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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