Transcript ICP - MS - Fakultas Farmasi Universitas Airlangga

Agilent 7500 Series ICP-MS
An Introduction
Presented By:
Ferdi Ferdian Kusnadhi
What is ICP-MS?
An inorganic (elemental) analysis technique
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
ICP-MS has the detection limits of
GFAA and the sample throughput of
ICP-OES
Agilent 7500ce ICP-MS System with
Collision Reaction Cell (CRC)
Reaction Gas Inlet
Multi-element interference removal by
on-axis octopole reaction cell
Fast simultaneous dual
mode detector (9 orders
dynamic range)
High
temperature
27MHz plasma
generator
Plasma
Octopole
Off-axis
Lens
Low flow sample
introduction system
High frequency
hyperbolic quadrupole
Agilent 7500 Series ICP-MS
Agilent 7500a (G3271A)
– Standard ICP-MS
Agilent 7500ce (G3272A)
Agilent 7500cs (G3273A)
•General purpose that does not
require collision
•Enviro, foods, biological...
•Semiconductor, R&D.
•Ultra low BECs at high plasma
power
•Cool plasma also available
•Standard ShieldTorch System for
cool plasma
• Upgradeable to ORS
•Robust Octopole Reaction
System (ORS)
•Superb capability in the
most complex matrix
•Flexibility
Different ways of
acquiring information
from a sample
1. Qualitative scan
2. Semiquantitative Analysis
3. Fully quantitative data
Primary Agilent ICP-MS Team in Asia Pacific
Dedicated
Application
s Support
Asia Pacific
Resource
Dedicated
Sales
Support
Dr Christopher Tye
Fan Chen
Dr Deng-yun Chen
Asia Pacific Business Development Manager
Based in Singapore
ICP-MS Product Specialist
SMT
Senior ICP-MS Applications Specialist
Greater China Based in China
Kung-yu
Chen
Yu-hong Chen
David
Wilkinson
ICP-MSProduct Support Engineer
Asia Pacific
Based in Australia
Peak ICP-MS/semiconductor
Sales Greater China
Based in Taiwan
ICP-MS Applications Specialist Greater China
Based in China
Jerry Leu
ICP-MS Product Specialist Greater China
Based in Taiwan
Fred Fryer
Senior ICP-MS Applications
Specialist South East Asia
Based in Australia
S Korea - 5
China - 8
Taiwan - 4
Hong Kong - 1
Vietnam - 1
Malaysia - 2
Factory Trained
Agilent ICP-MS
Service Engineers
(AP Region Only,
excluded JPN)
India - 1
Thailand - 1
Singapore - 2
Country with
Agilent ICP-MS
installed
No Agilent ICPMS installed
Australia - 5
New Zealand - 1
Application Notes of interest to the Semiconductor
Market
5989-4348EN 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 Pacific
Big 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!
What is ….
A Mass Spectrometer
ION SOURCE
Produces ions that are
DETECTOR
MASS FILTER
separated according to mass and
detected
Chemical Ionization (CI)
Electron Impact
Ionization (EI)
+
Electrospray
Ionization (ESI)
MM
MM
Atmospheric Pressure
Photo Ionization (APPI)
Atmospheric Pressure
Chemical Ionization (APCI)
Matrix Assisted Laser
Desorption Ionization
(MALDI)
M+
Time to Frequency
(TOFs only)
Time Of Flight (TOF)
M+ M++
M+ IonMTrap
M+M+ Quadrupole
M+
M+ +M+
M
M+
Electron Multiplier
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
Powerful semiquantitative analysis
• low ppb - ppt for all elements
• no standards needed
Wide elemental coverage - from Li U
Isotopic analysis
• 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
• 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
Calibration ranges
Hg (0.01 – 2ppb) – Std Mode
As (0.1 – 200 ppb) – He Mode
Se (0.1 – 200 ppb) – H2 Mode
Na (0.05 – 1180 ppm) – He Mode
Hg
As
Se
Na
Overall calibration range 10ppt (Hg) to
1180 ppm (Na) in a single method
- without attenuating ion transmission
to increase working range
Na
Typically, ICP-MS cannot measure
above 200ppm Na without changing
quad resolution or ion lens settings
Hg
Hg detection limit by 7500ce is about
3ppt – 7500ce can QUANTIFY at
10ppt!
7500ce can measure both Na and Hg
in the same run!
1180 ppm
Sodium
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
Spectrometry
Energy 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 Spectrometry
Energy 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*
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
$$
$
$$
$$$
Operating Cost
$$$
$$
$$
$$$
Interferences
* Agilent 7500 Series only - (other ICP-MS - 8 orders)
ICP-MS combines the sensitivity of GFAAS with the speed & flexibility
of OES while offering a wider dynamic range and fewer interferences!
1 ICP-MS:
The new standard for inorganic analysis
American Laboratory News, Nov.1998
Overview of Inorganic Analysis Techniques
Sequential Simultaneous
Criteria1
FAAS
GFAAS
ICP-OES
ICP-OES
ICP-MS
Detection Limits
+10ppb
+50 ppt
1 ppb
<1 ppb
sub-ppt
Linear Range (orders)
3-4
2-3
4-6
4-6
9*
Chemical
Many
Many
Some
Some
Some
Spectral
Some
Many
Some
Some
Some
Matrix
Many
Many
Some
Some
Few
Speed
Moderate
Slow
Slow
Fast
Fast
Elemental Coverage
Moderate
Poor
Good
Good
Excellent
Typical no.
50
35
55
55
70
Multi-element
No
No
Yes
Yes
Yes
N/A
No
Yes
Yes
Interferences
Simultaneous
N/A
* Agilent 7500
Series only - (other
ICP-MS 8 orders)
Sample Size
mL
uL
mL
mL
uL or mL
Capital Cost
$
$$
$
$$
$$$
Operating Cost
$
$$$
$$
$$
$$$
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
Fast
ICP-OES - most elements single
figure ug/L DLs and good
productivity
ICP-MS - most elements
single figure ng/L DLs
and very productive
GFAAS is a key target
market for ICP-MS!
FAAS – most elements
+10 ug/L DLs
Slow
mg/L (ppm)
GFAAS – most elements
sub-ug/L DLs; but poor
throughput
ug/L (ppb)
ng/L (ppt)
Agilent 7500 - 3 Sigma Detection Limits
<0.1 ppt
H
He
Standard pneumatic nebuliser
3 sec/mass integration time
* Class 1000 cleanroom with
ShieldTorch
0.1 - 1ppt
Li
0.8
*0.05
Be
0.2
Na
15
*0.04
Mg
1
*0.04
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
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
Cs
0.05
Ba
0.4
Hf
0.2
Ta
0.09
W
0.3
Re
0.3
Os
Ir
0.3
Fr
Ra
B
4
C
N
5000 250ppm
O
F
100
Ne
1 - 10 ppt
Al
5
*0.04
Si
500
P
40
S
>1000
Cl
>1000
Ar
Zn
1
*5
Ga
0.7
Ge
0.9
As
2
Se
20
Br
100
Kr
Ag
0.1
Cd
0.4
In
0.06
Sn
0.2
Sb
0.6
Te
1
I
0.8
Xe
Pt
0.5
Au
0.2
Hg
1
Tl
0.05
Pb
0.3
Bi
0.1
Po
At
Rn
>10 ppt
LA
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 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 !
Agilent 7500 ICP-MS
Merchantek UP 213
Laser Ablation
system
Laser
Sample
Ar Gas with
ablated
material
Connecting an LC to an ICP-MS
ICP torch
Q-pole mass filter
nebulizer &
spray
chamber
turbo
molecular
pump
gas controller
Ar gas
liquid chromatograph
rotary pump
turbo
molecular
pump
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 line
Modified torch with heated injector replaces
standard demountable torch. “Silicosteel” transfer
line and injector liner for inertness
GC capillary can be inserted to tip of injector or
terminated in GC oven
GC effluent injected directly into base of plasma –
essential for high boiling point compounds
Species 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
Li
7
32.8
31* ug/g
Be
9
1600
ng/g
B
11
38.8
ug/g
Na
23
2400
2400 ug/g
Mg
24
9.2
11.3* mg/g
Al
27
39.6
47* mg/g
Si
29
6
mg/g
K
39
8.4
12.1* mg/g
Ca
43
108
163* mg/g
Sc
45
10.8
8.3 ug/g
Ti
47
3280
3000* ug/g
V
51
64
66 ug/g
Cr
53
120
60 ug/g
Mn
55
560
631 ug/g
Fe
57
22.8
25.7* mg/g
Co
59
10.4
8.9 ug/g
Ni
60
44
26* ug/g
Cu
63
10
11 ug/g
Zn
66
96
104 ug/g
Ga
69
18
10* ug/g
Ge
72
2200
ng/g
As
75
16.4
13.4 ug/g
Se
82 0.4* ng/g
Br
79
8.4
ug/g
Elem mass Found
certified units
Br
79
8.4
ug/g
Rb
85
60
51 ug/g
Sr
88
108
108 ug/g
Y
89 internal
std ug/g
Zr
90
100
ug/g
Nb
93
12
12* ug/g
Mo
95
2240
2500* ng/g
Tc
99 ng/g
Ru
101 ng/g
Rh
103 ng/g
Pd
105
132
ng/g
Ag
107
440
ng/g
Cd
111
1560
1300* ng/g
In
115
44
ng/g
Sn
118
2840
ng/g
Sb
121
1920
1700 ng/g
Te
125 ng/g
I
127
7.2
ug/g
Cs
133
6
5.4 ug/g
Ba
137
156
159 ug/g
La
139
38.8
28 ug/g
Ce
140
76
61 ug/g
Pr
141
8.8
ug/g
Nd
146
32
30 ug/g
Values marked with an asterix * are
not fully certified and for
information only
Elem mass Found certified units
Sm
147
5.6
5.1 ug/g
Eu
153
1160
1000 ng/g
Gd
157
5.6
ug/g
Tb
159
720
600 ng/g
Dy
163
3280
3900 ng/g
Ho
165
720
ng/g
Er
166
2160
ng/g
Tm
169
248
ng/g
Yb
172
1860
2400 ng/g
Lu
175
228
300 ng/g
Hf
178
840
ng/g
Ta
181
760
800* ng/g
W
182
1640
ng/g
Re
185
28.8
ng/g
Os
189 ng/g
Ir
193 ng/g
Pt
195 ng/g
Au
197 ng/g
Hg
202 ng/g
Tl
205
600
ng/g
Pb
208
68
60 ug/g
Bi
209
308
ng/g
Th
232
1160
ng/g
U
238
3000
2600 ng/g
Typical Application Areas for ICP-MS
Environmental
Pharmaceutical
Geological
Drinking Water, Ambient Water,
Sea Water
Routine heavy metal
contamination
Soil, Rocks, Sediments
Soils, Sludges, Solid Waste
Drug discovery
Plant material/agriculture
Clinical trials
Speciation of Hg, As, Pb, and Sn
HPI
Clinical
R&D
Blood, Urine, Serum
QA/QC
Hair, Tissues
Semiconductor
Tooth, bone, tusk, shell, coral
analysis
Toxicology
Process Chemicals
Forensics
Nutrition/deficiency/vitamins
Contaminants in Si Wafers
Gun Shot Residue
Food Analysis
Photoresists & Strippers
Materials Characterization
Nutrition
Nuclear
Point of Origin
Toxic element and species
monitoring
Fuel production
Poisoning
Measurement of Radioisotopes
QA/QC
Primary Cooling Water
Hydrology
Isotope Ratio Studies
Laser Sampling
Archaeological
Artifact analysis, proof of origin
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
•
Market in decline
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
•
•
Market in decline
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
•
•
Market flat
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) Market is growing
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
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
Disadvantages
• multielement, fast
• relatively poor detection limits
• flexible element selection
• many spectral interferences
• well documented methods
• sample consumption high (1 to 5
mL/min)
• very good tolerance to dissolved
solids
• good linear dynamic range
• element flexibility
– limited in older systems
– speed of analysis compromised in
newer systems
ICP-MS
Advantages
Disadvantages
• 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
• 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, ICPOES and single element
detectors have been
replaced by a single 7500!
Price/Performance – How does ICP-MS Compare
With Other Inorganic Techniques ?
200
Inductively Coupled Plasma Mass Spectrometry (Quadrupole)
Typically 1ppt to 100ppm
150
Inductively Coupled Plasma Optical Emission Spectroscopy
Typically 1ppb to >1000ppm (Simultaneous)
100
Graphite Furnace Atomic
Absorption Typically
10ppt to 100ppb
50
Flame Atomic Absorption
Typically 50ppb to 500ppm
1ppt
10ppt
100ppt
1ppb
10ppb
100ppb
1ppm
Typical measurement range
10ppm
100ppm
1000ppm
Agilent 7500 Series ICPMS Features
1. Unmatched Interference Removal with ORS in He Mode
Spectral 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 GCICP-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!