Agilent 7500 Series ICP-MSAn Introduction

Presented By:

Ferdi Ferdian Kusnadhi

What is ICP-MS?

ICP - Inductively Coupled Plasma

• high temperature ion source

• decomposes, atomizes and ionizes the sample

MS - Mass Spectrometer

• featuring quadrupole mass analyzer

• mass range - 7 to 260 amu (Li to U...)

– separates all elements in rapid sequential scan

• ions measured using dual mode detector

– ppt to ppm levels

– isotopic information available

An inorganic (elemental) analysis technique

ICP-MS has the detection limits of GFAA and the sample throughput of ICP-OES

Low flow sample introduction system

High temperature 27MHz plasma generator

Multi-element interference removal by on-axis octopole reaction cell

High frequency hyperbolic quadrupole

Fast simultaneous dual mode detector (9 orders dynamic range)

Agilent 7500ce ICP-MS System withCollision Reaction Cell (CRC)

Off-axis Lens

Reaction Gas Inlet

OctopolePlasma

Agilent 7500 Series ICP-MS

Agilent 7500ce (G3272A)

•Enviro, foods, biological...

•Robust Octopole Reaction System (ORS)

•Superb capability in the most complex matrix

•Flexibility

Agilent 7500a (G3271A)– Standard ICP-MS

•General purpose that does not require collision

•Standard ShieldTorch System for cool plasma

• Upgradeable to ORS

Agilent 7500cs (G3273A)

•Semiconductor, R&D.•Ultra low BECs at high plasma power•Cool plasma also available

Different ways of acquiring information

from a sample

1. Qualitative scan2. Semiquantitative Analysis3. Fully quantitative data

Dr Christopher TyeAsia Pacific Business Development Manager

Based in Singapore

Dr Deng-yun ChenSenior ICP-MS Applications Specialist

Greater China Based in China

Yu-hong ChenICP-MS Applications Specialist Greater China

Based in China

Fan ChenICP-MS Product Specialist

SMT

Kung-yu Chen

Peak ICP-MS/semiconductor

Sales Greater ChinaBased in Taiwan

Fred FryerSenior ICP-MS Applications Specialist South East Asia

Based in Australia

David WilkinsonICP-MSProduct Support

Engineer Asia PacificBased in Australia Jerry Leu

ICP-MS Product Specialist Greater ChinaBased in Taiwan

Primary Agilent ICP-MS Team in Asia Pacific

Asia Pacific Resource

Dedicated Sales

Support

Dedicated Applicatio

ns Support

China - 8

Taiwan - 4

Hong Kong - 1

India - 1

Singapore - 2

Malaysia - 2

Thailand - 1

Australia - 5

S Korea - 5

Vietnam - 1

New Zealand - 1

Factory Trained Agilent ICP-MS Service Engineers(AP Region Only, excluded JPN)

Country with Agilent ICP-MS

installed

No Agilent ICP-MS

installed

Application Notes of interest to the Semiconductor Market5989-4348EN Determination of Impurities in Semiconductor Grade Hydrochloric Acid Using the Agilent 7500cs ICP-MS AN 12/2005

5988-8901EN Determination of Trace Metal Impurities in Semiconductor Grade Phosphoric Acid by High Sensitivity Reaction Cell ICP-MS AN 11/2004

5988-9190EN Analysis of Impurities in Semiconductor Grade Sulfuric Acid using the Agilent 7500cs ICP-MS AN 11/2004

5988-9529EN Characterization of Trace Impurities in Silicon Wafers by High Sensitivity Reaction Cell ICP-MS AN 11/2004

5988-9892EN Analysis of Impurities in Semiconductor Grade TMAH using the Agilent 7500cs ICP-MS AN 11/2004

5989-0629EN Direct Analysis of Photoresist and Related Solvents using the Agilent 7500cs ICP-MS AN 11/2004

5989-0321EN Analysis of Electroceramics Using Laser Ablation ICP-MS AN 10/2004

Agilent ICP-MS in Asia PacificBig Growth - Big Rewards!

In FY06 we sold 84 units (in calendar year 2006 = 108!)

Our market share in ‘06 is 45%!

Why do we win?

• Our technical advantages (especially the 7500ce) and the fact we have the best people supporting the field means we win most deals!

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What is ….

ION SOURCE MASS FILTER DETECTOR

Electron Impact Ionization (EI)

Atmospheric Pressure Chemical Ionization (APCI)

Electrospray Ionization (ESI)

Chemical Ionization (CI)

Matrix Assisted Laser Desorption Ionization (MALDI)

Time Of Flight (TOF)

Ion Trap

Quadrupole

Time to Frequency (TOFs only)

Electron Multiplier

Produces ions that are separated according to mass and detected

A Mass Spectrometer

Atmospheric Pressure Photo Ionization (APPI)

What Else Can Be Measured Using MS?

•Many of you have been successful in selling organic MS

• Used to get molecular or structural information from a sample

•What about inorganic MS?

• For characterising elements

• Only dealing with the Periodic Table

– Only 256 natural isotopes

• Generally only quantitative data required

•The difference between inorganic MS and organic MS lies primarily within one component of a mass spectrometer…..

THE SOURCE

Advantages of ICP-MS

Excellent detection limits

• low ppb - ppt for all elements

Wide elemental coverage - from Li - U

• over 70 elements measurable

High throughput

• all elements determined simultaneously

• 20 element run/3 replicates/washout in 3 minutes

Wide dynamic range

• linear over 9 orders

Powerful semiquantitative analysis

• no standards needed

Isotopic analysis

• isotope ratios

• isotope dilution

Routine technique

• many users run systems overnight

Small size

• saves lab space

• mobile installations

7500ce – Widest Analytical Range of ANY ICP-MS- these 4 calibration plots were generated simultaneously in a single run

1180 ppm Sodium

As

Se

Hg

Na

Calibration rangesHg (0.01 – 2ppb) – Std ModeAs (0.1 – 200 ppb) – He ModeSe (0.1 – 200 ppb) – H2 ModeNa (0.05 – 1180 ppm) – He Mode

Overall calibration range 10ppt (Hg) to 1180 ppm (Na) in a single method- without attenuating ion transmission to increase working range

NaTypically, ICP-MS cannot measure above 200ppm Na without changing quad resolution or ion lens settings

HgHg detection limit by 7500ce is about 3ppt – 7500ce can QUANTIFY at 10ppt!

7500ce can measure both Na and Hg in the same run!

Elemental Coverage of ICP-MS

Almost every element can be measured by ICP-MS (including actinides), mostly at extremely low limits of detection

The Majority of Elements Have ppt and Below Detection Limits

Over 70 elements can be analysed at trace levels

In the same measurement cycle

Over a wide dynamic range

Overview of Inorganic Analysis Techniques

Atomic Absorption Spectrometry Light having a wavelength characteristic of the analyte is passed through the sample. The amount of light absorbed is proportional to concentration.

ICP-Optical Emission SpectrometryEnergy from the plasma promotes an electron to a higher energy level (excitation). Electron falls back and emits light at a characteristic wavelength. Light emission is proportional to concentration

ICP-Mass SpectrometryEnergy from the plasma ejects electron from shell (ionization). Result is a positively charged analyte ion. Ions are separated by the mass spectrometer and measured. Ions measured are directly proportional to analyte concentration.

Sequential Simultaneous

Criteria1 GFAAS ICP-OES ICP-OES ICP-MS

Detection Limits ppt ppb ppb ppq-ppt

Linear Range (orders) 2-3 4-6 4-6 8-9*

Interferences Moderate Many Many Few

Speed Slow Slow Fast Fast

Elemental Coverage Poor Excellent Good Excellent

Multi-element No Yes Yes Yes

Simultaneous No No Yes Yes

Sample Size uL mL mL uL or mL

Capital Cost $$ $ $$ $$$

Operating Cost $$$ $$ $$ $$$* Agilent 7500 Series only - (other ICP-MS - 8 orders)

ICP-MS combines the sensitivity of GFAAS with the speed & flexibility of OES while offering a wider dynamic range and fewer interferences!

1 ICP-MS: The new standard for inorganic analysisAmerican Laboratory News, Nov.1998

Overview of Inorganic Analysis Techniques

Sequential Simultaneous

Criteria1 FAAS GFAAS ICP-OES ICP-OES ICP-MS

Detection Limits +10ppb +50 ppt 1 ppb <1 ppb sub-ppt

Linear Range (orders) 3-4 2-3 4-6 4-6 9*

Interferences

Chemical Many Many Some Some Some

Spectral Some Many Some Some Some

Matrix Many Many Some Some Few

Speed Moderate Slow Slow Fast Fast

Elemental Coverage Moderate Poor Good Good Excellent

Typical no. 50 35 55 55 70

Multi-element No No Yes Yes Yes

Simultaneous N/A N/A No Yes Yes

Sample Size mL uL mL mL uL or mL

Capital Cost $ $$ $ $$ $$$

Operating Cost $ $$$ $$ $$ $$$

* Agilent 7500 Series only - (other ICP-MS 8 orders)

GFAAS operating cost high due to consumables (furnace tubes) and operator time (sample prep, many reruns due to small dynamic range)

Who Uses Agilent ICP-MS WW ?

Over 2/3 of Agilent ICP-MS users Worldwide are either environmental or semiconductor, but other applications and lab types are extremely varied. Most users are in routine labs

Comparison of Metals Techniques - Speed vs Detection Power

ng/L (ppt)ug/L (ppb)mg/L (ppm)

Fast

Slow

GFAAS – most elements sub-ug/L DLs; but poor

throughput

FAAS – most elements +10 ug/L DLs

ICP-MS - most elements single figure ng/L DLs and very productive

ICP-OES - most elements single figure ug/L DLs and good

productivity

Typ

ical

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eed

of

An

alys

is

Typical Detection Limit

GFAAS is a key target market for ICP-MS!

Standard pneumatic nebuliser3 sec/mass integration time* Class 1000 cleanroom with ShieldTorch

0.1 - 1ppt

<0.1 ppt

1 - 10 ppt

>10 ppt

Agilent 7500 - 3 Sigma Detection Limits H

He

Li 0.8

*0.05

Be 0.2

B 4

C 5000

N 250ppm

O F 100

Ne

Na 15

*0.04

Mg 1

*0.04

Al 5

*0.04

Si 500

P 40

S >1000

Cl >1000

Ar

K 200 *0.2

Ca 300 *0.5

Sc 3

Ti 4

V 0.7

Cr 2

*0.08

Mn *0.2

Fe 100 *0.3

Co 1

0.3

Ni 6

*0.1

Cu 6

*0.02

Zn 1 *5

Ga 0.7

Ge 0.9

As 2

Se 20

Br 100

Kr

Rb 0.1

Sr 0.06

Y 0.09

Zr 0.08

Nb 0.1

Mo 0.3

Tc Ru 0.3

Rh 0.1

Pd 0.4

Ag 0.1

Cd 0.4

In 0.06

Sn 0.2

Sb 0.6

Te 1

I 0.8

Xe

Cs 0.05

Ba 0.4

LA

Hf 0.2

Ta 0.09

W 0.3

Re 0.3

Os Ir 0.3

Pt 0.5

Au 0.2

Hg 1

Tl 0.05

Pb 0.3

Bi 0.1

Po At Rn

Fr Ra

AC

LA La 0.07

Ce 0.08

Pr 0.06

Nd 0.08

Pm Sm 0.1

Eu 0.1

Gd 0.1

Tb 0.07

Dy 0.2

Ho 0.07

Er 0.2

Tm 0.03

Yb 0.2

Lu 0.04

AC Ac

Th 0.03

Pa U 0.03

Np Pu Am Cm Bk Cf Es Fm Md No Lr

Extending the Capabilities of ICP-MS

ICP-MS instruments can be coupled to different sample introduction devices that extend the overall usefulness

Laser Ablation ICP-MS

Liquid (or Ion) Chromatography ICP-MS

Gas Chromatography ICP-MS

Capillary Electrophoresis ICP-MS

Laser

Sample

Ar Gas with ablated material

Agilent 7500 ICP-MSMerchantek UP 213 Laser Ablation system

Laser Ablation ICP-MS

Pulsed Nd:YAG laser is used to ablate solid samples into the plasma

Useful for solids

• No dissolution process required

• Useful for bulk analysis and feature analysis

Oxide levels are much lower

• Interferences less of a problem

Expensive !

Connecting an LC to an ICP-MS

nebulizer &spraychamber

gas controller

ICP torch

turbomolecularpump

Q-pole mass filter

Ar gas

rotary pump

turbomolecularpump

liquid chromatograph

Agilent GC-ICP-MS Interface

GC-ICP-MS System used:

ICP-MS: Agilent 7500

GC: Agilent 6890

Interface: Agilent G3158A

Fully heated and insulated GC transfer lineModified torch with heated injector replaces standard demountable torch. “Silicosteel” transfer line and injector liner for inertnessGC capillary can be inserted to tip of injector or terminated in GC ovenGC effluent injected directly into base of plasma – essential for high boiling point compoundsSpecies decomposed to atoms - atoms then ionized and passed into MS

Key Benefits of ICP-MS

Wide Elemental Coverage

• Almost every element can be measured

Very low detection limits – ng/L or sub ng/L

• Equivalent to or lower than GFAAS (single-element technique)

Simple Mass spectra

• Only small number of peaks for each element

Very wide dynamic range

• Agilent systems provide 9 orders range – from <0.5ppt to >500ppm

High sample throughput

• Multi-element analysis in 3 to 4 minutes

Relatively few interferences

• Systems optimised to give minimal spectral interferences – low oxide (measured by CeO+/Ce+ ratio) and matrix interferences. Matrix-derived spectral interferences can be removed by collision/reaction cell

Semiquantitative analysis

Simple process

• spike sample with single internal standard

• acquire data

• software automatically corrects for

– mass bias (mass response)

– natural isotopic abundance

– ionisation potential

• print out data

Example Semiquantitative Analysis IEAE Soil - 7 standard

Elem mass Found certified units Elem mass Found certified units Elem mass Found certified unitsLi 7 32.8 31* ug/g Br 79 8.4 ug/g Sm 147 5.6 5.1 ug/gBe 9 1600 ng/g Rb 85 60 51 ug/g Eu 153 1160 1000 ng/gB 11 38.8 ug/g Sr 88 108 108 ug/g Gd 157 5.6 ug/gNa 23 2400 2400 ug/g Y 89 internal std ug/g Tb 159 720 600 ng/gMg 24 9.2 11.3* mg/g Zr 90 100 ug/g Dy 163 3280 3900 ng/gAl 27 39.6 47* mg/g Nb 93 12 12* ug/g Ho 165 720 ng/gSi 29 6 mg/g Mo 95 2240 2500* ng/g Er 166 2160 ng/gK 39 8.4 12.1* mg/g Tc 99 - ng/g Tm 169 248 ng/gCa 43 108 163* mg/g Ru 101 - ng/g Yb 172 1860 2400 ng/gSc 45 10.8 8.3 ug/g Rh 103 - ng/g Lu 175 228 300 ng/gTi 47 3280 3000* ug/g Pd 105 132 ng/g Hf 178 840 ng/gV 51 64 66 ug/g Ag 107 440 ng/g Ta 181 760 800* ng/gCr 53 120 60 ug/g Cd 111 1560 1300* ng/g W 182 1640 ng/gMn 55 560 631 ug/g In 115 44 ng/g Re 185 28.8 ng/gFe 57 22.8 25.7* mg/g Sn 118 2840 ng/g Os 189 - ng/gCo 59 10.4 8.9 ug/g Sb 121 1920 1700 ng/g Ir 193 - ng/gNi 60 44 26* ug/g Te 125 - ng/g Pt 195 - ng/gCu 63 10 11 ug/g I 127 7.2 ug/g Au 197 - ng/gZn 66 96 104 ug/g Cs 133 6 5.4 ug/g Hg 202 - ng/gGa 69 18 10* ug/g Ba 137 156 159 ug/g Tl 205 600 ng/gGe 72 2200 ng/g La 139 38.8 28 ug/g Pb 208 68 60 ug/gAs 75 16.4 13.4 ug/g Ce 140 76 61 ug/g Bi 209 308 ng/gSe 82 - 0.4* ng/g Pr 141 8.8 ug/g Th 232 1160 ng/gBr 79 8.4 ug/g Nd 146 32 30 ug/g U 238 3000 2600 ng/g

Values marked with an asterix * are not fully certified and for information only

Environmental

Drinking Water, Ambient Water, Sea Water

Soils, Sludges, Solid Waste

Plant material/agriculture

Speciation of Hg, As, Pb, and Sn

Clinical

Blood, Urine, Serum

Hair, Tissues

Toxicology

Nutrition/deficiency/vitamins

Food Analysis

Nutrition

Toxic element and species monitoring

QA/QC

Pharmaceutical

Routine heavy metal contamination

Drug discovery

Clinical trials

HPI

R&D

QA/QC

Semiconductor

Process Chemicals

Contaminants in Si Wafers

Photoresists & Strippers

Nuclear

Fuel production

Measurement of Radioisotopes

Primary Cooling Water

Typical Application Areas for ICP-MSGeological

Soil, Rocks, Sediments

Hydrology

Isotope Ratio Studies

Laser Sampling

Archaeological

Artifact analysis, proof of origin

Tooth, bone, tusk, shell, coral analysis

Forensics

Gun Shot Residue

Materials Characterization

Point of Origin

Poisoning

Metals Analysis can be Performed by 4 Different Techniques...FAAS (Flame Atomic Absorption Spectroscopy)

Good, cost effective tool for users that do not require low detection limits and typically only analyze 1 to 5 elements

• Low cost, cheap, ppm measurements

GFAAS (Graphite Furnace Atomic Absorption Spectroscopy)

Well documented but expensive analysis for users that require detection limits at the 50ppt level for only 1 to 5 elements

• high cost, low productivity sub ppb measurements on a limited number of elements• high operating cost - consumables (graphite tubes) and operator time

ICP-OES (Inductively Coupled Plasma Optical Emission Spectroscopy)

Good multielement technique for customers that require measurements at the ppb level only

• Cost effective multi element analysis at ppb levels• Also known as ICP-AES (Inductively Coupled Plasma Atomic Emission Spectroscopy)

ICP-MS (Inductively Coupled Plasma Mass Spectrometry)

Excellent technique for customers that require to measure samples over a wide dynamic range and that require low detection limits - can replace both GFAA AND ICPOES

• Cost effective, fast multielement analysis from low detection limits to high concentrations – good flexibility

Market in decline

Market in decline

Market is growing

Market flat

Graphite Furnace Atomic Absorption Spectroscopy (GFAAS)

Advantages

• good detection limits for some elements - e.g. Cr in whole blood

• well documented methods

• good tolerance to dissolved solids

• unattended operation

Disadvantages• very very slow sample throughput• poor linear dynamic range (3 orders)• short term precision not as good as

alternatives• very susceptible to chemical

interferences– strong reliance on background

correction hardware• slow method development• poor element flexibility• high running costs

ICP-OES - Simultaneous

Advantages

• multielement, fast

• flexible element selection

• well documented methods

• very good tolerance to dissolved solids

• good linear dynamic range

Disadvantages

• relatively poor detection limits

• many spectral interferences

• sample consumption high (1 to 5 mL/min)

• element flexibility

– limited in older systems

– speed of analysis compromised in newer systems

ICP-MS

Advantages

• excellent detection limits for most elements• most elements in Periodic Table available• good sample throughput• wide dynamic range (8 to 9 orders)• much simpler spectra than optical

techniques• low sample volume consumption• mass spec - so isotopic information

available• flexible quantitation methods

– "semiquantitative"– external calibrations– isotope ratios

Disadvantages

• dissolved solids/matrix effects - need to dilute samples more than other techniques

• capital cost high

• requires knowledgeable operator

Due to the wide elemental coverage of ICP-MS or

certain applications e.g. enviro - GFAAS, ICP-OES and single element

detectors have been replaced by a single 7500!

Price/Performance – How does ICP-MS Compare With Other Inorganic Techniques ?

100

200

50

150

1ppb 1000ppm10ppb 100ppb 1ppm 100ppm

Typ

ical

pri

ce r

ang

e U

S$k

Typical measurement range

Flame Atomic AbsorptionTypically 50ppb to 500ppm

Inductively Coupled Plasma Optical Emission SpectroscopyTypically 1ppb to >1000ppm (Simultaneous)

Inductively Coupled Plasma Mass Spectrometry (Quadrupole)Typically 1ppt to 100ppm

Graphite Furnace Atomic Absorption Typically 10ppt to 100ppb

10ppm100ppt10ppt1ppt

Agilent 7500 Series ICPMS Features

1. Unmatched Interference Removal with ORS in He ModeSpectral comparison showing removal of ALL polyatomic interferences in a complex sample matrix – only the Agilent ORS can do this, using He collision mode. No other ICP-MS can use He collision mode – requires the focusing power of an octopole (applies to 7500ce, 7500cs)

2. Detector Dynamic Range

9 orders detector range, gives 10x more concentration range available all any other competitors (applies to all 7500 Series)

3. Widest Analytical Measurement Range

Measurement of <10ppt Hg and >1000ppm Na – no other ICP-MS can do EITHER of these applications; the 7500ce can do both IN THE SAME RUN (applies to 7500ce)

4. Lowest Metal Oxides of any ICP-MS

CeO less than 0.1% - possible due to He collision mode removing CeO – no other ICP-MS can do this (applies to 7500ce, 7500cs)

Summary• Our product line up is perfectly aligned with the needs of the market, and is

perfectly positioned to beat our competition

– Price/performance

– Upgradeability

– Ease of use

– Best design and build quality

– Range of peripherals

– Speciation market is growing fast • we are the only ICP-MS vendor with expertise in LC-ICP-MS and GC-ICP-

MS

• all the key speciation labs and opinion leaders use Agilent ICP-MS

• We have the best hardware and applications support – because we have the best people!