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flexibility, and
capabilities with
Agilents ICP-MS and
Triple Quadrupole
ICPMS with Tandem
MS/MS capabilities
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
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
Page 7
ORS3 - a Kinetic Energy Discrimination tool for removing
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
Steven M. Wilbur
Agilent Technologies 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
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
...
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
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
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
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
O2 reaction gas
50Cr+/50V+/50Ti+
38Ar12C+
13C37Cl+
34S+ 34S16O+
17O +
2
16O18O+
Q1 Q2
MS/MS
34amu 50amu
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
100 gl-1
50 gl-1
10 gl-1
5 gl-1
Blank
Silicon & Phosphorus in Ethanol
MS/MS Mode
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.
RF power W 600
BEC was decreased to
1.4ppt with MS/MS scan. Sampling Depth mm 18
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
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.
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+
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
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
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
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.
54
July 10, 2013
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