ICS-5000ICS 5000Capillary Ion Chromatograph

Types of Surface Contamination

Organic Impurities

Particles

Organic Impurities

Adsorbed Molecules MetalsIons

S fSurface

14924

Standard Electronics Industry Methods Specifying Ion Chromatography (Part I)

● SEMI—Recommended Guidelines for Pure Waterfor Semiconductor Processingfor Semiconductor Processing

● ASTM—Guidelines for Electronics Grade Water● SEMI—Standard Test Method for Measurement of

Ionic Contamination on Semiconductor Lead Frames● SEMI—Standard Test Method for Trace Contaminants

in Molding Compoundsin Molding Compounds

12277

Standard Electronics Industry Methods Specifying Ion Chromatography (Part II)

● SEMI—Alternative to Wet Chemistry for the Analysis of Mixed Acid Etchantsof Mixed Acid Etchants

● U.S. Military—Adhesives, Polymeric, Specifications for Use in Microcircuits

● IPC—Standard for Measurement of Residues on Circuit Boards● IDEMA—Measurement of Extractable/Leachable

Anion Contamination Levels on Drive Components Anion Contamination Levels on Drive Components by Ion Chromatography

● IDEMA—Special Cations Analysis

12278

Main Menu

ICS-5000 - Dimension of Scale

Overlay of chromatograms from 2 mm and 0.4 mm with appropriate injection volumesj

Capillary (0.4 mm column) IC with 0.4 µL Injection Volume116

LithiumSodium

Potassium

MagnesiumCalcium

Conductivity

0

AmmoniaConductivity[µS]

16Lithium

Sodium

Ammonia

PotassiumMagnesium Calcium

Standard (4 mm column) IC with 40 µL Injection Volume

Conductivity

0 2 4 6 8 10 12 14R t ti Ti [ i ]

0

Conductivity[µS]

Retention Time [min]

Advantages of Capillary Ion Chromatography

● Capable of continuous operation with minimal intervention ● Ease of use, higher sample throughput, and improved calibration● Improved separation efficiency or speed● Improved trace analysis (10 µL injection = large loop injection)● Improved trace analysis (10 µL injection = large-loop injection)● Improved compatibility with MS and “small sample size”

applications● Possibilities of offering new selectivity for difficult applications

using new columns packed with more costly and difficult-to-make stationary phases stationary phases

Typical Operating Parameters for Conventional and Capillary RFIC™ Systemsp y y

Conventional RFIC Capillary RFIC

Column ID 4 mm 0.4 mm

Flow Rate 1.0 mL/min 10 µL/min

Injection Loop 25 µL 0.4 µL

Suppressor Dead Volume 60 µL 0.6 µL

EG C rrent (50 mM KOH) 80 4 mA 0 804 mA EG Current (50 mM KOH) 80.4 mA 0.804 mA

EG Current (200 mM KOH) 321.6 mA 3.216 mA

K+ Consumption/Year 26 3 Moles (50 mM KOH) 0 263 Moles (50 mM KOH) K+ Consumption/Year 26.3 Moles (50 mM KOH) 0.263 Moles (50 mM KOH)

H2O Consumption/Year 525 L 5.25 L

Separation of 9 Anions on a Capillary AS19 Column

)

Column: AS19 column(0.4 mm x 30 cm)

Eluent Source: Capillary EGC KOH cartridge 8.0

de (

1346

6) (1

4115

)72

)e

(165

88)

e (1

5542

)

(147

25)

(159

19)

rate

(150

46)

Sulfa

te (1

2730

) Eluent Source: Capillary EGC-KOH cartridge Eluent: 20 mM KOH Flow Rate: 10 µL/minTemperature: 30 °C

µS

Fluor

idCh

lorite

Br

omate

(14

37Ch

loride

Nitrit

Chlor

ate (

Brom

ide

Nit r S Temperature: 30 C

Suppressor: Electrolytic capillary anion suppressor

Overlay of 30 consecutive runs% retention time RSD: 0.06% for chloride to 0.22% fluoride

µ

0 0 20 00.0

Minutes0.0 20.0Minutes

Separation of 22 Anions on a Capillary AS19 Column

Column: Capillary AS19 column (0.4 mm x 250 mm)

16.0

lfate

Overlay of 30 consecutive runs% retention time RSD: 0.09% for arsenate to 0.18% for fluoride

Eluent Source: EGC-KOH cartridge Eluent: 10 mM KOH (0 to 10 min), 10 to 52 mM

KOH (10 to 42 min), 52 to 70 mM (42 to 45 min), 10 mM (45 to 50 min)

Sul

Selen

ate

Arse

nate

Flow Rate: 10 µL/minTemperature: 30 °CSuppressor: Electrolytic capillary anion suppressor

µS

e orite

hlorid

e

ate Oxa

late

mate

Phos

phate

umar

at

Fluor

ide

Aceta

teFo

rmat Ch

lBr

omate

Ch

Nitrit

e Chlor

ateBr

omide

Nitra

Malon

ate

dide

ulfate

Chro

m P Fu e

Thioc

yana

te

rchlor

ate0.0 50.0

0.0Minutes

IodTh

iosu Pe

0.0 50.0Minutes

Anions in Coke on a Capillary AS19 Column

Column: 0.4 x 250 mm AS19 and 0.4 x 50 mm AG19

60.0

Eluent: KOH (RFIC-EG)Gradient: 7 min 15 mM isocratic,

in 18 min to 60 mM gradientCol. Temp.: 30 °C

40.0

[µS

]

-Chl

orid

e

hosp

hate

trate

Col. Temp.: 30 CFlow Rate: 10 µL/minInj. Volume: 0.4 µLDetection: Suppressed ConductivitySample: Coke 1:10

20.0

ondu

ctiv

ity

4 -

itrat

e

-Sul

fate

11 -

Mal

ate

14 -

P h

17 -

Cit

Sample: Coke 1:10

10 0

C

7 -N 9

- 1

0.0 10.0 20.0 30.0-10.0

Retention Time [min]

Cation Standard on a Prototype Capillary CS16 Column

20.0 µS

m m um

Column: 0.4 x 250 mm CS16 and 0.4 x 50 mm CG16

15.0

y [µ

S]

thiu

m

Sod

ium

um 4 -

Pot

assi

um

5 - M

agne

siu

6 - C

alci

u

Eluent: MSA (RFIC-EG)Gradient: 6 mM in 30 min to 66 mM Col. Temp.: 40 °CFlow Rate: 0.010 mL/min

5 0

10.0

Con

duct

ivity

1 - L

it

2 -

3 - A

mm

oni u 4 5 Flow Rate: 0.010 mL/min

Inj. Volume: 0.4 µLDetection: Suppressed ConductivitySample: 6 Cation Standard 1:50

2 0

5.0

min

C

0.0 10.0 20.0 30.0-2.0 min

Retention Time [min]

Fast Separation of Six Cations on a Capillary CS12A-5 Column

20 1 23

5

4

6

Column: CS12A-5 column (0.4 mm x 15 cm)Eluent Source: Capillary EGC-MSA cartridge Eluent: 20 mM MSA

18 µL/min Flow Rate: 12 to 18 µL/minTemperature: 30 °CSuppressor: Electrolytic capillary cation suppressor

µS

14 µL/min

16 µL/minPeak Retention Time Concentration

at 18 µL/min (mg/L) (minutes)

1 Lithium 1 037 0 5 14 µL/min

12 µL/min

1 23 5

46

1. Lithium 1.037 0.5 2. Sodium 1.250 2.03. Ammonium 1.443 2.54. Potassium 1.813 5.0 5. Magnesium 4.507 2.56. Calcium 5.790 5.0

0.0 2.0 4.0 6.0 8.0 10.0 12.00

Minutes

Rapid Determination of Cations - Treated Waste Water

Column: CS12A-5 column (0.4 mm x 15 cm)Eluent Source: Capillary EGC-MSA cartridge Eluent: 28 mM MSA 1

Flow Rate: 18 µL/minTemperature: 30 °CSuppressor: Electrolytic capillary cation suppressor

O l f 20 ti Sample: Treated Waste Water (1:10 dilution)

Peak Concentration (mg/L)

Overlay of 20 consecutive runsRetention time RDS (n=20): 0.053% (calcium) to 0.28% (sodium)Peak area RSD (n=20): 0.5% (sodium) to 0.9% (magnesium)

1. Sodium 19.62. Potassium 0.83. Magnesium 3.54. Calcium 3.1

23

42

Trace Analysis Using Capillary Ion Chromatography

● Large-volume direct injection or pre-concentrationLarge volume direct injection or pre concentration

● A 10 µL injection onto a 0.4 mm ID column is equivalent to a 1000 µL injection onto a 4 mm I.D. column.

● Loading a 250 L sample onto a capillary concentrator can be accomplished with an AS autosampler in shorter time than loading a 25 mL sample onto a con entional concentrator ith an AS HV conventional concentrator with an AS-HV.

● Suitable for samples with low levels of matrix ions

Trace Analysis, Microbore IC

4 00

Reactor water sample, 75 ng/L Chloride

FluorideChloride 2 mm AS14 column

3.00

4.00 2 mm AS14 column0.38 mL/ min

2.00

µS

1.00

0.00

10 2015Retention time, minutes

2 mL Sample, Direct Injection

Inorganic Anions at Trace Concentrations with 10 µL Injection

Column: Prototype AS20 column (0.4 x 250 mm)Eluent Source: Capillary EGC-KOH cartridge Eluent: 35 mM KOH Flow Rate: 10 µL/minTemperature: 30 °CSuppressor: Electrolytic capillary suppressorDetection: Suppressed conductivityInjection Volume: 10 µL

0.22511

Injection Volume: 10 µL Peaks: 1. Thiosulfate 0.33 µg/L

2. Iodide 0.673. Thiocyanate 0.674. Perchlorate 1.0

µS4. Perchlorate 1.0

22 33 44

0 160.210

Minutes

1515

Trace Bromate in Drinking Water Large Loop (10 µL) Injections

2.0

Column: Capillary AS19 column (0.4 x 250 mm)2.0

Brom

ate

Eluent Source: Capillary EGC-KOH cartridge Eluent: 10 mM KOH (0 to 10 min), 10 to 52 mM

KOH (10 to 42 min), 52 to 70 mM (42 to 45 min) 10 mM (45 to 50 min)

µS

(42 to 45 min), 10 mM (45 to 50 min) Flow Rate: 10 µL/minTemperature: 30 °CSuppressor: Electrolytic capillary anion suppressor

Sunnyvale drinking waterSunnyvale drinking water + 2 ppb bromate

0.0 40.00.50

Minutes

Sunnyvale drinking water + 2 ppb bromate Sunnyvale drinking water + 4 ppb bromate

Separation of Inorganic Anions at Trace Concentrations10 µL Injection

0.47

Column: AS19 column (0.4 mm x 25 cm)Eluent Source: Capillary EGC-KOH cartridge Eluent: 20 mM KOH 1Flow Rate: 10 µL/minTemperature: 30 °CSuppressor: Capillary anion suppressor

1

3 7

µS

Detection: Suppressed conductivity Injection Volume: 10 µL

P k C t ti ( /L)

2 4 56

Peak Concentration (µg/L)1. Fluoride 0.2 2. Chloride 0.33. Nitrite 1.04. Bromide 1.05 Nit t 1 0

—— Standards in deionized water—— Deionized water

Minutes0.0 20.00.36

5. Nitrate 1.06. Carbonate 7. Sulfate 1.0

Trace Analysis Using Capillary Ion Chromatography

● Two-dimensional ion chromatography using a capillary column in the second dimension

● Perform large-loop injection and separation of matrix ions using a 4 mm ID column in the 1st dimension

F th i f i t t i t t l ft i i th 1 t● Focuses the ions of interest in a concentrator column after suppression in the 1stdimension

● Perform separation using a 0.4 mm ID column of different selectivity in the 2nd dimensiondimension

● Provide sensitivity enhancement that is proportional to the flow rate ratio (e.g. a factor of 100)

● Suitable for samples with high levels of matrix ions

ICS-5000 2D RFIC™ System Using a Capillary Column in the Second Dimension

Auto-

Waste

L

WWaste

Sampler Detector

CRD 200

L

W

CL

S

P

Pump

Suppressor

CL

S

P

Capillary Concentrator Column

0.4 mm Guard & Sample Loop

4 mm Guard & Analytical ColumnSuppressor

Capillary Pump

Analytical Column

DetectorDetector

Standard Bore: 4 mm, 1 mL/min Capillary: 0.4 mm, 10 L/min

Determination of Trace Perchlorate Using a 2D RFIC™ System with a Second-Dimension Capillary Column

1st dimension chromatogram

A. First-Dimension ConditionsColumn: IonPac® AG16, AS16, 4 mm Flow Rate: 1.0 mL/min

1.0

chromatogram1.0 S full scale Eluent: 65 mM KOH (EG)Suppressor: 4 mm SRS 300

Inj. Volume: 4000 µLTemperature: 30 °CB. Second-Dimension Conditions

µS

1

10.0

2 d di i

B. Second Dimension ConditionsColumn: Prototype AS20 (0.4 mm x 25 cm)Flow Rate: 10 µL/minEluent: 35 mM KOHSuppressor: Capillary Anion SuppressorTemperature: 30 °C

0.00.0 60.0

1

µS

2nd dimension chromatogram10 S full scale

Temperature: 30 CConcentrator: Capillary concentrator,

5000 µL of 1st dimension suppressed effluent (19 to 24 minutes)

Peak: 1 Perchlorate 1 0 g/L

1

0.0 60.00.0 Minutes2

Peak: 1. Perchlorate 1.0 g/L

Perchlorate Peak Area1st Dimension: 0.0115 µS*min2nd Dimension: 1.75 µS*minµ

Determination of Trace Perchlorate Using a 2D RFIC™ System with a Second-Dimension Capillary Column

A. First-Dimension ConditionsColumn: IonPac® AG16, AS16, 4 mm Flow Rate: 1.0 mL/min El t 65 M KOH (EG)

1.00

rate

Eluent: 65 mM KOH (EG)Suppressor: 4 mm SRS 300 Inj. Volume: 4000 µLTemperature: 30 °CB. Second-Dimension Conditions

Perch

lor

B. Second Dimension ConditionsColumn: Prototype AS20 (0.4 mm x 25 cm)Flow Rate: 10 µL/minEluent: 35 mM KOH (EG)Suppressor: Capillary Anion SuppressorT t 30 °C

µS

Temperature: 30 °CConcentrator: Capillary concentrator,

5000 µL of 1st dimension suppressed effluent (19 to 24 minutes)

Deionized Water 30 ng/L perchlorate in deionized water

29.0 44.00.00

Minutes

30 ng/L perchlorate in 1000 mg/L chloride,sulfate and bicarbonate

Determination of Perchlorate in Bottled Water Samples Using an ICS-5000 2D RFIC™ Systemg y

A. First-Dimension ConditionsColumn: IonPac® AG16 AS16 4 mm 2.5 hl

orat

e

Column: IonPac® AG16, AS16, 4 mm Flow Rate: 1.0 mL/min Eluent: 65 mM KOH (EG)Suppressor: 4 mm SRS 300 Inj. Volume: 4000 µL

Perc

h

Temperature: 30 °CB. Second-Dimension ConditionsColumn: Prototype AS20 (0.4 mm x 25 cm)Flow Rate: 10 µL/minEluent: 35 mM KOH (EG)

µSEluent: 35 mM KOH (EG)Suppressor: Capillary Anion SuppressorTemperature: 30 °CConcentrator: Capillary concentrator,

5000 µL of 1st dimension —— Brand A bottled water (263 ng/L perchlorate)B d B B ttl d t (38 5 /L hl t ) suppressed effluent (19 to 24 minutes)13

30 0 45 0-1.0

Minutes

—— Brand B Bottled water (38.5 ng/L perchlorate)—— 30 ng/L perchlorate in DI water—— DI water

30.0 45.0Minutes

Determination of Trace Bromate in a Bottled Water Sample Using an ICS-5000 2D Capillary RFIC System g p y y

0.5

e

A. First-Dimension ConditionsColumn: IonPac® AG19, AS19, 4 mm Fl R 1 0 L/ i

Brom

ate Flow Rate: 1.0 mL/min

Eluent: 10 to 60 mM KOH (EGC-KOH )Suppressor: 4 mm SRS 300 Inj. Volume: 1000 µLTemperature: 30 °C

µS

Temperature: 30 C

B. Second-Dimension ConditionsColumn: Prototype AS20 (0.4 mm x 25 cm)Flow Rate: 10 µL/min

O ( GC O )

—— Dionized water

Eluent: 35 mM KOH (EGC-KOH)Suppressor: Capillary Anion SuppressorTemperature: 30 °CConcentrator: Capillary concentrator,

2500 µL of 1st dimension —— Brand A bottled water (54 ng/L)—— 100 ng/L bromate in deionized water—— 30 ng/L bromate in deionized water

17.0 20.0 -0.3

Minutes

1

2500 µL of 1st dimension suppressed effluent (7.5 to 10 minutes)

Minutes

Operating Conditions of a Capillary IC System with MS/MS Detection

● Capillary IC System:● Column: Prototype AS20 (0.4 mm x 250 mm)● Eluent Source: Capillary EGC-KOH cartridge ● Flow Rate: 10 to 20 µL/min● Temperature: 30 °CTemperature: 30 C● Suppressor: Electrolytic capillary anion suppressor

operated in the external water mode (20 µL/min) ● ABI SCIEX API 2000TM MS/MS System:

P t dditi f t it il t 15 L/ i i d d 0 15 b ● Post-suppressor addition of acetonitrile at 15 µL/min via a grounded 0.15 mm bore mixing Tee

● Negative ESI with optimized probe position ● Optimized multiple reaction monitoring (MRM) channels for target analytes.

Determination of Inorganic and Organic Anions Using a Capillary IC and API 2000™ MS/MS System

Column: Prototype AS20 (0.4 mm x 250 mm)Eluent Source: Capillary EGC-KOH cartridge Eluent: 4-55 mM KOH Flow Rate: 15 µL/minTemperature: 30 °C

520006

11 Temperature: 30 CSuppressor: Electrolytic capillary anion suppressor Detection: API2000 MS/MS with post suppressor

addition of acetonitrile at 15 µL/min; Negative ESI

Injection vol.: 10 µLj µMRM (m/z)

Peaks: 1. Acetate 10 g/L 59/592. Formate 10 45/453. Chlorite 10 67/514. Bromate 10 126.7/110.8ns

ity, c

ps

8 5. Bromoacetate 10 137/78.86. Dichloroacetate 10 127/82.97. Dibromoacetate 10 214.7/170.78. Chlorate 10 83/66.99. Bromide 10 79/79

Inten

1

34 5

79

8

10. Nitrate 10 62/4611.Trichloroacetate 10 161/116.812.Tribromoacetate 10 250.8/78.813.Perchlorate 1.0 99/83

Minutes0.02000

2 10 12 13

28.0Minutes 28.0

Separation of Six Monosaccharides

Column: CarboPac PA 20 (0.4 mm x 150 mm)

T 30 °C

40

Temp.: 30 °CEluent: 10 mM KOH Flow Rate: 10 µl/minInj. Vol. : 0.4 LDetection: PAD (Carbohydrate Quadruple

30

2Detection: PAD (Carbohydrate Quadruple

Waveform)Electrode: ED Au

Sample: Standards (10 µM)

nC 20

4

3

1

Peaks: 1. Fucose (Fuc)2. Galactoseamine (GalN) 3. Glucoseamine (GalN)

10 64

5

4. Galactose (Gal)5. Glucose (Glc)6. Mannose (Man)

Minutes0 2 4 6 8 10 12

0

ICS-5000 Technology – Ease of Use

Guard and Separation ColumnCRD 200

Side view of ACESSide view of ACESSuppressor

Suppressor Injection ValveEG Degas

j

ICS-5000 System Top Values

● Just Add Water once a Quarter –Add Samples any TimeAdd Samples any Time

● Just Increase Sensitivity –Ultimate Sensitivity (IC x IC)

● Just Save Money● Just Save Money –Low Cost of Ownership

The Next Big Thing in IC is Small

Summary

● Capillary RFIC™ systems with suppressed conductivity detection offer highly reproducible isocratic and gradient separations of target analytes p g p g y

● Capillary RFIC™ systems provide improved capability for trace analysis

● Capillary RFIC™ systems can be used to achieve fast separation (Fast IC) ● Capillary RFIC™ systems can be used to achieve fast separation (Fast IC) and determination of common anions and cations

● Capillary RFIC systems with MS/MS and electrochemical detection are highly iti l ti l t lsensitive analytical tools

● Capillary RFIC systems leads to improved ion chromatographic methods for determination of ionic analytes in CMP consumables, chemicals, DI water and y , ,on post-CMP surfaces

Anion Sample

Peak Name Amount (ppt)

1.00

(ppt)F 24.033Cl 22.307

NO2 42 532NO2 42.532

µS

F Cl NO2

–0.200 5 10 15 20 26

Minutes23414

Anion Sample

Overlay of 20 Runs 0.206

FF

ClNO2

SO4µS NO2 Br NO3 PO4

–0.0744.1 10 15 20 23.7

Minutes23415

Cation Sample

Peak Name Amount (ppt)

0.500

(ppt)Li 11.511Na 28.403

NH4 13 499NH4 13.499K 15.197

Mg 7.729Ca 11 238

µSCa 11.238

Li Na NH4 KMg Ca

–0.1000 5 10 15 20 26Minutes

23420

Overlay—Cation Sample

Overlay of 20 Runs0.312

Peaks: 2. Li 6.7673. Na 9.2334. NH4 11.7805. MEA 12.440y0.3126. DEA 13.9537. — 14.5678. K 16.7579. TEA 17.477

10 17 853

µS

10. — 17.85311. Mg 21.72012. Ca 24.000

2

µS

3

1112

47 8 9

106

–0 029

5 96

6.1 10 15 20 24.70.029

Minutes23421

Cation Blank

1.00

µS

Na NH4 Mg Ca

–0.20

Minutes0 5 10 15 20 26

0.20

23423