Improving sensitivity, flexibility, and capabilities with Agilent’s ICP-MS and Triple QuadrupoleICPMS with Tandem MS/MS capabilities

For the Environmental, Petrochem and Semiconductor IndustriesJon Talbott, PhDApplication EngineerAgilent Technologies

Houston Symposium and Tradeshow, June 27, 2017

Presentation Outline

1. Background on ICP-MS and ICP-MS/MS

2. Unique product features of the Agilent 7700 ICP-MS and of the 8800 QQQ for analyzing tough samples in Your Industry

3. Environmental Regulations for Flue Gas Desulfurization Waste waters and ICPMS analyses

4. Direct Analysis for Metals in Gasoline and other organic matrices – conditions and results

5. Unique Petrochemical Applications using ICP-QQQ MS

6. Unique SemiCon Applications using ICP-QQQ MS

July 10, 20132

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General Capabilities of ICP-MS for Analyses in Aqueous Matrices

• Multi-elemental technique• High sensitivity• Low Detection Limits - ppt for most elements• Short analysis time (~ 3 min)• Wide linear dynamic range• Minimized interferences with Cell Technology• High Productivity – High Sx Throughput

Less well known that the Agilent ICP-MSs have some unique Product features that enhance their capabilities for analyzing

tough samples in the Petrochemical, Semiconductor and Environmental Industries – gasolines, kerosenes, naphthas,

FDG, SemiCon Chemicals

Agilent 7700 ICP-MS and 8800 ICP-MS/MS

7700 is Agilent’s high performance single quadrupole ICP-MS Many unique capabilities including HMI, ORS3

8800 is World’s first ICP-MS to offer MS/MS New modes of operation and performance with MS/MS modes Built upon the industry leading 7700 ICP-QMS platform with shared sample introduction, HMI, many

consumables, robustness, key hardware components and software platform

Revolutionize the MS arena!

Agilent 7700 Single Quad ICP-QMS

Agilent 8800Triple Quad ICP-MS/MS

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Agilent 7700 ICP‐MS System in Detail

High matrix introduction  (HMI) dilution 

gas inlet

Peltier‐cooled spray chamber

Off‐axis ion lens

Low‐flow Sample Introduction

Fast, frequency‐matching 27MHz RF generator

High‐performance vacuum system

Cell gas inlet

High‐frequency (3MHz) 

hyperbolic quadrupole

Fast, simultaneous dual mode 

detector (9 orders dynamic range)

High‐transmission, matrix tolerant 

interface

3rd generation OctopoleReaction 

System (ORS3)

Agilent 8800 ICP-MS/MS System in Detail

Low flow sample

introduction system

High matrix introduction

(HMI) technology

Fast, frequency-matching 27MHz

RF generator Efficient twin-turbo vacuum system

Dual conical Extraction and Omega lens focus ions across the mass range

9 orders dynamic range

electron multiplier (EM)

detector

Analyzer quad Q2: High frequency

hyperbolic quadrupole – selects ions that pass to detector

High-transmission, matrix tolerant interface

First quad Q1: High frequency hyperbolic quadrupole mass filter –

selects ions that enter the cell3rd generation collision/

reaction cell (ORS3) with up to 4 cell gas lines

Peltier-cooled spray

chamber

Robust, high-temperature plasma ion source

Key Product Features of the Agilent 7700x ICP-MS for Petrochemical, SemiCon and Environmental Industries

Unmatched matrix tolerance and unparalleled interference removal

ORS3 Octapole Reaction cell for removal of all polyatomic interferences

- better with both He and H2 modes for removal of polyatomics from organics

High Matrix Introduction (HMI) for unsurpassed Matrix Tolerance

- permits % level TDS samples to be run directly and routinely even the toughest samples can be handled with ease

O2 Option Gas MFC, that allows organics to be analyzed directly by ICPMS

- Auto setup of conditions

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ORS3 - a Kinetic Energy Discrimination tool for removing Polyatomic Interferences

Without it, Interferences from a complex acid matrix go from this

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… to this, with it!!

A single KED mode is very efficient at removing all polyatomic interferences!

And there’s still plenty of Sensitivity to obtain the lowest of Detection Limits

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High Matrix Introduction (HMI) is an online sample dilution technique that allows undiluted soil digestates and evenundiluted seawater to be analyzed directly.

No other MS instrument can make these claims!

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Key Benefit of High Matrix Interface (HMI)HMI shows good recoveries even in 3% Total Dissolved Solids

Analysis of Flue Gas Desulfurization Wastewater

Introduction USEPA wastewater effluent revision stricter air pollution controls applies to electric power industries requires low level determination of toxic metals

Steven M. WilburAgilent Technologies Inc.

Richard Burrows and Richard ClinkscalesTestAmerica Inc

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HMI Important in …. Environmental

FDGs pretty Nasty Matrices …. Synthetic FGD Interference Check Solution is a New Requirement

• Mixed Interference Check Solution (Synthetic FGD Wastewater)• Chloride, 5,000 mg/L

• Calcium, 2,000 mg/L

• Magnesium, 1,000 mg/L

• Sulfate, 2,000 mg/L

• Sodium, 1,000 mg/L

• Butanol, 2000ppmFGD-ICS-A Analyzed once per day•ISTDs must meet 60-125% requirements and analytes must be less than reporting limits

FGD-ICS-AB is “A” solution spiked with analyte elements at 40 ppb (Zn – 0.4 ppm, Al 4.0ppm). Must recover within 70–130 %

The combination of the highly robust plasma of the Agilent 7700x with HMI and ISIS discrete sampling allows routine analysis of this interference check solution and samples containing similar levels of dissolved solids UNDILUTED!

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Analysis of Flue Gas Desulfurization WastewaterLong Term Stability - Quality Control Check Recovery

Recovery of calibration check samples (CCVs) over 89 analyses

QC Summary including interference checks, matrix spike recoveries, memory

check, and continuing calibration verification

(CCV) and blank verification (CCB)

Biodiesel & KeroseneICP-QMS

Application

We examined very Challenging Aqueous Matrices (Seawater, FDGs) from the Environmental Industry ...

What about Organic Matrices?

General Problems for Organic Solvent analysis

• Plasma stability• Solvent volatility

– Cooled Spraychamber and RF generator design• Carbon deposition

– Add oxygen to plasma

• Matrix-based interferences• High carbon-based interferences plus “usual” plasma backgrounds

• “Difficult” elements often required at relatively low levels• Sulphur• Phosphorus• Magnesium• Etc…

Typical Conditions for Direct Analysis of Gasoline with Agilent 7700 ICP-MS

• Set HW Configuration for Organic Solvent Ignition Mode – Allows automated control of O2 during ignition process– Allows automatic RF Impedance matching

• Standard quartz concentric nebulizer and Scott-type double-pass quartz spray chamber used (No desolvation device necessary)

• Platinum interface cones used• O2 (as a 20% mix in Ar) added as Option Gas (to Aux gas) at torch with

optional mass flow controller (MFC) • Spray Chamber Temp set to -5 C to minimize solvent loading• Taper “organics” torch with a 1.0-mm id injector used

– Further improves plasma stability.• Carrier Gas reduced to ~ 0.7 L/min from typical 1.0 L/min

– reduces solvent loading, backs green bullet C2 off sampler

Direct Elemental Analysis of Biodiesel & KeroseneICP-QMS

Instrument Conditions

Direct Elemental Analysis of Biodiesel & KeroseneICP-QMS Detection Limits

Gasoline ApplicationICP-QMS

Application

Direct Elemental Analysis of GasolineICP-QMS

Instrument Conditions

Direct Elemental Analysis of GasolineICP-QMS Comparison of ORS Gas mode Data

Direct Elemental Analysis of GasolineICP-QMS Long Term Stability

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Q1 Q2Cell Detector

MS/MS increases selectivity, removing isobaric interference more effectively than ever. Agilent 8800 ICP-QQQ can measure difficult

elements in challenging matrix at lower concentration.

Mass analyzer ICP

Feature of ICP-MS Agilent 8800 Triple Quad ICP-MS (ICP-QQQ)

ICP-QQQ: How Does it Work?

ICP (plasma) and Interface: Forms and extracts ions from the sample (just like the 7700)

EM (detector): Measures the ions that are scanned by Q2 (just like the 7700)

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Q1 – controls ions that enter the cell

Mass filter• Consistent reactions w/iORS even if sample composition changes

ORS3 – collision/ reaction gas added• Ion size and/or reactions filter and are neutralized or moved

• Product ions are formed

Q2 – selects the target analyte mass • Interference-free analyte ions passed to EM

ASTS 2012

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MS/MS modes – filter ions entering ORS cell 1. On‐Mass Mode (Q1 and Q2 both set to target mass)

2. Mass‐Shift Mode (Q1 and Q2 set to different masses)

• Advanced Scanning Modes   ‐ for research and method development

A. Precursor Ion ScanB. Product Ion Scan C. Neutral Gain Scan

ICP-QQQ: Modes of Operation

ASTS 2012

1. On-Mass Measurement: Unreactive analyte does not react with chosen cell gas, remains at original m/z and so can be separated from reactive interferences. No new cell-formed interferences can occur at the analyte mass, since all non-target masses are rejected by Q1

With ICP-MS/MS, Q1 rejects all non-target masses, ensuring no new analyte/matrix product ions can form new overlaps on original analyte mass

How Reaction Mode Works in ICP-MS/MS

Reaction product ion

On-mass interference

AnalyteOff-mass

interference

Reaction gas

Interference M+MR+

Q1 set to analyte mass – rejects all non-target masses

Q2 set to original analyte mass – rejects any off-mass product ion(s)

Analyte

Interference reacts to form product ion

All non-target masses

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2. Mass-Shift Measurement: Reactive analyte promoted to a new product ion mass and separated from unreactive interferences.

With ICP-MS/MS, Q1 rejects all non-target masses, ensuring no existing ions (analyte, matrix, or polyatomic) can overlap new analyte product ion

How Reaction Mode Works in ICP-MS/MS

Original interfering ion

On-mass interference

AnalyteOff-mass

interference

Reaction gas

Analyte M+MR+

Q2 set to analyte product ion mass – rejects original interfering ions

Analyte product ion

Analyte reacts to form product ion

Q1 set to analyte mass – rejects all non-target masses

All non-target masses

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Oxygen Mass Shift for 34SWith MS/MS

50Cr+/50V+/50Ti+38Ar12C+

13C37Cl+

34S+

17O2+

16O18O+

O2 reaction gas

34S16O+

Q1MS/MS34amu

Q2

50amu

The mass difference between Q1 and Q2 is fixed (16) therefore a single transition is observed – the other oxygen isotopes are eliminated so the

original isotopic pattern is preserved!

Sulfur – Measured as SO+ in O2 ModeIsotopic Abundance of Mass Shifted Ions Maintained

Q1 – Q2 mass difference is 16, so only the + 16O transition is measuredEnsures S isotope abundance is maintained – no overlap from 32S18O+

on 34S16O+, for example

Supports confirmatory isotopes and IR/IDMS

32S16O+

33S16O+

34S16O+

Excellent isotopic template match for 32S, 33S, 34S (~ 30ppb S)

High background at 52 is due to 36Ar16O – S isotope at m/z 36 is too low to be analytically useful (except as a spike)

31 July 10, 2013

Unique ICP-MS/MS Analysesfor

Sulfur, Silicon, Phosphorus, Titanium & Arsenic

in Organic Matrices

Sulfur in Pure Ethanol

Instrument was set to monitor S and SO in a number of modes for comparison

• Single Quad (NoGas)• Single Quad (O2 Gas) – Q1 set as a bandpass filter• MS/MS (O2 Gas) – Q1 set at unit mass resolution

Tune Scan Type Q1 Q2 Name R DL BECNoGas Single Quad 32 S 0.910 11.806 1383.11 ug l-1NoGas Single Quad 33 S 0.752 157.615 4568.56 ug l-1NoGas Single Quad 34 S 0.971 10.550 615.15 ug l-1O2 Q Single Quad 32 S O/R O/R O/R ug l-1O2 Q Single Quad 33 S -0.675 -177.597 -1557.31 ug l-1O2 Q Single Quad 34 S 0.677 191.277 12336.87 ug l-1O2 Q Single Quad 48 32SO 0.999 3.555 53.80 ug l-1O2 Q Single Quad 49 33SO 0.975 99.790 1442.79 ug l-1O2 Q Single Quad 50 34SO 0.947 19.460 1849.35 ug l-1O2 MS/MS MS/MS 32 48 S 1.000 0.358 19.03 ug l-1O2 MS/MS MS/MS 33 49 S 0.999 2.860 19.84 ug l-1O2 MS/MS MS/MS 34 50 S 1.000 0.852 18.99 ug l-1

Calibration “spikes” in Ethanol32S, 33S and 34S Mass Shift Data

100 µgl-1

50 µgl-1

10 µgl-1

5 µgl-1

Blank

Silicon & Phosphorus in EthanolMS/MS Mode

• Optimal gases for silicon and phosphorus differ

– although P, S, As, Se can all be determined under O2

• Si provides better BEC’s under H2 MS/MS on-mass measurement

Mass Shift Mode with O2 On Mass Mode with H2

Ti and As in XyleneMass Shift Mode with NH3 and O2

Ammonia-Ti cluster measured at 132

TiNH2(NH3)4

Arsenic measured as AsO

As measured at 91

ICP-MS/MS Analysis of Sulfur, Phosphorus, Silicon

and Chlorine in a

N-methyl-2-pyrrolidone (NMP) Matrix

S, P, Si and Cl measurement in NMP

S, P, Si and Cl measurement in NMPMS/MS Mass Shift with O2 and H2

(Naoki Sugiyama Poster FP-1)

Applications of ICP-QQQ for SemiConductor Industry

Ultra trace Calcium measurement P and Ti measurement in Si matrix Ti and Zn in high purity Sulfuric Acid

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Three challenging applications to conventional ICP-MS are introduced today

SemiCon Application 1Ultra trace Calcium measurement

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Alkali metals and alkaline earth metals are elements that are strictly controlled in semiconductor manufacture since

contamination of those elements significantly deteriorates reliability of the insulating layer, affecting yield and performance

of final product. Argide overlap isotopes of the elements such as K+ and Ca+ causing big spectral interference problems. Agilent

8800 allows an ultra low BEC for Ca to be reached by effectively removing the interference due to the unique

reaction cell using MS/MS.

To remove 40Ar+ interference on 40Ca+, cool plasma ( RF=600-700W ) is an effective technique. MS/MS scan of ICP-QQQ further increases the

performance removing unwanted ions before cell.

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Application #1: Ultra trace measurement of Calcium Effect of MS/MS scan in cool plasma

parameter unit

RF power W 600

Sampling Depth mm 18

Carrier gas flow rate L/min. 0.7

Make up gas flow rate L/min. 1.0

Cool plasma condition BEC was 6.8ppt with single Quad scan.

BEC was decreased to 1.4ppt with MS/MS scan.

Single Quad scan : Q1 operates as ion guide. It emulates conventional ICP-MS.MS/MS scan : Q1 operates as 1-amu band-path. Unique to 8800 ICP-QQQ.

Addition of small amount of H2 into cell further improves the BEC. H2 totally scavenges remaining 40Ar+ ( slightly produced in cool plasma ) and provides an ultra low BEC.

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Application #1: Ultra trace measurement of Calcium Ultra low BEC for Ca

Cool plasma

BEC of 41ppq was achieved.

Calibration curve of Ca

SemiCon Application 2P and Ti measurement in Si matrix

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Silicon is the major substrate material used in semiconductor industry. Many ICP-MS systems are used in research lab but also in

QC labs, since impurity and contamination of metals causes significant impact on yield and performance of the final product.

In Si matrix sample such as Photovoltaic Silicon, VPD sample and TCS , Si polyatomic ions can cause spectral interference problems.

He collision cell and H2 reaction cell can measure trace level of Fe, Ni, Cu and Zn in 2000ppm Si removing interference .

But trace level analysis still challenging for P and Ti.

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Application #2: P and Ti measurement in Si matrixSpectra interference by Si matrix isotope Abundance % Interference

31P 100 30SiH+, 29H2+, 28SiH3+

46Ti 8.25 30SiO+

47Ti 7.44 28SiF+, 30SiOH+

48Ti 73.72 29SiF+, 28SiFH+

49Ti 5.41 30SiF+, 29SiFH+

56Fe 91.75 28Si2+

58Ni 68.08 30Si28Si+

60Ni 26.22 28SiO2+

63Cu 69.15 29Si16O18O+, 28SiOF+

65Cu 30.85 30SIOF+

64Zn 48.27 29SiOF+, 28SiOFH+

66Zn 27.98 28SiF2+, 30SiOFH+

68Zn 19.02 30SiF2+

Remaining problems

Concentration of Si in VPD sample varies with thickness of the oxide layer; 20-30ppm for naturally oxidized wafer and up to 2000ppm for thermally oxidized wafer. We dissolved bulk Si with HF/HNO3 to make 2000ppm synthetic VPD sample. Normal volume of VPD sample is not more than 0.5ml, so we used low flow PFA nebulizer ( C-flow 50; sample up take rate is 50μL/min ) with Agilent 8800. Three cell gas modes were used as shown . H2 and O2 cell gas are used for P and Ti, respectively.

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Application #2: P and Ti measurement in Si matrixSi analysis

mode Gas change time (s) element

NoGas 5 Li,be,B,Mg,Rb,Ru,Ag,Cs,Re,Hf,Pt, Au,Tl,Pb,Bi,Th,U

H2 15 Na,Al,P,K,Ca,Mn,Fe,Ga,Sr,Rh

O2 15 S,Ti,V,Cr,Co,Ni,Cu,Zn,Ge,As,Se,Zr,Nb,Mo,Pd,Cd,Sn,Sb,Te,Ba,Hf,Ta,W

Method for high conc. Si analysis

Agilent webinar 201347

Application #2: P and Ti measurement in Si matrixP method; measure P as PH4

+

1%HNO3 100ppm Si 100ppm Si +10ppb P

SiH2

SiH3

SiH

PH4PH3

SiH2+PH

SiH3+PH2

SiH4, SiH5

Q1=31 Ionic Species in H2 mode

Q2 1%HNO3 Si solution P solution31 NO, NOH 30SiH 31P32 NOH 30SiH2 31PH33 30SiH3 31PH234 31PH335 31PH4

SiH+P

In H2 reaction cell, SiH4+ and SiH5

+

are NOT formed. PH3+ and PH4

+

are free from interference of Si+.

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Application #2: P and Ti measurement in Si matrixP and Ti measurement in 2000ppm Si

Phosphorus TitaniumCell gas H2 O2Q1/ Q2 31/35 48/64

Analyte ion PH4+ TiO+

BEC in 2000ppm Si (ppt) 348 2.8DL in 2000ppm Si (ppt) 213 1.9

P Ti

P calibration plot in 2000ppm Si Ti calibration plot in 2000ppm Si

SemiCon Application 3Ti and Cr measurement in H2SO4

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Many chemicals are used in Semiconductor industry device for the cleaning process. The highest purity is required to those

chemicals and the required purity is getting stricter year by year with narrowing geometries of advanced semiconductor devices.

H2SO4 is a popular acid as well as HCl for the cleaning, but Sulfur polyatomic ions cause spectra interference problem on many

elements. It is especially challenging to measure Ti and Cr at trace level in high purity H2SO4.

He collision cell and H2 reaction cell can easily measure trace levels of Cu and Zn in a Sulfur matrix by removing the interference.

Trace level measurement of Ti and Cr is more challenging.

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Application #3: Ti and Cr measurement in H2SO4

Spectra interference by S matrix

isotope Abundance % Interference

46Ti 8.25 32SN+

47Ti 7.44 32SNH+

48Ti 73.72 32SO+, 34SN+

49Ti 5.41 32SOH+

52Cr 83.79 34S18O+

53Cr 9.501 34S18OH+

63Cu 69.15 32SNOH

65Cu 30.85 32S2H+

64Zn 48.27 32S2+, 32SO2+

66Zn 27.98 34SO2+

68Zn 19.02 34S2+

Remaining problems

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Application #3: Ti and Cr measurement in H2SO4

Ti reaction method Ti+ forms cluster ions with NH3. Below shows “product ion scan” of 48Ti + with NH3

cell gas. Preliminary test showed that a product ion TiNH(NH3)3+ ( Q2 = 114)

provided us the best BEC of Ti in a S matrix.

Sig

nal c

ts

Q2

Product ion of 48Ti+ ; 50ppb Ti std was nebulized.

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Application #3: Ti and Cr measurement in H2SO4

Cr reaction method Reaction of Cr+ with O2 is endothermic as shown below. Due to excess collision

energy, the oxidation reaction proceeds, allowing to detect Cr+ as CrO+. Cr+ + O2 → CrO+ + O ∆Hr = 1.36eV

Interfering SO+ is removed via chain reaction given below.

SO+ + O2 → SO2+ +O ∆Hr = 1.48eV

SO2+ + O2 → SO2 + O2

+ ∆Hr = - 0.25eV

Reaction cell method for Cr in S matrix

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Titanium ChromiumCell gas NH3 O2Q1/ Q2 48/114 52/68

Analyte ion TiNH(NH3)3+ CrO+

BEC in 10% H2SO4 (ppt) 2.0 4.0DL in 10% H2SO4 (ppt) 2.3 2.2

Ti Cr

Ti calibration plot in 10% H2SO4 Cr calibration plot in 10% H2SO4

Application #3: Ti and Cr measurement in H2SO4

Ti and Cr BEC in 10% H2SO4

Conclusions With it’s unique HMI and ORS3 capabilities, the Agilent

7700 ICP-MS is well suited for analysing the most challenging aqueous matrices in the Environmental Industry

Both the 7700 ICP-MS and the 8800 QQQ can also be used to determine metals directly in Petrochemicals.

MS/MS uniquely preserves isotopic information when using mass transitions

MS/MS offers truly unique capability and unprecedented control over cell-based reaction chemistry

July 10, 201354

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