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Improving sensitivity,

flexibility, and
capabilities with
Agilents ICP-MS and
Triple Quadrupole
ICPMS with Tandem
MS/MS capabilities

For the Environmental,


Petrochem and Semiconductor
Industries
Jon Talbott, PhD
Application Engineer
Agilent 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

2 July 10, 2013


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

Page 3
Agilent 7700 ICP-MS and 8800 ICP-MS/MS

7700 is Agilents high performance single quadrupole ICP-MS


Many unique capabilities including HMI, ORS3

8800 is Worlds 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 Agilent 8800


Single Quad Triple Quad
ICP-QMS ICP-MS/MS
Agilent7700ICPMSSysteminDetail
Offaxisionlens 3rd generation
Cellgasinlet Octopole
Highmatrix Reaction
Fast,simultaneous
introduction System(ORS3) dualmode
(HMI)dilution detector(9orders
gasinlet dynamicrange)

LowflowSample
Introduction
Highfrequency
(3MHz)
hyperbolic
quadrupole
Peltiercooled
spraychamber

Highperformance
vacuumsystem

Fast,frequency
matching27MHz
RFgenerator Hightransmission,
matrixtolerant
interface

Page 5
Agilent 8800 ICP-MS/MS System in Detail
Dual conical Extraction and First quad Q1: High frequency
Omega lens focus ions hyperbolic quadrupole mass filter 3rd generation collision/
High matrix across the mass range reaction cell (ORS3) with
selects ions that enter the cell
introduction up to 4 cell gas lines
(HMI)
technology

Low flow
sample 9 orders
introduction dynamic range
system electron
multiplier (EM)
detector
Peltier-
cooled
spray Analyzer quad Q2:
chamber High frequency
hyperbolic quadrupole
selects ions that
pass to detector
Fast, frequency-
matching 27MHz
RF generator Robust, high-temperature High-transmission, Efficient twin-turbo
plasma ion source matrix tolerant interface vacuum system
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

Page 7
ORS3 - a Kinetic Energy Discrimination tool for removing
Polyatomic Interferences

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


to this, with it!!

A single KED mode is very efficient at removing all


polyatomic interferences!

Page 8
And theres still plenty of Sensitivity to obtain the
lowest of Detection Limits

Page 9
High Matrix Introduction (HMI) is an online sample dilution
technique that allows undiluted soil digestates and even
undiluted seawater to be analyzed directly.

No other MS instrument
can make these claims!

Page 10
Key Benefit of High Matrix Interface (HMI)
HMI shows good recoveries even in 3% Total Dissolved Solids
HMI Important in . Environmental

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. Wilbur
Agilent Technologies Inc.

Richard Burrows and Richard Clinkscales


TestAmerica Inc

Page 12
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
The combination of the highly robust
Calcium, 2,000 mg/L plasma of the Agilent 7700x with HMI and
Magnesium, 1,000 mg/L ISIS discrete sampling allows routine
analysis of this interference check
Sulfate, 2,000 mg/L
solution and samples containing similar
Sodium, 1,000 mg/L levels of dissolved solids UNDILUTED!
Butanol, 2000ppm
FGD-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 70130 %
Analysis of Flue Gas Desulfurization Wastewater
Long 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)

Page 14
We examined very Challenging Aqueous Matrices
(Seawater, FDGs) from the Environmental Industry
...

What about Organic Matrices?

Biodiesel & Kerosene


ICP-QMS
Application
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 & Kerosene
ICP-QMS

Instrument Conditions
Direct Elemental Analysis of Biodiesel & Kerosene
ICP-QMS Detection Limits
Gasoline Application
ICP-QMS
Application
Direct Elemental Analysis of Gasoline
ICP-QMS

Instrument Conditions
Direct Elemental Analysis of Gasoline
ICP-QMS Comparison of ORS Gas mode Data
Direct Elemental Analysis of Gasoline
ICP-QMS Long Term Stability
Feature of ICP-MS
Agilent 8800 Triple Quad ICP-MS (ICP-QQQ)
Q1 Cell Q2 Detector

ICP Mass analyzer

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.
24
ICP-QQQ: How Does it Work?

ICP (plasma) and Interface:


Forms and extracts ions from
the sample (just like the 7700)

Q1 controls ions ORS3 collision/


that enter the cell reaction gas added Q2 selects the
Mass filter Ion size and/or target analyte mass
reactions filter and are Interference-free analyte
Consistent reactions w/i
neutralized or moved ions passed to EM
ORS even if sample
composition changes Product ions are formed

EM (detector): Measures the


ions that are scanned by Q2
(just like the 7700)

25 ASTS 2012
ICP-QQQ: Modes of Operation

MS/MSmodes filterionsenteringORScell
1. OnMassMode(Q1andQ2bothsettotargetmass)

2. MassShiftMode (Q1andQ2settodifferentmasses)

AdvancedScanningModes forresearchandmethod
development
A. PrecursorIonScan
B. ProductIonScan
C. NeutralGainScan

ASTS 2012
Page26
How Reaction Mode Works in ICP-MS/MS

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
Reaction
Reaction product ion
gas
On-mass
interference
Analyte Analyte
Off-mass
interference Interference
All non-target M+ MR+
masses
Q1 set to analyte Interference reacts Q2 set to original analyte
mass rejects all to form product ion mass rejects any off-
non-target masses mass product ion(s)

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

27 July 10, 2013


How Reaction Mode Works in ICP-MS/MS

2. Mass-Shift Measurement: Reactive analyte promoted to a new


product ion mass and separated from unreactive interferences.

Original
Reaction interfering ion
gas
On-mass
interference
Analyte
Analyte
product ion
Off-mass
interference Analyte
All non-target M+ MR+
masses
Q1 set to analyte Analyte reacts to Q2 set to analyte product
mass rejects all form product ion ion mass rejects original
non-target masses interfering ions

With ICP-MS/MS, Q1 rejects all non-target masses, ensuring no existing


ions (analyte, matrix, or polyatomic) can overlap new analyte product ion

28 July 10, 2013


Oxygen Mass Shift for 34S
With MS/MS

O2 reaction gas
50Cr+/50V+/50Ti+
38Ar12C+
13C37Cl+

34S+ 34S16O+

17O +
2
16O18O+

Q1 Q2
MS/MS
34amu 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 Mode
Isotopic Abundance of Mass Shifted Ions Maintained
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)
Q1 Q2 mass difference
32S16O+
is 16, so only the + 16O
33S16O+
transition is measured
34S16O+

Ensures S isotope
abundance is maintained
no overlap from 32S18O+
on 34S16O+, for example
Supports confirmatory
isotopes and IR/IDMS
31 July 10, 2013
Unique ICP-MS/MS Analyses
for
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 BEC
NoGas Single Quad 32 S 0.910 11.806 1383.11 ug l-1
NoGas Single Quad 33 S 0.752 157.615 4568.56 ug l-1
NoGas Single Quad 34 S 0.971 10.550 615.15 ug l-1
O2 Q Single Quad 32 S O/R O/R O/R ug l-1
O2 Q Single Quad 33 S -0.675 -177.597 -1557.31 ug l-1
O2 Q Single Quad 34 S 0.677 191.277 12336.87 ug l-1
O2 Q Single Quad 48 32SO 0.999 3.555 53.80 ug l-1
O2 Q Single Quad 49 33SO 0.975 99.790 1442.79 ug l-1
O2 Q Single Quad 50 34SO 0.947 19.460 1849.35 ug l-1
O2 MS/MS MS/MS 32 48 S 1.000 0.358 19.03 ug l-1
O2 MS/MS MS/MS 33 49 S 0.999 2.860 19.84 ug l-1
O2 MS/MS MS/MS 34 50 S 1.000 0.852 18.99 ug l-1
Calibration spikes in Ethanol
32S, 33S and 34S Mass Shift Data

100 gl-1
50 gl-1
10 gl-1
5 gl-1
Blank
Silicon & Phosphorus in Ethanol
MS/MS Mode

Mass Shift Mode with O2 On Mass Mode with H2


Optimal gases for silicon and phosphorus differ
although P, S, As, Se can all be determined under O2

Si provides better BECs under H2 MS/MS on-mass measurement


Ti and As in Xylene
Mass 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 NMP
MS/MS Mass Shift with O2 and H2

(Naoki Sugiyama Poster FP-1)


Applications of ICP-QQQ for
SemiConductor Industry

Three challenging applications to conventional


ICP-MS are introduced today

Ultra trace Calcium measurement


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

40
SemiCon Application 1
Ultra trace Calcium measurement

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.

41
Application #1: Ultra trace measurement of Calcium
Effect of MS/MS scan in cool plasma
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.

Cool plasma condition


BEC was 6.8ppt with
single Quad scan. parameter unit

RF power W 600
BEC was decreased to
1.4ppt with MS/MS scan. Sampling Depth mm 18

Carrier gas flow rate L/min. 0.7

Make up gas flow rate L/min. 1.0

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.

42
Application #1: Ultra trace measurement of Calcium
Ultra low BEC for Ca
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.

Cool plasma

Calibration curve of Ca

BEC of 41ppq
was achieved.

43
SemiCon Application 2
P and Ti measurement in Si matrix

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.

44
Application #2: P and Ti measurement in Si matrix
Spectra interference by Si matrix
isotope Abundance % Interference
31P 100 30SiH+, 29H2+, 28SiH3+
46Ti 8.25 30SiO+
Remaining
47Ti 7.44 28SiF+, 30SiOH+
problems
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+

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.

45
Application #2: P and Ti measurement in Si matrix
Si analysis
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 50L/min ) with Agilent 8800. Three cell gas
modes were used as shown . H2 and O2 cell gas are used for P and Ti, respectively.

Method for high conc. Si analysis


Gas change
mode element
time (s)
Li,be,B,Mg,Rb,Ru,Ag,Cs,Re,Hf,Pt,
NoGas 5 Au,Tl,Pb,Bi,Th,U
Na,Al,P,K,Ca,Mn,Fe,Ga,Sr,Rh
H2 15

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

46
Application #2: P and Ti measurement in Si matrix
P method; measure P as PH4+

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

Q1=31 Ionic Species in H2 mode


SiH3+PH2
Q2 1%HNO3 Si solution P solution
31 NO, NOH 30SiH 31P
SiH
32 NOH 30SiH2 31PH SiH+P
33 30SiH3 31PH2

34 31PH3

35 31PH4 SiH2+PH
SiH3
In H2 reaction cell, SiH4+ and SiH5+
are NOT formed. PH3+ and PH4+
are free from interference of Si+. SiH2
PH3 PH4

SiH4, SiH5 Agilent webinar 2013


47
Application #2: P and Ti measurement in Si matrix
P and Ti measurement in 2000ppm Si
P calibration plot in 2000ppm Si Ti calibration plot in 2000ppm Si

P Ti

Phosphorus Titanium
Cell gas H2 O2
Q1/ Q2 31/35 48/64
Analyte ion PH4+ TiO+
BEC in 2000ppm Si (ppt) 348 2.8
DL in 2000ppm Si (ppt) 213 1.9

48
SemiCon Application 3
Ti and Cr measurement in H2SO4
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.

49
Application #3: Ti and Cr measurement in H2SO4
Spectra interference by S matrix
isotope Abundance % Interference
46Ti 8.25 32SN+
Remaining
47Ti 7.44 32SNH+
problems
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+

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.

50
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.
Signal cts

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


Q2

51
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

52
Application #3: Ti and Cr measurement in H2SO4
Ti and Cr BEC in 10% H2SO4
Ti calibration plot in 10% H2SO4 Cr calibration plot in 10% H2SO4

Ti Cr

Titanium Chromium
Cell gas NH3 O2
Q1/ Q2 48/114 52/68
Analyte ion TiNH(NH3)3+ CrO+
BEC in 10% H2SO4 (ppt) 2.0 4.0
DL in 10% H2SO4 (ppt) 2.3 2.2

53
Conclusions
With its 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

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July 10, 2013
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