2

ICP Instrumentation
 Objectives
• Identify the individual components of an ICP

• Discuss the different configurations of an ICP

• Define the purpose of each component

• Sample Introduction
• Torches
• RF Generators
• Optics
• Detectors
 Plasma Emission
• Convert the Analyte Solution Into Free Atoms and/or Ions in the
Plasma
• Sample must be introduced into plasma as an aerosol
• Accomplished Using
– Nebulizer
– Spray Chamber
– Torch
• Transport sample to plasma
– Generate an Aerosol
– Introduce Aerosol into Plasma
• Prevent Nebulizer Blockage
• Prevent Injector Tube Blockage
Figure: Major components and layout of a typical ICP-OES instrument
 Sequential ICP Schematic

Exit Slit

Detector
Computer

Grating
Entrance Slit
RF
Ar Generator

Autosampler
 Introducing Sample to Plasma
• Step one: create aerosol
– Nebulizer and spraychamber
• Step two: aerosol penetration into plasma
– Nebulizer gas pressure through torch injector tube

• Step three: conversion of analyte into free atoms and/or ions in the plasma
• High temperature of plasma produces atoms, ions and excited state species.
• Light energy emitted when excited species returns to ground state.
 Nebulizers
• Convert solution into an aerosol
• Sample is pumped into the nebulizer
– Collision with high pressure Ar nebulizer gas creates fine sample
droplets
• Type of nebulizers:
– Pneumatic (V-groove, Glass Concentric)
– Ultrasonic
– Direct injection
– Microconcentric
 Examples of Pneumatic Nebulizers
• Glass Expansion Nebulizers
– Conikal - glass concentric - standard all purpose
– SeaSpray - glass concentric - designed for up to 20% salt solutions and 75 µm
particulates
– MicroMist - glass concentric - available with uptake rates of 50-600 µL/min
– Slurry - glass concentric -designed to tolerate high particle loads (150 µm) with
excellent stability
– PolyCon - polyimide concentric - can nebulize 10% HF - uptake rates from 50-
5000 µL/min
 Pneumatic Nebulizers

Concentric nebulizer used for ICP-OES.

• Glass concentric nebulizer

– Standard on axial instruments
– Many types available(C, K, Seaspray)
– Glass concentric - sample passes through capillary
– argon gas stream at high velocity flows parallel to capillary
– exhibits good long-term stability
– low volume uptake
– Type C for radial ICP
– Type K (low flow - 0.7 L/min) for axial ICP
 V-groove nebulizer, a variation of the Babington nebulizer

V-groove nebulizer
• Standard on radial instruments
• High dissolved solids capability
• Inert - can run HF
• V-groove nebulizer
• sample emerges through relatively large opening
• high concentrations of dissolved solids can be run without clogging
• made from Peek (polyether ether ketone), hence inert for HF solutions
Figure: Cross-flow nebulizer.

The operation of cross-flow nebulizers is often compared to that of a perfume

atomizer. Here a high speed stream of argon gas is directed perpendicular to the
tip of a capillary tube (in contrast to the concentric or micro-concentric nebulizers
where the high-speed gas is parallel to the capillary). The solution is either drawn
up through the capillary tube by the low-pressure region created by the high-speed
gas or forced up the tube with a pump. In either case, contact between the
high-speed gas and the liquid stream causes the liquid to break up into an aerosol.
Cross-flow nebulizers are generally not as efficient as concentric nebulizers at
creating the small droplets needed for ICP analyses. However, the larger diameter
liquid capillary and longer distance between liquid and gas injectors minimize
clogging problems.
Figure: Babington nebulizer.

The Babington nebulizer, shown above, works by allowing the liquid to flow over a
smooth surface with a small hole in it. High-speed argon gas emanating from the
hole shears the sheet of liquid into small drops. This nebulizer is the least
susceptible to clogging and can nebulize very viscous liquids.
 Ultrasonic Nebulizer (1)

Cetac - USN 5000AT +

Ultrasonic Nebulizer
• Efficiency is about 10% compared to concentric at 1-2%
• About 5-10X increase in signal
• Gives lower detection limits than other nebulizers
• Can be used with axial or radial instruments
 Ultrasonic Nebulizer (2)

Close-Up of U5000AT + Sample Aerosol

Ultrasonic Nebulizer
• Sample is fed onto a tranducer plate operated at 1.4 Mhz
• High density of droplet produced
• Dense aerosol cloud seen in spraychamber
 Ultrasonic Nebulizer (3)

Ultrasonic Nebulizer
• Water vapor removed in condenser to prevent destabilization of the plasma
• Improvement of efficiency due to production of “dry” aerosol
• USN connected directly to torch
 Spraychamber
• Sorts aerosol droplets created in the nebulization process by size
• Removes larger droplets
• Types of spraychamber
– Double pass
• Sturman Masters
• Twister
• Scott
– Single pass
• Cyclonic
 A

Figure: Typical spray chambers used with ICP-OES.

A - Scott double pass type,
B - conical single-pass type with impact bead.
 Spraychambers
Glass Cyclonic - smaller volume
To Plasma

To Drain

•Glass cyclonic spray chamber

• Single pass design
• Supplies more solvent to plasma than Sturman-Masters
 Spraychambers
Sturman-Masters - double pass
Aerosol to
Torch

Sample Sample
Inlet Flow

Pump to Drain
•Sturman-Masters spray chamber
• Double pass design
• Removes larger droplets generated in the nebulization process
• Inert material construction
• For both designs the nebulizer is inserted off-center to start sample in circular
flow pattern
• Both spray chambers are pumped to remove waste liquids
• Spray chamber and nebulizer is removed when using the Ultrasonic nebulizer
 Spraychambers
Sturman-Masters • Low volume
• Glass cyclonic
(Double Pass shown)

Sturman-Masters spray chamber Glass cyclonic spray chamber

• double pass design • double pass “Twister” design
• removes larger droplets generated • Supplies finer aerosol to plasma
in the nebulization process
• inert material construction
 Torches
• Confines Ar gases to form plasma
• Insulates the induction coil from the plasma
• Directs the sample into the plasma
• Types of torches
– One piece quartz
– Semi-demountable
• various sizes and types of injector tubes
– Fully demountable
• various sizes and types of injector tubes
• allows replacement of outer and/or inner tube
• Detection limits similar with both designs
• Demountable
• Used for HF samples, gasoline.
 Radial Torch
• Radial torch systems use a ceramic and
metal Snout piece to purge the optical
path for analysis of wavelengths below
190 nm.
• The snout can be removed if these lower
wavelengths are not being analyzed.

Main components in radial torch box

• Induction coils
• Provides high coupling efficiency of RF into plasma
• Bonnet
• Prevents plasma arcing onto coils
• Snout
• Provides capability of purging space between plasma and pre-
optics window
• Improves signals for sub 190nm wavelengths
 Standard Torches
Standard torch (low power/low flow)
• has three concentric fused silica glass tubes
30 mm • auxiliary gas passes through intermediate tube
• Raises the plasma to prevent melting of torch
• prevents build-up of salt or carbon on tip of
injector tube
• sample aerosol flows through innermost tube
• diameter influences residence time and
dispersion

RADIAL
• Standard injector ID = 1.4 mm

20 mm AXIAL
RADIAL AXIAL • Outer tube is 30 mm longer than RADIAL
torch
• Standard injector ID = 2.4 mm
 Semi Demountable Torch
• Semi Demountable torches:
– To increase injector orifice
• high dissolved solids
– To decrease amount of solvent in plasma
• Volatile organics
– When sample requires inert material for
injector
• HF solutions
 Fully Demountable Torch
• Demountable torches are used:
– To increase injector orifice for high dissolved solids
– To decrease amount of solvent in plasma
• volatile organics
– When sample requires inert material for injector
• HF solutions
Fully Demountable Torch
• adaptable for high concentrations of dissolved solids
• corrosion resistant for HF solutions
• increase auxiliary gas to maximum to lift plasma away
from the torch
• alumina injector tube
- not recommended for Si and Al analysis
- to minimize Si and Al contamination use lower power
• can adjust height in torch
• quartz injector tube also available
 Plasma Viewing
• Radial viewing (Torch Vertical)
Central Channel •Axial viewing (torch horizontal)
•Emission viewed along central channel axis
Viewing Volume •Sensitivity & D.L.'s increased by 2-3 times
•Has more interferences than for radial torch
Fireball

Slit Height • Axial viewing (Torch Horizontal)

Work Coils Depth of field

Central
Channel

Fireball Viewing Volume

Work Coils
•Radial viewing (torch vertical)
•Emission viewed from small window in
analytical zone
 RF Generator
• Provides radio frequency power to the induction coil
– Two isolated frequencies used
• 40.68MHz and 27.12MHz
• Types of RF generator
– Free running
• power is fixed
• Frequency adjusted within a narrow band according to sample
loading in the plasma
– Crystal controlled
• frequency is fixed
• power varies
 Effect of Frequency
• The higher the frequency the thinner the plasma
• Thinner plasmas give:
• greater linearity (less self absorption)
• lower backgrounds
• higher signal for some elements

• Better performance from thinner plasmas

• Less absorption of emitted light energy in thinner plasmas
• Improves linear dynamic range
• Has lower backgrounds

• Higher frequency is better for organic solvents

 Optical Spectrometers
• Gathers light energy from an emission source and separates it into
component wavelengths
• Optical designs
– Sequential
• collects data from all emission wavelengths in sequence
• Moves from one wavelength to another for the measurement
– Simultaneous
• collects data from all emission wavelengths at the same time
 Optical Designs
• Two types of wavelength selectors:
– Monochromator: optical components are moved to isolate specific
wavelengths
• Czerny-Turner has two concave mirrors
• Ebert - uses only one large concave mirror
– Polychromator: optical components remain fixed producing multiple
wavelengths
• Rowland circle has multiple slits and multiple PMT's
• Echelle grating gives overlapping spectra that are sorted by a prism
(cross dispersion).
• Spectral wavelengths appear as dots rather than "lines"

Varian Simultaneous ICP’s use Echelle Gratings

• Monochromators (movable grating):

• Polychromators (fixed grating)
Monochromator (sequential) Czerny-Turner
Detector Exit Slit

Grating

Entrance Slit
Plasma
•Czerny-Turner monochromator
•Emission from plasma focused onto grating
•Grating rotated by a stepper motor which moves spectrum across
secondary slit
•Uses slower scanning to accurately locate the spectral line.
•Uses single PMT
•Has maximum flexibility in choice of analytical lines (advantage)
•Has lower sample throughput than simultaneous (disadvantage)
 Polychromators (1) Rowland circle

Photomultiplier Exit Slits

Tubes

Entrance Slit Diffraction

Plasma Grating
(fixed)
•Rowland Circle
•Multiple PMT’s located at appropriate wavelength positions along focal plane
•Can have up to 60 PMT detectors
•Need to specify wavelengths and concentration ranges before manufacture
•Need to specify matrix-spectral interferences
 Polychromators (2)
Echelle
Polychromator

•Echelle Polychromator
•A “three dimensional” spectrum is created by directing the diffracted light from a fixed
low resolution grafting (about 80 lines/mm) to a dispersing element such as a prism or
another cross-dispersing grating.
•The prism separates the spectrum into its component orders providing a two
dimensional array of orders and wavelengths.
•Detection is through a Charge Transfer Device (CTD) commonly a CCD or CID
•Uses three transfer optics to direct light form plasma through entrance slit and into
polychromator
•• Collimating mirror focuses light onto grating which disperse the wavelengths
•• • Produces a two dimensional array of orders and wavelengths
•Second mirror focuses light onto CCD camera
•Chip is curved because the prism bends light differently vs. wavelength
 Diffraction Gratings (1)
• An optical surface that disperses light into a spectrum.
– Polychromatic light incident on the grating is dispersed so that each
wavelength is reflected from the grating at a slightly different angle.
• Gratings consist of equally spaced parallel grooves, formed on a reflective
coating and deposited on a substrate
• Two types:
– Echellette - fixed dispersion in one plane
- fixed good for low orders
– Echelle - variable dispersion in two planes
– Have good efficiency in high orders
 Diffraction Gratings (2)
Two types of grating manufacture

Ruled: parallel grooves mechanically scribed into a reflective surface Al)

• Ruled gratings have imperfections (periodic spacing, groove parallelism,
groove form etc)
•Gives rise to interferences or "ghost" images resulting from overlapping
wavelengths

Holographic: parallel grooves produced by a photographic process

•Produced by exposing photoresists to an interference pattern produced by
crossing two laser beams
• Free of "ghosts"
• Have lower stray light than ruled
• Can be made much larger than ruled gratings
• Currently photoresist technology does not allow production of
sufficiently deep grooves to produce Echelle holographic gratings.
 Diffraction Gratings (3)
1 1
2

1- Echellette
• In Echellette grating light is reflected off long side of groove.
• Echellette grating has a large number of grooves
• Resolution is related to the number of grooves
2- Echelle
• In Echelle grating light is reflected off narrow side of groove
• Echelle grating has small number of grooves
• Resolution is improved by increasing the blaze angle and order
 Detectors
• Converts light energy (photon beam) to electrical current
• Types of Detectors:
– Photomultiplier tube (PMT)
– Solid state detector
• Charge coupled Detector/device (CCD)
• Charge injection Detector/device (CID)
 Photomultiplier Tube
(Commonly used in Rowland Circle and Sequential ICPs)

Insulator Anode *100 Million Amplification of Signal

Dynode’s
e- (9-13)
e- e- e-e-
Photocathode e- e-
-
e-
e e-
e- e-
e-
Light
Energy
Quartz
Window

Photomultiplier tube
• Photons strike light sensitive cathode
• Electrons are expelled.
• Electrons are attracted to dynode plate at positive potential.
• More electrons expelled (flow of current)
• Repeated 9 to 13 times
• Signal amplified 108 times.
 Solid State CCD Detector (1)

• Solid state detector

• CCD camera
• Semi-conductor chip mounted in center
 CCD – How does it work?
• A CCD is a semiconductor device that converts light (photons) to a current
– The photon ejects an electron from an underlying semiconductor layer
creating a ‘hole’ in the material
– The ‘hole’ can be moved by electodes positioned on the surface of the
semiconductor
• This creates a measurable current
• Distinguishing feature
– The charge needs to be moved down the column of the array before
entering a serial register
• This is read sequentially by the amplifier
• Advantages of CCDs include
• High quantum efficiency,
• Excellent charge transfer efficiency,
• Low readout noise,
• Low dark current that decreases with lowering temperatures
• The image from a CCD is read out by transfer to a storage register, followed
by horizontal transfer of pixel charge along the row to the output electronics
 Solid State CID Detector

CID Operation

• Each pixel of a CID is defined by the intersection of a row (sense) and column (collection) gate
electrode.
• By changing the potentials applied to the sense and collection electrodes, the amount of photo
generated charge can be measured by moving it within the pixel element and measuring the
voltage induced by this movement.
• After the pixel is interrogated the charge may be either injected into the substrate (DRO Destructive
Read-Out) or returned to the collection gate (Nondestructive Read-Out).
• Further integration or the readout process may be repeated to improve signal to noise ratio.
• A single read of a CID is approximately 180 electrons, which is 10 to 100 times that of a CCD.
• Multiple NDRO’s improve the SNR proportionally to the square root of the number of reads.
 Computer

• Data Analysis and Collection

• Calibration Data
• Statistics wavescan
close
• Background Correction stop
help

• Hardware Control clear

print
overlay
– RF Power
– Viewing Height
DEC
– Gas Flows
– Peristaltic Pump
DEC
– Auto Sampler
• END