the power and electronics industries. In the both of these industries, impurities must be minimized and monitored to prevent corrosion or scaling, and degradation in demineralization processes. Learn about the analysis of ppb concentrations of ionic contaminants in high purity water using two easy methods: a direct large volume injection and concentration of a large volume injection, using electrolytically generated hydroxide eluents on a Reagent-Free™ Ion Chromatography system (RFIC™).

1. 1
The world leader in serving science
Kirk Chassaniol
Product Applications Manager
NA Ion Chromatography Sales Support
Thermo Fisher Scientific
May 6, 2014
Analyzing Low Ionic Concentrations in
Pure Water

2. 2
Agenda
• Importance of pure water in the electronics
industry
• Corrosion related failures
• Ion chromatography
• Innovation and Ease of Use solutions
• IC systems
• Strategies for trace analysis
• Summary
• Questions

3. 3
Electronics Industries
• Deionized water is used throughout the electronics industries
• Integrated circuit devices, disk drives, and printed circuit boards
• Ionic contaminants at low concentrations (part per trillion to
part per billion) can cause product defects during
manufacturing processes resulting
• Costly rework
• Costly loss of material/product at wafer or device level
• Costly early product failures
• Loss of revenue, consumer/customer confidence, and market share
• Semiconductor Equipment Materials International (SEMI)
only recommends ion chromatography for inorganic anion
determinations

4. 4
Hard Disk Drive (HDD)
• Competitive industry with 3 to 6 month product cycles
• Magnetic materials susceptible to corrosion
• Similar failure mechanisms as semiconductor devices
• Platter: polished aluminum substrate
• Magnetic recording
• Lubricated surface and diamond-like coatings at angstrom thickness
• High rotation speed (4000–15,000 rpms)
• Head: magnetic read-write device bonded by adhesive onto a
metal foil (Gimble)
• Alumina substrate sculptured to fly or lightly touch platter
• Writer: multiple angstrom thickness layers of
para magnetic and non magnetic layers
• Reader: ferrous nickel HeadGimble

5. 5
Corrosion Pitting – Disk Drive
Pace Technologies.
http://www.metallographic.com/
Technical/Metallography-Intro.html
Fujitsu. http://pr.fujitsu.com/en/news/2001/12/6-3b.jpg
Johannes Windeln, Applied Surface Science Volume 179,
Issues 1–4, 16 July 2001, Pages 167–180.
Magnetic Head
Platter

6. 6
Semiconductor Devices
• Competitive industry with short product cycles
• End of Life is typically 5 years
• Contain multiple integrated circuits
• Manufactured typically from silicon wafers, circuits are
deposited or plated by patterns created with polymeric
photoresist
• Multiple corrosion processes
• Pure deionized water is used hundreds of times during the
manufacturing process
• Contaminants
• Distort normal dopant profiles
• Create inversion layers
• Cause shorts and circuit malfunctions

7. 7
Corrosion of Semiconductor Devices
Electromigration
Ion migration
Aluminum corrosion
Panasonic. Failure Mechanism of Semiconductor Devices.
http://www.semicon.panasonic.co.jp/en/aboutus/pdf/t04007be-3.pdf

8. 8
Printed Circuit Board
• Typically a longer product cycle than semiconductor devices &
HDDs
• Rework: increases contamination, costs, and higher fail rate
• Many corrosive processes
• Solder fluxes, plating, solder baths, cleaning, manual soldering with
more corrosive fluxes
• Lower clearance devices with higher chances of contamination
• Failure
• Reworked spot
• Scrapped board
• Dendrite/soft short (early life or intermitent failures)
• Hard shorts, in severe cases can cause fires
• Poor yields, increased rework costs, loss in profit

9. 9
Printed Circuit Board
Foresite Laboratories
www.residues.com/picture_library.html
Dendritic Growth
Whiskers
Corrosion from Solder
Flux

10. 10
Ion Chromatography

11. 11
Ease of Use and Innovation – Eluent Generation
Just Add Water
• Allows both isocratic and gradient separations
• Eliminates manually prepared eluents
• Increased sensitivity S/N because of improved suppression
of hydroxide eluents

12. 12
Continuous Innovation
• Continuously advancing IC technology
• Widest range of chemistry columns to optimize ionic
separations
• Continuously advancing new generations of hydroxide
optimized and carbonate columns
• Capillary size columns, capillary-capable IC systems
• Introduced smaller particle columns and high-pressure
capable systems
• New generations of suppressor and detector technologies

13. 13
Data
Management
Conductivity
Detector
High-Pressure
Non-Metallic
Pump
Eluent
Generator
(OH– or H+)
Waste
Sample Inject
(Autosampler) Recycle
Mode
Detection
Water/
Eluent
CR-TC
Cell
Effluent
Electrolytic
Eluent
Suppressor
Separation Column
Ion Chromatography System
RFIC, Innovation
and Ease-of Use
behind the curtain

14. 14
A Complete Family of Ion Chromatography Systems
Thermo Scientific
Dionex ICS-1100
Basic Integrated
Ion Chromatography
System
Thermo Scientific
Dionex ICS-900
Starter Line Ion
Chromatography
System
Thermo Scientific
Dionex ICS-1600
Standard
Integrated Ion
Chromatography
System
Thermo Scientific™
Dionex™ ICS-2100
Reagent-Free™ Ion
Chromatography
(RFIC™) System
Thermo Scientific™ Dionex™
ICS-5000+ HPIC™ Ion
Chromatography System
Thermo Scientific
Dionex ICS-4000
Capillary HPIC Ion
Chromatography
System
RFIC
HPIC

15. 15
Advantages of Suppressed Conductivity
Time
F
-
Cl - SO4
2-
F - Cl -
SO4
2-
Time
µS
µS
Without Suppression
With Suppression
Eluent (KOH)
Sample F-, Cl-, SO4
2-
Ion-Exchange
Separation Column
Anion Electrolytically
Regenerating
Suppressor
in H2O
KF, KCI, K2SO4
in KOH
Injection Valve
Counter ions
HF, HCI, H2SO4

16. 16
KOH, H2
Dionex Electrolytically Regenerated Suppressors
WasteWaste
Anode
Detector
H
+
+ O2 H2 + OH–
H2O H2O
H2O H2O
Cation-
Exchange
Membranes
OH–
Cathode
K+, X– in KOH
H+
+ OH–
H2O
H+
+ X–
H+
, X–
in H2O
H+
H2O, O2
H2O 2H
+
+ ½ O2 + 2e
–
K+
2 H2O + 2e
–
2OH
–
+ H2

17. 17
Strategies for Trace Analysis

18. 18
The Process for Working in Trace Analysis
• Keep the work environment and supplies clean
• Sample collection
• Use a clean sample container made from low ionic-leachable materials
• Avoid exposure or contact with the environment
• Sample handling
• Avoid any contact with the sample
• Use gloves with the lowest particle, lowest ionic contamination available
• Minimize exposure to lab environment and personnel
• Sample analysis
• Use clean containers and 18.2 MΩ-cm resistivity deionized water for the
water source
• Clean the autosampler and the IC system
• Use recommended columns for trace analysis

19. 19
Strategies for Trace Analysis
• Large Loop Direct Injection
• Concentrate a large volume of sample
• Large Loop or Concentrate onto a smaller i.d. column

20. 20
Large Loop Injection
• Increase the sample injection volume
• Characteristic large water dip with retention times later than
typical retention times
• Inject more sample, 4 to 40x the standard volume
• Sample loading
• Pressurized container
• Auxillary pump (Thermo Scientific Dionex AXP pump)
• Autosamplers
• Thermo Scientific Dionex AS-AP Autosampler
• Thermo Scientific Dionex AS-HV Autosampler
• Secondary pump: an extra pump from DP module
• Thermo Scientific Dionex ICS-5000+ HPIC IC system

21. 21
Concentrate the Sample by Reducing the Water
Matrix
• Load a large volume injection onto a concentrator column
• Concentrator column is positioned in the sample loop ports
on the injection valve
• Sample concentrating process
• Sample is loaded onto the concentrator column
• Ions are retained on the column and excess water flows to waste
• Injection valve switches to inject position
• Concentrated sample is eluted by the eluent
• Sample loading
• Dionex AXP auxillary pump
• Dionex AS-AP Autosampler
• Dionex AS-HV Autosampler
• Extra pump from the DP module

22. 22
Use a Smaller I.D. Column
• Large Loop Direct Injection or Concentrate Modes
• Based on the ratio of the radius’ squared
• 4 mm to 0.4 mm, 100x apparent increase in sample injection
• (r = 2) versus (r = 0.2). r2: 4 / 0.04 = 100
• 2 mm to 0.4 mm, 25x apparent increase in sample injection
• (r = 1) versus (r = 0.2). r2: 1 / 0.04 = 25
• 4 mm to 3 mm, 1.8x apparent increase in sample injection
• (r = 2) versus (r = 1.5). r2: 4 / 2.25 = 1.8
• 4 mm to 2 mm, 4x apparent increase in sample injection
• (r = 2) versus (r = 1). r2: 4 / 1 = 4

23. 23
Large Loop Direct Injection

24. 24
Large Volume Direct Injection on the 4 mm Dionex
IonPac AS17-C Column
Column: Thermo Scientific™ Dionex™
IonPac™ AG17-C, AS17-C, 4  250 mm
Gradient: 1 mM KOH (0–10 min),
1–12 mM KOH (10–14 min),
12–20 mM KOH (14–20 min)
Eluent Source: Thermo Scientific Dionex EG KOH cartridge
Flow Rate: 1.5 mL/min
Inj. Volume: 1000 µL
Detection: Suppressed conductivity,
Thermo Scientific™ Dionex™ ASRS™
Anion Self Regenerating Suppressor,
recycle mode
Temperature: 30 C
Sample: Deionized water + anions
Peaks:
1. Fluoride 1.0 µg/L 9. Nitrate 5 µg/L
2. Acetate 10 10. Benzoate 20
3. Formate 10 11. Bromide 5
4. Acrylate 10 12. Nitrate 5
5. Methacrylate 10 13. Oxalate 10
6. Chloride 5 14. Phthalate 10
7. Nitrite 5 15. Phosphate 10
8. Bromide 5
0
Minutes
12
11
10
9
8
7
5
64
3
2
1
5 10 15 20 25 30
-0.10
1.00
14
13
15
µS

25. 25
Column : Dionex IonPac AG15, AS15-5µm
(3  150 mm)
Gradient: 7 mM KOH (0–5 min),
7–60 mM KOH (5–12 min),
60 mM KOH (12–20 min),
7 mM KOH (20–25 min)
Eluent Source: Dionex EG KOH cartridge
Temperature: 30 C
Flow Rate: 0.7 mL/min
Inj. Volume: 1000 µL
Detection: Suppressed conductivity,
Dionex SRS Suppressor, 2 mm,
recycle mode
Peaks:
1. Fluoride 0.32 µg/L 8. Sulfate 0.83 µg/L
2. Glycolate 0.84 9. Oxalate 0.82
3. Acetate 1.1 10. Bromide 2.9
4. Formate 1.2 11. Nitrate 0.87
5. Chloride 0.34 12. Phosphate 2.9
6. Nitrite 0.35
7. Carbonate --
1
2
3 4
5 6
7
8
9
10
11
12
Minutes
2015105
µS
0
0.5
Using a 3 mm 5 µm Resin Particle Dionex IonPac
AS15-5µm Column

26. 26
Concentration of a Large Sample Volume

27. 27
0 5 10 15 20
Minutes
-0.5
4
µS
1
2
3
4
5
7
8
9 10
11
6
Concentrating of a Large Volume Injection on a 2 mm
Dionex IonPac AS15 Column
Column: Dionex IonPac AG15, AS15,
2  250 mm
Gradient: 10 mM (0–4 min),
10–40 mM (4–14 min),
40–60 mM (14–18 min)
Eluent Source: Dionex EG KOH cartridge
Temperature: 30 C
Flow Rate: 0.5 mL/min
Detection: Suppressed conductivity,
Dionex ASRS Suppressor,
AutoSuppression, recycle
mode
Conc: Column: Dionex IonPac AC15, 2  50 mm
Sample Volume: 20 mL
Peaks: 1. Fluoride 0.1 µg/L
2. Acetate 0.1
3. Formate 0.1
4. Chloride 0.1
5. Nitrite 0.1
6. Carbonate -
7. Sulfate 0.1
8. Oxalate 0.1
9. Bromide 0.1
10. Nitrate 0.1
11. Phosphate 0.1

28. 28
Concentrating of a Large Volume Injection on a
Capillary IC System
IC System: Thermo Scientific Dionex ICS-5000+ HPIC
capillary IC
Columns: Dionex IonPac AS15 (9 µm), 0.4 × 250 mm
Gradient: 7 mM KOH (0–10 min),
7–32 mM KOH (10–16 min),
32–50 mM KOH (16–30 min),
50–65 mM (30–33 min), 7 mM KOH (33–38 min)
Eluent Source: Dionex EGC-KOH capillary cartridge
Temperature: 30 C
Flow Rate: 12 µL/min
Detection: Suppressed conductivity, Thermo Scientific™
Dionex™ ACES™ 300 Anion Capillary Electrolytic
Suppressor, recycle mode
Conc. Column: Thermo Scientific™ Dionex™
IonSwift™ MAC-100, 0.5  80 mm
Sample Volume:180 µL
Sample: A. Deionized water
B. Deionized water + standard
A B A B
Peaks (µg/L):
1. Fluoride 0.018 0.48 5. Sulfate 0.075 4.72
2. Chloride 0.12 2.49 6. Bromide — 2.36
3. Nitrite 0.042 2.53 7. Nitrate 0.15 2.58
4. Carbonate — — 8. Phosphate — 2.15
1.6
µS
-0.3
1
2
3
4
5
6
7
8
0 38Minutes
A
B

29. 29
Trace Metal Analysis

30. 30
Trace Metal Analysis
Contamination of trace concentrations of metals
• Can cause deposition of contaminants
• Can cause occlusion
• Indicator of corrosion process
• Analysis
• Large volume injection or concentration
• Ions are separated chelating eluent
• Using a mixed cation/anion exchange column
• Post-column addition of a chromophore
• Detection by absorbance at visible light, 530 nm

31. 31
Analysis of Transition Metals Using Concentration of a
Large Volume Sample and a 2 mm i.d. column
Column: Dionex IonPac CG5A, CS5A
(2  250 mm)
Eluent: PDCA
Eluent Flow Rate: 0.3 mL/min
Post Column Reagent: PAR at 0.15 mL/min
Concentrator Column: Dionex IonPac TCC-2
Concentration: Dionex auxillary pump,
2 mL/min for 15 min
Sample Volume: 30 mL
Detection: Absorbance, Vis, 530 nm
Peaks: 1. Iron 1.0 µg/L
2. Copper 1.0
3. Nickel 1.0
4. Zinc 1.0
5. Cobalt 1.0
6. Cadmium 1.0
7. Manganese 1.0
mAU
1
2
3
4
5
7
0 2 4 6 8 10 12 14
Minutes
200
0
6

32. 32
Determination of Cr(VI) in Drinking Water
Using Optimized EPA Method 218.6
0
0 2 4 6 8
Cr(VI)
mAU
Minutes
Cr(VI)
Column: Dionex IonPac NG1, AS7, 4 mm
Eluent: 250 mM (NH4)2SO4
100 mM NH4OH
Flow Rate: 1.0 mL/min
Inj. Volume: 1000 µL
Postcolumn Reagent: 2 mM Diphenylcarbizide
10% CH3OH
1 N H2SO4
0.33 mL/min
Reaction Coil: 750 µL
Detector: Absorbance, Vis, 530 nm
Sample: A: Sunnyvale municipal
drinking water
B: Sample A + 0.2 µg/L Cr(VI)
Peak: A B
Cr(VI)) 0.055 0.245 µg/L
B
A
2

33. 33
Conclusion
• Trace ion analysis is needed in the electronics industries to
minimize corrosion-related contamination and maintain
product quality
• Dionex ion chromatography methods and instrumentation
provide easy and innovative ways to determine trace
contamination
• Reagent-Free Eluent Generation provides greater sensitivity,
method flexibility, and ease-of-use
• New innovations provide greater analytical capabilities
• Advancements in column chemistry
• 4 µm particle columns and high-pressure capable IC systems
• Capillary IC methods and systems

34. 34
Thank You!
WS71084_E 05/14S