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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
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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
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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
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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
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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
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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
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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
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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
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Printed Circuit Board
Foresite Laboratorieswww.residues.com/picture_library.html
Dendritic Growth
Whiskers
Corrosion from Solder Flux
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Ion Chromatography
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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
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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
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Data Management
ConductivityDetector
High-Pressure Non-Metallic Pump
Eluent Generator
(OH– or H+)
Waste
Sample Inject(Autosampler) Recycle
Mode
Detection
Water/Eluent
CR-TC
CellEffluent
Electrolytic Eluent
Suppressor
Separation Column
Ion Chromatography System
RFIC, Innovation and Ease-of Use behind the curtain
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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
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Advantages of Suppressed Conductivity
Time
F -Cl - SO4
2-
F - Cl - SO42-
Time
µS
µS
Without Suppression
With Suppression
Eluent (KOH)
Sample F-, Cl-, SO42-
Ion-ExchangeSeparation Column
Anion Electrolytically RegeneratingSuppressor
in H2O
KF, KCI, K2SO4
in KOH
Injection Valve
Counter ions
HF, HCI, H2SO4
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KOH, H2
Dionex Electrolytically Regenerated Suppressors
WasteWasteAnode
Detector
H+ + O2 H2 + OH–
H2O H2O
H2O H2O
Cation- Exchange
Membranes
OH–
CathodeK+, 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
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Strategies for Trace Analysis
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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
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Strategies for Trace Analysis
• Large Loop Direct Injection
• Concentrate a large volume of sample
• Large Loop or Concentrate onto a smaller i.d. column
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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
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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
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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
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Large Loop Direct Injection
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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 CSample: 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
0Minutes
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
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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 CFlow 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. Oxalate0.82
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
89
10
11
12
Minutes
2015105
µS
0
0.5
Using a 3 mm 5 µm Resin Particle Dionex IonPac AS15-5µm Column
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Concentration of a Large Sample Volume
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0 5 10 15 20
Minutes
-0.5
4
µS
1
23
4
5
78
9 10
11
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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 cartridgeTemperature: 30 CFlow Rate: 0.5 mL/minDetection: Suppressed conductivity,
Dionex ASRS Suppressor,AutoSuppression, recycle mode
Conc: Column: Dionex IonPac AC15, 2 50 mmSample 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 0.110. Nitrate 0.111. Phosphate 0.1
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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 mmGradient: 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 cartridgeTemperature: 30 CFlow Rate: 12 µL/minDetection: Suppressed conductivity, Thermo Scientific™
Dionex™ ACES™ 300 Anion Capillary ElectrolyticSuppressor, recycle mode
Conc. Column: Thermo Scientific™ Dionex™ IonSwift™ MAC-100, 0.5 80 mm
Sample Volume:180 µLSample: A. Deionized water
B. Deionized water + standard
A B A BPeaks (µg/L):1. Fluoride 0.018 0.48 5. Sulfate 0.075 4.722. Chloride 0.12 2.49 6. Bromide — 2.363. Nitrite 0.042 2.53 7. Nitrate 0.15 2.584. Carbonate — — 8. Phosphate — 2.15
1.6
µS
-0.3
1
2
3
4
5
67
8
0 38Minutes
A
B
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Trace Metal Analysis
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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
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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: PDCAEluent Flow Rate: 0.3 mL/minPost Column Reagent: PAR at 0.15 mL/minConcentrator Column: Dionex IonPac TCC-2Concentration: Dionex auxillary pump,
2 mL/min for 15 minSample Volume: 30 mLDetection: Absorbance, Vis, 530 nm
Peaks: 1. Iron 1.0 µg/L2. Copper 1.03. Nickel 1.04. Zinc 1.05. Cobalt 1.06. Cadmium 1.07. Manganese 1.0
mAU
1
2
3
4
5
7
0 2 4 6 8 10 12 14
Minutes
200
0
6
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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 Diphenylcarbizide10% CH3OH1 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
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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
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Thank You!
WS71084_E 05/14S
