In the name of God

Ion Collectors and Detectors

Presented by: Elham Ghaemi

Ion Collectors and Detectors:

Some ideal characteristics of Ion Collectors and Detectors,
1. Ideally should measure the intensity of the total ion beam
2. Should be able to get multiple detectors without interference
3. High Sensitivity
4. Wide dynamic range
5. High linearity
6. Low Noise
7. No changes in behavior over time
8. Easy to Use
Not possible to meet all of these characteristics at the same
time
Ion Beam Measurement Characteristics:
Made up of individual ions arriving at the detector at an average
rate that is a measure of the number of ions generated at the
source
Theoretically at least the rate of ions entering the detector is a
measure of the amount of that isotope in the sample
Theoretically if we ratio the rates of two isotope beams this
ratio is the ratio of the two isotopes in the sample:
Where R1 is the rate of isotope 1, R2 is the rate of isotope 2, S1
is the amount of isotope 1 in the sample and S2 is the amount
of isotope 2 in the sample.

Measurements:

How do we measure the rates?
We can measure the rate directly--that is, directly count the number of ions
appearing at the detector over a certain period of time.
This is known as ion or pulse counting.

The ion beam is an electric current,
We can measure some parameter associated with electric currents and use
this as a proxy for the rate.
This is known as analog measurement.
We can measure charge, current or voltage (we will discuss this in more
detail when we discuss the associated electronics).
We will discuss types of detectors first
Mass Spectrometry Ion Detectors:
1. Faraday Cup

2. Electron Multiplier and Channel Electron Multiplier

3. Microchannel Plate

4. Daly Detector (Scintillation Counter or Photomultiplier)
1. Faraday Cups:
Technically more an ion collector than detector.
Basically what the name implies: a cup the ions enter and
transfer their charge to the cup.
Charge is usually transferred to electronics outside the vacuum
system.
Type of electronics determines whether measured as charge,
current or voltage.
Faraday Cups:

Components:
-A defining slit allowing one focused beam to pass to the detector
-A secondary electron suppressor
-Faraday cage collecting the ion beam
-Electronics.

Measurement:
Current striking the collector electrode is measured,
Collector is attached to high-ohm resistor (10^10-
10^12Ohm),
The potential drop across the resistor is measured.



Faraday Cups:
The faraday cup seems simple but in practice becomes quite
complicated.
The first and major complication is that the ions entering have
energies significantly higher than the work function of the cup
material (stainless steel, carbon, graphite).
This causes the generation of free electrons (know as secondary
electrons).
If a secondary electron leaves the cup this makes the charge on
the cup look like an additional + ion has entered.

Faraday Cups :

What determines the number of secondary electrons?
Mass of ions
Energy of ions
Charge on ions
Angle of incidence
Material of cup
Nature of ion (monatomic vs. polyatomic)

How can we reduce the effect of secondary electrons?
Passive and Active techniques
Faraday Cups :
Passive
Make cup of material that generates fewer secondary
electrons
Make cup deep and narrow
Prevent Beam from hitting side of cup
Active
Magnetic field to confine electrons to cup
Slit plate (repellor plate) placed before cup with negative
voltage, electrons that leave cup are forced back into the cup.

Faraday Cups :
Magnetic field plus repellor plate reduces secondary electron loss to a few
hundred parts per million or less Ions can also enter the cup and be reflected
without giving up their charge, a positive plate can be placed in front of the
negative repellor to reflect back these ions.
Faraday Cups :
Faraday Cups can go bad.
Material in the ion beams can be deposited on the surface of the
cup (or even react with it).
This surface layer can generate copious secondary electrons.
Coating the cup with graphite (or making it out of graphite)
enhances the lifetime and also reduces secondary electron
generation.
Faraday Cups :
Some characteristics of faraday cups,
Can be made thin (~2mm) so multiple cups can be placed in the
MS and closely spaced peaks can be measured.
Beam intensities of 10-18 A and up can be measured (depends
mostly on the electronics used), typical dynamic range of 10^5
(again mainly dependent on electronics).
As long as secondary electron generation and ion reflection are
controlled, the linearity, sensitivity and accuracy depend
mainly on the electronics, although residual cup effect usually
remain (generally placed under the description of cup
efficiency).
Generally run in analog mode.


Electron Multiplier:
Faraday Cups are limited in sensitivity and dynamic range.
Electron multipliers and similar devices (e.g. Daly Detector) can
improve sensitivity and dynamic range.
All of these devices first use the ions to generate electrons and then
amplify the electrons.
Basic electron multiplier:
Incoming ion generates electrons at the first
dynode, the number depends on similar factors
as secondary electrons in faraday cup.
As electrons cascade to next dynode they
release more electrons (typically one to two
electrons, depends on voltage difference
between dynodes).
Electron Multiplier:
High gains (up to 10^7 in some cases) mean high sensitivities.
Each ion produces narrow pulse of electrons at final dynode
Both analog and ion counting possible.
Number of electrons at final dynode proportional to efficiency
of electron production at first dynode.
Linear response at low gains and ion rate.
Gain can be varied by adjusting voltage.

Electron Multiplier:

Some problems with multipliers:
At high gains and count rates response becomes non-linear.
First dynode can be damaged by ions and tends to degrade over
time.
Mass dependence of electron production at first dynode.
Spurious ions generated by electrons.
Closely spaced pulses cannot be separated (not a problem in
analog mode), known as dead time.
Must be shielded from external magnetic and electric fields.


Electron Multiplier:

Variation on Electron Multiplier-the continuous dynode
multiplier or channeltron:




Can be made very small and in different shapes, can be small
enough to substitute for faraday cups.
Suffers many of the same problems as EM.
Problems with ion damage can be mitigated with conversion
dynode.
Microchannel Plate Ion Detector:
Channeltrons can be made very small and stacked together.
These microchannel plates can be made large and cover a wide
area.
Useful in Time-of-Flight mass spectrometer and wherever the
beam covers a large area.
Microchannel plates have improved time resolution over other
detectors.
However, they suffer from many of the same problems as other
multipliers.
20
Microchannel Plate Ion Detector:

An array of 10^4-10^7miniature electron multipliers, oriented
parallel to one another. Channel dia10-100 microns; length/dia40-
100. Channel axes are oriented at a small angle (~8) to the MCP
input surface.
Channel matrix is treated to optimize the secondary emission
characteristics,
Parallel electric contact to each channel is provided by
deposition of metallic coating on the front and rear surfaces,
Gain 104-single, 106-7-dual and Z stack-108,
Fast response time sub ns.

Microchannel Plate Ion Detector
Array of tiny channel electron multipliers (usually glass
capillaries coated with electron-emissive material) - 12.525
m in diameter and 12mm long.
Around 10 million tubes are stacked side by side to form a
thin plate structure.
Used in TOF MS

Advantages:
Fast - time response <1 ns, High sensitive
Disadvantages:
expensive, short lifetime
Microchannel Plate Ion Detector:

Microchannel Plate Ion Detector:

Daly Detector:

The Daly Detectors gets around some of the problems of
traditional multipliers:
Daly Characteristic:
Advantages:

Knob more robust than first dynode of EM,
Smaller mass dependence,
Lower noise for same current gain,
High current gains, 1 ion gives 1 to 5 electrons at knob, each
electron gives 5 to 10 photons at the scintillator, each photon,
gives 2 to 10 electrons at the first dynode of the PM,
Signal Pulse intensity usually well above noise intensities,
Linear wide dynamic range (10-21 to 10-13 A).
Daly Characteristic:
Disadvantages:
Complicated
Large footprint
Longer dead time
Scintillator damaged by high electron currents and heat

Analytical Chemistry, Vol. 79, No. 4, February 15, 2007
Analytical Chemistry, Vol. 79, No. 4, February 15, 2007
Analytical Chemistry, Vol. 79, No. 4, February 15, 2007
Analytical Chemistry, Vol. 79, No. 4, February 15, 2007
Analytical Chemistry, Vol. 79, No. 4, February 15, 2007
Electronics-Analog Mode:
Current measurement mode most common and usually
involves a current to voltage converter (CVC):
The OpAmp must be a special one:
High input impedance i.e., must look like a large resistor to the
beam current (>100x the feedback resistance).
High open loop gain (>10,000).
As long as the OpAmp meets these criteria the actual values are
irrelevant, the converter follows the behavior defined by the
equation above.
The converter behavior depends mainly on the feedback
resistor:
To get reasonable voltage output for typical faraday current
range (10-15 to 10-9 A) means we need a large value resistor,
a typical value is 10^11 ohms, so for a beam current of 10-11
A we would have an output voltage of 1V.
Electronics-Analog Mode-Feedback Resistor:
Such high ohm resistors have problems:
Sensitive to environmental factors
Typical temperature coefficient about 100ppm/oC
Sensitive to humidity
Resistors are usually glass or epoxy encapsulated
CVC placed in evacuated, temperature controlled
housing
Resistance depends on voltage across resistor
Voltage coefficients can range from 50 to 500 ppm/V
There can be step changes in the resistance

Small virtual capacitance across resistor slows its response to
changes in voltage:
Typical values are a few pF
1/e response time = R x C = 10^11 x 2 x 10-12 = 0.2 s
So for a step voltage change across the resistor it would take
about 2.3 sec for it to get within 10ppm of the new value and
this is a good response time
This response time means we need to wait for the CVC to
respond to changes in beam current, for example when
switching masses
This effect can be reduced by choosing fast resistors and by
electrically compensating for the response time.
Schematic response curves
The beam intensity here goes to zero instantly but in practice
there is also a magnet response time that slows beam switching.

Additional Comments about CVC
The sensitivity of the CVC is dependent on the size of the
feedback resistor.
Increasing RF increases the sensitivity but at a price,
Response times and noise increase with higher RF.

The CVC can be used for Faraday Cups and Multipliers running
in analog mode.
For multipliers in analog mode, the high current gains of the
multiplier means that smaller resistors can be used (10^9 ohms
is typical).
In this case capacitors are often added to slow the response of
the CVC to filter out the high frequency noise associated with
multipliers.
Because of the limitations of response times and noise Faradays
combined with CVC are limited to about 10-17 A, CVCs
combined with multipliers can give us another factor of 10 or so.
By measuring charge directly however we can extend the
faraday cup sensitivity, this is done by replacing the feedback
resistor with a capacitor.

Charge Measurement:
More sensitive than CVC, a 100fF capacitor and 10-17 A beam
gives a 0.1 mv/s voltage change (same current even with 10^12
ohm resistor gives 0.01 mv voltage output).
Charge Measurement:
Disadvantages:
derivative of voltage needs to be measured.
Capacitor needs to be reset.
Small stable capacitors hard to make and need to be kept in stable
environment.


Pulse or Ion Counting:





Typical (and highly simplified) Pulse Height Spectrum for Ion
Counter
Ion Counting:
Dead Time: Two or more closely spaced ions are counted as
single pulse
Can be corrected.

Breaks down at high count rates.

Some Final Miscellaneous Comments:

All detectors add a bias to the signal measurement that is
mass dependent
This bias is small for faradays but can be large for EMs, Channeltrons and
Dalys especially for low masses
An example:
MIT noble gas machine give 40Ar/36Ar for air of ~300 (accepted values =
295.5?) for faraday measurement
Same measurement on multiplier give ~287

These biases can also be signal size dependent

Does this limit our precision?
Questions:
1. Describe briefly the operation of a faraday cup and its electronics for two
voltage and charge measurements?
2. What is the most important and determinative noise in a faraday cup
measurements?
3. What are secondary electrons and how we can overcame the associated problem
in a faraday cup?
4. What factors can affect the number of secondary electrons in a faraday cup?
5. What are the advantages and disadvantages of electron multipliers compared
with faraday cup?
6. what parameters can affect the gain of a simple electron multiplier?
7. What is the dead time in electron multipliers and what problem does it cause?
8. What are the advantages of a microchannel plate detector and why it is generally
used with time of flight mass analyzer?
9. Draw a schematic diagram of a Daly detector and explain how does it operate?
10. Why Daly detectors produce higher current gains than electron multipliers?
THE END